CA1052633A - Freeze/thaw indicator - Google Patents

Abstract

FREEZE/THAW INDICATOR

ABSTRACT OF THE DISCLOSURE

A freeze-thaw indicator for evidencing thawing of frozen foods in freezer compartments which has a float disposed in the container containing an aqueous solution of urea. The float is frozen in place in an immersed condition in the urea and rises only when the aqueous solution has been subjected to thawing temperatures over a time sufficient to completely liquify the aqueous solution. The strength of the aqueous solution is adjusted so that it will not liquify during the freeze thaws cycles of frost-free-type of refrigerators.

Description

F R E E Z E / T H A W I N D I C A T O R

BACKGROUND OF THE INVENTION

Field of_the Invention This invention relates to indicators for evidencing when frozen foods in freezer compartments have been subject to temperatures above a previously selected temperature for a sufficient time to result in deterioration of the food and relates, in particular, to indicators for use in frost-free-type refrigerators and freezers having heating devices which periodically heat the walls of the freezer compartment for a length of time sufficient to remove ice and frost from the walls.

Prior Art The preservation of food during storage has long been accomplished by means of refrigeration which keeps the food in a frozen cond.~tion so that degradation by enzymes and bacteria is prevented. Those experienced in the science of refrigeration have found that frozen food must be main-tained near 0F. and should not rise above 5F. for any extended period of storage or enzymatic or bacterial action or both can take place with the result that changes in taste and the development of toxic substances can occur. In many cases, power failure or improper operation of equipment have ~' ~ 30 resulted in the temperature rising above 5F. for extended periods or even complete thawing has taken place. Sub-sequent resumption of power re-freezes the food and in many -1~)5;~33 cases the thawing cycle escapes detection. It is, there~ore, not known that the food may be in a dangerous condition for human consumption.

A number of devices have been invented to detect whether a thawing and subsequent freezing cycle have taken place. Most of these devices have made use of irrev,ersible damage caused to emulsions, gels, frangible partitions, capsules,or of the deformation of cast geometrical shapes of ice. These types of inventions, being irreversible, can only be used once. Consequently, every time the refrigera-tor is defrosted,they must be replaced. ~hey will also suffer permanent damage if subjected to freezing during storage or shipment. A lesser number of devices have been lnvented which are re-usable and in some cases would operate as described in convent~onal refrigerators. However, most modern refrigerators are of the frost-free-type which operate on the principle that, twice a day, they pass through a heating cycle to remove accumulated surface frost.
During the course of this defrosting cycle the temperature in the refrigeration compartment rises between 40F. and 45F. and the elapsed time for the equipment to change from 0F. up to over 40F. and back down again to 0F. takes about 1 1/2 hours.
None of the pre-described devices which claim to be usable in temperature ranges of less than 0F. up to 32F., are usable in frost-free refrigerators unless they are replaced or re-set twice a day, as they are activated during each frost-free heat cycle. Consequently, it would be impossible, under normal usage of the refrigerator, to determine whether such inventions had been set off by 105;~33 improper operation ~f the equipment or whether they had been caused to function during the heating cycle. It is, there-fore, the object of the present invention to provide a means of determining whether frost-free refrigeration equip-ment will maintain a pre-selected temperature between 0F.
and 32F. during the periods between the frost-free heating cycles. The present device is not activated during the heating cycle and is re-usable so that it may be re-used in case of shut-down for repairs or if changing refrigerators.
The present invention is based on both a unique engineering concept and a very unique harmless chemical solution which provides for successful operation under exposure to the heat cycle in frost-free equipment.

