All-tetra-coordinated Mg soda-lime-silica glass and preparation method thereof

Abstract

The invention discloses all-tetra-coordinated Mg soda-lime-silica glass and a preparation method thereof, and belongs to the technical field of glass preparation. The glass comprises the following components in percentage by mole: 40-45% of a network former, 30-40% of a network intermediate, 15-30% of a network modifier, 80-90% of bridged oxygen in a glass network and 10-20% of non-bridged oxygen, and all Mg in the invention is tetra-coordinated and enters the network in the form of magnesium oxide tetrahedron. The soda-lime-silicate glass is prepared by a high-temperature melting three-step method, so that the soda-lime-silicate glass with excellent mechanical property, physical and chemical stability, lower glass transition temperature, excellent transparency and excellent performance is prepared, and meanwhile, the soda-lime-silicate glass has the advantages of high production efficiency and low production cost.

Description

Technical Field

[0001] The invention relates to the technical field of glass preparation, in particular to a full four-coordinated Mg soda-lime-silica glass and a preparation method thereof. Background Art

[0002] Soda-lime silicate glass (soda-lime-silica glass) is the largest glass system produced in the world today. Its main chemical composition is Na 2 O-CaO-SiO 2 . This glass system is widely used in human production and life, such as architectural glass, bottle glass, container packaging materials, etc. Bottle glass, as one of the main application areas of soda-lime-silica glass, needs to be in contact with various liquids and gases for a long time, so there are high requirements for its chemical stability. Since silicate glass is generally not alkali-resistant, and acids other than hydrofluoric acid generally do not react directly with glass, water resistance becomes the main evaluation indicator of the chemical stability of soda-lime-silica glass. The erosion of soda-lime-silica glass by water begins with the dissolution of alkali metal ions in the glass. The H + Replace Na in glass + , the bridging oxygen connected to Si in the silicon-oxygen skeleton is replaced by OH, and the reaction product Si(OH) 4 It is a polar molecule that polarizes the surrounding water molecules to form silica gel, making the structure loose. When it is exposed to changes in temperature or external vibration, it may fall off and flake off. Bottles and cans of glass used to hold food and medicine need to improve the water resistance of the glass as much as possible to avoid such phenomena.

[0003] Although the process flow of soda-lime-silica glass is relatively mature, the amorphous irregular network structure characteristics of glass without fixed bond length and angle, inherent brittleness and melt-quenching process characteristics determine that how to determine its various properties through glass formula is an urgent problem to be solved in the modern soda-lime-silica glass industry. At the same time, the brittleness of glass also limits its application in more fields. Therefore, strengthening mechanical properties, improving physical and chemical stability, optimizing preparation processes, designing and manufacturing high-strength glass and glass toughening and strengthening have always been important topics in the glass industry. Summary of the invention

[0004] In order to overcome the above-mentioned deficiencies of the prior art, the object of the present invention is to provide a fully tetra-coordinated Mg soda-lime-silica glass and a preparation method thereof.

[0005] The object of the present invention is achieved through the following technical scheme: a fully four-coordinated Mg soda-lime-silica glass, comprising:

[0006] The glass has the following composition according to molar percentage:

[0007]

[0008] Wherein, the glass network former is a silicon-oxygen tetrahedron [SiO 4 ]; the glass network intermediate is an aluminum oxide tetrahedron [AlO 4 ]、MgO tetrahedron [MgO 4 ]; the glass network modifier is sodium ion (Na + ), potassium ion (K + ), calcium ions (Ca 2+ ).

[0009] Furthermore, the additive is CaF 2 , NaF, AlF 3 、Na 2 SO 4 , K 2 SO 4 One or more mixtures thereof.

[0010] Furthermore, the bridging oxygen and non-bridging oxygen of the glass have the following ratios in mole percentage:

[0011] Bridging oxygen: 80-90%; non-bridging oxygen: 10-20%;

[0012] The bridging oxygen is an oxygen atom connected to two glass network formers at the same time, and the non-bridging oxygen is an oxygen atom connected to one glass network former and one glass network intermediate.

