Method for preparing brown glass bottle by ion exchange method

Abstract

The invention discloses a method for preparing a brown glass bottle through an ion exchange method, and belongs to the technical field of glass surface modification. Through Ag < + > / K < + > synergetic ion exchange, a composite layer with shading and enhancing functions is successfully constructed on the surface of soda-lime glass, and the final product has the following outstanding advantages that the brown silver-loaded layer is prepared on the surface of a glass bottle, so that the inner surface of the glass bottle is not influenced, complete shading is realized in a key ultraviolet band, and photosensitive contents are protected; the original bottle is a colorless sodium-calcium glass bottle, an iron-carbon coloring agent does not need to be additionally added, and iron ions can be prevented from permeating into a glue container to cause pollution; the treatment temperature is far lower than the glass softening point, and the energy consumption is low; only the surface of the finished glass bottle is treated without changing a basic glass formula, so that the flexibility is high, and the cost is controllable; potassium-sodium exchange is carried out in the exchange process, so that the mechanical strength of the glass bottle is improved.

Description

Technical Field

[0001] This invention belongs to the field of glass surface modification technology, specifically, it relates to a method for preparing brown glass bottles by ion exchange. Background Technology

[0002] Glass is widely used as a packaging material due to its excellent chemical stability and barrier properties. For photosensitive substances, such as high-end adhesive products, brown glass bottles are often used to block specific wavelengths of light and prevent the contents from deteriorating.

[0003] Currently, the industrial production of brown glass bottles mainly employs traditional bulk coloring techniques. This involves introducing colorants such as iron and carbon into the glass batch, and forming a brown color through a sulfur-carbon coloring reaction during glass melting. However, this method has significant limitations: First, the coloring process requires extremely high process control, especially as the stability of the valence state of iron is difficult to grasp. This can easily lead to the precipitation of trace amounts of iron ions when the prepared glass bottles contain acidic or polar contents, thus contaminating high-end adhesive products sensitive to metal ions and posing a quality and safety hazard. Second, this technique is a bulk coloring method, where the colorant is distributed throughout the entire glass body. This not only requires high purity of raw materials but also fails to specifically modify the main light-incident surfaces, resulting in shortcomings in both economy and functionality. Furthermore, brown glass bottles prepared using traditional methods do not receive specific reinforcement in terms of mechanical strength, posing a risk of breakage due to mechanical damage during subsequent transportation and use.

[0004] Therefore, the industry urgently needs to develop a new method for preparing brown glass bottles that can avoid the risk of introducing iron ion contamination, achieve selective surface coloring to optimize performance and cost, and is expected to simultaneously improve the mechanical strength of glass containers. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing brown glass bottles by ion exchange.

[0006] The objective of this invention can be achieved through the following technical solutions: A method for preparing brown glass bottles by ion exchange includes the following steps: A1. Immerse the glass bottle in acetone, then put it into an ultrasonic cleaner for ultrasonic cleaning to remove grease and organic contaminants from the inner and outer surfaces. Then, use anhydrous ethanol and ultrapure water for ultrasonic cleaning respectively. Place the cleaned glass bottle in a drying oven to dry it, ensuring that there is no residual moisture on the surface, and obtain a pretreated glass bottle. A2. Place the pretreated glass bottle in a muffle furnace for preheating to obtain a preheated glass bottle; then place potassium nitrate and silver nitrate in a crucible and heat them in a muffle furnace until they melt, then remove them to obtain a molten mixed salt. A3. Quickly immerse the preheated glass bottle in the molten mixed salt to ensure that the outer surface is completely covered for ion exchange. After the ion exchange is completed, remove the bottle and immediately transfer it to the preheated muffle furnace. Then close the furnace door and allow it to cool naturally to room temperature. Remove the bottle and perform ultrasonic cleaning to remove any trace amounts of salt adhering to the surface. After drying, the brown glass bottle is obtained.

[0007] As a further technical solution, the ultrasonic cleaner has a frequency of 28kHz and a power of 300W.

[0008] As a further technical solution, the ultrasonic cleaning time is 20-30 minutes.

[0009] As a further technical solution, the drying temperature is 100-120℃ and the time is 30-60min.

[0010] As a further technical solution, the preheating temperature is 270-300℃ and the time is 5-10 minutes.

[0011] As a further technical solution, the mass ratio of potassium nitrate to silver nitrate is 99.5:0.5-99.8:0.2.

[0012] As a further technical solution, the heating and melting temperature is 290-340℃.

[0013] As a further technical solution, the ion exchange time is 25-35 minutes.

