RU2707612C1 - Strengthened glass vessel (versions) and glass vessel strengthening method (versions) - Google Patents

Abstract

FIELD: manufacturing technology.SUBSTANCE: invention relates to a method of producing strengthened glass vessels. According to the first version, the surface of the vessel is coated with at least one reinforcing layer having thickness of 5–50 nm, containing tin dioxide or titanium dioxide, and single-wall carbon nanotubes, with content of 0.05–1 wt%. At that, reinforcing layer is applied on hot end of process line on surface of molded vessel, having surface temperature of 450–750 °C. According to the second version, the surface of the vessel is coated with at least one reinforcing layer having thickness of 40–100 nm, containing a polymer base in the form of modified polyethylene, and single-wall carbon nanotubes at their content of 0.05–0.2 wt%. Reinforcing layer is applied at the cold end of the processing line, at the vessel surface temperature of 80–120 °C.EFFECT: high strength of glass vessels.20 cl, 6 ex

Description

The invention relates to glass vessels, mainly to glass containers and technologies for the production of hardened vessels, it can be used in the manufacture of various types of glass products in glass and other industries.

Glass is characterized by exceptional chemical resistance, which makes it attractive for use as a material for containers for food, beverages, medicines, chemicals, perfumes, cosmetics, etc.

At the same time, glass is a brittle material, and for this reason glass products, in particular containers, require special measures to strengthen them.

Such measures, for example, include the application of protective reinforcing coatings to the outer surface of a glass container. In this case, inorganic and organic coatings are used, which significantly change the properties of the glass surface and improve the mechanical characteristics of the products, in particular, increase the hydrophobicity of the surface, which reduces the softening effect of surface-active media and, above all, air moisture.

Thus, a glass vessel is known having a coating on its outer side, comprising at least a pair of layers, of which the first layer contains carbon nanotubes and / or graphene, and the second layer is deposited on the first layer and is made by electrostatic coloring liquid or powder paints, or by electrostatic deposition of metal [Patent RU No. 2553015 IPC B65D 1/00]. The first (inner) coating layer provides increased adhesion of the second (outer) layer, which, in turn, prevents the penetration of light into the vessel through its walls and provides decorative properties of the vessel.

This vessel is adopted as a prototype of the invention.

Its disadvantage is insufficient hardening, since the layers of the applied coating solve the other problems mentioned above.

The present invention solves the problem of creating a glass vessel of high strength, in particular glass containers: bottles, cans, etc. with high strength.

Known methods of hardening glass vessels by applying on its surface reinforcing layers. Closest to the claimed method of hardening glass vessels is a method of hardening glass products by applying to the product surface two reinforcing layers [Patent RU No. 2597419, IPC C03C 17/34]. The first reinforcing layer is obtained by applying a composition containing an organometallic compound (organotin or organotitanium) and single-walled carbon nanotubes. It is applied to the surface of the glass after forming the products (at the so-called “hot end” of the production line). A second reinforcing layer is obtained by applying a composition containing a colloidal polymer base and single-walled carbon nanotubes. It is applied to the glass surface after cooling the product to 80 ° C (at the so-called “cold end” of the production line). The content of carbon nanotubes in the reinforcing layers is from 0.005% to 0.2 mass. %

This method is adopted as a prototype of the invention.

The disadvantages of the prototype are the necessity of applying two protective layers, which is not always economically feasible. In some cases, applying only one protective layer is sufficient.

The present invention solves the problem of creating a method of hardening of blood vessels, allowing to reduce labor costs for hardening of blood vessels and the ability to vary the number of hardening layers.

In terms of creating a toughened glass vessel, the problem is solved by the fact that there are two options for these vessels.

The first variant of a toughened glass vessel is characterized by the fact that at least one reinforcing layer having a thickness of 5-50 nm containing tin dioxide or titanium dioxide and single-walled carbon nanotubes in an amount of 0.05-1 mass is applied to its surface. %

Single-walled carbon nanotubes in the reinforcing layer have an average ratio of their length and diameter of at least 3000.