[0013] The present invention also provides a method for preparing the fully tetra-coordinated Mg soda-lime-silica glass, comprising the following steps:

[0014] Step 1: Add 42-45% SiO 2 、18-24%Al 2 O 3 、10-16%MgCO 3 , 6-10% NaCO 3 4-10% KCO 3 5-10% CaCO 3 As raw materials, [SiO 4 ]、[AlO 4 ]、[MgO 4 ]、Na + , K + , Ca 2+ , calculate the mass of each raw material according to the molar percentage ratio, weigh the required mass of powder raw materials respectively, mix the raw materials evenly and then perform ultra-fine grinding;

[0015] Step 2, melting the ultrafinely crushed mixed powder at 1100-1500° C. for 1-2 hours, pouring the melt into a mold and rapidly cooling it to form a matrix glass; crushing the matrix glass and grinding it into powder;

[0016] Step 3, the powder obtained in step 2 is fully ground and mixed with the additive, and then melted at 1400-1600° C. for 2-3 hours, poured into a mold, rapidly cooled to 200° C., and then naturally cooled to room temperature to obtain a glass block;

[0017] Step 4: anneal the glass block obtained in step 3 at 300-400° C. for 2-4 hours to eliminate stress, and obtain soda-lime-silica glass after surface grinding and polishing.

[0018] Furthermore, in the step 3, the rapid cooling is performed at a cooling rate of 25°C / min.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] 1. The present invention analyzes the influence of glass components and network structure on glass performance. The mechanical properties of glass are mainly affected by the degree of bonding, bond energy and the proportion of partial covalent bonds. The introduction of free oxygen by metal ions such as Na and K causes the silicon-oxygen network to break, produces two non-bridging oxygens, and neutralizes the excess charge of the non-bridging oxygens. The ratio of bridging oxygen and non-bridging oxygen in the network structure is effectively controlled by regulating the number of introduced metal ions. In addition, the increase of Na will lead to a decrease in the number of bridging oxygens in the network, a corresponding decrease in the number of partial covalent bonds and an increase in the number of deviating sub-bonds, resulting in a decrease in the mechanical properties of the glass. The increase of Al can improve the network connectivity of the glass and increase the proportion of partial covalent bonds. The increase in Al content will improve the mechanical properties of the glass. The inhibitory effect of Ca on Na and the increase in Ca content can improve the chemical stability of the glass to a certain extent. The present invention analyzes the mechanism of mechanical property changes of soda-lime-silica glass from the perspective of components, atomic structure and network structure, and prepares soda-lime-silica glass with excellent mechanical properties by optimizing the component ratio.

[0021] 2. Magnesium in different coordination states has differences in chemical properties, physical characteristics and stability. Four-coordinated magnesium is usually more stable and has better thermal stability and resistance to chemical corrosion. The presence of six-coordinated and eight-coordinated magnesium will increase the brittleness of the glass, reduce heat resistance, and easily cause phase changes that destroy the glass network structure, resulting in reduced stability of the glass. The present invention increases the activity of magnesium ions by adjusting the melting temperature, so that magnesium can exist stably with a lower coordination number during the melting process; optimizes the cooling rate, increases the cooling rate without significantly affecting the mechanical properties of the glass, captures magnesium in a four-coordinated state, and prevents it from re-coordinating to a six-coordinated or eight-coordinated structure. The Mg ions are basically present in a four-coordinated form, with [MgO4 ] enters the silicon-oxygen network in the form of tetrahedron. By preparing soda-lime-silica glass with all four-coordinated magnesium, the comprehensive properties of the glass can be significantly improved, making it suitable for more diversified industrial uses.

[0022] 3. The present invention improves the mechanical properties, chemical stability and glass transition temperature of soda-lime-silica glass by adjusting the number of network former ions, network intermediate ions, network modifier ions and other ions in the glass network structure, regulating the number of partial bonds and partial covalent bonds in the glass network structure, changing the network connectivity, the ratio of bridging oxygen and non-bridging oxygen, and the interaction between the ions. The composition ratio of the glass of the present invention is optimized to ensure that it is easy to process and shape while maintaining good performance. During the preparation process, by controlling the melting temperature and time, the magnesium ions can form a four-coordinate state under specific conditions and remain stable during the cooling process. The fully four-coordinated Mg soda-lime-silica glass prepared by the present invention exhibits excellent comprehensive properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 A flow chart of a method for preparing a fully tetra-coordinated Mg soda-lime-silica glass provided in an embodiment of the present invention;

[0024] Figure 2 X-ray diffraction patterns of the glasses obtained in Examples 1-3 of the present invention;

[0025] Figure 3 The figure is a diagram of the amount of 0.01N standard hydrochloric acid required to titrate 25ml of test solution in various embodiments of the present invention;

[0026] Figure 4 is a stress-strain curve diagram of the glass obtained in Example 1 of the present invention;

[0027] Figure 5 is a stress-strain curve diagram of the glass obtained in Example 2 of the present invention;

[0028] Figure 6 is a stress-strain curve diagram of the glass obtained in Example 3 of the present invention;

[0029] Figure 7 is a stress-strain curve diagram of the glass obtained in Example 4 of the present invention;

[0030] Figure 8 This is a stress-strain curve diagram of the glass obtained in Example 5 of the present invention. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention is clearly and completely described. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. The purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as those generally understood by technicians in the field to which the invention belongs.