[0014] This invention utilizes K in molten salt + Ag + Na on the outer surface of the glass bottle + An exchange occurs, and a silver-loaded layer is prepared on the outer surface of the glass bottle, in which silver ions (Ag) are present. + It has a strong photosensitivity; when exposed to light, it will directly oxidize and change color, being reduced to silver atoms (Ag). 0 Subsequently, silver ions and silver atoms can form different types of silver clusters, such as ion pairs Ag2. + (Ag) 0 -Ag + ) and Ag2 2+ (Ag) + -Ag + ), trimer Ag3 + and Ag3 2+ This process turns the glass bottle brown, and the addition of potassium salts also increases the mechanical properties of the glass bottle.

[0015] In the preparation process of this invention, step A1 aims to remove residual ions and utilize the polarity of ethanol and water to hydroxylate the glass surface, forming a hydrophilic active surface; the preheating process in step A2 eliminates micro-stress on the glass surface, improves its thermal stability, prevents cracking when molten salt is subsequently added, and simultaneously activates the migration ability of sodium ions on the surface; in step A3, during the ion interaction, Ag in the molten salt... + and K + Na on the glass surface + An exchange reaction occurs; the furnace is naturally cooled to room temperature, which can effectively eliminate thermal stress and stabilize the newly formed surface structure.

[0016] The beneficial effects of this invention are: This invention utilizes Ag + / K + Synergistic ion exchange successfully constructed a composite layer with both light-shielding and light-enhancing functions on the surface of soda-lime glass, resulting in the following outstanding advantages in the final product: Advantage 1: The present invention prepares a brown silver-loaded layer on the surface of the glass bottle without affecting the inner surface of the glass bottle, and completely blocks light in the key ultraviolet band to protect the photosensitive contents. Advantage 2: The original bottle is a colorless soda-lime glass bottle, which does not require the addition of iron and carbon colorants, thus avoiding the contamination caused by iron ions seeping into the gel-based containers. Advantage 3: The processing temperature is much lower than the glass softening point, resulting in low energy consumption; and only the surface of the finished glass bottle is treated, without the need to change the basic glass formula, which is highly flexible and cost-controllable. Advantage 4: Potassium and sodium exchange occur simultaneously during the exchange process, increasing the mechanical strength of the glass bottle. Attached Figure Description

[0017] The invention will now be further described with reference to the accompanying drawings.

[0018] Figure 1 The graph shows the transmittance as a function of wavelength for Embodiment 1 and Comparative Example 2 of the present invention. Figure 2 This is a graph showing the relationship between the types of ions precipitated and their corresponding ion concentrations after water resistance tests were conducted on Examples 1 and Comparative Examples 1-2 of the present invention. Detailed Implementation

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] Example 1 A method for preparing brown glass bottles by ion exchange includes the following steps: A1. Immerse the colorless soda-lime glass bottle in acetone, then put it into an ultrasonic cleaner (frequency 28kHz, power 300W) and ultrasonically clean for 30 minutes to remove grease and organic contaminants from the inner and outer surfaces. Then, ultrasonically clean it with anhydrous ethanol and ultrapure water respectively. Place the cleaned glass bottle in a drying oven and dry it at 120℃ for 30 minutes to ensure that there is no residual moisture on the surface, thus obtaining a pretreated glass bottle. A2. Place the pretreated glass bottle in a muffle furnace and preheat it at 280℃ for 10 minutes to obtain a preheated glass bottle; then place potassium nitrate and silver nitrate (the mass ratio of potassium nitrate to silver nitrate is 99.5:0.5) in a crucible and heat it in a muffle furnace at 340℃ until it melts. Remove it to obtain a molten mixed salt. A3. Quickly immerse the preheated glass bottle in the molten mixed salt, ensuring that the outer surface is completely covered. After ion exchange for 30 minutes, remove it and immediately transfer it to a preheated muffle furnace at 280°C. Then close the furnace door and allow it to cool naturally to room temperature. Remove it and perform ultrasonic cleaning to remove trace amounts of salt adhering to the surface. Dry it at 120°C for 30 minutes to obtain a brown glass bottle.