The average diameter of single-walled carbon nanotubes is 1.2-2.5 nm, and their average length is not less than 5 microns.

The reinforcing layer of this embodiment is applied to the surface of the vessel in the chamber by simultaneously and separately feeding into it atomized organotin or organotitanium compounds and an atomized aqueous suspension of single-walled carbon nanotubes at a content of 0.005-1 mass. %

The second variant of the toughened glass vessel is characterized by the fact that at least one reinforcing layer 40-100 nm thick is deposited on its surface, which contains a polymer base in the form of modified polyethylene, and single-walled carbon nanotubes with their content of 0.05-0.2 mass %

Used single-walled carbon nanotubes have an average ratio of their length and diameter of at least 3000.

The average diameter of the used single-walled carbon nanotubes is 1.2-2.5 nm, and their average length is not less than 5 microns.

The reinforcing layer according to this embodiment is applied to the surface of the vessel by spraying a mixture of an aqueous solution of a polymer base in the form of a modified polyethylene and an aqueous suspension of single-walled carbon nanotubes, when their content in the said mixture is 0.00025-0.001 mass. %

In terms of creating a method for hardening glass vessels, the problem is solved by the fact that there are two options for the named method.

The first variant of the method for hardening glass vessels involves applying at the hot end of the processing line to the surface of the molded vessel a reinforcing layer containing organotin or organotitanium compounds and single-walled carbon nanotubes, the application of the reinforcing layer being carried out at a vessel surface temperature of 450-750 ° C in a chamber into which and separately served sprayed organotin or organotitanium compound and atomized aqueous suspension containing 0.005-1 mass. % single-walled carbon nanotubes.

A suspension of single-walled carbon nanotubes may additionally contain a dispersant that is selected from the range of: nonionic surfactants - polyethylene glycols (PEG), or polyvinylpyrrolidones (PVP), or BRIDGES (Brij), or TRITONS (Triton), or TWIN (Tween); or anionic surfactants — carboxylic acids or their salts, or alkyl sulfates, or alkyl sulfonates, or alkyl aryl sulfonates, or cellulose derivatives, or naphthalene derivatives; or cationic surfactants are salts of primary, or secondary, or tertiary, aliphatic amines, or quaternary ammonium bases.

The single-walled carbon nanotubes used in the method have an average ratio of their length and diameter of at least 3000.

The average diameter of the used single-walled carbon nanotubes is 1.2-2.5 nm, and the average length is not less than 5 microns.

When preparing a suspension of single-walled carbon nanotubes, an ultrasonic dispersant and / or microfluidic processor are used,

and / or a high-speed mixer, moreover, the amount of energy input is 0.5-30 kW * hour per 1 kg of suspension.

The second variant of the method for hardening glass vessels involves applying at the cold end of the processing line to the surface of the molded and cooled vessel a hardening layer containing a polymer base in the form of modified polyethylene and single-walled carbon nanotubes, the hardening layer being applied at a surface temperature of the vessels of 80-120 ° C by spraying a mixture containing an aqueous solution of a polymer base and an aqueous suspension of single-walled carbon nanotubes, moreover, the content of nanotubes in cm B is 0,00025-0,001 wt. %

An aqueous suspension of single-walled carbon nanotubes may additionally contain a dispersant, which is selected from the range of: nonionic surfactants - polyethylene glycols (PEG), or polyvinylpyrrolidones (PVP), or BRIDGES (Brij), or TRITON (Triton), or TWIN (Tween); or anionic surfactants — carboxylic acids or their salts, or alkyl sulfates, or alkyl sulfonates, or alkyl aryl sulfonates, or cellulose derivatives, or naphthalene derivatives; or cationic surfactants are salts of primary, or secondary, or tertiary, aliphatic amines, or quaternary ammonium bases.

Used carbon nanotubes have an average ratio of their length and diameter of at least 3000.

