In many applications, it is desirable to fill a container with a heated material and to then seal the container while the material is still in a heated state so as to sterilize the product and package and make the product safe for consumption. For example, various types of beverages are packaged in “hot-fill” containers fabricated from polyethylene terephthalate (PET). Typically, such containers are filled and capped at temperatures around 185° F. A container can deform when exposed to a liquid that has been heated above the glass transition temperature (Tg) of the material from which the container is formed. Moreover, steam and/or other heated gas in a sealed container headspace will condense as the container contents cool. Headspace condensation produces a vacuum in sealed hot-filled containers.
Most hot-fill beverage containers are designed to operate at or near atmospheric pressure. If such a container has a significant internal vacuum after it is sealed, it will deform and may buckle upon cooling. To avoid such distortion, any internal pressure that is significantly lower than external atmospheric pressure should be minimized and/or the container provided with appropriate structural support. Various techniques have been developed in this regard. For example, some PET container designs include movable vacuum panels or movable bases. Some hot-fill beverage containers have a thicker wall construction. These features result in heavier PET containers and increased material cost, however. Other techniques also have various drawbacks. Accordingly, there remains a need for additional techniques and devices that can reduce and/or relieve vacuum generated by hot-filling of deformable containers.
This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key or essential features of the invention.
In at least some embodiments, an adsorber material element is used relieve a vacuum that results from cooling of heated contents in a sealed container. An interior volume of that container may be filled or partially filled with a heated material. The heated material may be or may include a liquid. In some embodiments, the heated material may be a beverage or other food product intended for consumption by a human or animal. The container may be formed from any of a variety of materials and may have any of a variety of shapes. In some embodiments, the container may be formed from polyethylene terephthalate (PET) or other deformable material. The container may be at least partially filled with liquid above 150° F. and sealed. After sealing, one or more gases may be released from an adsorber material and into the interior volume of the sealed container. As the contents of the container cool, the release of gas(es) from the adsorber material relieves vacuum that would otherwise develop. In at least some embodiments, the gas release is initially gradual, with full release of gas occurring after the contents of the container have cooled below the Tg of the container material.
In some embodiments, an adsorber material insert may be incorporated into a container closure. Multiple closures may be stored in a pre-charging chamber to pre-charge the closure inserts with one or more gases. As containers are filled with heated beverage, closures may be dispensed from the pre-charging chamber and used to seal filled containers.
Additional embodiments are described herein.
Some embodiments are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements.
In at least some embodiments, an adsorber material element is used relieve a vacuum that results from cooling of heated contents in a sealed container. As used herein, a “vacuum” refers to a pressure within an internal volume of a sealed container that is less than a pressure in an external space that surrounds the sealed container. As also used herein, “relieving” a vacuum includes reducing a vacuum, i.e., reducing the difference between a pressure within a sealed container internal volume and a pressure in the external space that surrounds the container. “Relieving” a vacuum may also include completely eliminating a vacuum, i.e., causing the container internal volume pressure to be equal to or greater than an external space pressure. “Relieving” a vacuum may also encompass avoiding creation of a vacuum, e.g., releasing gas from an adsorber material at a rate that is sufficiently fast to prevent an container internal volume pressure from becoming less than an external space pressure as the container contents cool.
In some embodiments, an adsorber material element may be in the form of an insert. That insert, which may include one or multiple types of adsorber materials, may be housed in a closure used to seal the container. Prior to placement of an insert-housing closure onto a container filled with heated material and sealing the container, the adsorber material(s) may be pre-charged (also known as pre-loaded) with one or more gases. Those gases can include, without limitation, nitrogen (N2), methane (CH4), ethane (C2H4), carbon dioxide (CO2), and/or other gases. When the container is filled and ready for capping, the closure (which includes the pre-charged adsorber material(s)) is placed onto the container and the container is sealed. Gas is released from the adsorber material(s) housed in the insert. The release of gas from the adsorber material(s) as the container contents cool relieves the vacuum associated with cooling of those contents and condensing of vapor and/or gases in the container headspace. Additional aspects of methods and devices according to these and other embodiments are described below.
Closure 100a is configured for attachment to a threaded neck finish of a polyethylene terephthalate (PET) beverage container in a conventional manner. In particular, a cavity 102a in the underside of housing 101a is configured to receive a finish portion of a container neck. For reference purposes,
The upper end of cavity 102a terminates in a liner well 105a. Closure 100a further includes a disc-shaped liner 106a positioned in liner well 105a. Similar to liners of conventional beverage container closures, liner 106a acts to seal a container when closure 100a is secured to a container neck finish. Specifically, bottom surface 107a of liner 106a is pressed against a sealing surface on the top edge of a neck finish when closure 100a is tightened onto that neck finish.