[0032] In view of the deficiencies in the prior art, the inventors of this study have made creative efforts. After long-term research and extensive practice, the inventors of this study have been able to propose the technical solution of the present invention. The principle conditions of the proposed technical solution are now further explained.

[0033] The principle conditions of the technical solution of the present invention include: (1) the structural unit of the glass network is a tetrahedron, the oxygen atom is located at the vertex position of the network structural unit, and the glass former ion (Si, Al) is located at the center of the structural unit; (2) the structural units are connected by the vertex of the disordered three-dimensional space continuous network, and there is no connection through the common face or common edge. The silicon oxygen tetrahedron is connected to other silicon oxygen tetrahedrons or aluminum oxygen tetrahedrons through the vertex, and the aluminum oxygen tetrahedron and magnesium oxygen tetrahedron are connected to the silicon oxygen tetrahedron through the vertex; (3) the network modifier ions (Na, K, Ca) are used as non-bridging oxygen and aluminum oxygen tetrahedron charge compensators and are uniformly distributed outside the network former. The distribution mode of the glass network former and the glass network modifier in the glass network is analyzed by partial radial distribution function, bond angle distribution and coordination number.

[0034] In summary, the atoms inside the glass are mainly connected by partial covalent bonds, so the glass has a very high theoretical strength and hardness. However, due to the stress concentration caused by the presence of internal unevenness, defects and microcracks, the actual strength of the glass is usually much lower than the theoretical strength. In addition, the interaction between glass and water is an important issue for the long-term durability of silicate glass. Whether inside the glass or on the glass surface, the corrosive effect of the solvent and the ions contained therein will have a significant impact on the properties of the glass. Although there have been many experimental and theoretical studies on the reaction mechanism between silicate glass and water, there is still a lack of clear theoretical conclusions. Therefore, the present invention combines molecular dynamics simulation to study the influence of glass component ratio, glass network structure and topological structure on glass mechanical properties, thermal properties and chemical stability. On this basis, by adjusting the network structure of the glass, the corresponding relationship between the structural analysis results and the chemical stability is found, the corresponding relationship between the glass composition and the network structure analysis results is further determined, the main factors affecting the chemical stability are determined, and the strengthening scheme is selected in a targeted manner. In addition, under the premise of not affecting the mechanical strength and chemical stability as much as possible, the components are designed to reduce the glass transition temperature to achieve the purpose of reducing production costs.

[0035] like Figure 1 As shown, the embodiment of the present invention provides a method for preparing a fully four-coordinated Mg soda-lime-silica glass, comprising the following steps:

[0036] S1, using silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), magnesium carbonate (MgCO 3 ), sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), calcium carbonate (CaCO 3 ) were introduced as raw materials into silicon-oxygen tetrahedrons [SiO 4 ]、aluminum oxide tetrahedron [AlO 4 ]、MgO tetrahedron [MgO 4 ]、Sodium ion (Na + ), potassium ion (K + ), calcium ions (Ca 2+ ), calculate the mass of each raw material according to the molar percentage ratio, weigh the required mass of powder raw materials respectively, pour them into a mortar and mix them evenly, and grind the mixed materials into ultrafine powder.

[0037] S2, melting the mixed powder obtained in step S1 at 1100-1500° C. for 1-2 hours, pouring the melt into a mold and rapidly cooling it to form a matrix glass; crushing the matrix glass and grinding it into powder.

[0038] S3. Grind and mix the powder obtained in step S2 and the auxiliary raw materials thoroughly, then melt them at 1400-1600° C. for 2-3 hours, pour them into a mold, quickly cool them to 200° C., and naturally cool them to room temperature to obtain a glass block.

[0039] S4, annealing the glass block obtained in step S3 at 300-400° C. for 2-4 hours to eliminate stress, and obtaining soda-lime-silica glass after surface grinding and polishing.