Super-cooling of liquids in freeze/thaw detectors i8 a ma~or problem as the well known methods of starting crystallization, such as stirring, shaking, seeding, etc., are not practical in such devices and even the addition of substances, such as silver iodide can be ineffective. Glycols, alcohols (eg. benzyl alcohol), o-dichlorobenzene for example, can be kept for weeks at temperatures lower than their publ.shed freezing points without solidifying. Tests have indicated that aqueous solutions of glycols, sucrose, sorbitol, mannitol, alcohol, glycerol, sodium chloride, calcium chloride, magnesium chloride, acetic acid, and ammonium chloride formed slushes - when frozen and were difficult, even with extensive freezing, to form a homogeneous solid which did not have a portion of `~ liquid liquor within its mass. A solution of ammonia in water was found to freeze sharply and solidly, but it was found that it, along with all the above chemicals and solutions, melted readily when subjected to even one heat cycle of frost-free refrigerator. It was also found, that when such solutions :105'~33 were adjusted to ~reeze between 0F. and 26F., that the solutions that had the lower freezing points were much quicker to melt during the frost-free cycle. Samples of vegetable oils and fats were selected which froze sharply between temperatùres of 0F. and 14F. but were found to melt more readily in the frost-free heat cycle than many of the chemicals tested. Aqueous glycol solutions and vegetable oils were placed in separate vials so that the vials were half-filled. These vials were hal~ imbedded in 2 1/2 inch cubes of foamed urethane insùlation and frozen. When these insulated samples were exposed to the heat cyclè of a frost-free refrigerator, all samples were readily melted.

SUMMARY OF THE INVENTION

The present invention provides an indicator which uses the liquid which can be frozen completely solid at 12.5F. and will not melt when a pre-determined quantity is subject to repeated exposure to heat cycles of the conventional frost-free refrigerator.

The indicator of the present invention comprises a float which is immersed and frozen in place in a liquid and which only rises when the liquid thaws after being subject to temperatures in excessive of a pre-determined time.

A detailed description following, related to the drawings, gives exemplification of apparatus according to the invention which, however, is capable or expression in means other than those particularly described and illustrated.

105'~33 D ES CR I PT I ON OF TH E DRAW INGS

Fig. 1 is a cross-sectional view of one embodiment of the invention shown in an activating position, Fig. 2 is a perspective view of a cylindrical design of float, also shown in Fig. 1, Fig. 3 is one form of cap and float depressor, also shown in Fig. 1, Fig. 4 is another cross-sectional view of the device shown in Fig. 1, Fig. 5 is a pers'pective view of another embodiment of the indicator.

Referring to Fig. 1, which shows one embodiment, 1 the invention has a cylindrical container la with an open top end and an exaggerated taper on the lower half. This container is preferrably made of a transparent flexible plastic, such as polypropylene, but may be made of any other suitable transparent material such as glass. The numerical reference 2 (also shown in Fig. 2), designates a cylindricalfloat 2 which fits loosely in the container la. This float 2 is of thin-walled construction and has abouyancy component 3 consisting of preferrably a light-weight foamed plastic disc. The walls ~05'~f~33 o~ the component float have holes 4 located just above the buoyant disc 3 and also about half-way up the walls of th~
float cylinder. This float is composed preferrably of a light-weight plastic material such as polyethylene and is colored preferrably bright red, although some other color may be used.
The buoyancy of the float is so designed that the upper edge of the float will rise to the top of the outer container when the float is immersed in a liquid 4.5 used in the device.
This liquid (subsequently described) is used to fill the outer container in such a manner that when the float is depressed to the bottom of the container la(as shown in Fig. l) the liquid is slightly above the upper lip of the cylindrical float. A Cap 5, with an attached depressor vane 6, can be snapped on the top of the container la in two positions (as shown in Fig8. 1 and 4). In Fig. 1 it is shown holding down the float and in Fig. 4 it is shown projecting upwards, outside of the container. This cap is composed preferrably of polyethlene but any other noncorrosive suitable material may be used. An outer mask 7 covers the lower half of the container so that the liqu~d and depressed float are hidden ; from view. The upper edges of this mask are arranged to extendslightly above the edges of the liquid. The mask may consist of any covenient material, such as paint, foil or a label. A
base 8 is attached to the lower end of the outer container to provide stability for standing the container in an upright position.

The liquid which is an aqueous solution of urea in the proportion by weight of not less than ohe part urea ana ~ two parts water freezes sharply at 12.5F. without any proble~s encountered with super-cooling.

