Carbonated beverage bottles with patterned bubble release

Abstract

Carbonated soft drink containers, and methods of making the same, where the container includes a pattern of nucleation sites that enable controlled bubble release onto the patterned nucleation sites when the container is opened.

Description

CARBONATED BEVERAGE BOTTLES WITH PATTERNED BUBBLE RELEASECROSS REFERENCE TO RELATED APPLICATONS

[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 686,552, filed on August 23, 2024, which is hereby incorporated by reference in its entirety.TECHNICAL FIELD

[0002] The present application relates generally to bottles and other types of containers for carbonated beverages, and more particularly relates to bottles and other types of containers with controlled patterned bubble release therein, methods of manufacture, and methods of use.BACKGROUND

[0003] Many types of carbonated beverages are known. These beverages contain dissolved carbon dioxide and other gases as a result of fermentation (e.g., beer, sparkling wines, etc.) or by the addition of the gases (e.g., carbonated soft drinks and the like). Through the process of effervescence, these beverages discharge the dissolved gases in part via bubbling. The nature of the bubbles and the bubbling process may have an impact on flavor release, mouth feel, visual effect, and other characteristics of the drinking experience for the consumer.

[0004] In the case of carbonated soft drinks and the like, varying levels of carbonation may be used. Carbonated beverages, including soft drinks, typically have a gas volume range of between about 2.5 GV to 5 GV. Generally, the carbonated beverage is enclosed within a container, such as a bottle or can, and the container is sealed for delivery to the consumer. The liquid and the gas of the beverage remain largely at equilibrium while the container is sealed. Specifically, the partial pressure of a given gas above a solution is proportional to the concentration of the gas dissolved in the solution. When the container is opened, however, the partial pressure of the gas in the head space falls. The equilibrium of the beverage within the container thus ends and the dissolved gas in the liquid quickly seeks to escape. The result is the formation of bubbles within the liquid as the gas escapes. The bubbles generally form at nucleation sites along the base or the walls within the container and are produced and released in a largely random and uncontrolled manner.

[0005] Therefore, there is a desire for bottles and other types of containers with improved bubble release mechanisms and controls. Such mechanisms and controls preferably can provide an improved consumer experience, an improved consumer recognition of the beverage, and an improved beverage taste without significant additional costs and other drawbacks.SUMMARY

[0006] Carbonated beverage containers having controlled patterned bubble release are provided. In one aspect, a carbonated beverage container is provided, the beverage container having a base, a sidewall contiguous with and positioned about the base, an inner surface, a plurality of nucleation sites positioned on a first portion, and a second portion of the inner surface which is absent nucleation sites, where the nucleation sites are hydrophobic and configured to promote formation and / or adhesion of bubbles from a carbonated beverage contained in the container, and the second portion of the inner surface is hydrophilic. Release can be controlled where the nucleation sites are hydrophobic and configured to promote formation and / or adhesion of the bubbles.

[0007] In some aspects, the container is a plastic bottle. In some aspects, the plastic bottle includes polyethylene terephthalate (PET). In some aspects, the second portion of the inner surface of the container is coated with a superhydrophilic coating, and the first portion of the inner surface is free of the superhydrophilic coating. The water contact angle of the superhydrophilic coating is between about 0° to about 5°, and the water contact angle of the nucleation sites is between about 50° to about 100°. In some aspects, the superhydrophilic coating includes SixOyCz, and is deposited onto the inner surface of the container using Plasma Enhanced Chemical Vapor Deposition (PECVD). In some aspects, the superhydrophilic coating comprises SiiOi s C0.02. In some aspects, the pattern is a name, a drawing, a logo or a trademark, or another source identifier.

[0008] In another aspect, a method of controlling the release of bubbles in a carbonated beverage in a container is provided, the method including the steps of providing a carbonated beverage container comprising an inner surface, applying a superhydrophilic coating to the inner surface of the container, and creating a plurality of nucleation sites on the inner surface of the container in a desired pattern by removing a portion of the superhydrophilic coating, where, when the container is filled with the carbonated beverage and capped, removal of the cap willcause bubbles to form along the pattern of the plurality of nucleation sites. In some aspects, the method also includes the step of applying a hydrophobic coating to the inner surface of the container before applying the superhydrophilic coating, where the hydrophobic coating improves formation and adhesion of the bubbles along the pattern of the plurality of nucleation sites once a portion of the hydrophilic coating is removed to expose the underlying hydrophobic coating and form the nucleation sites. In some aspects, the method also includes the step of applying a second superhydrophilic coating to the inner surface of the container after creating the plurality of nucleation sites, where application of the second hydrophilic coating prevents adhesion of the bubbles to the nucleation sites, creating the illusion of dynamic bubbling across the nucleation sites.

[0009] In some aspects, the superhydophilic coating includes SixOyCz, and is applied by Plasma Enhanced Chemical Vapor Deposition (PECVD). In some aspects, the PECVD is performed at about 1500 W to about 2500 W and about 30 to about 50 Pa for about 3 seconds to about 5 seconds. In some aspects, the superhydrophilic coating is removed from the inner surface of the container to create the plurality of nucleation sites via etching, more specifically, laser etching. In some aspects, the container is a polyethylene terephthalate (PET) bottle.