[0040] The beneficial effects of the present invention are verified by the following examples:

[0041] Example 1

[0042] Step S1: According to the molar percentage ratio, weigh 2.79g SiO 2 , 1.22g Al 2 O 3 , 0.55g KCO 3 , 0.95 g NaCO 3 , 1.0 g CaCO 3 、1.01g MgCO 3 Powder raw materials, SiO 2 、Al 2 O 3 , KCO 3 、NaCO 3 、CaCO 3 MgCO 3 The powdered raw materials are poured into a mortar and mixed evenly, and then the mixed materials are ultra-finely ground and placed in a corundum crucible. 2 Accounting for 45% of the total molar number of powder raw materials, glass network intermediate raw material powder Al 2 O 3 MgCO 3 The glass network modifier raw material powder KCO accounts for 20% and 12% of the total molar number of the powder raw materials respectively. 3 、NaCO 3 、CaCO 3 They account for 4%, 9% and 10% of the total molar number of powder raw materials respectively.

[0043] Step S2: The mixed powder obtained in step S1 is melted at 1500° C. for 1 hour, and then the melt is poured into a mold for cooling and forming to obtain a matrix glass block. The matrix glass block is then crushed and ground into powder.

[0044] Step S3: Weigh a certain amount of the matrix glass powder obtained in step S2, and weigh the matrix glass powder, 0.5% CaF2 and 0.5% Na 2 SO 4 , pour it into a mortar, grind and mix it evenly, then put it into a corundum crucible, melt it at 1600℃ for 2 hours, pour it into a mold and quickly cool it to 300℃ at a cooling rate of 25℃ / min, then cool it naturally to room temperature to obtain a glass block, anneal the obtained glass block at 300℃ for 4 hours to eliminate stress, and after surface grinding and polishing with alcohol, transparent soda-lime-silica glass can be obtained.

[0045] The X-ray diffraction of the glass ceramic obtained in this example is as follows Figure 2 As shown by the black line in the middle. After measurement, the proportion of bridging oxygen in the soda-lime-silica glass network is about 90%, and the proportion of non-bridging oxygen is about 10%. The average coordination numbers of the cations are: SiO (4), AlO (3.998), NaO (6.013), CaO (5.913), MgO (4.039), Si and Al are basically strictly four-coordinated, and at the same time, the proportion of Mg four-coordinated is more than 98%. The mechanical properties, chemical stability and related physical properties of the glass were tested. The stress-strain curve of the soda-lime-silica glass obtained in this embodiment at a thickness of 0.6 mm is shown as follows: Figure 4 As shown, the bulk modulus of the soda-lime-silica glass is 52.96 GPa, the shear modulus is 25.48 GPa, the elastic modulus is 65.86 GPa, and the transmittance is greater than 90% in the visible light wavelength range. After being immersed in an acetic acid solution with a pH value of 2.9 for 5 hours, the soda-lime-silica glass did not delaminate. The water resistance of the soda-lime-silica glass was tested by titration. Figure 3 As shown, the amount of 0.01N standard hydrochloric acid required for titrating 25mL of the test solution in this embodiment is 0.55mL, indicating that the obtained soda-lime-silica glass has excellent water resistance. According to the standard, the glass obtained in this embodiment is subjected to an alkali resistance test, and the test shows that the soda-lime-silica glass obtained in this embodiment exhibits excellent alkali resistance.

[0046] Example 2

[0047] Step S1: According to the molar percentage ratio, weigh 2.40g SiO 2 , 1.84 g Al 2 O 3 , 1.38 g KCO 3 , 1.06 g NaCO 3 , 1.0 g CaCO 3 、1.01g MgCO 3 Powder raw materials, SiO 2 、Al 2 O 3 , KCO 3 、NaCO 3、CaCO 3 MgCO 3 The powdered raw materials are poured into a mortar and mixed evenly, and then the mixed materials are ultra-finely ground and placed in a corundum crucible. 2 Accounting for 40% of the total molar number of powder raw materials, glass network intermediate raw material powder Al 2 O 3 MgCO 3 The total molar amount of the powder raw materials is 18% and 12%, respectively, and the glass network modifier raw material powder KCO 3 、NaCO 3 、CaCO 3 They account for 10%, 10% and 10% of the total moles of powder raw materials respectively.

[0048] Step S2: The mixed powder obtained in step S1 is melted at 1400° C. for 1.5 hours, and then the melt is poured into a mold for cooling and forming to obtain a matrix glass block. The matrix glass block is then crushed and ground into powder.

[0049] Step S3: Weigh a certain amount of the matrix glass powder obtained in step S2, and weigh the matrix glass powder, 0.5% CaF 2 , 0.3%Na 2 SO 4 , 0.4%K 2 SO 4 , pour it into a mortar, grind and mix it evenly, then put it into a corundum crucible, melt it at 1500℃ for 2.5 hours, pour it into a mold and quickly cool it to 300℃ at a cooling rate of 25℃ / min, then cool it naturally to room temperature to obtain a glass block, anneal the obtained glass block at 400℃ for 4 hours to eliminate stress, and after surface grinding and polishing with alcohol, transparent soda-lime-silica glass can be obtained.