1~5;~633 A solution of urea, prepared by dissol~ing 50 grams of urea in 100 grams of water, will freeze sharply at 12.5 F.
without any problems being encountered with super-cooling.
It was found that increasing the amount of urea to 60 grams, or more, to 100 grams of water did not lower the freezing point any further. These stronger solutions still freeze sharply at 12.5 F. Such solutions of urea freeze completely solid at 12.5 F. and will not melt when a 25 ml. sample is subjected to repeated exposures to the heat cycles of frost-free refrig-erators. Such solutions are also:

(1) odourless

(2) non-toxic

(3) of sharply defined melting point when frozen

(4) free of super cooling effects

(5) stable during storage

(6) economical and easy to manufacture

(7) of high specific heat in the solid frozen state

(8) of high heat of fusion when in the solid frozen state

(9) of low conductivity of heat

(10) of high solubility of the solute

(11) of very high negative heat of solution of the solute

(12) non-reactive with components of the device

(13) very buoyant (1~) sufficiently high in solubility of solute at low temperatures to maintain required temperatures as a result of the effects of negative heat of solution (15) not melted when subjected to the heating/defrosting cycle of a frost-free refrigerator, but do melt if the temperature between heating cycles is sustained at an unsafe temperature (for example 5 F.).

16)5'~t;33 Small amounts of magnesium chloride can be added to the pre-described urea solution so that the freezing point can be adjusted to a preferred 6 F. and that such frozen solution, tested with 25 ml. volumes, will not liquify when subjected to continuous exposure to successive frost-free heat cycles. The adjustment for freezing point is not limited to 6 F. but can be set between 0 F. and 32 F. 6 F. is preferred as it is slightly above the 5 F. required for safe food storage. The magnesium chloride can be added to solutions if the freezing point is desired to be lower than 12.5 F.
Three examples of suitable solutions are as follows:

Example 1. 60 grams of urea are dissolved in 100 ml.
of water. This solution solidifies at 12.5 F.
Example 2. 10 grams of magnesium chloride (MgC12 6H2O) and 60 grams of urea are dissolved in 100 ml.
of water. This solidifies sharply at +10 F.

Example 3. 14 grams of magnesium chloride (MgCl - 6H2~) and 60 grams of urea are dissolved in 100 ml.
of water. This solution solidifies sharply at +6 F.

It is also preferable to add a suitable non-toxic odourless, taint-free preservative such as alkyl trimethylam-monium bromide, which is effective in amounts of 0.15 percent to 0.3 percent of the total weight of the solution.

The urea solution described behaves as follows when subjected to temperatures near the desired 0 F. to 5 F.

The pure urea solution (Example 1) shows a slight `~05'~:;33 separation of crystals of urea, due to reduced solubility, at 23 F. These crystals seed the solution and prevent super-cooling when the solution reaches its freezing point of 12.5 F. Large masses of interlocking crystals of urea are thrown out of solution, due to reduced solubility as the temperature is reduced to the freezing point of the re-maining solution. This mass of urea crystals and frozen urea solution become firmly locked into place, within and around the float, rendering the float immobile. The spec-ific heat and heat of fusion of the mass remains high. When the temperature in the freezing compartment rises to over 40 F. during the heat cycle of defrosting, this frozen mass does not melt. Although urea is very soluble, its rate of solution is slow, particularly at lower temperatures. Urea crystals absorb large quantitites of heat when dissolving in water (they are endothermic). Consequently, as the tempera-ture is rapidly rising in the freezing compartment during defrosting, the precipitated urea crystals cause the mixture to be "self-cooling" and prevents a rapid rise in temperature within the frozen mass. Consequently, the float 2 is pre-- vented from rising within the container as it can not lift the solid mass above the surface. However, if the tempera-tures within the freezer compartment does not return to a sustained 12.5 F. (using Example 1 urea solution) shortly after defrosting has occurred the frozen mass of urea will melt and the float will rise into view, indicating a mal-function. In similar fashion, for example, the urea-magnesium chloride solution (Example 3) will indicate whether the freezer temperatuxe has not been maintained at 6 F. or lower between defrosting cycles.

