Glass material for packaging container and preparation method thereof

Abstract

The present invention belongs to the field of glass technology, and particularly relates to a glass material for packaging containers and a preparation method thereof. The glass material for packaging containers comprises the following components in parts by weight: 70-80 parts of SiO2, 5-10 parts of Al2O3, 4-6 parts of Na2O, 0.5-2 parts of K2O, 0.1-1 parts of Li2O, 3-6 parts of La2O3, 1-4 parts of CeO2, and 3-6 parts of a compound of CaO and ZnO; wherein the mass ratio of CaO to ZnO is (2-4): (1-2). By adding three alkali metal oxides of Na2O, K2O, and Li2O, a mixed alkali effect can be achieved, thereby improving the mechanical properties of the glass material. The introduction of lanthanum and cerium rare earth elements has a certain repairing effect on the glass network, further improving the mechanical properties of the glass material.

Description

Technical Field

[0001] The invention belongs to the technical field of glass, and particularly relates to a glass material for packaging containers and a preparation method thereof. Background Art

[0002] Glass can be seen everywhere in our daily life. As a common packaging and protective material, glass is widely used in aerospace, energy, construction, and automobile fields. As one of the common inorganic non-metallic materials, glass is generally made by melting a variety of inorganic minerals, such as quartz sand, boric acid, barium carbonate, barite, feldspar, limestone, etc., which are all common glass raw materials.

[0003] Oxide glass was first discovered and widely used in the fields of construction, automobiles, energy, aerospace, etc. Later, with the rapid development of science and technology, various new types of glass emerged, such as chalcogenide glass and metallic glass. These glass systems are mainly used in optics, electronics, optoelectronics and other fields.

[0004] As one of the most common types of glass, silicate glass is glass with silicon dioxide as its main component. Silicate glass is widely used. For example, glass-ceramics made of aluminosilicate glass are used in the field of electronic equipment due to their high light transmittance, strong scratch resistance, impact resistance, crack resistance and strong drop resistance. Since silicate glass has good safety, impact resistance and penetration resistance, it is often used as packaging and protective glass, with explosion-proof and impact-proof functions. When silicate glass is processed and produced as specific safety glass, it can also meet the market applications of bulletproof glass, ship glass, aerospace vehicles, combat aircraft windows, weapon instrument windows, bank glass partitions, private villa doors and windows, tourist sightseeing plank roads, cable cars, etc.

[0005] The mechanical strength of traditional silicate glass is generally low. Generally, the glass samples are subjected to physical tempering and chemical toughening to improve its mechanical strength. The strength of the treated glass can be greatly improved. In recent years, there have been many studies on aluminosilicate system glasses at home and abroad. In silicate glass, when the content of network modifiers (such as Na2O and CaO, etc.) is higher than that of Al2O3, the aluminum ions are mainly located in the aluminum oxide tetrahedrons. At this time, the network structure of the glass is mainly composed of silicon oxide tetrahedrons and aluminum oxide tetrahedrons connected to each other. Compared with silicon oxide tetrahedrons, aluminum oxide tetrahedrons have a larger volume, so there are more voids inside the glass, which is conducive to the activity of alkali metal ions. Therefore, it is often chemically toughened (ion exchange) by using alkali metal cations with larger ionic radius (such as K + ) to replace the alkali metal cations with smaller ionic radius (such as Na +), so a crowding effect will occur, resulting in the formation of a large compressive stress layer. After strengthening, the mechanical properties of the glass, such as compression and bending resistance, are significantly improved. However, it contains a high content of alumina, which will increase the difficulty of glass melting and forming. On the one hand, the higher melting temperature accelerates the loss of refractory materials. More importantly, aluminosilicate glass is mainly produced by the overflow process, which is costly. Soda-lime-aluminosilicate glass combines the advantages of soda-lime-silica glass and aluminosilicate glass. The melting temperature and forming temperature are relatively low, and the production process is relatively simple and the output is high. Therefore, it has great market potential in the fields of packaging, construction, transportation, etc. However, glass packaging containers are often impacted and collided during transportation and use. At the same time, glass packaging containers generate a certain internal pressure after shaking, which significantly increases the phenomenon of glass packaging containers breaking, limiting their scope of application. Summary of the invention

[0006] The object of the present invention is to provide a glass material for packaging containers and a preparation method thereof, which greatly improves the mechanical properties of the glass container and meets the use requirements of various containers.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] A glass material for packaging containers, comprising the following components in parts by weight:

[0009] SiO2 70-80 parts, Al2O3 5-10 parts, Na2O 4-6 parts, K2O 0.5-2 parts, Li2O 0.1-1 parts, La2O3 3-6 parts, CeO2 1-4 parts, CaO and ZnO compound 3-6 parts; the mass ratio of CaO and ZnO is (2-4): (1-2). Aluminosilicate glass is a type of glass material that is widely used in silicate system glass. As a network intermediate oxide, [AlO4] can connect [SiO4] and the network outer body to a certain extent, repair the network structure of aluminosilicate glass, enhance the mechanical strength, elastic modulus and hardness of aluminosilicate glass, enhance the chemical stability of aluminosilicate glass and reduce its crystallization tendency. However, Al2O3 has a high melting point, which will increase the high-temperature viscosity of aluminosilicate, so its addition amount should be controlled.

[0010] In order to improve the mechanical properties of aluminosilicate glass, the present invention adds a certain amount of alkali metal oxides, alkaline earth and alkaline earth-like metal oxides and rare earth elements. Alkali metal oxides are network-modified oxides, among which Na2O and K2O have relatively low field strengths and can provide free oxygen well, playing the role of "breaking the network" in the glass network; while lithium ions have relatively high field strengths and play an accumulation effect in the network structure. This characteristic helps to improve the surface tension and crystallization ability of the glass. By adding three alkali metal oxides, Na2O, K2O and Li2O, a mixed alkali effect can be achieved to improve the mechanical properties of the glass material.

[0011] However, the introduction of network modifiers has destroyed the network structure of the glass to a certain extent. In order to solve this problem, the present invention adds a certain amount of rare earth oxides. The introduction of lanthanum and cerium rare earth elements has a certain repairing effect on the glass network and improves the mechanical properties of the glass material. Furthermore, the amount of CeO2 is 1.5-2.5 parts. The rare earth cerium atomic radius is relatively large. Excessive use will cause lattice distortion and destroy the glass network structure. CaO belongs to alkaline earth metal oxides, and zinc oxide belongs to alkaline earth metal oxides. The presence of the above-mentioned metal oxide cations is beneficial to reducing defects in the glass; at the same time, it has a strong polarizing effect, which can reduce the melting temperature of aluminosilicate glass and improve the processing performance of aluminosilicate glass. The proportion of CaO should not be less than ZnO, because calcium has a smaller ionic radius than zinc, and has a higher bonding strength with oxygen, which can provide a stronger glass network structure.

[0012] Furthermore, the glass material for packaging container comprises the following components in parts by weight:

[0013] SiO2 73-77 parts, Al2O3 6-8 parts, Na2O 4-5 parts, K2O 1-1.5 parts, Li2O 0.3-0.8 parts, La2O3 4-5 parts, CeO2 1.5-2.5 parts, CaO and ZnO composite 4-5 parts; wherein the mass ratio of CaO to ZnO is (2-4): (1-2).

[0014] Further, the weight of K2O is 1-1.5 parts.

[0015] Furthermore, the mass ratio of CaO to ZnO is 2:1.

[0016] Furthermore, the glass material for packaging container comprises the following components in parts by weight:

[0017] 75 parts of SiO2, 7 parts of Al2O3, 5 parts of Na2O, 1.2 parts of K2O, 0.5 parts of Li2O, 4 parts of La2O3, 2 parts of CeO2, and 4 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 2:1.

[0018] On the other hand, the present invention also provides a method for preparing a glass material for a packaging container, comprising the following steps:

[0019] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0020] (2) heating and melting the mixture to obtain a glass melt;

[0021] (3) The molten glass is poured into a mold to form and anneal the mold to obtain a glass material for packaging containers.

[0022] Furthermore, the heating melting temperature in step (2) is 1550-1650°C.

[0023] Furthermore, the annealing temperature in step (3) is 550-570°C. Glass materials undergo drastic temperature changes during the production process, which can cause internal thermal stress. If annealing is not performed, the glass products may break by themselves during subsequent use and storage. After annealing, the internal stress is reduced, preventing the glass products from breaking during use and improving their physical and chemical properties.

