Water-resistant strong-alkali-resistant high-zirconium low-aluminum glass as well as preparation method and application thereof

Abstract

The invention discloses water-resistant and strong-alkali-resistant high-zirconium low-aluminum glass as well as a preparation method and application of the water-resistant and strong-alkali-resistant high-zirconium low-aluminum glass. The water-resistant and strong-alkali-resistant high-zirconium low-aluminum glass is prepared from the following raw materials in percentage by weight: 62.0 to 68.0 percent of SiO2, 1.0 to 5.0 percent of Al2O3, 0.1 to 0.3 percent of TiO2, 12.5 to 13.8 percent of ZrO2, 6.0 to 15.0 percent of Na2O, 5.0 to 8.0 percent of K2O, 0.1 to 3.0 percent of Li2O, 0 to 1.0 percent of La2O3 and 1.0 to 2.0 percent of Sb2O3. The preparation method comprises the following steps: directly adding uniformly mixed ingredients into a platinum crucible preheated to 1400-1500 DEG C, putting the platinum crucible into a lifting furnace, preserving heat at 1480-1500 DEG C for 40-60 minutes, taking out the crucible, and pouring melt on a mold; and after the molten liquid is formed, quickly transferring the molten liquid into an annealing furnace, preserving heat at 530-540 DEG C for 30 minutes, and cooling to room temperature along with the furnace to obtain the water-resistant strong-alkali-resistant high-zirconium low-aluminum glass. The problems that existing water-resistant glass mainly depends on boron, but boron oxide is easy to volatilize, and melting is difficult due to high melting temperature are solved.

Description

Technical Field

[0001] The present invention belongs to the field of glass, and in particular relates to a water-resistant and alkali-resistant high-zirconium and low-aluminum glass, and a preparation method and application thereof. Background Art

[0002] Glass materials are widely used in the packaging of injections, biological products, high-end preparations and other medicines due to their good chemical stability, barrier properties and safety. However, traditional pharmaceutical glass such as soda-lime glass and low-borosilicate glass have limitations in key properties such as water resistance and acid and alkali resistance, and are difficult to meet the packaging needs of strong acids, strong alkalis or long-term storage of medicines. With the improvement of international pharmaceutical standards and the development of domestic high-end preparations, higher requirements are placed on the water resistance of pharmaceutical glass. Pharmaceutical glass is used to contain injections, oral liquids, vaccines, biological preparations and other medicines, and needs to be in contact with liquid medicines or humid environments for a long time. If the water resistance is poor, the metal ions in the glass (such as Na + , K + ) may precipitate, causing changes in the pH of the drug solution, the formation of precipitation or impurities, and even causing drug deterioration, failure, or safety risks. Currently, improving the water resistance of pharmaceutical glass mainly relies on the element boron (B2O3), but boron oxide is volatile. Furthermore, traditional high-zirconium glass, due to its melting temperature of ≥1600°C, results in high energy consumption and severe equipment corrosion.

[0003] Patent application CN103058514A discloses the formula and production method for a first-class water-resistant glass for molded injection bottles. The chemical composition of the glass is SiO2: 77.88%; Al2O3: 1.8%; Mo: 0.4%; B2O3: 12.6%; R2O: 7.3%; and Fe2O3: 0.02%. M represents divalent alkaline earth metals (Ca, Mg, and Ba); and R represents divalent alkaline earth metals (K and Na). This glass tube is first-class water-resistant, but it suffers from boron volatilization and a high silica content, resulting in high melting temperatures and difficulty in melting.

[0004] Patent application CN110963704A discloses a highly water-resistant neutral borosilicate glass and its preparation method. The glass is composed of the following raw materials by weight: 69-73% SiO2, 2-5% Al2O3, 1-2.5% ZrO2, 8-11% B2O3, 0-0.5% MgO, 0-1% CaO, 5-8% Na2O, 0-1% K2O, 0-1.5% BaO, and 1-4% ZnO. This glass significantly improves water resistance, but the glass has a high melting temperature, making it difficult to melt. Furthermore, boron phase separation is evident, making it difficult to control defects.