[0010] In a further aspect, a method of forming nucleation sites on an inner surface of a polyethylene terephthalate (PET) bottle for controlling release of bubbles in a carbonated beverage contained within the bottle, the method including the steps of providing the bottle, coating the inner surface of the bottle with a superhydrophilic coating, and selectively removing a portion of the superhydrophilic coating to form a pattern of nucleation sites, where the coating is removed via etching, where the inner surface of the bottle, coated with the superhydrophilic coating, has a water contact angle of about 0° to about 5°, and where the nucleation sites are inherently hydrophobic and have a water contact angle of about 50° to about 100°, such that bubbles form and / or adhere only to the nucleation sites and not the inner surface of the bottle from which the superhydrophilic coating has been removed.

[0011] In some aspects, the superhydrophilic coating comprises Si1O1.8C0.02, and the superhydrophilic coating is applied onto the inner surface of the bottle using Plasma Enhanced Chemical Vapor Deposition (PECVD). In some aspects, the method also includes the step of applying a hydrophobic coating to the inner surface of the bottle before applying the superhydrophilic coating, where the presence of the hydrophobic coating improves formationand / or adhesion of bubbles at the nucleation sites. In some aspects, the method also includes the step of applying a second superhydrophilic coating to the inner surface of the bottle after selectively removing the coating to form the pattern of nucleation sites, wherein the second hydrophilic coating prevents adhesion of bubbles to the nucleation sites to create a dynamic bubble pattern within the bottle. In some aspects, the method also includes the step of removing the superhydrophilic coating to form a plurality of nucleation sites on a base of the bottle, and then applying a second superhydrophilic coating to the inner surface of the bottle to form a consistent stream of dynamic bubbles within the bottle.BRIEF DESCRIPTION OF THE DRAWINGS

[0012] FIG. 1 is a side view of a beverage container, according to one or more embodiments of the present disclosure.

[0013] FIG. 2 is a side view of a portion of a container side wall with nucleation sites in a pattern, according to one or more embodiments of the present disclosure.

[0014] FIG. 3 is a side view of a portion of a container side wall with bubbles in a pattern, according to one or more embodiments of the present disclosure.

[0015] FIG. 4 depicts the minimal nucleation of CO2 bubbles in a clear carbonated beverage packaged in a PET bottle coated with a hydrophilic SiOx coating, according to one or more embodiments of the present disclosure.

[0016] FIG. 5 depicts the nucleation of CO2 bubbles in a clear carbonated beverage packaged in a PET bottle coated with hydrophobic SiOx coating, according to one or more embodiments of the present disclosure.

[0017] FIG. 6A is a schematic representation of a PET bottle coated with a superhydrophilic coating, depicting an exemplary bubble within a nucleation site, according to one or more embodiments of the present disclosure.

[0018] FIG. 6B is a schematic representation of a PET bottle coated with a hydrophobic adhesion coating and a superhydrophilic coating, depicting an exemplary bubble within a nucleation site, according to one or more embodiments of the present disclosure.

[0019] FIG. 6C is a schematic representation of a PET bottle coated with a hydrophobic coating and a superhydrophilic coating, depicting an exemplary bubble within a nucleation site, according to one or more embodiments of the present disclosure.

[0020] FIG. 6D is a schematic representation of a PET bottle coated with a hydrophobic adhesion coating, a hydrophobic coating, and a superhydrophilic coating, depicting an exemplary bubble within a nucleation site, according to one or more embodiments of the present disclosure.

[0021] FIGS. 7A-7B are beverage containers, where the inner surface is coated with hydrophilic coating, a portion of which is removed to form nucleation sites, according to one or more embodiments of the present disclosure.

[0022] FIG. 8 depicts an automated etching system for forming nucleation sites on the interior surface of a beverage container, according to on or more embodiments of the present disclosure.

[0023] FIG. 9 is a schematic representation of a PET bottle coated with a hydrophobic coating and a superhydrophilic coating, with a pattern of etched nucleation sites, according to one or more embodiments of the present disclosure.

[0024] FIG. 10 is a beverage container, the inner surface is coated with a hydrophilic coating, a portion of which is removed and coated again to form nucleation sites. The formation of bubbles forming a dynamic pattern, forming on the nucleation sites and traveling upward in the bottle, can be seen, according to one or more embodiments of the present disclosure.

[0025] FIG. 11 is a bottle with dynamic nucleation sites on the base of the bottle, according to one or more embodiments of the present disclosure.DETAILED DESCRIPTION

[0026] Carbonated beverages are popular for their refreshing and attractive qualities, primarily due to the carbonation. Carbonation involves adding carbon dioxide (CO2) to the main ingredient of the drink (i.e., water) under pressure. The pressure allows a substantial amount of carbon dioxide to dissolve into the water, with the amount being proportional to the pressure applied. When a bottle is opened, the pressure inside drops rapidly, and the liquid momentarily retains more dissolved carbon dioxide than it can sustain at the new, lower pressure. At this new low pressure, carbon dioxide transforms from being molecularly dissolved in the liquid to its gaseous form at specific sites, which are typically imperfections, or crevices, in the container wall, and form bubbles. For example, if the radius of curvature of the gas pocket is larger than the critical radius, a bubble will form. The radius of curvature may be predicted using the following equation:

[0027] where y is the surface tension and PL and Po are the equilibrium vapor pressures of the gas in the liquid in supersaturated form and on the free surface above the liquid, respectively.

[0028] Gas pockets created by crevices reduce the energy barrier for carbon dioxide molecules to aggregate and form a bubble, which promotes nucleation (i.e., bubble formation). Upon nucleation, the bubbles grow because more carbon dioxide migrates into them from the surrounding supersaturated liquid and rise due to the difference in the density between the gas inside the bubble and the liquid. Rising bubbles either burst quickly, or in some cases, join to create a foam head.