The average diameter of single-walled carbon nanotubes is 1.2–2.5 nm, and their average length is at least 5 μm.

When preparing a suspension of single-walled carbon nanotubes, an ultrasonic dispersant and / or microfluidic processor and / or high-speed mixer are used, moreover, the amount of energy input is 0.5-30 kW * h per 1 kg of suspension.

The present invention is implemented in the following way.

A first embodiment of a toughened glass vessel is obtained by applying a reinforcing layer to the hot end of a processing line according to a first embodiment of the vessel strengthening method described above.

To do this, the formed vessels having a surface temperature of 450-750 ° C are sent to a special chamber, into which a sprayed organotin or organotitanic compound and a sprayed aqueous suspension containing 0.005-1 mass are also simultaneously and separately delivered in space. % single-walled carbon nanotubes.

During the advancement of the vessels inside the chamber, a mixture of atomized organometallic matter and nanotubes settles on them, forming a reinforcing layer on the surface of the vessel. The speed of movement of the vessels in the chamber is chosen such that the formed reinforcing layer has a thickness of 5-50 nm. The resulting reinforcing layer contains tin dioxide or titanium dioxide, and single-walled carbon nanotubes when they are contained in the reinforcing layer of 0.05-1 mass. %

Thus, the first version of the hardened vessel is obtained.

To obtain a second embodiment of a toughened glass vessel, a reinforcing layer is applied at the cold end of the processing line, as described in the second embodiment of the method. To this end, a reinforcing layer containing a polymer base in the form of modified polyethylene and single-walled carbon nanotubes is applied to the surface of the molded and cooled vessel, and the application of the reinforcing layer is carried out at a vessel surface temperature of 80-120 ° C by spraying a mixture containing an aqueous solution of a polymer base and an aqueous suspension single-walled carbon nanotubes, moreover, the content of nanotubes in the mixture is 0,00025-0,001 mass. %

In this way, a second embodiment of the hardened vessel is obtained.

It should be noted that the hardened vessel may contain only one reinforcing layer according to the first or second options.

Also, both reinforcing layers can be applied to the vessel: they can be applied sequentially: first, the first version of the layer at the hot end of the production line, and then the second version of the layer at the cold end of the production line.

Tests of hardened vessels showed that they have increased strength compared to standard values. The average standard size of a bottle with a standard reinforcing layer is 24.2 bar, expressed as the value of resistance to average hydrostatic pressure.

When applying a reinforcing layer at the hot end of the production line in accordance with the invention, the vessels have a resistance value of 32.1 bar to an average internal hydrostatic pressure.

When applying a reinforcing layer at the cold end of the production line in accordance with the invention, the vessels have a resistance value of 29.6 bar to an average internal hydrostatic pressure.

When applying two reinforcing layers at the hot and cold ends of the production line in accordance with the invention, the vessels have a resistance value of 35.7 bar to an average internal hydrostatic pressure.

In addition to the above advantages provided by the present invention, when hardening glass vessels by the described method, the amount of substandard products was reduced from 6.5% to 1.3%.

Example 1

Obtaining a protective layer on glass bottles at the “hot end” of the production line.

An aqueous suspension is prepared from carbon nanotubes and water. To do this, they are mixed with each other, with a nanotube content of 0.005 mass. % and add a dispersant from a number of polyvinylpyrrolidones (molecular weight of the polymer ~ 40 kDa) in an amount of 0.02 mass. %, after which they act on the mixture with ultrasound.

Molded bottles having a surface temperature of 450 ° C. are sent to a special chamber, into which a sprayed organotin compound and a sprayed aqueous suspension containing 0.005 mass are simultaneously but separately delivered. % single-walled carbon nanotubes.

As vessels move inside the chamber at a speed of 200 vessels per minute, a mixture of atomized organometallic matter and nanotubes settles on them, forming a reinforcing layer on the surface of the vessel to a thickness of 5 nm. The obtained reinforcing layer contains tin dioxide and single-walled carbon nanotubes when their content in the reinforcing layer is 0.05 mass. %

The average resistance to the internal hydrostatic pressure of the obtained vessels is 32.1 bar.