[0050] The X-ray diffraction of the glass ceramic obtained in this example is as follows Figure 2 As shown by the red line in the middle. After measurement, the bridging oxygen accounts for 80% of the soda-lime-silica glass network, and the non-bridging oxygen accounts for 20%. The average coordination numbers of the cations are SiO(4), AlO(4), NaO(5.744), CaO(5.71), and MgO(4.057). Si and Al are basically strictly four-coordinated. At the same time, the four-coordinated Mg accounts for more than 98%. The mechanical properties, chemical stability and related physical properties of the glass were tested. The stress-strain curve of the soda-lime-silica glass obtained in this embodiment at a thickness of 0.6 mm is shown as follows: Figure 5As shown, the bulk modulus of the soda-lime-silica glass is 54.59 GPa, the shear modulus is 22.13 GPa, the elastic modulus is 58.49 GPa, and the transmittance is greater than 90% in the visible light wavelength range. After being immersed in an acetic acid solution with a pH value of 2.9 for 5 hours, the soda-lime-silica glass did not show obvious delamination. The water resistance of the soda-lime-silica glass was tested by titration, as shown in FIG. Figure 3 As shown, the amount of 0.01N standard hydrochloric acid required for titrating 25mL of the test solution in this embodiment is 1.56mL. The test shows that the water-resistant chemical stability of the soda-lime-silica glass obtained in this embodiment is poor. According to the standard, the alkali resistance test of the glass obtained in this embodiment is carried out, and the test shows that the soda-lime-silica glass obtained in this embodiment exhibits good alkali resistance.

[0051] Example 3

[0052] Step S1: According to the molar percentage ratio, weigh 2.58g SiO 2 , 2.24 g Al 2 O 3 , 1.11 g KCO 3 , 0.80 g NaCO 3 , 0.75 g CaCO 3 、1.01g MgCO 3 Powder raw materials, SiO 2 、Al 2 O 3 , KCO 3 、NaCO 3 、CaCO 3 MgCO 3 The powdered raw materials are poured into a mortar and mixed evenly, and then the mixed materials are ultra-finely ground and placed in a corundum crucible. 2 Accounting for 43% of the total molar number of powder raw materials, glass network intermediate raw material powder Al 2 O 3 MgCO 3 The total molar amount of the powder raw materials is 22% and 12%, respectively, and the glass network modifier raw material powder KCO 3 、NaCO 3 、CaCO 3 They account for 8%, 7.5% and 7.5% of the total molar number of powder raw materials respectively.

[0053] Step S2: The mixed powder obtained in step S1 is melted at 1100° C. for 2 hours, and then the melt is poured into a mold for cooling and forming to obtain a matrix glass block. The matrix glass block is then crushed and ground into powder.

[0054] Step S3: Weigh a certain amount of the matrix glass powder obtained in step S2, and weigh the matrix glass powder, 0.3% CaF 2 , 0.2%NaF, 0.3%Na 2 SO 4 and 0.4% K 2 SO 4 , pour it into a mortar, grind and mix it evenly, then put it into a corundum crucible, melt it at 1400℃ for 3 hours, pour it into a mold and quickly cool it to 300℃ at a cooling rate of 25℃ / min, then cool it naturally to room temperature to obtain a glass block, anneal the obtained glass block at 300℃ for 4 hours to eliminate stress, and after surface grinding and polishing with alcohol, transparent soda-lime-silica glass can be obtained.

[0055] The X-ray diffraction of the glass ceramic obtained in this example is as follows Figure 2 As shown by the middle blue line. After measurement, the proportion of bridging oxygen in the soda-lime-silica glass network is 83%, and the proportion of non-bridging oxygen is 17%. The average coordination numbers of the cations are SiO (4), AlO (3.999), NaO (5.46), CaO (5.94), and MgO (4.029), respectively. Si and Al as network formers are basically strictly four-coordinated. At the same time, the proportion of Mg four-coordinated is also more than 98%. The mechanical properties, chemical stability and related physical properties of the glass were tested. The stress-strain curve of the soda-lime-silica glass obtained in this embodiment at a thickness of 0.6 mm is shown as follows: Figure 6 As shown, the bulk modulus of the soda-lime-silica glass is 43.28 GPa, the shear modulus is 21.97 GPa, the elastic modulus is 56.37 GPa, and the transmittance is greater than 88% in the visible light wavelength range. After being immersed in an acetic acid solution with a pH value of 2.9 for 5 hours, the soda-lime-silica glass did not delaminate. The water resistance of the soda-lime-silica glass was tested by titration. Figure 3 As shown, the amount of 0.01N standard hydrochloric acid required for titrating 25mL of the test solution in the embodiment is 0.68mL. The test shows that the soda-lime-silica glass obtained in this embodiment has good water resistance. The alkali resistance test of the glass obtained in this embodiment is performed according to the standard, and the test shows that the soda-lime-silica glass obtained in this embodiment also shows good alkali resistance.