[0029] In some embodiments, the bubbles remain stable and, upon bursting, can nucleate again almost immediately to maintain a still image effect. In some embodiments, the initially stationary bubbles can be made to move continuously along predetermined paths, forming designated shapes without wandering off course. This process offers a controlled and visually fascinating display within the packaging. The formation of these bubbles may require that the carbonated beverage have a gas volume of at least about 1 GV and a pressure of at least about 2 pounds per square inch (psi).

[0030] While the containers and methods disclosed herein are generally described with reference to soft drinks, or carbonated soft drinks, it would be understood that the present containers and methods may be suitable for use with any carbonated beverage, including but not limited to beer or sparkling wine (e.g., champagne).

[0031] Moreover, the ingredients of the beverage within the containers disclosed herein may impact bubble formation as described herein. Certain beverage ingredients may influence the surface tension of the beverage, which can differently affect static versus dynamic imaging. For example, in low surface tension drinks like beer, the presence of proteins and carbohydrates may facilitate movement of CO2 bubbles even on highly hydrophobic nucleation sites. This behavior is not observed, however, in beverages like carbonated soft drinks and champagne.

[0032] The present disclosure may be further understood with reference to the following definitions.

[0033] The term “carbonated soft drink (CSD)” bottles or containers as used herein is used herein to refer to containers of this disclosure that are designed for use under pressure, such as carbonation, without specific limitations as to the intended contents of the container. Generally,the term “container” is used interchangeably with the term “bottle” unless the context requires otherwise.

[0034] As used in the specification and the appended claims, the singular forms “a”, “an”, and “the” include plural referents, unless the context clearly dictates otherwise. Thus, for example, reference to “a laser” includes a single laser as well as any combination of more than one laser if the context indicates or allows, such as multiple etching lasers that are used in combination.

[0035] Throughout the specification and claims, the word “comprise” and variations of the word, such as “comprising” and “comprises”, means “including but not limited to”, and is not intended to exclude, for example, other additives, components, elements, or steps. While compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components or steps.

[0036] Reference throughout this specification to “one embodiment,” “an embodiment,” or “embodiments” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places in the disclosure are not necessarily all referring to the same embodiment. Furthermore, the particular features, aspects, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0037] “Optional” or “optionally” means that the subsequently described element, component, step, or circumstance can or cannot occur, and that the description includes instances where the element, component, step, or circumstance occurs and instances where it does not.

[0038] Unless indicated otherwise, when a range of any time is disclosed or claimed, for example, a range of sizes, numbers, percentages, and the like, it is intended to disclose or claim individually each possible number that such a range could reasonably encompass, including any sub-ranges or combinations of sub-ranges encompassed therein. When describing a range of measurements such as sizes or percentages, every possible number that such a range could reasonably encompass can, for example, refer to values within the range with one significant figure more than is present in the end points of a range, or refer to values within the range with the same number of significant figures as the end point with the same number of significantfigures, as the context indicates or permits. For example, when describing a range of percentages such as from 85% to 95%, it is understood that this disclosure is intended to encompass each of 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, and 95%, as well as any ranges, subranges, and combinations of sub-ranges encompassed therein.

[0039] Values or ranges may be expressed herein as “about”, from “about” one value, and / or to “about” another particular value. When such values or ranges are expressed, other embodiments disclosed include the specific amount recited, from the one particular value, and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that there a number of values disclosed therein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. In another aspect, use of the term “about” means ± 20% of the stated value, ± 15% of the stated value, ± 10% of the stated value, ± 5% of the stated value, or ± 1% of the stated value.

[0040] Referring now to the drawings, FIG. 1 depicts a beverage container 100 as described herein. According to a preferred embodiment, the container 100 may be a bottle 110. The bottle 110 may be made out of glass, plastics, resins, or other types of materials. The material of the bottle 110 is preferably transparent, or substantially transparent. According to a preferred embodiment, the bottle 110 comprises poly(ethylene terephthalate) (PET). The bottle 110 may be any convenient size or shape. For example, the bottle may be a 500 ml bottle, similar to those that are widely commercially available.

[0041] In embodiments, the bottle includes a base 120, a sidewall 130, a neck 140, and an opening 150. The opening 150 may be enclosed by a cap 160 or other type of enclosure. The interior of the bottle 110 comprises an inner surface which may include a number of nucleation sites 170, as shown in FIGS. 2-3. The nucleation sites 170 serve to create bubbles 180 within the bottle 110 when the cap 160 is removed and the pressure from the carbonated beverage within the bottle 110 is released. The nucleation sites 170 may be positioned on the inner surface of the bottle around the base 120 and / or the sidewall 130 of the bottle 110. According to a preferred embodiment, the nucleation sites 170 are present on the sidewall 130 of the bottle 110. Any number of nucleation sites 170 may be used. The size, shape, and position of the nucleation sites 170 may vary. The nucleation sites 170 may be created in a number of ways, as described in greater detail herein.

[0042] The nucleation sites 170 may be positioned within the bottle such that the bubbles create a pattern of other type of controlled visual impression. As shown in FIG. 2, the nucleation sites 170 may be positioned about the sidewall 130 of the bottle 110 so as to create a nucleation site pattern 200. In this example, the pattern 200 may be a logo, trademark, other type of source identification, saying, name, artistic design, or a combination thereof. FIG. 3 illustrates that the bubbles 180 may adhere to nucleation sites to form a bubble pattern 300. Specifically, single isolated bubbles 180 or ensembles of bubbles 180 may be created to form the bubble pattern 300 over the nucleation sites and the nucleation site pattern. In this way, the nucleation site pattern and the bubble pattern 300 are the same (i.e., the patterns represent the same logo, trademark, source identification, saying, name, and / or artistic design).