Example 2

Obtaining a protective layer on glass bottles at the “hot end” of the production line.

An aqueous suspension is prepared from nanotubes and water. To do this, they are mixed with each other, with the content of nanotubes 1 mass. % and add a dispersant from a number of polyvinylpyrrolidones (molecular weight of the polymer ~ 40 kDa) in an amount of 4 wt. %, after which they act on the mixture with ultrasound.

Molded bottles having a surface temperature of 750 ° C are sent to a special chamber into which the atomized titanium-organic compound and atomized are simultaneously but separately separated.

an aqueous suspension containing 1 mass. % single-walled carbon nanotubes.

When vessels are advanced inside the chamber at a speed of 200 vessels per minute, a mixture of atomized organometallic matter and nanotubes settles on them, forming a reinforcing layer on the surface of the vessel so that the formed reinforcing layer has a thickness of 50 nm. The resulting reinforcing layer contains titanium dioxide and single-walled carbon nanotubes when they are contained in the reinforcing layer of 1 mass. %

The average resistance to the internal hydrostatic pressure of the obtained vessels is 32.1 bar.

Example 3

Obtaining a protective layer on glass bottles at the "cold end" of the production line.

An aqueous suspension is prepared from carbon nanotubes and water. To do this, they are mixed with each other, with a nanotube content of 0.005 mass. %) and add a dispersant from a number of polyvinylpyrrolidones (molecular weight of the polymer ~ 40 kDa) in an amount of 0.02 mass. %, after which they act on the mixture with ultrasound. The resulting suspension is mixed with an aqueous solution of a polymer base in the form of a modified polyethylene until the content of nanotubes in the mixture is 0,00025 mass. %).

The resulting mixture is applied to the outer surface of the vessels by spraying it onto bottles moving along the conveyor. The surface temperature of the bottles is 80 ° C.

The obtained reinforcing layer with a thickness of 40 nm contains a polymer base and single-walled carbon nanotubes when their content in the reinforcing layer is 0.05 mass. %

The average resistance to the internal hydrostatic pressure of the obtained vessels is 29.6 bar.

Example 4

Obtaining a protective layer on glass bottles at the "cold end" of the production line.

An aqueous suspension is prepared from carbon nanotubes and water. To do this, they are mixed with each other, with a nanotube content of 0.02 mass. % and add a dispersant from a number of polyvinylpyrrolidones (molecular weight of the polymer ~ 40 kDa) in an amount of 0.08 mass. %, after which they act on the mixture with ultrasound. The resulting suspension is mixed with an aqueous solution of a polymer base in the form of a modified polyethylene until the content of nanotubes in a mixture of 0.001 mass. %

The resulting mixture is applied to the outer surface of the vessels by spraying it onto bottles moving along the conveyor.

The surface temperature of the bottles is 120 ° C. The obtained reinforcing layer with a thickness of 100 nm contains a polymer base and single-walled carbon nanotubes with a content of 0.2 mass in the reinforcing layer. %

The average resistance to the internal hydrostatic pressure of the obtained vessels is 29.6 bar.

Example 5

Obtaining a protective layer on glass bottles on the hot and cold end of the production line.

An aqueous suspension is prepared from carbon nanotubes and water. To do this, they are mixed with each other, with a nanotube content of 0.005 mass. % and add a dispersant from a number of polyvinylpyrrolidones (molecular weight of the polymer ~ 40 kDa) in an amount of 0.02 mass. %, after which they act on the mixture with ultrasound.

Molded bottles having a surface temperature of 450-750 ° C are sent to a special hot hardening chamber, into which a sprayed organotin compound and a sprayed aqueous suspension containing 0.005 wt. %) single-walled carbon nanotubes.