Unlike conventional liners, however, liner 106a holds an adsorber material insert 120a. Insert 120a contains one or more adsorber materials that have been selected based on an ability to adsorb a desired gas under one set of conditions and to then release the adsorbed gas under a different set of conditions. For example, the adsorber material(s) may adsorb the selected gas(es) under conditions that comprise a relatively high concentration of the selected gas(es) at a relatively high pressure. The adsorber material(s) may release the adsorbed gas(es) under conditions that comprise a lower pressure and/or the presence of added moisture.
Gases that may be adsorbed and then released into a container according to various embodiments include, without limitation, one or more of the following: nitrogen (N2), methane (CH4), ethane (C2H6) and carbon dioxide (CO2). Gases that are minimally soluble in liquid (or other container contents) may be preferred in at least some embodiments. In some embodiments, an adsorber material insert or other type of adsorber material element may only be pre-charged with a single type of gas. When that adsorber material element is later exposed to the sealed container interior, that single type of gas is released. In other embodiments, an adsorber material element or collection of adsorber material elements may be pre-charged with multiple types of gases. When that adsorber material element or element collection is later exposed to the sealed container interior, each of those multiple types of gas may be released. In at least some embodiments, multiple gas adsorber material elements may be utilized to control the rate and release characteristics of adsorbed gas(es) as a function of time.
Numerous types of adsorber materials are known in the art, including, without limitation, zeolites, carbon, carbon nanotubes and metal organic frameworks (MOFs). One example of an MOF that may be used in some embodiments and that can be used to adsorb CO2, CH4 and/or N2 is available under the trade name BASOLITE C300 from Sigma-Aldrich Co. LLC of St. Louis, Mo., US. Other adsorbers that can be used include, without limitation, 13X zeolite, activated carbon and 5A zeolite. These materials, which can also be used to adsorb CO2, CH4 and/or N2, are well-known and commercially available from numerous sources.
In some embodiments, an adsorber material insert or other adsorber material element may only include a single type of adsorber material. For example, an insert may be configured to adsorb a single gas, e.g., gas A. Adsorber material X adsorbs gas A, and thus an adsorber material insert configured to adsorb (and subsequently release) gas A might only include adsorber material X. In other embodiments, an adsorber material element may be comprised of multiple different types of adsorber materials. As another example, an adsorber material insert may be configured to adsorb two different types of gas, e.g., gas B and gas C. Adsorber material Y may be a good adsorber of gas B but a poor adsorber of gas C. Similarly, adsorber material Z may be a good adsorber of gas C but a poor adsorber of gas B. Thus, an adsorber insert configured to adsorb (and subsequently release) gases B and C could contain a mixture of adsorber materials Y and Z. Alternatively, multiple adsorber inserts containing different types of adsorbers could be used to release one or more gases.
In some embodiments, insert 120a is formed as a solid disc before being embedded into liner 116a. In addition to one or more adsorber materials, insert 120a may include one or more binder materials (e.g., clay, fibers, polymers, waxes, cements) so as to maintain the integrity of insert 120a as a solid disc. In some embodiments, insert 120a is solid, but may have a different shape so as to maximize exposed surface area. For example, instead of a solid disc, insert 120a could be in the form of a solid spur with multiple spokes. In still other embodiments, the adsorber material(s) of insert 120a may be in granular form. For example, insert 120a could be in the form of a pouch formed by an outer membrane holding particles of adsorber material(s). Examples of such an embodiment are described below in connection with
Liner 106a includes a semipermeable region 108a located directly under insert 120a. Semipermeable region 108a allows gas escaping from insert 120a to pass through liner 106a and reach an interior volume of a container sealed by closure 100a. Region 108a also allows some moisture from that interior volume to reach insert 120a. As explained in further detail below, such moisture may in some embodiments trigger the release of gas from insert 120a. In the embodiment of closure 100a, liner 106a is formed from two types of material. The first type of material is used for semipermeable region 108a and the second type is used for the remainder of liner 106a. The second type of material is not permeable to gas or moisture. Examples of materials that can be used for the non-permeable portions of liner 106a include, without limitation, aluminum foil laminated elements. Examples of materials from which semipermeable region 108a can be formed include, without limitation, thermoplastic elastomers (TPEs), styrene ethylene butylene styrene (SEBS) terpolymer and ethylene vinyl acetate (EVA).