[0005] Patent application document with publication number CN119569331A discloses a high alkali-resistant glass, its preparation method and application. The raw materials include: 64-67wt% SiO2, 0.2-0.4wt% Al2O3, 0.1-0.2wt% TiO2, 14-18wt% ZrO2, 16.7-18wt% Na2O, 0.1-0.2wt% K2O and 0.5-1wt% Sb2O3. However, its high ZrO2 content makes it difficult to melt, and its water resistance weight loss is 10.72-17.48g / dm 2 , when the liquid medicine is stored for a long time, its water resistance is poor. Summary of the Invention

[0006] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a high-zirconium, low-aluminum glass that is resistant to water and strong alkali, and its preparation method and application, which solves the problem that the existing water-resistant glass mainly relies on the boron element, but boron oxide is volatile, and the high melting temperature makes melting difficult.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A water-resistant and alkali-resistant high-zirconium low-aluminum glass, the raw materials of which include 62.0-68.0wt.% SiO2, 1.0-5.0wt.% Al2O3, 0.1-0.3wt.% TiO2, 12.5-13.8wt.% ZrO2, 6.0-15.0wt.% Na2O, 5.0-8.0wt.% K2O, 0.1-3.0wt.% Li2O, 0-1.0wt.% La2O3 and 1.0-2.0wt.% Sb2O3.

[0009] Furthermore, the water-resistant weight loss of the high-zirconium low-aluminum glass is 0.71 mg / dm 2 the following.

[0010] Further, the raw materials include 62.0 wt.% SiO2, 4.4 wt.% Al2O3, 0.2 wt.% TiO2, 13.8 wt.% ZrO2, 7.1 wt.% Na2O, 8.0 wt.% K2O, 2.5 wt.% Li2O, 1.0 wt.% La2O3, and 1.0 wt.% Sb2O3.

[0011] A method for preparing water-resistant and alkali-resistant high-zirconium low-aluminum glass, characterized by comprising the following steps:

[0012] Step 1: Weigh the raw materials according to the ratio and sieve them until they are fully mixed;

[0013] Step 2: Add the mixed ingredients from step 1 directly into a platinum crucible preheated to 1400-1500°C, place it in a lifting furnace and keep it at 1480-1500°C for 40-60 minutes, then take out the crucible and pour the melt into the mold;

[0014] Step 3: After the melt is formed, it is quickly transferred to an annealing furnace, kept at 530-540°C for 30 minutes, and then cooled to room temperature along with the furnace to obtain water-resistant and alkali-resistant high-zirconium low-aluminum glass.

[0015] Application of high-zirconium, low-aluminum glass that is resistant to water and strong alkali in drug storage.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] The present invention has a relatively low aluminum oxide content, but still achieves excellent chemical stability and mechanical properties through synergistic action with zirconium oxide. 1.0-5.0 wt.% of Al2O3 connects [ZrO6] units through Al-O-Zr bonds, reducing non-bridging oxygen defects. The appropriate addition of Al2O3 helps to strengthen the network structure of the glass, improve its corrosion resistance and hardness, and avoids the problems of glass melting difficulties and decreased processing performance that may be caused by excessive Al2O3 content. 12.5-13.8 wt.% of ZrO2 is embedded in the silicon-oxygen network as [ZrO6], filling the gaps and forming Zr-O-Si bonds, thereby improving the structural density. The synergistic mechanism of the three ions combined with the ternary mixed alkali effect of Na2O, K2O and Li2O further enhances the performance of the glass: the high field strength of Li+ can enhance the strength of the silicon-oxygen bond, reduce the network formation energy, and reduce the melting temperature to below 1500°C (100-200°C lower than traditional boron-containing glass). Na+ and K+ reduce the structural defects caused by a single alkali metal through the "mixed alkali effect", and improve the melting performance by adjusting the viscosity of the glass. At the same time, the three ions form a composite protective layer on the glass surface, hindering the penetration of H2O molecules and reducing the migration of alkali metal ions, thereby significantly improving water resistance and alkali resistance. The combined effect of the three reduces the water resistance weight loss to 0.71 mg / dm 2 The following increases the glass's water resistance by 3-6 times compared to traditional medium-boron silicate glass, while also reducing energy consumption by approximately 25%. The synergistic effect of high zirconium and low aluminum in this invention, combined with a boron-free system, addresses the dual technical bottlenecks of existing high-zirconium glass, which is difficult to melt at high temperatures, and boron-containing glass, which is prone to boron volatilization. It also improves the glass's machinability and reduces production energy consumption, resulting in significant economic benefits. It is suitable for applications requiring high chemical stability and mechanical properties.