[0024] Beneficial effects: The present invention adds a certain amount of alkali metal oxides, alkaline earth metal oxides, quasi-alkaline earth metal oxides and rare earth elements to the aluminosilicate glass material. The addition of three alkali metal oxides, Na2O, K2O and Li2O, can produce a mixed alkali effect, thereby improving the mechanical properties of the glass material. The introduction of lanthanum and cerium rare earth elements has a certain repairing effect on the glass network, thereby improving the mechanical properties of the glass material. CaO and ZnO are metal oxides, and the presence of the above-mentioned metal oxide cations is beneficial to reducing defects in the glass; at the same time, they have a strong polarization effect, which can reduce the melting temperature of aluminosilicate glass and improve the processing properties of aluminosilicate glass. The glass material for packaging containers prepared by the process of the present invention greatly improves the mechanical properties of the glass container and meets the use requirements of various containers. DETAILED DESCRIPTION

[0025] The experimental methods in the following examples of the present invention, where no specific conditions are specified, are usually carried out under conventional conditions or under conditions recommended by the manufacturers. The various commonly used chemical reagents used in the examples are all commercially available products.

[0026] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0027] The terms "including" and "having" and any variations thereof of the present invention are intended to cover non-exclusive inclusions. For example, a process, method, device, product or equipment comprising a series of steps is not limited to the listed steps or modules, but may optionally include steps not listed, or may optionally include other steps inherent to these processes, methods, products or equipment.

[0028] Example 1

[0029] A glass material for packaging containers, comprising the following components in parts by weight:

[0030] 70 parts of SiO2, 5 parts of Al2O3, 4 parts of Na2O, 1 part of K2O, 0.1 parts of Li2O, 3 parts of La2O3, 1.5 parts of CeO2, and 3 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 2:1.

[0031] A method for preparing a glass material for a packaging container comprises the following steps:

[0032] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0033] (2) heating and melting the mixture to obtain a glass melt; the heating and melting temperature is 1580°C;

[0034] (3) The molten glass is poured into a mold for forming, and annealed at 550°C to obtain a glass material for packaging containers.

[0035] Example 2

[0036] A glass material for packaging containers, comprising the following components in parts by weight:

[0037] 80 parts of SiO2, 10 parts of Al2O3, 6 parts of Na2O, 1.5 parts of K2O, 1 part of Li2O, 6 parts of La2O3, 2.5 parts of CeO2, and 6 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 4:1.

[0038] A method for preparing a glass material for a packaging container comprises the following steps:

[0039] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0040] (2) heating and melting the mixture to obtain a glass melt; the heating and melting temperature is 1650°C;

[0041] (3) The molten glass is poured into a mold for forming, and annealed at 570°C to obtain a glass material for packaging containers.

[0042] Example 3

[0043] A glass material for packaging containers, comprising the following components in parts by weight:

[0044] 70 parts of SiO2, 10 parts of Al2O3, 4 parts of Na2O, 1.5 parts of K2O, 1 part of Li2O, 3 parts of La2O3, 1.5 parts of CeO2, and 6 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 2:1.

[0045] A method for preparing a glass material for a packaging container comprises the following steps:

[0046] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0047] (2) heating and melting the mixture to obtain a glass melt; the heating and melting temperature is 1630°C;

[0048] (3) The molten glass is poured into a mold for forming, and annealed at 560°C to obtain a glass material for packaging containers.

[0049] Example 4

[0050] A glass material for packaging containers, comprising the following components in parts by weight:

[0051] 72 parts of SiO2, 6 parts of Al2O3, 4.5 parts of Na2O, 1.2 parts of K2O, 0.3 parts of Li2O, 4 parts of La2O3, 1.8 parts of CeO2, and 4 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 2:1.5.

[0052] A method for preparing a glass material for a packaging container comprises the following steps:

[0053] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0054] (2) heating and melting the mixture to obtain a glass melt; the heating and melting temperature is 1590°C;

[0055] (3) The molten glass is poured into a mold for forming, and annealed at 570°C to obtain a glass material for packaging containers.

[0056] Example 5

[0057] A glass material for packaging containers, comprising the following components in parts by weight:

[0058] 77 parts of SiO2, 8 parts of Al2O3, 5 parts of Na2O, 1.4 parts of K2O, 0.8 parts of Li2O, 5 parts of La2O3, 2.2 parts of CeO2, and 5 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 3:1.