Closure 100b differs from closure 100a because of liner 106b. Unlike liner 106a, where semipermeable region 108a is formed from a different material than other portions of liner 106a, semipermeable region 108b of liner 106b is formed from the same non-permeable material used to form other portions of liner 106b. So that region 108b will allow gas released from insert 120b to reach a container interior volume and allow moisture from the container interior to reach insert 120b, a plurality of small pores 109b are formed in region 108b.
Closure 100c includes an adsorber insert 120c that differs from the solid inserts 120a and 120b of
Semipermeable region 108a of closure 100a liner 106a may also act to moderate the rate at which gas diffuses from insert 120a to a container interior. In a similar fashion, region 108b of liner 106b (closure 100b) and membrane 121c (element 120c within liner 106c of closure 100c) may also act to moderate the rate at which gas diffuses from an adsorber insert to a container interior.
Closures 100a-100c can be fabricated in a variety of ways. For example, insert 120a-120c could first be formed. In some embodiments, and depending on the adsorber material(s) selected, insert 120a or 120b might be formed by molding the selected adsorber material(s) in a matrix of one or more binder materials to form a solid disc. As indicated above, insert 120c could be formed by sealing the selected adsorber material(s) between sheets of membrane material. The non-permeable portion of liner 106a may molded into place around insert 120a, after which semipermeable region 108a could be molded into place. After molding of liner 106a is complete, liner 106a could be placed into well 105a of housing 101a. Housing 101a could be injection molded in a conventional manner. In other embodiments, a previously formed insert 120a could be placed in a well of housing 101a and liner 106a could be molded in place around insert 120a. Similar operations could be used to fabricate closures 100b or 100c, with modifications to accommodate differences in the various embodiments. For example, pores 109b in closure 100b could be formed during the process of molding liner 106b by using small pins or other mold elements.
To dispense a closure from pre-charging chamber 200 for use in sealing a container, outer door 204, inner door 203 and vent valve 206 are closed. Gas G valve 205 is opened and dispensing chamber 202 is pressurized to 6 bars (or to the same pressure as main chamber 201, if different), and then valve 205 is closed Inner door 203 is then opened, a closure 100 is moved from main chamber 201 to dispensing chamber 202, and inner door 203 is closed. Vent valve 206 is then opened to release the excess pressure within dispensing chamber 202, after which outer door 204 is opened and closure 100 is moved from dispensing chamber 202 to the capping machine. For convenience,
Immediately upon being exposed to atmospheric pressure, the pre-charged adsorber material insert within the dispensed closure 100 begins to release gas G. Accordingly, and as shown in
This is shown schematically in
As further shown in
Sealed container 220 may then be passed through a cooling tunnel (not shown). As container 220 passes through the cooling tunnel, it may be sprayed with water so as to lower the temperature of liquid 224 to approximately 165° F. As the temperature of liquid 224 drops, gas G continues to be released from insert. This release of gas G continues to relieve vacuum within interior region 220.
Step 300 includes at least partially filling an interior volume of a container with a heated material. In some embodiments the container is filled, but in other embodiments the container may not be completely filled. The container can have any of various shapes. In some embodiments, and as is shown in
The container can also be formed of various materials. In at least some embodiments, the container is formed from a deformable material such as PET. In other embodiments, the container is formed from one or more other types of plastic materials. Such other plastic materials can include, without limitation, polyethylene naphthalate or other resins with a Tg of greater than 75° C. In still other embodiments, the container may be formed from one or more other plastic or non-plastic deformable materials. In yet other embodiments, the container may include one or more non-deformable portions. As used herein, an element is “non-deformable” if it does not show any noticeable deformation to the naked eye when a container incorporating the element is subjected to an unrelieved vacuum pressure caused by content cooling.
In some embodiments, the heated material placed into the container during step 300 is, or includes, a liquid. In at least some embodiments, the heated material is a beverage or other food product intended for consumption by a human or animal. The beverage or other food product may have any of numerous formulations, consistencies and/or textures. The beverage or other food product may be viscous, thin or watery, may or may not have inclusions (e.g., fruit pulp), etc. In some embodiments, the beverage or other food product may be gelatinous or a slurry. Examples of heated liquids with which a container may be at least partially filled in step 300 include, without limitation, fruit juices, sports drinks and other beverages, as well as dairy products. The heated material placed into the container in step 300 may be a mixture of other materials.
The temperature to which the material is heated at the time of filling in step 300 may also vary by embodiment. That temperature may depend, at least in part, on the material being placed into the container. As used herein, “heated” means significantly above room temperature. In at least some embodiments, a material is heated to at least 150° F. during the at least partial filling of step 300. In other embodiments, the material is heated to at least 160° F., to at least 165° F., to at least 170° F., to at least 175° F., to at least 180° F., to at least 185° F., or higher, during the at least partial filling of step 300.