[0018] The holding time has an important influence on the formation of the glass network structure. A shorter holding time may lead to an imperfect glass network structure, while an excessively long holding time may cause problems such as component stratification. The present invention optimizes the holding time to 40-60 minutes to achieve the best density of the glass network structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The infrared spectra of Examples 1 to 4 are shown.

[0020] Figure 2 This is a graph showing the weight loss changes of Examples 1 to 6 after being corroded in deionized water at 98° C. for 1 hour. DETAILED DESCRIPTION

[0021] The specific contents of the present invention are further explained in detail below with reference to the embodiments.

[0022] The present invention constructs a highly dense silicon-oxygen network through a boron-free design (ZrO2 12.5-13.8wt.%, Al2O3 1.0-5.0wt.%) and alkali metal regulation (6.0-15.0wt.% Na2O), significantly improving water resistance (HGB1 level), acid resistance, and alkali resistance (all reaching the first-level standard), while avoiding the volatilization defects and component stratification problems of traditional boron-containing glass.

[0023] A high-zirconium, low-aluminum glass that is resistant to water and strong alkali, in which high content of ZrO2 fills the network gaps to inhibit ion migration, and low content of Al2O3 reduces structural defects in alkaline environments. 4+ As a high-field strength cation, [ZrO6] octahedra are embedded in the silicon-oxygen network, filling gaps and connecting broken Si-O bonds, thereby increasing the density of the glass structure. Al2O3 can form relatively stable Si-O-Al bonds with SiO2, enhancing the connectivity of the glass network. Furthermore, a small amount of Al2O3 can introduce an appropriate amount of non-bridging oxygen, improving the chemical stability of the glass and preventing the degradation of chemical durability caused by excessive non-bridging oxygen. High ZrO2 content forms a highly stable zirconium-oxygen polyhedron structure in the glass, which interweaves with the aluminum-oxygen tetrahedron introduced by low Al2O3 content (≤5 wt.%) to build a denser and more uniform glass network. This dense network structure effectively reduces porosity and defects within the glass, thereby reducing the possibility of intrusion by corrosive media. Combined with the Sb2O3 clarification process, the glass achieves a uniform composition and is free of bubbles and stones; the melting temperature is low (1480-1500°C). This formula has low raw material cost, simple process, no need for special equipment, and excellent chemical stability. It is suitable for scenarios with strict requirements on water resistance, such as biological preparations, alkaline injections, and long-term storage of drug solutions.

[0024] The present invention uses quartz sand as a raw material to introduce SiO2 and alumina as a raw material to introduce Al2O3. SiO2, as a glass-forming oxide, acts as a skeleton in the glass structure. Al2O3, as an intermediate oxide, reduces the tendency of glass to crystallize and forms aluminum-oxygen tetrahedra with SiO2, strengthening the network structure and improving mechanical strength and water resistance. The ternary mixed alkali system of Na2O, K2O, and Li2O employed exhibits a significant synergistic effect. The sodium, potassium, and lithium ions in the ternary mixed alkali system form a dense protective layer on the glass surface, effectively inhibiting water molecules from corroding the glass network. Simultaneously, the addition of lithium ions strengthens the silicon-oxygen bonds in the glass network and reduces the breakage of these bonds by water molecules. Furthermore, the ternary mixed alkali system improves the chemical stability of the glass and reduces the mobility of alkali metal ions in the glass, thereby significantly enhancing the glass's water resistance. Lithium ions have a high field strength and can effectively reduce the formation energy of the glass network, thereby lowering the glass's melting temperature. At the same time, the synergistic effect of sodium and potassium ions can further reduce the viscosity of the glass, allowing the glass to melt and clarify well at lower temperatures. La2O3, as a network-external oxide, can form relatively stable chemical bonds with other components in the glass, making the network structure denser and tighter, thereby reducing the pores and defects inside the glass, reducing the possibility of chemical penetration and diffusion, and enhancing the glass's resistance to acids, alkalis and other chemicals, thereby improving its chemical stability.