[0059] A method for preparing a glass material for a packaging container comprises the following steps:

[0060] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0061] (2) heating and melting the mixture to obtain a glass melt; the heating and melting temperature is 1640°C;

[0062] (3) The molten glass is poured into a mold for forming, and annealed at 560°C to obtain a glass material for packaging containers.

[0063] Example 6

[0064] A glass material for packaging containers, comprising the following components in parts by weight:

[0065] 75 parts of SiO2, 7 parts of Al2O3, 5 parts of Na2O, 0.5 parts of K2O, 0.5 parts of Li2O, 4 parts of La2O3, 2 parts of CeO2, and 4 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 2:1.

[0066] A method for preparing a glass material for a packaging container comprises the following steps:

[0067] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0068] (2) heating and melting the mixture to obtain a glass melt; the heating and melting temperature is 1630°C;

[0069] (3) The molten glass is poured into a mold for forming, and annealed at 560°C to obtain a glass material for packaging containers.

[0070] Example 7

[0071] A glass material for packaging containers, comprising the following components in parts by weight:

[0072] 75 parts of SiO2, 7 parts of Al2O3, 5 parts of Na2O, 2 parts of K2O, 0.5 parts of Li2O, 4 parts of La2O3, 2 parts of CeO2, and 4 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 2:1.

[0073] A method for preparing a glass material for a packaging container comprises the following steps:

[0074] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0075] (2) heating and melting the mixture to obtain a glass melt; the heating and melting temperature is 1630°C;

[0076] (3) The molten glass is poured into a mold for forming, and annealed at 560°C to obtain a glass material for packaging containers.

[0077] Example 8

[0078] A glass material for packaging containers, comprising the following components in parts by weight:

[0079] 75 parts of SiO2, 7 parts of Al2O3, 5 parts of Na2O, 1.2 parts of K2O, 0.5 parts of Li2O, 4 parts of La2O3, 1 part of CeO2, and 4 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 2:1.

[0080] A method for preparing a glass material for a packaging container comprises the following steps:

[0081] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0082] (2) heating and melting the mixture to obtain a glass melt; the heating and melting temperature is 1630°C;

[0083] (3) The molten glass is poured into a mold for forming, and annealed at 560°C to obtain a glass material for packaging containers.

[0084] Example 9

[0085] A glass material for packaging containers, comprising the following components in parts by weight:

[0086] 75 parts of SiO2, 7 parts of Al2O3, 5 parts of Na2O, 1.2 parts of K2O, 0.5 parts of Li2O, 4 parts of La2O3, 4 parts of CeO2, and 4 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 2:1.

[0087] A method for preparing a glass material for a packaging container comprises the following steps:

[0088] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0089] (2) heating and melting the mixture to obtain a glass melt; the heating and melting temperature is 1630°C;

[0090] (3) The molten glass is poured into a mold for forming, and annealed at 560°C to obtain a glass material for packaging containers.

[0091] Example 10

[0092] A glass material for packaging containers, comprising the following components in parts by weight:

[0093] 75 parts of SiO2, 7 parts of Al2O3, 5 parts of Na2O, 1.2 parts of K2O, 0.5 parts of Li2O, 4 parts of La2O3, 2 parts of CeO2, and 4 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 2:1.

[0094] A method for preparing a glass material for a packaging container comprises the following steps:

[0095] (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture;

[0096] (2) heating and melting the mixture to obtain a glass melt; the heating and melting temperature is 1630°C;

[0097] (3) The molten glass is poured into a mold for forming, and annealed at 560°C to obtain a glass material for packaging containers.

[0098] Comparative Example 1

[0099] Its components and preparation process are basically the same as those of Example 10, except that 0 parts of La2O3, 3.3 parts of CeO2, and 6.7 parts of a composite of CaO and ZnO are used; wherein the mass ratio of CaO to ZnO is 2:1.

[0100] Comparative Example 2

[0101] Its components and preparation process are basically the same as those of Example 10, except that 5 parts of La2O3, 0 parts of CeO2, and 5 parts of a composite of CaO and ZnO are used; wherein the mass ratio of CaO to ZnO is 2:1.

[0102] Comparative Example 3

[0103] Its components and preparation process are basically the same as those of Example 10, except that La2O3 is 6.7 parts, CeO2 is 3.3 parts, and the composite of CaO and ZnO is 0 parts.