Step 305 includes sealing the container after the filling (or partial filling) of the container with the heated material. In some embodiments, and as described in connection with
A closure need not be used in all embodiments. In some embodiments, for example, the sealing operations of step 305 might include welding or otherwise permanently closing an opening on the container. For example, in some embodiments an adsorber insert similar to insert 120a might be wrapped in a semi-permeable material intended to withstand long-term immersion in the material within a sealed container. A supply of such inserts could be pre-charged in a chamber in a manner similar to the manner in which closures 100 are pre-charged in chamber 200 in the embodiment of
Step 310 includes releasing a gas from an adsorber material element into an interior volume of the container after the container has been sealed. This adsorber material element is pre-charged with one or more gases such that those one or more gases are adsorbed into pores on the surface of the adsorber material(s). Prior to sealing the container in step 305, the adsorber material element is placed in a location so that gas(es) released from the adsorber material can flow into the container interior volume. In some embodiments, and as described in connection with
Once the container is sealed, exposure to conditions within the container interior volume (e.g., pressure drop, moisture) cause one or more gases to be released from adsorber material element. The released gas(es) flow into the container interior volume. As the heated material in the container cools, the ongoing release of gas(es) from the adsorber material element relieves vacuum caused by the cooling of the container contents.
Different gases and/or combinations of gases can be released during step 310 in various embodiments. As indicated above, those gases include, without limitation, nitrogen (N2), methane (CH4), ethane (C2H4) and carbon dioxide (CO2). Other gases can include, without limitation, hydrogen (H2) and helium (He). In some embodiments, gases with low aqueous solubility are selected so as to reduce the volume of gas that must be released so as to relieve vacuum. Numerous materials can be used as an adsorber material in an adsorber material element according to various embodiments. Those materials include, without limitation, the materials previously identified. An adsorber material element may also include other binders and other compounds to maintain the adsorber material(s) as a monolithic element. An adsorber material element may include adsorber materials in granular or other loose form that are contained by a membrane or other barrier. An adsorber material element may contain a single type of adsorber material (e.g., so as to adsorb and release a single gas) or may contain multiple types of adsorber materials (e.g., so as to adsorb and release multiple gases).
In at least some embodiments, it is desirable to avoid deforming a container when a product filling that container is at a temperature above the Tg of the container material. This helps to avoid permanently expanding the container material to create an even larger internal volume. As a result, container shape and integrity can be maintained.
So as to avoid permanently deforming the container when the contents are above the container material Tg, an adsorber, a matrix containing the adsorber and/or a semipermeable liner region surrounding the adsorber can be selected to result in a timed release of adsorbed gas. In particular, the adsorber, matrix and/or liner region can be selected so that the container is not overpressurized while the container contents are above Tg for the container material. Instead, gas is released gradually so that most of the adsorbed gas is released after the container contents cool below the container material Tg. For example, the adsorber, matrix and/or liner region can be selected so that less than 50% of the adsorbed gas is released upon filling of the container with heated product, and so that the remainder is released after the product has cooled below the container material Tg. One non-limiting example of an adsorber and matrix meeting this criteria is described below.
In some additional embodiments of methods according to
In further embodiments, gas(es) G can be added to the container using a pressurized capping device during step 305.
An adsorber insert was formed by compounding approximately 2 grams of zeolite 13X in EVA so that the EVA was approximately 70% loaded with the zeolite. The insert was charged with N2 at 10 bar for over a day. The insert was then placed in a closure used to cap a 20 ounce PET container that had been filled with hot water heated to 185° F. The container was allowed to cool in room temperature air. Internal pressure in the container increased from approximately −0.8 psig to approximately −0.7 psig in the first five hours after filling. The internal pressure progressively reached approximately −0.05 psig overnight. The container exhibited no appreciable buckling after 24 hours and was firm to grip.
The foregoing description of embodiments has been presented for purposes of illustration and description. The foregoing description is not intended to be exhaustive or to limit embodiments to the precise form explicitly described or mentioned herein. Modifications and variations are possible in light of the above teachings or may be acquired from practice of various embodiments. The embodiments discussed herein were chosen and described in order to explain the principles and the nature of various embodiments and their practical application to enable one skilled in the art to make and use these and other embodiments with various modifications as are suited to the particular use contemplated. Any and all permutations of features from above-described embodiments are the within the scope of the invention.