[0025] The raw materials do not contain B2O3, which avoids the deterioration of the glass melt caused by boron volatilization, which not only increases raw material consumption and reduces quality, but also corrodes the kiln and shortens the kiln life.

[0026] Example 1

[0027] A method for preparing water-resistant and alkali-resistant high-zirconium low-aluminum glass comprises the following steps:

[0028] Step 1, according to 65.8wt.% SiO2, 1.4wt.% Al2O3, 0.2wt.% TiO2, 13.3wt.% ZrO2, 13.0wt.% Na2O, 5.0wt.% K2O, 0.1wt.% Li2O, 0.2wt.% La2O3 and 1.0wt.% Sb2O3; weigh the raw materials and sieve them until they are fully mixed to obtain a batch material;

[0029] Step 2: Add the mixed ingredients from step 1 directly into a platinum crucible preheated to 1400°C, place it in a lifting furnace and keep it at 1500°C for 50 minutes, then take out the crucible and pour the melt onto the mold;

[0030] Step 3: After the melt is formed, it is quickly transferred to an annealing furnace, kept at 530°C for 30 minutes, and then cooled to room temperature along with the furnace to obtain water-resistant and alkali-resistant high-zirconium low-aluminum glass.

[0031] The high zirconium and low aluminum glass prepared in this example was tested. The water resistance loss was tested by the weight method. The maximum weight loss of the glass was 2.01 mg / dm 2 ; It has level one water resistance and level one alkali resistance, and its hardness is tested to be 708.9Hv. In a long-term compatibility test with phenytoin sodium, the lead dissolution amount is 0.07μg / mL, and the prescribed limit is 1.5μg / mL, which meets the FDA's requirement for "no significant heavy metal migration" for injection packaging materials.

[0032] Example 2

[0033] A method for preparing water-resistant and alkali-resistant high-zirconium low-aluminum glass comprises the following steps:

[0034] Step 1, according to 64.6wt.% SiO2, 2.4wt.% Al2O3, 0.2wt.% TiO2, 13.5wt.% ZrO2, 11.9wt.% Na2O, 5.5wt.% K2O, 0.5wt.% Li2O, 0.4wt.% La2O3 and 1.0wt.% Sb2O3; weigh the raw materials and sieve them until they are fully mixed to obtain a batch material;

[0035] Step 2: Add the mixed ingredients from step 1 directly into a platinum crucible preheated to 1400°C, place it in a lifting furnace and keep it at 1490°C for 50 minutes, then take out the crucible and pour the melt into the mold;

[0036] Step 3: After the melt is formed, it is quickly transferred to an annealing furnace, kept at 530°C for 30 minutes, and then cooled to room temperature along with the furnace to obtain water-resistant and alkali-resistant high-zirconium low-aluminum glass.

[0037] The high zirconium and low aluminum glass prepared in this embodiment was tested. The water resistance loss was tested by the weight method. The maximum weight loss of the glass was 1.93 mg / dm 2 ; Water resistance level 1, alkali resistance level 1, hardness test result is 727.0Hv, long-term compatibility test with phenytoin sodium, lead dissolution amount is 0.05μg / mL, and the prescribed limit is 1.5μg / mL, which meets the FDA requirement of "no significant heavy metal migration" for injection packaging materials.

