CN111909550A - Coating for improving cracking resistance of medicinal glass surface and preparation method and application thereof - Google Patents
Coating for improving cracking resistance of medicinal glass surface and preparation method and application thereof Download PDFInfo
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- CN111909550A CN111909550A CN202010787741.4A CN202010787741A CN111909550A CN 111909550 A CN111909550 A CN 111909550A CN 202010787741 A CN202010787741 A CN 202010787741A CN 111909550 A CN111909550 A CN 111909550A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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Abstract
The invention relates to the technical field of new glass materials, and particularly discloses a coating for improving the cracking resistance of the surface of medicinal glass, and a preparation method and application thereof. The coating for improving the cracking resistance of the surface of the medicinal glass is characterized in that: the coating is prepared by taking tetraethoxysilane, ethanol, deionized water, nitric acid and aluminum nitrate as raw materials through a sol-gel method; the prepared coating solution comprises silicon dioxide and aluminum oxide. The glass coating is prepared by adopting a sol-gel method, the outer surface of the medicinal glass can be sprayed at room temperature, microcracks on the surface of the glass are effectively filled, heating and curing are not needed, energy consumption can be greatly reduced compared with the traditional glass coating material, and the economic benefit is considerable; furthermore, the glass after spraying still maintains high transparency, i.e. the coating does not adversely affect the appearance of the glass.
Description
(I) technical field
The invention relates to the technical field of new glass materials, in particular to a coating for improving the cracking resistance of the surface of medicinal glass, and a preparation method and application thereof.
(II) background of the invention
The glass industry is an important basic raw material industry, is closely related to the life and production of people, and plays an important role in national economy. The glass and the processed products thereof are widely applied to packaging, building, transportation, decoration and fitment, electronic information, solar energy utilization and other emerging industries. In particular, the medicinal glass has good chemical stability, heat-resistant stability, smoothness, transparency, easy cleaning and disinfection, good sealing performance and other physical and chemical properties, and is widely used for packaging biological agents, freeze-dried powder injections, vaccines, blood agents and other medicines.
However, glass is a brittle material, and although it has micro plasticity, its yield elongation stage is very small, and particularly when a sudden applied load is applied, the particles in the glass break apart from each other in time to make a compliant deformation flow. For medicinal glass, friction and collision inevitably occur during the production, storage and transportation of the medicinal glass. For a long time, researchers in the field of glass materials have sought to improve the mechanical properties of glass, in particular the "crack resistance".
The production process of the molded bottle medicinal glass mainly comprises two methods of blowing and pressure-blowing molding. In any molding method, microcracks inevitably exist on the surface of the glass product, and the microcracks tend to become stress concentration positions when the glass is subjected to external load, so that the actual strength of the glass is far lower than the theoretical strength of the glass. Therefore, how to control the formation of microcracks in the glass material and limit the propagation of cracks is the key to improving its mechanical properties.
The currently common glass surface strengthening process includes: physical reinforcement (tempering), chemical reinforcement (ion exchange), coating method reinforcement, and the like. Wherein, the physical tempering is more suitable for plate glass, and the homogenization of stress distribution is difficult to realize for products with complex shapes (such as bottle glass); the ion exchange time of the molten salt method is long, the method is not suitable for mass production lines, the variability of molten salt components is not beneficial to quality control, and the problem of environmental pollution of waste liquid exists; the implementation process of the spraying process is relatively simple, and continuous online operation is easy to realize. For example: the hot end spraying agent mainly adopts organic tin compound or inorganic tin compound, namely: between the bottle making machine and the annealing furnace, the glass bottle can still in a glowing state is subjected to surface spraying treatment by adopting a nozzle or atomizing equipment, which is helpful for improving the hardness and the impact strength of glass, but the volatilization of organic matters also has certain pollution to the environment. In addition, in order to improve the surface lubricity and brightness of the glass product, so-called "cold-end spraying agents" are generally sprayed, wherein the cold-end spraying agent is mainly aqueous polymer solution or polymer emulsion, the spraying temperature of the cold-end spraying agent is about 100 ℃, and the defects such as stripes and the like are generated when the temperature is lower than 90 ℃.
The sol-gel method for preparing nano particles has the advantages of simple process, low temperature and the like, and has important application in many fields in recent years, and a plurality of related patents are obtained, such as: a process for preparing antioxidizing composite coating on the surface of carbon fibres (ZL 201510429877.7) discloses an Al-type composite coating on the surface of carbon fibres2O3-SiO2-TiO2An anti-oxidation composite coating; the composite ceramic coating preparation method (ZL 200810159025.0) discloses a method for preparing composite ceramic powder by a sol-gel method; a preparation and sealing process of a high-temperature resistant sealing agent (application No. 200910063903.3) discloses a ceramic coating, which comprises the following steps: al with mica flakes, whisker silicon or hexagonal boron nitride as filler2O3-SiO2And (3) a sol hole sealing agent. The above patents require either high temperature heating or fillers during application, resulting in higher costs.
To date, there has been no report of glass coatings with good crack resistance that can be used for pharmaceutical glasses and cured at room temperature without the need for heating.
