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CN-122011810-A - Protective coating for inner wall of container glass and preparation method thereof

CN122011810ACN 122011810 ACN122011810 ACN 122011810ACN-122011810-A

Abstract

The invention discloses a protective coating for the inner wall of container glass and a preparation method thereof, belonging to the technical field of coatings. The protective coating is of a composite film structure and comprises an inner layer formed by oxides of silicon, aluminum, zirconium and titanium and an outer layer formed by pure silicon oxide, wherein the mass ratio of each element in the inner layer is 80-100% of silicon element, 0-10% of aluminum element, 0-10% of zirconium element and 0-3% of titanium element by taking the total mass of the four elements as 100%. The invention forms a functionally complementary gradient compact barrier by adopting a specific double-layer composite structure. The structure not only can cooperatively separate out a plurality of ions, but also has the advantages of firm combination and good thermal stability, thereby remarkably improving the chemical stability and the service life of the glass container.

Inventors

  • SU WENJING
  • LIU CHANG
  • BAO TIAN
  • TANG YONGKANG
  • Yan Rongkang
  • LI GANG

Assignees

  • 中建材玻璃新材料研究院集团有限公司

Dates

Publication Date
20260512
Application Date
20260113

Claims (7)

  1. 1. The protective coating for the inner wall of the container glass is characterized by being of a composite film structure and comprising an inner layer formed by oxides of silicon, aluminum, zirconium and titanium and an outer layer formed by pure silicon oxide, wherein the mass ratio of each element in the inner layer is 80-100% of silicon element, 0-10% of aluminum element, 0-10% of zirconium element and 0-3% of titanium element based on 100% of the total mass of the four elements of silicon, aluminum, zirconium and titanium.
  2. 2. A method for preparing a protective coating for an inner wall of a container glass, characterized in that it comprises the steps of: Step 1, preparing mixed sol, namely dissolving corresponding silicon source, aluminum source, zirconium source and titanium source precursors in an organic solvent according to the mass ratio of each element in the inner layer of the step 1, adding an acid catalyst to adjust the pH value to 2-3 at room temperature to 60 ℃, continuously reacting for 8-12h, and standing for ageing to obtain mixed sol; Step 2, one-time coating and heat treatment, namely immersing a clean glass container into the mixed sol for coating, wherein the dipping time is 50-70s, the liquid level lifting speed is 0.5-1.5mm/min, then pre-treating for 4-6min at 90-110 ℃ and then heat treating for 8-12min at 450-520 ℃; And 3, secondary coating and heat treatment, namely immersing the glass container treated in the step 2 into pure silica sol for coating again, wherein the immersion time is 50-70s, then heat treating for 8-12min at 450-520 ℃, and finally forming the protective coating on the inner wall of the glass.
  3. 3. A method of producing a protective coating for the inner wall of a container glass according to claim 2, wherein the silicon source is ethyl orthosilicate.
  4. 4. A method of producing a protective coating for the inner wall of a container glass according to claim 2, wherein the aluminum source is aluminum nitrate.
  5. 5. The method for preparing a protective coating for the inner wall of a container glass according to claim 2, wherein the zirconium source is one of zirconyl nitrate, zirconium n-propoxide, zirconium tert-butoxide.
  6. 6. The method for preparing a protective coating for the inner wall of a container glass according to claim 2, wherein the titanium source is one of tetrabutyl titanate and titanium tetrachloride.
  7. 7. The method for preparing a protective coating for the inner wall of a container glass according to claim 2, wherein the organic solvent is one of absolute ethyl alcohol, isopropyl alcohol and n-butyl alcohol.

Description

Protective coating for inner wall of container glass and preparation method thereof Technical Field The invention belongs to the technical field of coatings, and particularly relates to a protective coating for the inner wall of container glass and a preparation method thereof. Background Glass is often used for transporting and storing liquid reagents, especially for biopharmaceutical formulations and highly purified reagents, due to its excellent thermal and chemical stability. However, due to the direct contact of the reagent with the inner wall of the glass container, migration of elemental ions inevitably occurs at the interface during long-term storage, and certain components in the glass are eluted in the form of ions and enter the reagent, resulting in exceeding of impurity ion content, further affecting reagent quality and even causing high purity reagent failure or drug safety problems in severe cases. The main ions dissolved into the reagent comprise alkali metal ions (such as sodium and potassium), alkaline earth metals (such as calcium, magnesium and barium) and metal element ions such as aluminum with higher content in the glass. At present, inorganic silicon or organic silicon materials are often used to form single-layer, multi-layer or even composite films on the inner wall of glass to block the migration of ions. However, the penetration capacities of ions of different elements are different, and it is difficult to completely and effectively inhibit the dissolution of all ions only by means of a silicon-based system. Accordingly, in order to solve the above problems, the present invention provides a protective coating for the inner wall of container glass and a method for preparing the same. Disclosure of Invention The invention aims to overcome the defects of the prior art and provides a protective coating for the inner wall of container glass and a preparation method thereof. The aim of the invention can be achieved by the following technical scheme: The protective coating for the inner wall of the container glass is of a composite film structure and comprises an inner layer formed by oxides of silicon, aluminum, zirconium and titanium and an outer layer formed by pure silicon oxide, wherein the mass ratio of each element in the inner layer is 80-100% of silicon element, 0-10% of aluminum element, 0-10% of zirconium element and 0-3% of titanium element based on 100% of the total mass of the four elements of silicon, aluminum, zirconium and titanium. The preparation method of the protective coating comprises the following steps: Step 1, preparing mixed sol, namely dissolving corresponding silicon source, aluminum source, zirconium source and titanium source precursors into an organic solvent according to the mass ratio of the inner layer elements, adding an acid catalyst to adjust the pH value to 2-3 at room temperature to 60 ℃, continuously reacting for 8-12h, and standing for aging to obtain mixed sol; Step 2, one-time coating and heat treatment, namely immersing a clean glass container into the mixed sol for coating, wherein the dipping time is 50-70s, the liquid level lifting speed is 0.5-1.5mm/min, then pre-treating for 4-6min at 90-110 ℃ and then heat treating for 8-12min at 450-520 ℃; And 3, secondary coating and heat treatment, namely immersing the glass container treated in the step 2 into pure silica sol for coating again, wherein the immersion time is 50-70s, then heat treating for 8-12min at 450-520 ℃, and finally forming the protective coating on the inner wall of the glass. More preferably, the silicon source is ethyl orthosilicate. More preferably, the aluminum source is aluminum nitrate. More preferably, the zirconium source is one of zirconyl nitrate, zirconium n-propoxide and zirconium tert-butoxide. More preferably, the titanium source is one of tetrabutyl titanate and titanium tetrachloride. More preferably, the organic solvent is one of absolute ethyl alcohol, isopropyl alcohol and n-butyl alcohol. Compared with the prior art, the invention has the beneficial effects that: (1) The invention breaks through the limitations of the components and functions of the traditional single silicon coating by adopting a multi-component composite system of silicon, aluminum, zirconium and titanium oxides. The composite coating can simultaneously and effectively separate the dissolution and migration of alkali metal ions, alkaline earth metal ions and other metal ions in glass, realizes comprehensive and synergistic inhibition of precipitation of various ions, and remarkably improves the universality and reliability of coating protection. (2) The invention has simple preparation method of the coating sol through an optimized sol-gel process and a precisely controlled heat treatment system, and the prepared coating is firmly combined with the glass matrix and shows excellent heat stability and mechanical durability. Even in an acidic or alkaline environment, the coating can still kee