[0056] Example 4

[0057] Step S1: According to the molar percentage ratio, weigh 2.64g SiO 2 , 2.14 g Al 2 O 3 , 0.83 g KCO 3 , 0.95 g NaCO 3 , 1.0 g CaCO 3、0.84g MgCO 3 Powder raw materials, SiO 2 、Al 2 O 3 , KCO 3 、NaCO 3 、CaCO 3 MgCO 3 The powdered raw materials are poured into a mortar and mixed evenly, and then the mixed materials are ultra-finely ground and placed in a corundum crucible. 2 Accounting for 44% of the total molar number of powder raw materials, glass network intermediate raw material powder Al 2 O 3 MgCO 3 The total molar amount of the powder raw materials is 21% and 10%, respectively, and the glass network modifier raw material powder KCO 3 、NaCO 3 、CaCO 3 They account for 6%, 9% and 10% of the total molar number of powder raw materials respectively.

[0058] Step S2: The mixed powder obtained in step S1 is melted at 1200° C. for 2 hours, and then the melt is poured into a mold for cooling and forming to obtain a matrix glass block. The matrix glass block is then crushed and ground into powder.

[0059] Step S3: Weigh a certain amount of the matrix glass powder obtained in step S2, and weigh the matrix glass powder, 0.3% CaF 2 , 0.2% NaF and 0.5% K 2 SO 4 , pour it into a mortar, grind and mix it evenly, then put it into a corundum crucible, melt it at 1400℃ for 3 hours, pour it into a mold and quickly cool it to 300℃ at a cooling rate of 25℃ / min, then cool it naturally to room temperature to obtain a glass block, anneal the obtained glass block at 300℃ for 4 hours to eliminate stress, and after surface grinding and polishing with alcohol, transparent soda-lime-silica glass can be obtained.

[0060] After measurement, the proportion of bridging oxygen in the soda-lime-silica glass network is 89%, the proportion of non-bridging oxygen is 11%, and the average coordination number of each cation is SiO(4), AlO(4), NaO(5.675), CaO(5.942), MgO(4.018), Si and Al are basically strictly four-coordinated, and the proportion of Mg four-coordinated is more than 98%. The mechanical properties, chemical stability and related physical properties of the glass were tested. The stress-strain curve of the soda-lime-silica glass obtained in this embodiment at a thickness of 0.6 mm is shown in FIG. Figure 7As shown in the figure, the bulk modulus of the soda-lime-silica glass is 49.12 GPa, the shear modulus is 21.94 GPa, the elastic modulus is 57.29 GPa, and the transmittance is greater than 90% in the visible light wavelength range. After being immersed in an acetic acid solution with a pH value of 2.9 for 5 hours, the soda-lime-silica glass did not delaminate. The water resistance of the soda-lime-silica glass was tested by titration. Figure 3 As shown, the amount of 0.01N standard hydrochloric acid required for titrating 25mL of the test solution in this embodiment is 0.59mL. The test shows that the soda-lime-silica glass obtained in this embodiment has excellent water resistance. The alkali resistance test of the glass obtained in this embodiment is performed according to the standard, and the test shows that the soda-lime-silica glass obtained in this embodiment exhibits excellent alkali resistance.

[0061] Example 5

[0062] Step S1: According to the molar percentage ratio, weigh 2.79g SiO 2 , 2.45g Al 2 O 3 , 0.55g KCO 3 , 0.64 g NaCO 3 , 0.5 g CaCO 3 、1.35g MgCO 3 Powder raw materials, SiO 2 、Al 2 O 3 , KCO 3 、NaCO 3 、CaCO 3 MgCO 3 The powdered raw materials are poured into a mortar and mixed evenly, and then the mixed materials are ultra-finely ground and placed in a corundum crucible. 2 Accounting for 45% of the total molar number of powder raw materials, glass network intermediate raw material powder Al 2 O 3 MgCO 3 The total molar amount of the powder raw materials is 24% and 16%, respectively, and the glass network modifier raw material powder KCO 3 、NaCO 3 、CaCO 3 They account for 4%, 6% and 5% of the total molar number of powder raw materials respectively.