[0038] Example 3

[0039] A method for preparing water-resistant and alkali-resistant high-zirconium low-aluminum glass comprises the following steps:

[0040] Step 1, according to 63.5wt.% SiO2, 3.4wt.% Al2O3, 0.2wt.% TiO2, 13.6wt.% ZrO2, 10.3wt.% Na2O, 6.5wt.% K2O, 1.0wt.% Li2O, 0.5wt.% La2O3 and 1.0wt.% Sb2O3; weigh the raw materials and sieve them until they are fully mixed to obtain a batch material;

[0041] Step 2: Add the mixed ingredients from step 1 directly into a platinum crucible preheated to 1400°C, place it in a lifting furnace and keep it at 1485°C for 50 minutes, then take out the crucible and pour the melt into the mold;

[0042] Step 3: After the melt is formed, it is quickly transferred to an annealing furnace, kept at 530°C for 30 minutes, and then cooled to room temperature along with the furnace to obtain water-resistant and alkali-resistant high-zirconium low-aluminum glass.

[0043] The high zirconium and low aluminum glass prepared in this example was tested. The water resistance loss was tested by the weight method. The maximum weight loss of the glass was 1.36 mg / dm 2 ; Water resistance level 1, alkali resistance level 1, hardness test result is 731.7Hv, long-term compatibility test with phenytoin sodium, lead dissolution amount is 0.04μg / mL, and the prescribed limit is 1.5μg / mL, which meets the FDA requirement of "no significant heavy metal migration" for injection packaging materials.

[0044] Example 4

[0045] A method for preparing water-resistant and alkali-resistant high-zirconium low-aluminum glass comprises the following steps:

[0046] Step 1, according to 62.3wt.% SiO2, 4.4wt.% Al2O3, 0.2wt.% TiO2, 13.7wt.% ZrO2, 9.2wt.% Na2O, 7.0wt.% K2O, 1.5wt.% Li2O, 0.7wt.% La2O3 and 1.0wt.% Sb2O3; weigh the raw materials and sieve them until they are fully mixed to obtain a batch material;

[0047] Step 2: Add the mixed ingredients from step 1 directly into a platinum crucible preheated to 1400°C, place it in a lifting furnace and keep it at 1480°C for 60 minutes, then take out the crucible and pour the melt onto the mold;

[0048] Step 3: After the melt is formed, it is quickly transferred to an annealing furnace, kept at 530°C for 30 minutes, and then cooled to room temperature along with the furnace to obtain water-resistant and alkali-resistant high-zirconium low-aluminum glass.

[0049] The high zirconium and low aluminum glass prepared in this embodiment was tested. The water resistance loss was tested by the weight method. The maximum weight loss of the glass was 0.97 mg / dm 2 ; Water resistance level 1, alkali resistance level 1, hardness test result is 752.8Hv, long-term compatibility test with phenytoin sodium, lead dissolution amount is 0.02μg / mL, and the prescribed limit is 1.5μg / mL, which meets the FDA requirement of "no significant heavy metal migration" for injection packaging materials.

[0050] Example 5

[0051] A method for preparing water-resistant and alkali-resistant high-zirconium low-aluminum glass comprises the following steps:

[0052] Step 1, according to 62.2wt.% SiO2, 4.4wt.% Al2O3, 0.2wt.% TiO2, 13.8wt.% ZrO2, 8.1wt.% Na2O, 7.5wt.% K2O, 2.0wt.% Li2O, 0.8wt.% La2O3 and 1.0wt.% Sb2O3; weigh the raw materials and sieve them until they are fully mixed to obtain a batch material;

[0053] Step 2: Add the mixed ingredients from step 1 directly into a platinum crucible preheated to 1400°C, place it in a lifting furnace and keep it at 1480°C for 60 minutes, then take out the crucible and pour the melt onto the mold;

[0054] Step 3: After the melt is formed, it is quickly transferred to an annealing furnace, kept at 530°C for 30 minutes, and then cooled to room temperature along with the furnace to obtain water-resistant and alkali-resistant high-zirconium low-aluminum glass.