[0043] The nucleation sites 170 may have varying sizes and shapes and hence promote the creation of bubbles 180 of differing sizes and shapes in specific types of carbonated beverages. The size, shape, height, and spacing of the nucleation sites may also determine the manner in which bubbles 180 collect on the nucleation sites. For example, a line of nucleation sites 170 will create a line of bubbles 180, and so forth. Likewise, the delivery rate of bubbles 180 may vary based on the nature of the nucleation site and / or the nature of the carbonated beverage.

[0044] In embodiments, the bubble pattern 300 is positioned behind a label (not shown). The label may obscure the bubble pattern 300 and / or bubbles 180, requiring a consumer to first remove the label prior to opening the bottle 110 in order to reveal the pattern.

[0045] In embodiments, as shown in FIGS. 2-3, the pattern 200, 300 is a logo. For example, as shown in FIG. 2, the pattern 200 may be the “Dynamic Ribbon” trademark of The Coca-Cola Company. The pattern 300 of FIG. 3 shows the words “Coca-Cola”, also a trademark of The Coca-Cola Company. However, the invention of the present disclosure is not limited to the patterns 200, 300 depicted herein. Any word or design may be used. The creation and use of bubble patterns 300 when the bottle 110 is opened may promote branding and other consumer recognition, or may be used to promote specifical events or brand partnerships.

[0046] Lively and effervescent packaging, enhanced by bubbles that morph into meaningful shapes and characteristics, not only elevates the sensory experience and enriches taste perception, but also is visually captivating. These engaging transformations into shapes and characters offer delightful surprises, building a connection with consumers and adding a unique appeal to the packaged carbonated beverage product.

[0047] The nucleation sites 170 may be produced in a number of different ways. The nature of the material of the bottle 110 may also impact which technique is appropriate for a given bottle or container type.

[0048] In embodiments, the bubbles remain securely in place for an extended period, and upon bursting, bubbles will re-form on the nucleation sites almost instantly, forming a consistent and lasting visual element visible through the packaging. Once the bubbles are disturbed, such as when taking a sip from the bottle, the bubbles reappear quickly so long as the carbonated liquid level remains above the characters.

[0049] In embodiments, the bubbles move dynamically in a trail, ascending only through specified patterns such as letters, words, or shapes, on the inner surface of the package, providing consumers with a continuous and captivating display.

[0050] In embodiments, the nucleation sites 170 are formed by altering the surface properties of the container 100, specifically, of a bottle 110 formed of PET. Because nucleation and formation of carbon dioxide bubbles may depend on several factors, including package material surface properties, these alterations can effectively control bubble nucleation. Other factors relevant to nucleation and formation of carbon dioxide bubbles may include, but are not limited to, the amount of dissolved gas and / or the liquid temperature.

[0051] In embodiments, the surface hydrophilicity of PET is manipulated to differentiate between nucleation sites and all other parts of the bottle. More specifically, nucleation sites may be formed by increasing the hydrophobicity of the surface of the PET, while the remainder of the bottle surface (i.e., the entire inner surface except for the nucleation sites) is superhydrophilic. The following water contact angles may be used to define varying degrees of hydrophilic and hydrophobic surfaces. Surfaces are deemed superhydrophilic when their water contact angle is between about 0° and about 5°, hydrophilic when their water contact angle is between about 5° and about 50°, hydrophobic when their water contact angle is between about 50° and about 100°, and superhydrophobic when their water contact angle exceeds about 100°.

[0052] In embodiments, the entire bottle 110 except for the areas where the bubble pattern 300 is to be displayed, maintains a hydrophilic surface where the water contact angle is less than about 50°. Even more preferably, the bottle 110 (except the nucleation site pattern 200) maintains a superhydrophilic surface where the water contact angle is between about 0° and about 5°. Such surfaces inherently resist the formation of bubbles thereon, creating a clear,bubble-free backdrop. This pristine background is helpful to offer a striking contrast to the bubbles 180, enhancing the visual appeal and clarity of the bubble pattern 300 being formed on hydrophobic nucleation sites 170, where the water contact angle is between about 50° and about 100°, or superhydrophobic nucleation sites 170 where the water contact angle is greater than about 100°.

[0053] Superhydrophilic surfaces are those that have a high affinity for water. Displacing water molecules to form bubbles therefore requires a large amount of energy, making superhydrophilic surfaces less conducive to gas bubble formation. And even when bubbles do form on superhydrophilic surfaces, the natural propensity of water to spread out prompts these bubbles to burst. This is shown in FIG. 4, for example, where a clear beverage container 100 having an interior surface that is superhydrophilic is shown. This container 100 is filled with a carbonated beverage 10, and very few bubbles are present and / or visible on the interior surface of the container 100.

[0054] Conversely, enhancing the hydrophobicity of the PET bottle surface, particularly to the point where the water contact angle is about 50° and above, encourages the formation of carbon dioxide gas bubbles, especially around surface imperfections. Hydrophobic surfaces offer a reduced energy barrier for gas molecules to transition from a dissolved state to bubble formation. Because hydrophobic surfaces require displacing fewer water molecules, gas bubbles may be more easily formed on such surfaces with diminished water-surface interactions. This is shown in FIG. 5, for example, where a clear beverage container 100 having an interior surface that is hydrophobic is shown. This container 100 is filled with a carbonated beverage 10, and a large number of bubbles 180 are present.