Disclosure of the invention
The invention provides a coating which is applied at room temperature and does not need heating curing and is used for improving the cracking resistance of the surface of medicinal glass, and a preparation method and application thereof, aiming at overcoming the defects of the prior art.
The invention is realized by the following technical scheme:
a coating for improving the cracking resistance of a pharmaceutical glass surface, characterized in that: the coating is prepared by taking tetraethoxysilane, ethanol, deionized water, nitric acid and aluminum nitrate as raw materials through a sol-gel method; the prepared coating solution comprises silicon dioxide and aluminum oxide.
The coating is prepared by a sol-gel method, the process is simple, the cost is relatively low, and the existence of silicon dioxide and aluminum oxide ensures that the coating has the characteristics of strong chemical bonding property with the cross section of a glass substrate and ageing resistance.
The preparation method of the coating for improving the cracking resistance of the surface of the medicinal glass comprises the following steps:
(1) mixing ethyl orthosilicate, ethanol, deionized water and nitric acid at room temperature to obtain a mixed solution;
(2) stirring the mixed solution at 60 ℃ for 3 hours, and cooling to room temperature;
(3) and at room temperature, dropwise adding 1.5M aluminum nitrate solution into the mixed solution, and continuously stirring for 2 hours to obtain the solution for the glass coating.
Preferably, in the step (1), the molar ratio of the ethyl orthosilicate, the ethanol, the deionized water and the nitric acid is 1: 4.2-4.7: 2.2-2.8: 0.03-0.05; further preferred is a molar ratio of 1:4.5:2.5: 0.04.
preferably, in the step (3), the aluminum nitrate solution is added in an amount such that the molar ratio of silicon dioxide to aluminum oxide is 9.5-8: 1; further preferred is a molar ratio of 9: 1.
the application of the coating comprises the following steps:
the medicinal glass bottle conveyed by the caterpillar band is discharged from the annealing kiln and exposed in the air, and when the temperature is reduced to below 30 ℃, the coating solution is sprayed on the glass on line by a spraying pump, wherein the spraying thickness is 50-300 nanometers.
Preferably, the coating thickness is 60 to 200 nm, more preferably 60 to 150 nm.
The glass coating is prepared by adopting a sol-gel method, the outer surface of the medicinal glass can be sprayed at room temperature, microcracks on the surface of the glass are effectively filled, heating and curing are not needed, energy consumption can be greatly reduced compared with the traditional glass coating material, and the economic benefit is considerable; furthermore, the glass after spraying still maintains high transparency, i.e. the coating does not adversely affect the appearance of the glass.
(IV) description of the drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a graph of the Vickers hardness indentation of uncoated soda-lime-silica glass for pharmaceutical use held at a load of 0.2 kg for 15 seconds;
FIG. 2 is a graph of the Vickers hardness indentation of a coated thickness of a soda-lime-silica glass for pharmaceutical use of example 3 held at a load of 0.2 kg for 15 seconds.
(V) detailed description of the preferred embodiments
A coating for improving the resistance of a glass surface to cracking in accordance with the present invention is further illustrated by the following specific examples, of which example 3 is the preferred example.
Example 1:
according to the molar ratio of each component, namely: tetraethoxysilane (TEOS): ethanol: deionized water: nitric acid =1: 4.3:2.2:0.03, and the four liquids are mixed uniformly at room temperature in sequence; then stirring the mixed solution at 60 ℃ for 3 hours, and cooling to room temperature; and (3) dropwise adding an aluminum nitrate solution with the molar concentration of 1.5M into the solution at room temperature according to the proportion (the molar ratio of silicon dioxide to aluminum oxide is 9.5: 1), and continuously stirring for 2 hours to obtain a solution for the glass coating for later use.
The soda-lime-silica medical glass bottle transported by the crawler passes through an annealing kiln and is exposed in the air, and when the temperature is reduced to room temperature, the solution is sprayed on the outer surface of the glass, and the spraying thickness is 50 nanometers. The sprayed soda-lime-silica glass for medical use did not develop crack propagation at the tip of the indentation after being held under a load of 0.2 kg for 15 seconds.
Example 2:
the difference between this example and example 1 is the molar ratio of the components, namely: tetraethoxysilane (TEOS): ethanol: deionized water: nitric acid =1: 4.6:2.6: 0.04; and the molar ratio of silicon dioxide to aluminum oxide is 8: 1; the spray thickness was 300 nm.
The sprayed soda-lime-silica glass for medical use did not develop crack propagation at the tip of the indentation after being held under a load of 0.2 kg for 15 seconds.
Example 3:
the difference between this example and example 1 is the molar ratio of the components, namely: tetraethoxysilane (TEOS): ethanol: deionized water: nitric acid =1:4.5:2.5: 0.04; and the molar ratio of silicon dioxide to aluminum oxide is 9: 1; the spray thickness was 60 nm.
The sprayed soda-lime-silica glass for medical use did not develop crack propagation at the tip of the indentation after being held under a load of 0.2 kg for 15 seconds.