[0021] Example 2 A method for preparing brown glass bottles by ion exchange includes the following steps: A1. Immerse the colorless soda-lime glass bottle in acetone, then put it into an ultrasonic cleaner (frequency 28kHz, power 300W) and ultrasonically clean for 20 minutes to remove grease and organic contaminants from the inner and outer surfaces. Then, ultrasonically clean it with anhydrous ethanol and ultrapure water respectively. Place the cleaned glass bottle in a drying oven and dry it at 100℃ for 60 minutes to ensure that there is no residual moisture on the surface, thus obtaining a pretreated glass bottle. A2. Place the pretreated glass bottle in a muffle furnace and preheat it at 300℃ for 10 minutes to obtain a preheated glass bottle; then place potassium nitrate and silver nitrate (the mass ratio of potassium nitrate to silver nitrate is 99.8:0.2) in a crucible and heat it in a muffle furnace at 340℃ until it melts. Remove it to obtain a molten mixed salt. A3. Quickly immerse the preheated glass bottle in the molten mixed salt, ensuring that the outer surface is completely covered. After ion exchange for 35 minutes, remove it and immediately transfer it to a preheated muffle furnace at 300°C. Then close the furnace door and allow it to cool naturally to room temperature. Remove it and perform ultrasonic cleaning to remove trace amounts of salt adhering to the surface. Dry it at 100°C for 60 minutes to obtain a brown glass bottle.

[0022] Comparative Example 1 Immerse the colorless soda-lime glass bottle in acetone, then place it in an ultrasonic cleaner (frequency 28kHz, power 300W) for 30 minutes. Then, ultrasonically clean it with anhydrous ethanol and ultrapure water respectively. Place the cleaned glass bottle in a drying oven and dry it at 100℃ for 60 minutes to ensure that there is no residual moisture on the surface, thus obtaining the glass bottle.

[0023] Comparative Example 2 The glass bottle is colored by adding iron and carbon to the glass bottle formula using traditional glass coloring methods.

[0024] The transmittance of the glass bottles from Example 1 and Comparative Example 2 was tested at different wavelengths, and the results are as follows: Figure 1 As shown; then, according to GB 12416.2-90 standard, alkali leaching and water resistance tests were performed on Example 1 and Comparative Examples 1-2. The solutions in the glass bottles after the water resistance test were subjected to ICP-MS testing, and the test results are as follows. Figure 2 As shown; from Figure 1 It can be seen that the transmittance of the brown glass bottle prepared in Example 1 of this invention is almost the same as that of Comparative Example 2, and the transmittance is 0 at 193nm and 248nm, which can meet the storage requirements of some gel-like containers; from Figure 2 It can be seen that no iron ions were precipitated in Example 1 and Comparative Example 1, while a trace amount of iron ions were precipitated in Comparative Example 2, which is not conducive to the storage of some adhesive substances. Therefore, the glass surface modification technology field of the present invention has important application value.

[0025] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0026] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing brown glass bottles by ion exchange, characterized in that, Includes the following steps: A1. Immerse the glass bottle in acetone, then put it into an ultrasonic cleaner for ultrasonic cleaning, and then ultrasonically clean it with anhydrous ethanol and ultrapure water respectively, and then dry it to obtain a pretreated glass bottle. A2. Place the pretreated glass bottle in a muffle furnace for preheating to obtain a preheated glass bottle; then place potassium nitrate and silver nitrate in a crucible and heat them in a muffle furnace until they melt, then remove them to obtain a molten mixed salt. A3. Quickly immerse the preheated glass bottle in the molten mixed salt for ion exchange. After the ion exchange is completed, remove the bottle and immediately transfer it to a preheated muffle furnace. Allow it to cool naturally to room temperature in the furnace, remove the bottle, ultrasonically clean it, and dry it to obtain a brown glass bottle.

2. The method for preparing brown glass bottles by ion exchange according to claim 1, characterized in that, The ultrasonic cleaner has a frequency of 28kHz and a power of 300W.

3. The method for preparing brown glass bottles by ion exchange according to claim 1, characterized in that, The ultrasonic cleaning time is 20-30 minutes.

4. The method for preparing brown glass bottles by ion exchange according to claim 1, characterized in that, The drying temperature is 100-120℃ and the time is 30-60 minutes.

5. The method for preparing brown glass bottles by ion exchange according to claim 1, characterized in that, The preheating temperature is 270-300℃, and the time is 5-10 minutes.

6. The method for preparing brown glass bottles by ion exchange according to claim 1, characterized in that, The mass ratio of potassium nitrate to silver nitrate is 99.5:0.5-99.8:0.

2.

7. The method for preparing brown glass bottles by ion exchange according to claim 1, characterized in that, The heating and melting temperature is 290-340℃.

8. The method for preparing brown glass bottles by ion exchange according to claim 1, characterized in that, The ion exchange time is 25-35 min.

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