[0055] This strategic manipulation of surface properties, and the creation of specifically formed nucleation sites 170, directs bubble 180 formation in a highly precise manner, which consequentially creates an interactive and visually captivating display for consumers.

[0056] In embodiments, Plasma Enhanced Chemical Vapor Deposition (PECVD) is used to achieve the desired hydrophilic or hydrophobic modifications to beverage containers as those described herein. PECVD utilizes precursor supply gases like HMDSO (hexamethyldisiloxane, [(CHs)3Si]2O), HMDSN (hexamethyldisilazane, [(CH3)3Si]2NH), and O2, which are fragmented and then reacted under a high-energy plasma environment generated through a high voltage RF or microwave generator to create a specialized SixOyCz reaction product coating. This method isalso highly adaptable. By modulating the stoichiometry of the precursor reactants and adjusting the power settings, the hydrophilicity of the coating can be meticulously fine-tuned to achieve optimum results. PECVD may also improve the barrier properties of the container, making it more appropriate for augmenting carbonated soft drink packaging.

[0057] In embodiments, a SixOyCz coating is applied via PECVD under reduced pressure within a microwave plasma environment. In these embodiments, HMDSO and O2 are precursor gases, where about 10 seem (standard cubic centimeter per minute) to about 15 seem HMDSO and about 1000 to about 2000 seem O2 are reacted in a microwave generator to form the SixOyCz reaction product coating. The microwave generator may be operated at between about 1500 W (Watts) to about 2500 W, at an average pressure of about 30 Pa (Pascal) to about 50 Pa for between 3 to 5 seconds. According to a preferred embodiment, about 12 seem HMDSO and about 1400 seem O2 are reacted in a reduced-pressure microwave environment at about 1900 W and about 35-45 Pa for about 3.6 seconds to form the SixOyCz reaction product coating. In embodiments, the SixOyCz has the following composition: x is 1, y is between about 1.5 to about 2, such as between about 1.6 to about 1.9, between about 1.7 to about 1.9, or about 1.8, and C is less than about 5% of the total SixOyCz composition, such as less than 3% of the total composition, less than 2% of the total composition, or less than 1% of the total composition.According to a preferred embodiment, the resulting SixOyCz coating has a composition of SiiOi.8 C0.02, where C is less than 2% of the total composition.

[0058] In embodiments, superhydrophilic coatings are deposited using a liquid aerosol and gas precursor reacted under atmospheric pressure. For example, 2-(N,N-dimethylamino) ethyl methacrylate (DMAEMA) may be reacted to form a superhydrophilic coating on a bottle surface. The plasma polymerization of DMAEMA, facilitated by nitrogen as either a carrier or reactive gas, initiates the polymerization process within an atmospheric pressure plasma environment. The DMAEMA's N,N-dimethylamino group enhances the coating's hydrophilic nature, thereby enhancing water molecule interaction and wettability.

[0059] In embodiments, the hydrophilicity of the carbonated soft drink container surface is modified using silane chemical treatments, laser processing, layer-by-layer deposition, or a combination thereof.

[0060] In embodiments, additional coating layers (i.e., coating layers provided in addition to the superhydrophilic coatings described herein) may be used to further modify the surfaceproperties of the beverage container 100. Exemplary coating systems 400 as shown and described with respect to FIGS. 6A-6D.

[0061] As shown in FIG. 6A, a PET bottle 110 may be coated with the superhydrophilic coating 402, where the superhydrophilic coating 402 may be any of the superhydrophilic coatings described herein. A nucleation site 170 may be formed to trap a bubble 508 in the etched space within the superhydrophilic coating 402. The gap in the coating (i.e., the nucleation site 170) enables bubble 180 formation and retention on the surface of the bottle 110 (which is hydrophobic PET) beneath the superhydrophilic coating 402, where the water contact angle is between about 60° to about 70°.

[0062] However, adhesion of the superhydrophilic coating 402 to the bottle 110 may be improved by first applying an adhesion coating layer 404 to the bottle 110 prior to depositing the superhydrophilic coating 402, as shown in FIG. 6B. In embodiments, the adhesion coating layer 404 is hydrophobic and has a water contact angle of between about 60° to about 70°, similar to PET from which the bottle 110 is formed.

[0063] In embodiments, as shown in FIG. 6C, a hydrophobic coating 406 may first be deposited onto the bottle 110 prior to depositing the superhydrophillic coating 402. While nucleation sites do form on the inherently hydrophobic PET bottle 110 after application of just the superhydrophilic coating 402, first depositing a hydrophobic coating 406 may be effective to improve formation and / or adhesion of said bubbles 180 to the nucleation sites 170. In some embodiments, as shown in FIG. 6D, an adhesion layer 404 may also be deposited onto the bottle 110 prior to depositing the hydrophobic coating 406 and superhydrophilic coating 402.

[0064] The adhesion layer 404 and / or the hydrophobic coating 406 may be deposited using the same or different method as the superhydrophillic coating 402. For example, in some embodiments, the adhesion layer 404 and / or the hydrophobic coating 406, like the superhydrophilic coating 402, may be deposited by PECVD or another method. In other embodiments, the adhesion layer 404 and / or the hydrophobic coating 406 are deposited by PECVD and the superhydrophilic coating 402 is deposited using another method, or the adhesion layer 404 and / or the hydrophobic coating 406 are deposited using an alternative method and the superhydrophilic coating 402 is depositing using PECVD.