As shown in the attached figures 1 and 2, compared with the uncoated glass, the sprayed glass has no phenomenon of crack propagation at the tip of an indentation under the action of load, and only the crack of the coating occurs, namely the crack of the glass surface is inhibited by the existence of the coating.
Example 4:
the difference between this example and example 1 is the molar ratio of the components, namely: tetraethoxysilane (TEOS): ethanol: deionized water: nitric acid =1:4.7:2.3: 0.03; and the molar ratio of silicon dioxide to aluminum oxide is 9.2: 1; the spray thickness was 150 nm.
The sprayed soda-lime-silica glass for medical use did not develop crack propagation at the tip of the indentation after being held under a load of 0.2 kg for 15 seconds.
Example 5:
the difference between this example and example 1 is the molar ratio of the components, namely: tetraethoxysilane (TEOS): ethanol: deionized water: nitric acid =1: 4.3:2.7: 0.04; and the molar ratio of silicon dioxide to aluminum oxide is 8.9: 1; the spray thickness was 150 nm.
The sprayed soda-lime-silica glass for medical use did not develop crack propagation at the tip of the indentation after being held under a load of 0.2 kg for 15 seconds.
Example 6:
the difference between this example and example 1 is the molar ratio of the components, namely: tetraethoxysilane (TEOS): ethanol: deionized water: nitric acid =1: 4.2:2.8: 0.05; and the molar ratio of silicon dioxide to aluminum oxide is 8.4: 1; the spray thickness was 150 nm.
The sprayed soda-lime-silica glass for medical use did not develop crack propagation at the tip of the indentation after being held under a load of 0.2 kg for 15 seconds.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (9)
1. A coating for improving the cracking resistance of the surface of medicinal glass is characterized in that: the coating is prepared by taking tetraethoxysilane, ethanol, deionized water, nitric acid and aluminum nitrate as raw materials through a sol-gel method; the prepared coating solution comprises silicon dioxide and aluminum oxide.
2. The method of claim 1, wherein the method comprises the steps of: (1) mixing ethyl orthosilicate, ethanol, deionized water and nitric acid at room temperature to obtain a mixed solution; (2) stirring the mixed solution at 60 ℃ for 3 hours, and cooling to room temperature; (3) and at room temperature, dropwise adding 1.5M aluminum nitrate solution into the mixed solution, and continuously stirring for 2 hours to obtain the solution for the glass coating.
3. The method of claim 2, wherein: in the step (1), the molar ratio of ethyl orthosilicate, ethanol, deionized water and nitric acid is 1: 4.2-4.7: 2.2-2.8: 0.03-0.05.
4. The method of claim 2, wherein: in the step (3), the adding amount of the aluminum nitrate solution is that the mol ratio of the silicon dioxide to the aluminum oxide is 9.5-8: 1.
5. the production method according to claim 3, characterized in that: the molar ratio of the ethyl orthosilicate to the ethanol to the deionized water to the nitric acid is 1:4.5:2.5: 0.04.
6. the method of claim 4, wherein: the mole ratio of the silicon dioxide to the aluminum oxide is 9: 1.
7. use of a coating for improving the resistance of a pharmaceutical glass surface to cracking according to claim 1, characterized in that: the medicinal glass bottle conveyed by the caterpillar band is discharged from the annealing kiln and exposed in the air, and when the temperature is reduced to below 30 ℃, the coating solution is sprayed on the glass on line by a spraying pump, wherein the spraying thickness is 50-300 nanometers.
8. Use according to claim 7, wherein the coating thickness is 60-200 nm.
9. Use according to claim 8, characterized in that: the thickness of the coating is 60-150 nm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010787741.4A CN111909550A (en) | 2020-08-07 | 2020-08-07 | Coating for improving cracking resistance of medicinal glass surface and preparation method and application thereof |
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| CN202010787741.4A CN111909550A (en) | 2020-08-07 | 2020-08-07 | Coating for improving cracking resistance of medicinal glass surface and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654348A (en) * | 2009-09-08 | 2010-02-24 | 武汉理工大学 | Preparation of high-temperature resistant hole sealing agent and hole sealing technique |
| CN107841164A (en) * | 2017-10-30 | 2018-03-27 | 上海艾谡新材料有限公司 | A kind of antireflective coated solution and preparation method and the production method of photovoltaic glass |
| CN108892979A (en) * | 2018-06-19 | 2018-11-27 | 张文霞 | One kind is for environment friendly heat resistant refractory coating and preparation method thereof |
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2020
- 2020-08-07 CN CN202010787741.4A patent/CN111909550A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654348A (en) * | 2009-09-08 | 2010-02-24 | 武汉理工大学 | Preparation of high-temperature resistant hole sealing agent and hole sealing technique |
| CN107841164A (en) * | 2017-10-30 | 2018-03-27 | 上海艾谡新材料有限公司 | A kind of antireflective coated solution and preparation method and the production method of photovoltaic glass |
| CN108892979A (en) * | 2018-06-19 | 2018-11-27 | 张文霞 | One kind is for environment friendly heat resistant refractory coating and preparation method thereof |
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