As vessels move inside the chamber at a speed of 200 vessels per minute, a mixture of atomized organometallic matter and nanotubes settles on them, forming a reinforcing layer on the surface of the vessel to a thickness of 5 nm. The obtained reinforcing layer contains tin dioxide and single-walled carbon nanotubes when their content in the reinforcing layer is 0.05 mass. %

Then, the suspension obtained as a result of ultrasonic treatment is mixed with an aqueous solution of a polymer base in the form of modified polyethylene until the content of nanotubes in the mixture is 0,00025 mass. %).

The resulting mixture is applied to the outer surface of the vessels by spraying it onto bottles moving along the conveyor. The surface temperature of the bottles is 80 ° C. The obtained reinforcing two-layer coating with a thickness of 40 nm contains tin dioxide, a polymer base and single-walled carbon nanotubes when their content in the reinforcing layer is 0.05 mass. %).

The average resistance to the internal hydrostatic pressure of the obtained vessels is 35.7 bar.

Example 6

Obtaining a protective layer on glass bottles on the hot and cold end of the production line.

An aqueous suspension is prepared from carbon nanotubes and water. To do this, they are mixed with each other, with a nanotube content of 0.02 mass. % and add a dispersant from a number of polyvinylpyrrolidones (molecular weight of the polymer ~ 40 kDa) in an amount of 0.08 mass. %, after which they act on the mixture with ultrasound.

Molded bottles having a surface temperature of 750 ° C. are sent to a special hot-hardening chamber, into which at the same time, but separately, the atomized titanium-organic compound and the atomized aqueous suspension containing 1 mass are fed. % single-walled carbon nanotubes.

When vessels are advanced inside the chamber at a speed of 200 vessels per minute, a mixture of atomized organometallic matter and nanotubes settles on them, forming a reinforcing layer on the surface of the vessel so that the formed reinforcing layer has a thickness of 50 nm. The resulting reinforcing layer contains titanium dioxide and single-walled carbon nanotubes when they are contained in the reinforcing layer of 1 mass. %

Then, the suspension obtained as a result of ultrasonic treatment is mixed with an aqueous solution of a polymer base in the form of modified polyethylene until the content of nanotubes in the mixture is 0,00025 mass. %

The resulting mixture is applied to the outer surface of the vessels by spraying it onto bottles moving along the conveyor. The surface temperature of the bottles is 120 ° C. The obtained reinforcing two-layer coating with a thickness of 100 nm contains titanium dioxide, a polymer base and single-walled carbon nanotubes when they are contained in the reinforcing layer of 0.2 mass. %).

The average resistance to the internal hydrostatic pressure of the obtained vessels is 35.7 bar.

Claims (20)