[0065] In embodiments where the hydrophobic coating is applied by PECVD, HMDSO can be reacted under low pressure microwave conditions to form a hydrophobic coating. Forexample, about 50 seem to 70 seem HMDSO may be reacted at about 750 W to about 1500 W at 10 Pa to 30 Pa for a duration of about 1 to 100 seconds to form a coating. According to a preferred embodiment, the hydrophobic coating is formed by using about 60 seem HMDSO reacted at about 1000-1200 W and about 20 Pa for a duration of about 3-15 seconds.

[0066] After coatings are deposited, a pattern may be etched to remove the at least the superhydrophilic coating. In some embodiments, the hydrophobic coating may also be removed by the etching. Removal of the hydrophobic coating however does not impact formation of nucleation sites. For example, as shown in FIG. 6B, the nucleation site 170 may be formed in the etched space within the superhydrophilic coating 402 and / or hydrophobic coating 404. In other words, the bubble may be formed and retained on the hydrophobic coating (having a water contact angle of about 90°) and / or the inherently hydrophobic PET surface (having a water contact angle of between about 60° to about 70°).

[0067] In embodiments where the PET is first coated with hydrophobic coating, nucleation sites may more effectively retain bubbles therein. In other words, the patterns may be more distinctly formed when PET bottle is coated with hydrophobic coating, then superhydrophilic coating, as shown in FIG. 6B, before etching nucleation sites in the desired pattern. Without being bound by theory, the patterns are thought to be more stable with a prior hydrophobic coating because the bubble is still in contact with the side walls of the hydrophobic coating even after etching a pattern.

[0068] After the superhydrophilic coating (in addition to an adhesion layer and / or a hydrophobic coating, if desired) is applied to the inner surface of the bottle 110, nucleation sites are created in the form of a pattern. In some embodiments, the nucleation sites are formed on the inner surface of the sidewall 130 of the bottle. In other embodiments, the nucleation sites 170 are formed on the inner surface of the sidewall 130 and the inner surface of the base 120 of the bottle.

[0069] As shown in FIGS. 7A-7B, the superhydrophilic coating may be removed from the bottle 110 in the desired nucleation site pattern 200 to form the nucleation sites 170, where bubbles 180 collect to form a stationary bubble pattern 300 on the interior surface of the bottle 110 when it is filled with a carbonated beverage 10. Removal of the superhydrophilic coating exposes the bottle 110, preferably formed of PET, which has an inherently hydrophobic surface. The hydrophobic nucleation sites 170 thereby facilitate bubble 180 formation and adhesion alongthe nucleation site pattern 200. When the cap is removed from the bottle 110, the bubbles 180 forming the bubble pattern 300 may begin to dissipate.

[0070] In embodiments, the nucleation sites 170 are etched into the coated bottle. In some embodiments, the nucleation sites 170 are hand etched using the appropriate tools (e.g., a metal pick). In other embodiments, a robotic system is configured to etch the nucleation sites 170. In further embodiments, the nucleation sites 170 are created by laser etching. Laser etching and marking is common for printing the date and product codes on the outside of bottles. The use of multiple low power lasers focused such that the total power at the common focal point is much greater may allow for etching on the backside of a material (i.e., on the inside of a bottle). That is, lasers or another high intensity light source may be used to remove the superhydrophilic coating from the inner surface of the bottle to form nucleation sites 170 in a desired pattern 200.

[0071] In embodiments, an automated etching system may be used to etch the nucleation sites 170 into the coated bottle 110. A computer-controlled etching system 500, such as that shown in FIG. 8, is used to etch the nucleation sites 170 into the coated bottle 110. The etching system 500 may include a plotter apparatus 502 having a drawing head 504 configured to hold a magnetic drawing pen 506. The drawing head 504 is configured to extend beyond the primary framework of the plotter apparatus 502 to interface with a bottle holding platform 508, which securely positions a bottle 110 in a horizontal orientation. The drawing head 504 may facilitate transfer of a predetermined vector-based graphical design from a computer 510 onto the exterior surface of the bottle 110 with high precision.

[0072] To etch the nucleation pattern onto the interior surface of the bottle 110, a magnet 512 is placed on the inside of the bottle 110, where the magnet 512 firmly adheres to the internal surface of the bottle 110 through the magnetic coupling force exerted by the magnetic drawing pen 506 located on the exterior of the bottle. In some embodiments the magnet 512 is a cylindrical magnet having a height of about 1 mm and a diameter of about 1 mm. In some embodiments, an electromagnetic arm 514 is provided to position the magnet 512 at the beginning of the etching process, and to remove the magnet 512 from the bottle 110 once etching is complete.

[0073] The program on the computer 510 powers the drawing arm 404 to, via the magnetic drawing pen 506, trace the programed pattern onto the exterior of the bottle 110. With the magnet 512 engaged to the drawing pen 506 through the bottle 110, the magnet 512 is pulledalong the same pattern being traced by the drawing pen 506. As a result of the magnetic force between the magnet 512 and the magnetic drawing pen 506, the magnet 512 effectively etches the pattern into the coating on the interior surface of the bottle 110, without impacting or damaging the surface of the bottle 110 itself. Depending on the number of coatings and / or thicknesses of the coating layer(s), the magnetic force can be adjusted (i.e., by modifying the side of the magnet) to ensure the correct force is being applied to effectively etch the nucleation sites 170 and nucleation site pattern 200 into the interior surface of the coated bottle 110.

[0074] While certain methods for forming nucleation sites 170 have been described in detail herein, the nucleation sites 170 may be formed using any type of etching or engraving method known in the art.