It is preferred that the volume of solution used _ g _ iOS'~33 in the present invention should be approximately 25 ml. to 30 ml. but is not intended to be restricted to such volumes.

The present invention is used in the following manner. Referring to Fig. 1, cap 5 with attached depressor vane 6 is snapped onto the top of the outer container 1 with the depressor vane resting on the upper edges of the float 2, holding the float beneath the solution as shown in Fig. 1. The device is then placed in a vertical position in the freezer compartment and cooled until the enclosed liquid has solidified. Solidification is obvious as the liquid becomes opaque white in colour, hiding the float from view even when viewed from an upper angle through the clear upper walls of the cylinder. The liquid freezes solid in about three hours at 0 F. At this time the float is firmly `
locked in the submerged position by an interlocking mass of crystals and frozen solution. The cap is then removed, in-verted and replaced with the depressor vane 6 extended up-ward outside the container as shown in Fig. 4. The device is then ready to indicate any undesirable rise in tempera-ture above the pre-selected range between 0 F. and 32 F., other than the designed rise in temperature during the de-frosting cycles.

In the event of malfunction of the equipment or of power failure, when the temperature rises above the desired level (preferably +5 F.) during the period between the de-frosting cycles, the solution will melt and the coloured float will rise, exposing itself to view through the trans-parent upper portion of the device, indicating that the stored food has been subjected to unsafe storage conditions. If power resumes and re-frèezing occurs, the brightly coloured 105'~ 3 exposed float remains in its elevated position indicating that a thawing and re-freezing cycle has occurred. If a partial condition of thawing occurs between the period of deErosting cycles, the float will only rise part of the way, as its movement upward is retarded by masses of crystals and partly frozen liquid, both of which are trapped inside the float, and the buoyant force on the float is insufficient to lift the partially melted mass above the surface of the melted portion of the liquid. Consequently, this device can give a quantitative evaluation of the dearee of thawing that has taken place. The mask 7 completely hides the color of the float, if by chance~ the float touches the walls of the container while being frozen.

Fig. 5 shows another embodiment 20 which has a float 21 and cap 22. A matching outer square container cor-responding to container la is not shown. The cap 22 in this case is not required to be inverted during use. An indicator mark 23 located on the cap 22 is rotated 90 degrees to change the position of depressor legs 24 which are used in similar fashion to the depressor vane, described in Fig. 3. These depressor legs, in the position illustrated, impinge on lugs 25 holding the float submerged while the solution is being frozen. Once frozen, the cap 22 is rotated 90 degrees so that the legs will clear the lugs on the float, allowing the float to rise.

Claims (2)

1. A freeze-thaw indicator for evidencing when temper-atures in a freezer compartment rise above a pre-determined value comprising, an elongated hollow, transparent casing having one open end, said casing being shaped to form a fluid chamber adapted to be placed within the freezer compartments in an upright position, a freezable fluid in said fluid chamber, said freezable fluid having pre-deter-mined freezing and thawing temperatures and being formed as an equeous solution of urea and magnesium chloride containing by weight 0.10 to 0.14 parts magnesium chloride, not less than one part of urea and two parts of water, a float adapted to be immersed and frozen in said freezable fluid so as to rise and float in the fluid when the fluid reaches a liquid state so as to evidence when ambient temperatures within the freezer compartment have risen above the thawing temperature of the fluid, a reversable cap to provide a fluid tight seal to the fluid chamber, securable in two positions securely fitted to the open top of the container and having a depressor foot adapted in one position of the cap for depressing the float to an immersed condition in the fluid temporarily until the fluid has frozen and subsequently being reversed to seal the container

2. An indicator as claimed in claim 1, including an opaque mask adapted to cover the outside lower half of the fluid casing, arranged to extend slightly above the surface level of the freezable fluid so that the liquid and float, in the depressed position are hidden from view.