[0055] The high zirconium and low aluminum glass prepared in this example was tested. The water resistance loss was tested by the gravimetric method. The maximum weight loss of the glass was 0.82 mg / dm 2 ; Water resistance level 1, alkali resistance level 1, hardness test result is 794.2Hv, long-term compatibility test with phenytoin sodium, lead dissolution amount is 0.02μg / mL, and the prescribed limit is 1.5μg / mL, which meets the FDA requirement of "no significant heavy metal migration" for injection packaging materials.

[0056] Example 6

[0057] A method for preparing water-resistant and alkali-resistant high-zirconium low-aluminum glass comprises the following steps:

[0058] Step 1, according to 62wt.% SiO2, 4.4wt.% Al2O3, 0.2wt.% TiO2, 13.8wt.% ZrO2, 7.1wt.% Na2O, 8.0wt.% K2O, 2.5wt.% Li2O, 1.0wt.% La2O3 and 1.0wt.% Sb2O3; weigh the raw materials and sieve them until they are fully mixed to obtain a batch material;

[0059] Step 2: Add the mixed ingredients from step 1 directly into a platinum crucible preheated to 1400°C, place it in a lifting furnace and keep it at 1480°C for 60 minutes, then take out the crucible and pour the melt onto the mold;

[0060] Step 3: After the melt is formed, it is quickly transferred to an annealing furnace, kept at 530°C for 30 minutes, and then cooled to room temperature along with the furnace to obtain water-resistant and alkali-resistant high-zirconium low-aluminum glass.

[0061] The high zirconium and low aluminum glass prepared in this example was tested. The water resistance loss was tested by the weight method. The maximum weight loss of the glass was 0.71 mg / dm 2 ; Water resistance level 1, alkali resistance level 1, hardness test result is 800.25Hv, long-term compatibility test with phenytoin sodium, lead dissolution amount is 0.01μg / mL, and the prescribed limit is 1.5μg / mL, which meets the FDA requirement of "no significant heavy metal migration" for injection packaging materials.

[0062] Example 7

[0063] A method for preparing water-resistant and alkali-resistant high-zirconium low-aluminum glass comprises the following steps:

[0064] Step 1, according to 68wt.% SiO2, 5.0wt.% Al2O3, 0.1wt.% TiO2, 12.5wt.% ZrO2, 6.0wt.% Na2O, 5.3wt.% K2O, 0.1wt.% Li2O, 1.0wt.% La2O3 and 2wt.% Sb2O3; weigh the raw materials and sieve them until they are fully mixed to obtain a batch material;

[0065] Step 2: Add the mixed ingredients from step 1 directly into a platinum crucible preheated to 1500°C, place it in a lifting furnace and keep it at 1490°C for 40 minutes, then take out the crucible and pour the melt onto the mold;

[0066] Step 3: After the melt is formed, it is quickly transferred to an annealing furnace, kept at 535°C for 30 minutes, and then cooled to room temperature along with the furnace to obtain water-resistant and alkali-resistant high-zirconium low-aluminum glass.

[0067] The high-zirconium, low-aluminum glass prepared in this example was tested for water resistance loss using a gravimetric method, with a maximum weight loss of 1.98 mg / dm². The glass also achieved level one water resistance and level one alkali resistance, with a tested hardness of 720.9 Hv. In a long-term compatibility test with phenytoin sodium, the lead release was 0.07 μg / mL, exceeding the prescribed limit of 1.5 μg / mL and meeting the FDA's requirement for "no significant heavy metal migration" for injectable packaging.