[0075] In embodiments, it may be desirable to form dynamic bubbles, where bubbles are transient along nucleation sites forming the desired pattern. In other words, bubbles may be present on the nucleation sites for only a moment, and then create a bubble trail within the carbonated beverage along a similar pattern. Dynamic bubbling still requires formation of nucleation sites to initiate bubble formation, but should not have such a strong hydrophobicity that the bubbles are retained on the nucleation site as otherwise described with respect to the static patterns.

[0076] To achieve this effect, nucleation sites may have a lesser water contact angles (i.e., should be more hydrophilic) than nucleation sites for the formation of static patterns. In embodiments, an additional superhydrophilic coating may be deposited onto the inner surface of the bottle after the nucleation sites have been formed, using any of the methods as previously described. As shown in FIG. 9, a dynamic coating system 600 includes applying a first layer 602 of a superhydrophilic coating to the interior surface of a PET bottle 110. After the first layer 602 is applied to the bottle 110, a nucleation site 170 may be etched in the first coating layer 602. A second layer 604 of the superhydrophilic coating is then added on top of the first layer 602. In this way, a bubble 180 may still be formed on the nucleation site 170, but the bubbles 180 do not adhere to the nucleation site 170 as with the static coatings. This creates a dynamic pattern effect, creating the illusion of a moving pattern or that the dynamic bubbles 190 are traveling upward along a path resembling the pattern (see, e.g., FIG. 10).

[0077] In other embodiments, this may also be done on the base of the bottle to create the illusion of dynamic “champagne” bubbles 190 moving through the carbonated beverage in thebottle. This can be in addition to the etched pattern on the sidewall, or alone. Nucleation sites 170 on the base 120 are formed the same way as described, and can be in a random configuration (see, e.g., FIG. 11) or a pattern.

[0078] Other types of manufacturing techniques may be used herein to form the nucleation sites. Likewise, combinations of the different manufacturing techniques may be used herein so as to form varying types of nucleation sites. The varying types of nucleation sites may produce varying types of bubbles and different types of bubble release.

[0079] The use of nucleation sites thus serves to control the formation of the bubbles when the container 100 or the bottle 110 is opened. The positioning of nucleation sites 170 also provides bubble patterns 300 so as to provide a unique visual impression when the bottle 110 is opened. This may increase consumer recognition of the brand of the beverage, or of the beverage contained in the bottle 110. The nucleation sites 170 may therefore provide an improved consumer experience every time a bottle 110 is opened.

[0080] This invention can be further understood with reference to the following non-limiting examples.EXAMPLESExample 1 - Static Image

[0081] Bottles were coated using an InnoPET Plasmax 2Q coating machine, which features two stations, each accommodating four bottles. The following process parameters were employed to coat PET bottles with varying degrees of surface hydrophilicity. Due to issues related to thermal mismatch and adhesion, it is not advisable to apply a superhydrophilic SiOx layer directly onto the PET surface in high-stress environments, such as those found in CSD packaging. Therefore, an adhesion layer (Layer 1) is applied first, before adding the hydrophilic layer to ensure proper functionality and durability.

[0082] While the following parameters were chosen for specific examples of this invention, similar surface properties can be achieved with different combinations of gas flows and microwave (MW) power. For superhydrophilic surfaces (Layer 2), a high O2 / HMDSO ratio (80- 120) combined with high MW power (>1300) is more suitable. Conversely, for hydrophobic layers with a contact angle greater than 75°, low MW power with only HMDSO is sufficient. Superhydrophilic surfaces applied using this method typically exhibit a SixOyCz composition where x is 1, y is between about 1.5 to about 2.0, preferably between about 1.7 to about 1.9, orabout 1 .8, and where C is less than about 5%, preferably about less than 2%, of the total composition. For example, the superhydrophilic coating may have the following composition: Si 1O1.8 Co.02, where C is less than 2% of the total composition. For example, the hydrophobic coating may have the following composition: SiiOo.eCi.The hydrophobic layer coating shown in Table 2 may have a water contact angle greater than 75°, preferably between about 90° to about 100°, and exhibit a SixOyCz composition where x is 1, y is between about 0.3 to about 0.9, preferably between about 0.5 to about 0.7, or about 0.6, and z is between about 1.7 to 1.2, preferably about 1.6. For example, the hydrophobic coating may have the following composition: SiiOo.6Ci.6.Table 1. Coating Parameters for Superhydrophilic SurfaceTable 2. Coating Parameters for the Hydrophobic Surface

[0083] The water contact angle was determined using Ossila Contact Angle equipment. The superhydrophilic coating exhibited a water contact angle of zero degrees, signifying complete wetting of the surface and precluding any recordable measurement. The water contact angle of the hydrophobic coating layer, on the other hand, was 90° to 97°. This hydrophobic coating may also have a composition of SiiOo.eCi e. These values, however, may differ slightly depending on carbon contamination on the surface.

[0084] For stationary imaging with CSD bubbles, uncoated PET bottles with a water contact angle of 55° to 70° (depending on the resin grade) were coated with an adhesion and a subsequent superhydrophilic layer using the aforementioned parameters. Characters were then lightly inscribed onto the inner wall of the bottle, penetrating through to the PET layer.Subsequently, the bottles were filled with a clear CSD product. The difference in contact angles between the uncoated PET layer and the superhydrophilic layer is substantial enough to provide clear character definitions. However, if a hydrophobic layer is applied onto the PET prior to adding the superhydrophilic layer, bubble definition and stability improves.