1. A glass vessel, on the surface of which is applied at least one reinforcing layer containing carbon nanotubes, characterized in that the reinforcing layer has a thickness of 5-50 nm, contains tin dioxide or titanium dioxide, and carbon nanotubes are single-walled and their content in the reinforcing layer is 0.05-1 mass. % 2. The vessel according to claim 1, characterized in that the single-walled carbon nanotubes have an average ratio of their length and diameter of at least 3000. 3. The vessel according to claim 1, characterized in that the average diameter of single-walled carbon nanotubes is 1.2-2.5 nm, and their average length is not less than 5 microns. 4. The vessel according to claim 1, characterized in that the reinforcing layer is deposited on its surface in the chamber by simultaneously and separately feeding into it a sprayed organotin or organotitanium compound and an atomized aqueous suspension of single-walled carbon nanotubes at a concentration of 0.005-1 mass. % 5. A glass vessel, on the surface of which is applied at least one reinforcing layer containing carbon nanotubes, characterized in that the reinforcing layer has a thickness of 40-100 nm, contains a polymer base in the form of modified polyethylene, and carbon nanotubes are single-walled and their content in the reinforcing layer is 0.05-0.2 mass. % 6. The vessel according to claim 5, characterized in that the single-walled carbon nanotubes have an average ratio of their length and diameter of at least 3000. 7. The vessel according to claim 5, characterized in that the average diameter of single-walled carbon nanotubes is 1.2-2.5 nm, and their average length is not less than 5 microns. 8. The vessel according to claim 5, characterized in that the reinforcing layer is deposited on its surface by spraying a mixture of an aqueous solution of a polymer base in the form of a modified polymer and an aqueous suspension of single-walled carbon nanotubes, when their content in the said mixture is 0.00025-0.001 mass. % 9. The method of hardening glass vessels according to claim 1, comprising applying at the hot end of the processing line to the surface of the formed vessel a reinforcing layer containing organotin or organotitanium compounds and single-walled carbon nanotubes, characterized in that the application of the reinforcing layer is carried out at a vessel surface temperature of 450-750 ° C in a chamber into which a sprayed organotin or organotitanium compound and a sprayed aqueous suspension containing 0.005-1 ma are simultaneously and separately delivered a. % single-walled carbon nanotubes. 10. The method according to p. 9, characterized in that the aqueous suspension of single-walled carbon nanotubes further comprises a dispersant. 11. The method according to p. 10, characterized in that the dispersant is selected from the series: nonionic surfactants - polyethylene glycols (PEG), or polyvinylpyrrolidones (PVP), or BRIDZHI (Brij), or TRITON (Triton), or TWEEN (Tween ); or anionic surfactants — carboxylic acids or their salts, or alkyl sulfates, or alkyl sulfonates, or alkyl aryl sulfonates, or cellulose derivatives, or naphthalene derivatives; or cationic surfactants are salts of primary, or secondary, or tertiary, aliphatic amines, or quaternary ammonium bases. 12. The method according to p. 9, characterized in that the carbon nanotubes have an average ratio of their length and diameter of at least 3000. 13. The method according to p. 9, characterized in that the average diameter of single-walled carbon nanotubes is 1.2-2.5 nm, and the average length is not less than 5 microns. 14. The method according to p. 9, characterized in that when preparing a suspension of single-walled carbon nanotubes, an ultrasonic disperser and / or microfluidic processor and / or high-speed mixer are used, moreover, the amount of energy input is 0.5-30 kWh per 1 kg of suspension. 15. The method of hardening glass vessels according to claim 5, comprising applying at the cold end of the processing line to the surface of the molded and cooled vessel a reinforcing layer containing a polymer base and single-walled carbon nanotubes, characterized in that the application of the reinforcing layer is carried out at a vessel surface temperature of 80-120 ° C by spraying a mixture containing a polymer base in the form of modified polyethylene and an aqueous suspension of single-walled carbon nanotubes, moreover, the content of nanotubes in the mixture with nent 0.00025-0.001 wt. % 16. The method according to p. 15, characterized in that the aqueous suspension of single-walled carbon nanotubes further comprises a dispersant. 17. The method according to p. 16, characterized in that the dispersant is selected from the range of: nonionic surfactants - polyethylene glycols (PEG), or polyvinylpyrrolidones (PVP), or BRIDGES (Brij), or TRITONS (Triton), or TWINs (Tween ); or anionic surfactants — carboxylic acids or their salts, or alkyl sulfates, or alkyl sulfonates, or alkyl aryl sulfonates, or cellulose derivatives, or naphthalene derivatives; or cationic surfactants are salts of primary, or secondary, or tertiary, aliphatic amines, or quaternary ammonium bases. 18. The method according to p. 15, characterized in that the carbon nanotubes have an average ratio of their length and diameter of at least 3000. 19. The vessel according to p. 15, characterized in that the average diameter of single-walled carbon nanotubes is 1.2-2.5 nm, and their average length is not less than 5 microns. 20. The method according to p. 15, characterized in that when preparing a suspension of single-walled carbon nanotubes, an ultrasonic disperser and / or a microfluidic processor and / or high-speed mixer are used, moreover, the input energy is 0.5-30 kWh per 1 kg of suspension.