[0068] Example 8

[0069] A method for preparing water-resistant and alkali-resistant high-zirconium low-aluminum glass comprises the following steps:

[0070] Step 1, according to 62wt.% SiO2, 1.0wt.% Al2O3, 0.3wt.% TiO2, 12.5wt.% ZrO2, 15.0wt.% Na2O, 5.0wt.% K2O, 3.0wt.% Li2O and 1.2wt.% Sb2O3; weigh the raw materials and sieve them until they are fully mixed to obtain a batch;

[0071] Step 2: Add the mixed ingredients from step 1 directly into a platinum crucible preheated to 1450°C, place it in a lifting furnace and keep it at 1500°C for 55 minutes, then take out the crucible and pour the melt into the mold;

[0072] Step 3: After the melt is formed, it is quickly transferred to an annealing furnace, kept at 540°C for 30 minutes, and then cooled to room temperature along with the furnace to obtain water-resistant and alkali-resistant high-zirconium low-aluminum glass.

[0073] The high zirconium and low aluminum glass prepared in this example was tested. The water resistance loss was tested by the weight method. The maximum weight loss of the glass was 2.03 mg / dm 2 ; It has level one water resistance and level one alkali resistance, and its hardness is tested to be 700.2Hv. In a long-term compatibility test with phenytoin sodium, the lead dissolution amount is 0.08μg / mL, and the prescribed limit is 1.5μg / mL, which meets the FDA's requirement for "no significant heavy metal migration" for injection packaging materials.

[0074] Figure 1 The infrared spectra of Examples 1 to 4 are shown in FIG. 5 , 500-700 cm -1 The peak intensity increases with the increase of Al2O3 content (A1→A4), indicating that the cooperative network of Al2O3 and ZrO2 is gradually improved; 1000-1200cm -1 This is the Si-O-Si bond stretching vibration peak. The peak width of sample A4 becomes narrower, reflecting the improvement of network density.

[0075] Figure 2The weight loss of samples of Examples 1-6 and ordinary neutral borosilicate glass after being corroded in deionized water at 98°C for 1 hour using the gravimetric method is shown in FIG. 1 , wherein Examples 1 to 6 are six groups of examples, respectively. Figure 2 The weight loss of different types of glass is shown, among which the glass of Example 1 (Al2O3 content 1.4wt.%) has the highest weight loss, about 6.79mg / dm 2 As the Al2O3 content increases, the weight loss of the glasses from Example 2 to Example 4 gradually decreases. The weight loss of the glass from Example 4 (Al2O3 content 4.4 wt.%) is the lowest, about 0.97 mg / dm 2 This shows that the increase of Al2O3 content can significantly improve the water resistance of glass. The weight loss of borosilicate glass (about 6.2 mg / dm 2 ) is close to that of the glass of Example 1, and its corrosion resistance is lower than that of the glasses of Examples 2 to 6. When the Al2O3 content is increased to above 1.0wt.%, it forms an Al-O-Zr bond synergistic network with ZrO2: Al 3+ Filling the ZrO2 octahedron gaps with aluminum oxide tetrahedrons reduces non-bridging oxygen defects in the glass structure, increasing the density of the silicon oxide network by more than 30%. The ternary mixed alkali system of Na2O, K2O, and Li2O also makes a significant contribution to the improvement of water resistance. Experiments show that when the Li2O content in the ternary mixed alkali system increases from 0.1wt.% to 2.5wt.%, the density of the glass network increases by 15%-20%, and the water resistance weight loss increases from 2.01mg / dm 2 Reduced to 0.71 mg / dm 2 This is because Li+ has a small radius and high field strength, which allows it to enter the gaps in the silicon-oxygen network, replacing Na+ and K+ with large radii, thus reducing network gaps. At the same time, Na+ and K+ form a charge barrier at the interface layer to prevent H+ from invading. The three achieve a dual water-resistant mechanism of "structural densification-interface protection" through the difference in ion radius and charge compensation effect. La2O3 is a network exogenous oxide, La 3 + The ionic radius is large, and when added to the glass, it will destroy the original glass network structure and reduce the degree of network connectivity, making the glass easier to melt at a lower temperature to form glass liquid.