[0104] Comparative Example 4

[0105] Its components and preparation process are basically the same as those of Example 10, except that 4 parts of La2O3, 2 parts of CeO2, and 4 parts of a composite of CaO and ZnO are used; wherein the mass ratio of CaO to ZnO is 1:2.

[0106] The internal pressure resistance and impact resistance of the glass materials for packaging containers prepared in the above embodiments and comparative examples were tested in accordance with GB4544-2020, and the results are shown in Tables 1 and 2.

[0107]

[0108] It can be seen from the data in Table 1 and Table 2 that the present invention adds a certain amount of alkali metal oxides, alkaline earth metal oxides, alkaline earth-like metal oxides and rare earth elements to the aluminosilicate glass material. By adding three alkali metal oxides, Na2O, K2O and Li2O, a mixed alkali effect can be achieved, thereby improving the mechanical properties of the glass material. The introduction of lanthanum and cerium rare earth elements has a certain repairing effect on the glass network, thereby improving the mechanical properties of the glass material. CaO and ZnO are metal oxides, and the presence of the above metal oxide cations is beneficial to reducing defects in the glass; at the same time, they have a strong polarization effect, which can reduce the melting temperature of aluminosilicate glass and improve the processing properties of aluminosilicate glass. Comparative Examples 1-3 show that mixing alkali metal and alkaline earth metal oxides improves the performance of rare earth oxide modified glass materials. Specifically, alkali metal oxides are network-modified oxides, and by adding three alkali metal oxides, Na2O, K2O and Li2O, a mixed alkali effect can be achieved, thereby improving the mechanical properties of the glass material. The introduction of lanthanum and cerium rare earth elements has a certain repairing effect on the glass network, thereby further improving the mechanical properties of the glass material. CaO and ZnO belong to alkaline earth and alkaline earth-like metal oxides. The presence of the above metal oxide cations is conducive to reducing defects in the glass; at the same time, they have a strong polarization effect, which can reduce the melting temperature of aluminosilicate glass and improve the processing performance of aluminosilicate glass. Comparative Example 4 shows that the amount of CaO cannot be less than that of ZnO, because calcium has a smaller ion radius than zinc, has a higher bonding strength with oxygen, and can provide a stronger glass network structure. The above embodiments and comparative examples show that the glass material for packaging containers prepared by the process of the present invention greatly improves the mechanical properties of the glass container and meets the use requirements of various containers.

[0109] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents the selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present application.

Claims

1. A glass material for packaging containers, characterized in that: It is composed of the following components in parts by weight: SiO2 70-80 parts, Al2O3 5-10 parts, Na2O 4-6 parts, K2O 1-1.5 parts, Li2O 0.1-1 parts, La2O3 3-6 parts, CeO2 1.5-2.5 parts, CaO and ZnO composite 3-6 parts; wherein the mass ratio of CaO to ZnO is (2-4): (1-2).

2. The glass material for packaging container according to claim 1, wherein: It is composed of the following components in parts by weight: SiO2 73-77 parts, Al2O3 6-8 parts, Na2O 4-5 parts, K2O 1-1.5 parts, Li2O 0.3-0.8 parts, La2O3 4-5 parts, CeO2 1.5-2.5 parts, CaO and ZnO composite 4-5 parts; wherein the mass ratio of CaO to ZnO is (2-4): (1-2).

3. The glass material for packaging container according to claim 1, characterized in that: The mass ratio of CaO to ZnO is 2:

1.

4. The glass material for packaging container according to claim 1, characterized in that: It is composed of the following components in parts by weight: 75 parts of SiO2, 7 parts of Al2O3, 5 parts of Na2O, 1.2 parts of K2O, 0.5 parts of Li2O, 4 parts of La2O3, 2 parts of CeO2, and 4 parts of a composite of CaO and ZnO; the mass ratio of CaO to ZnO is 2:

1.

5. The method for preparing a glass material for a packaging container according to claim 1, wherein: The following steps are involved: (1) Weighing each component according to its weight and mixing them evenly to obtain a mixture; (2) heating and melting the mixture to obtain a glass melt; (3) The molten glass is poured into a mold to form and anneal the glass material for packaging containers.

6. The method for preparing a glass material for a packaging container according to claim 5, characterized in that: The heating melting temperature in step (2) is 1550-1650°C.

7. The method for preparing a glass material for a packaging container according to claim 5, characterized in that: The annealing temperature in step (3) is 550-570°C.

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