[0063] Step S2: The mixed powder obtained in step S1 is melted at 1400° C. for 1.5 hours, and then the melt is poured into a mold for cooling and forming to obtain a matrix glass block. The matrix glass block is then crushed and ground into powder.

[0064] Step S3: Weigh a certain amount of the matrix glass powder obtained in step S2, and weigh the matrix glass powder, 0.5% NaF, 0.3% Na 2 SO 4 and 0.2%K 2 SO 4 , pour it into a mortar, grind and mix it evenly, then put it into a corundum crucible, melt it at 1500℃ for 3 hours, pour it into a mold and quickly cool it to 300℃ at a cooling rate of 25℃ / min, then cool it naturally to room temperature to obtain a glass block, anneal the obtained glass block at 300℃ for 4 hours to eliminate stress, and after surface grinding and polishing with alcohol, transparent soda-lime-silica glass can be obtained.

[0065] After measurement, the proportion of bridging oxygen in the soda-lime-silica glass network is 86%, the proportion of non-bridging oxygen is 14%, and the average coordination number of each cation is SiO(4), AlO(4), NaO(5.462), CaO(5.698), MgO(4.066), Si and Al are basically strictly four-coordinated, and the proportion of Mg four-coordinated is more than 98%. The mechanical properties, chemical stability and related physical properties of the glass were tested. The stress-strain curve of the soda-lime-silica glass obtained in this embodiment at a thickness of 0.6 mm is shown in FIG. Figure 8 As shown, the bulk modulus of soda-lime-silica glass is 49.64 GPa, the shear modulus is 20.18 GPa, the elastic modulus is 53.31 GPa, and the transmittance is greater than 90% in the visible light wavelength range. After being immersed in an acetic acid solution with a pH value of 2.9 for 5 hours, the soda-lime-silica glass shows a purple-blue interference color, but no obvious delamination occurs. The water resistance of the soda-lime-silica glass is tested by titration, as shown in FIG. Figure 3 As shown, the amount of 0.01N standard hydrochloric acid required for titrating 25ml of the test solution in this embodiment is 0.65mL. The test shows that the soda-lime-silica glass obtained in this embodiment has good water resistance. The alkali resistance test of the glass obtained in this embodiment is carried out according to the standard, and the test shows that the soda-lime-silica glass obtained in this embodiment exhibits good alkali resistance.

[0066] The soda-lime-silica glass product prepared in the above embodiment was subjected to relevant performance tests in accordance with relevant international standards and domestic standards, as follows.

[0067] The chemical analysis method of soda-lime-silica glass is carried out in accordance with the standard specified in GB / T 1347-2008.

[0068] The water resistance test method of soda-lime-silica glass is carried out in accordance with the standard specified in GB / T 6582-2021.

[0069] The acid resistance test method of soda-lime-silica glass is carried out in accordance with the standard GB / T 7962.14-2010.

[0070] The alkali resistance test method of soda-lime-silica glass is carried out in accordance with the standard specified in GB / T 7962.21-2019.

[0071] The mechanical properties test method of soda-lime-silica glass is carried out in accordance with the standard GB / T 33870-2019.

[0072] The average coordination number of cations, the proportions of each component, the performance test results, and the amount of reagents used in the performance test process of each embodiment of the present invention are shown in Tables 1 to 4.

[0073] Table 1: Average coordination number of the main cations in each example

[0074] Atom Pairs SiO AlO NaO CaO MgO Example 1 4 3.998 6.013 5.913 4.039 Example 2 4 4 5.744 5.71 4.057 Example 3 4 3.999 5.46 5.94 4.029 Example 4 4 4 5.675 5.942 4.018 Example 5 4 4 5.462 5.698 4.066

[0075] Table 2: Proportions of bridging oxygen (BO), non-bridging oxygen (NBO), network former, network intermediate, and network modified form in each example

[0076]

[0077] Table 3: Mechanical properties of the glass prepared in each embodiment

[0078] Performance (Gpa) Example 1 Example 2 Example 3 Example 4 Example 5 Bulk modulus 52.96 54.59 43.28 49.12 49.64 Shear modulus 25.48 22.13 21.97 21.94 20.18 Elastic modulus 65.86 58.49 56.37 57.29 53.31

[0079] Table 4: Amount of 0.01N standard hydrochloric acid required for titrating 25 ml of test solution in each example (unit: ml)

[0080]