[0076] The appropriate addition of Al2O3 helps strengthen the glass's network structure, improving its corrosion resistance and hardness. It also avoids the difficulties in glass melting and reduced processing performance that can result from excessive Al2O3 content, thereby improving glass machinability and reducing production energy consumption, resulting in significant economic benefits. Compared to traditional borosilicate glass (melting temperature ≥ 1600°C), the present invention utilizes the charge matching effect of Al2O3 and ZrO2 to reduce the high-temperature viscosity of the glass, lowering the melting temperature to 1480-1500°C and reducing energy consumption by approximately 25%, as shown in Table 1.

[0077] Table 1

[0078]

[0079] The high-zirconium, low-aluminum glass prepared by the present invention has low melting temperature, excellent glass-forming properties, simple preparation process, good chemical stability, and water-resistant weight loss can be reduced to 2.0 mg / dm 2 Below, compared with traditional borosilicate glass (6.2mg / dm 2 ) is increased by more than 60%, and its performance in hardness is particularly outstanding. Its hardness range is 700.2Hv-802.0Hv, which is significantly improved compared to traditional glass. It is suitable for storing freeze-dried dosage forms of biological products such as new crown vaccines and recombinant protein drugs, for strongly alkaline drugs such as phenytoin sodium solution (pH>12) and concentrated sodium bicarbonate solution, for high-end drugs such as monoclonal antibody drugs and tumor-targeted preparations that require an ultra-long shelf life of more than 5 years, artificial tears, glaucoma treatment drugs and other ophthalmic preparations that have extremely high requirements on the purity and safety of packaging materials. Therefore, the preparation of a high-zirconium and low-aluminum glass that is resistant to water and strong alkali by this method has considerable economic and social benefits and broad application prospects, so the preparation method of the present invention has a very broad application prospect.

[0080] The above are merely preferred embodiments of the present invention. It should be understood that the present invention is not limited to the forms disclosed herein and should not be construed as excluding other embodiments. Rather, the present invention can be used in various other combinations, modifications, and environments and can be modified within the scope of the present invention through the above teachings or techniques or knowledge in the relevant fields. Modifications and variations made by those skilled in the art without departing from the spirit and scope of the present invention should be within the scope of protection of the appended claims.

Claims

1. A high-zirconium, low-aluminum glass that is resistant to water and strong alkali, characterized in that: The raw materials include 62.0-68.0wt.% SiO2, 1.0-5.0wt.% Al2O3, 0.1-0.3wt.% TiO2, 12.5-13.8wt.% ZrO2, 6.0-15.0wt.% Na2O, 5.0-8.0wt.% K2O, 0.1-3.0wt.% Li2O, 0-1.0wt.% La2O3 and 1.0-2.0wt.% Sb2O3.

2. The water-resistant and alkali-resistant high-zirconium low-aluminum glass according to claim 1, characterized in that: The water-resistant weight loss of the high-zirconium low-aluminum glass is 0.71 mg / dm 2 the following.

3. The water-resistant and alkali-resistant high-zirconium low-aluminum glass according to claim 1, characterized in that: The raw materials include 62.0 wt.% SiO2, 4.4 wt.% Al2O3, 0.2 wt.% TiO2, 13.8 wt.% ZrO2, 7.1 wt.% Na2O, 8.0 wt.% K2O, 2.5 wt.% Li2O, 1.0 wt.% La2O3 and 1.0 wt.% Sb2O3.

4. A method for preparing high-zirconium low-aluminum glass according to any one of claims 1 to 3, characterized in that: The following steps are involved: Step 1: Weigh the raw materials according to the ratio and sieve them until they are fully mixed; Step 2: Add the mixed ingredients from step 1 directly into a platinum crucible preheated to 1400-1500°C, place it in a lifting furnace and keep it at 1480-1500°C for 40-60 minutes, then take out the crucible and pour the melt into the mold; Step 3: After the melt is formed, it is quickly transferred to an annealing furnace, kept at 530-540°C for 30 minutes, and then cooled to room temperature along with the furnace to obtain water-resistant and alkali-resistant high-zirconium low-aluminum glass.

5. Use of the high-zirconium, low-aluminum glass according to claim 1 in drug storage.

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