[0085] While inscriptions were manually applied for the purpose of this Example, it would be understood that other high precision inscription methods may be used.Example 2 - Dynamic Image

[0086] For dynamic imaging with CSD bubbles, characters were first inscribed onto the inner PET wall having a water contact angle of 55° to 70° (depending on the resin grade). The inside of the PET bottle was then coated with an adhesion and a subsequent superhydrophilic layer using the aforementioned parameters. Subsequently, the bottles were filled with a clear CSD product. This technique not only enables dynamic effervescence through distinct characters but also initiates effervescence at any part of the bottle, such as along the side wall or from the base.

[0087] Those skilled in the art will readily appreciate that many modifications to the exemplary embodiments disclosed herein are possible without materially departing from the novel teachings and advantages according to this disclosure. Accordingly, all such modifications and equivalents are intended to be included within the scope of this disclosure as defined in the following claims. Therefore, it is to be understood that resort can be had to various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit and scope of the appended claims.

Claims

CLAIMS1. A carbonated beverage container comprising: a base; a sidewall contiguous with and positioned about the base; an inner surface; a plurality of nucleation sites positioned on a first portion of the inner surface of the sidewall in a pattern; and a second portion of the inner surface which is absent nucleation sites; wherein the nucleation sites are hydrophobic and configured to promote formation and / or adhesion of bubbles from a carbonated beverage contained within the container, and the second portion of the inner surface is hydrophilic.

2. The carbonated beverage container of claim 1, wherein the container comprises a plastic bottle.

3. The carbonated beverage container of claim 2, wherein the plastic bottle comprises polyethylene terephthalate (PET).

4. The carbonated beverage container of claim 1, wherein the second portion of the inner surface of the container is coated with a superhydrophilic coating, and wherein the first portion of the inner surface is free of the superhydrophilic coating.

5. The carbonated beverage container of claim 4, wherein a water contact angle of the superhydrophilic coating is between about 0° to about 5°, and wherein a water contact angle of the nucleation sites is between about 50° to about 100°.

6. The carbonated beverage container of claim 4, wherein the superhydrophilic coating comprises SixOyCz, and is deposited onto the inner surface of the container using Plasma Enhanced Chemical Vapor Deposition (PECVD).

7. The carbonated beverage container of claim 6, wherein the superhydrophilic coating comprises Si1O1.s C0.02.

8. The carbonated beverage container of claim 1, wherein the pattern is a logo or a trademark, or another source identifier.

9. A method of controlling the release of bubbles in a carbonated beverage in a container, the method comprising: providing a carbonated beverage container comprising an inner surface; applying a superhydrophilic coating to the inner surface of the container; and creating a plurality of nucleation sites on the inner surface of the container in a desired pattern by removing a portion of the superhydrophilic coating; wherein, when the container is filled with the carbonated beverage and capped, removal of the cap will cause bubbles to form along the pattern of the plurality of nucleation sites.

10. The method of claim 9, further comprising applying a hydrophilic coating to the inner surface of the container before applying the superhydrophilic coating, wherein the hydrophobic coating improves formation and adhesion of the bubbles along the pattern of the plurality of nucleation sites.

11. The method of claim 9, further comprising applying a second superhydrophilic coating to the inner surface of the container after creating the plurality of nucleation sites, wherein application of the second hydrophilic coating prevents adhesion of the bubbles to the nucleation sites, creating the illusion of dynamic bubbling across the nucleation sites.

12. The method of claim 9, wherein the superhydophilic coating comprises SixOyCz, and wherein the superhydrophilc coating is applied by Plasma Enhanced Chemical Vapor Deposition (PECVD).

13. The method of claim 12, wherein the PECVD is performed at about 1500 W to about 2500 W and about 30 to about 50 Pa for about 3 seconds to about 5 seconds.

14. The method of claim 9, wherein the superhydrophilic coating is removed from the inner surface of the container to create the plurality of nucleation sites via etching, more specifically, laser etching.

15. The method of claim 9, wherein the container is a polyethylene terephthalate (PET) bottle.

16. A method of forming nucleation sites on an inner surface of a polyethylene terephthalate (PET) bottle for controlling release of bubbles in a carbonated beverage contained within the bottle, the method comprising: providing the bottle; coating the inner surface of the bottle with a superhydrophilic coating; and selectively removing a portion of the superhydrophilic coating to form a pattern of nucleation sites, where the coating is removed via etching; wherein the inner surface of the bottle, coated with the superhydrophilic coating has a water contact angle of about 0° to about 5°, and wherein the nucleation sites are inherently hydrophobic and have a water contact angle of about 50° to about 100°, such that bubbles form and / or adhere only to the nucleation sites and not the inner surface of the bottle from which the superhydrophilic coating has been removed.

17. The method of claim 16, wherein the superhydrophilic coating comprises SiiOi.s C0.02 , and wherein the superhydrophilic coating is applied onto the inner surface of the bottle using Plasma Enhanced Chemical Vapor Deposition (PECVD).

18. The method of claim 16, further comprising applying a hydrophobic coating to the inner surface of the bottle before applying the superhydrophilic coating, wherein the presence of the hydrophobic coating improves formation and / or adhesion of bubbles at the nucleation sites.

19. The method of claim 16, wherein the method further comprises applying a second superhydrophilic coating to the inner surface of the bottle after selectively removing the coating to form the pattern of nucleation sites, wherein the second hydrophilic coating prevents adhesion of bubbles to the nucleation sites to create a dynamic bubble pattern within the bottle.

20. The method of claim 16, further comprising removing the superhydrophilic coating to form a plurality of nucleation sites on a base of the bottle, and then applying a second superhydrophilic coating to the inner surface of the bottle to form a consistent stream of dynamic bubbles within the bottle.

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