[0081] As shown in the table above, Si and Al as network formers are basically strictly four-coordinated, and there is only one coordination mode of four-coordinated. The coordination numbers of Na and Ca are between four and six, indicating that they exist in more than one coordination form. Mg basically exists in the form of four-coordinated, with [MgO 4] enters the silicon-oxygen network in the form of tetrahedrons. The network formers Al and Si in the network components affect the proportion of covalent bonds in the system. The increase in the number of network formers will increase the proportion of covalent bonds in the glass, thereby affecting the mechanical properties of the glass. Network modifiers Na, Ca, etc. in the network components affect the mechanical properties of the glass by changing the network connectivity. The increase or decrease in their content will affect the network connectivity. Metals such as Na and K have a network interrupting effect in the network, introducing free oxygen, destroying the bridging oxygen in the network, reducing the connectivity of the network, and causing an increase in non-bridging oxygen in the network, thereby affecting the performance of the glass. The Na and Ca ions in soda-lime-silica glass will preferentially bond with the two oxygen atoms of the same network former. At the same time, the number of bridging oxygens in soda-lime-silica glass with a lower alkali content is relatively large, and the probability of Na and Ca ions bonding with non-bridging oxygen is reduced. The change in Al content also causes the role of sodium ions as charge compensators to change.

[0082] The present invention aims at the problems of low mechanical strength, limited physicochemical stability, and glass transition temperature limiting process temperature in the application of soda-lime-silica glass in bottle glass, and summarizes the relationship between the components, structures, and properties of soda-lime-silica glass by combining molecular dynamics simulation and experimental analysis. The mechanical properties such as elastic modulus of glass samples were simulated by using structural features such as partial radial distribution function, bond angle distribution function, coordination number, bridging oxygen, and ring size distribution, and then further verified by experiments. The influence of glass components, distribution, and network structure on glass properties was inferred by combining molecular dynamics simulation and experiments, and the formula and experimental conditions of soda-lime-silica were optimized accordingly. The soda-lime-silica glass prepared by the present invention has excellent mechanical properties and good physicochemical stability.

[0083] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, although the embodiments of the present invention have been shown and described, it is understood by those of ordinary skill in the art that many modifications and changes can be made without departing from the principles and spirit of the present invention. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and use the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A fully four-coordinated Mg soda-lime-silica glass, characterized in that: include: The glass has the following composition according to molar percentage: Glass network former: 40-45%; Glass network intermediates: 30-40%; Glass network modifier: 15-30%; Additives: 1-1.5%; Among them, the glass network former is silicon-oxygen tetrahedron; the glass network intermediate is aluminum-oxygen tetrahedron and magnesium-oxygen tetrahedron; the glass network modifier is Na + , K + , Ca 2+ .

2. The fully tetra-coordinated Mg soda-lime-silica glass according to claim 1, characterized in that: The additive is a mixture of one or more of CaF2, NaF, AlF3, Na2SO4, and K2SO4.

3. The fully tetra-coordinated Mg soda-lime-silica glass according to claim 1, characterized in that: The bridging oxygen and non-bridging oxygen of the glass have the following ratios in mole percentage: Bridging oxygen: 80-90%; non-bridging oxygen: 10-20%; The bridging oxygen is an oxygen atom connected to two glass network formers at the same time, and the non-bridging oxygen is an oxygen atom connected to one glass network former and one glass network intermediate.

4. A method for preparing the fully tetra-coordinated Mg soda-lime-silica glass according to any one of claims 1 to 3, characterized in that: The following steps are involved: (1) 42-45% SiO2, 18-24% Al2O3, 10-16% MgCO3, 6-10% NaCO3, 4-10% KCO3, and 5-10% CaCO3 are introduced as raw materials into silicon-oxygen tetrahedron, aluminum-oxygen tetrahedron, magnesium-oxygen tetrahedron, and Na + , K + , Ca 2+ , calculate the mass of each raw material according to the molar percentage ratio, weigh the required mass of powder raw materials respectively, mix the raw materials evenly and then perform ultra-fine grinding; (2) melting the ultrafinely crushed mixed powder at 1100-1500° C. for 1-2 hours, pouring the melt into a mold and rapidly cooling it to form a matrix glass; crushing the matrix glass and grinding it into powder; (3) grinding and mixing the powder obtained in step (2) with the additives, melting at 1400-1600° C. for 2-3 hours, pouring into a mold, rapidly cooling to 200° C., and then naturally cooling to room temperature to obtain a glass block; (4) Annealing the glass block obtained in step (3) at 300-400° C. for 2-4 hours to eliminate stress, and then surface grinding and polishing to obtain soda-lime-silica glass.

5. The preparation method according to claim 4, characterized in that: In the step (3), the rapid cooling is performed at a cooling rate of 25°C / min.

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