CA1052632A - Indicating device - Google Patents
Indicating deviceInfo
- Publication number
- CA1052632A CA1052632A CA208,819A CA208819A CA1052632A CA 1052632 A CA1052632 A CA 1052632A CA 208819 A CA208819 A CA 208819A CA 1052632 A CA1052632 A CA 1052632A
- Authority
- CA
- Canada
- Prior art keywords
- wick
- liquid
- pad
- indicating
- fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K3/00—Thermometers giving results other than momentary value of temperature
- G01K3/02—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values
- G01K3/04—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values in respect of time
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
Abstract
Abstract Indicating device suitable for visibly measuring parameters such as time, temperature, and time-temperature relationships. The device comprises in combination a porous fluid carrying pad, a wick material for said fluid, and an indicator means whereby the progress of fluid along the wick material can be visibly indicated and used to measure the passage of time, the exposure to a given minimum temperature, or a time-temperature relationship. The combination is adapted to regulate migration of fluid from the fluid source to the wick material.
Description
910,731 105;~f~32 INDICATING DEVICE `
The present invention relates to an lmproved indlcating device adapted to measure the progress of rluid along.a wick material, which progress can be determined and relat;ed to a particular time interval, a particular tempera-~ure, or a particular t-ime-temp~ra~ure~-relationshlpO` The lnvention also relates to mean~ for controlling the selec-tlon of the time interval or the time-temperature interval W}~ch c-an be`indicatedO
Tn~se i~ndicating devices are use~ul for attaching bo periæhablè items to lndlcate the length of tlme they have been on the marketer's shelf. Aslde from the applicatlon to varlous food products, other perlshable or temperature sensltive ltems oan oarry the indicating device of the present inventionO Photographic materials which must be used withln a limited time after manufacture can have these chemical timers attached to the package and activated at the time Or manufactureO A readily visible signal will appear when the materials have been in commerce for a given perlod of tlmeO
. The devices may, by proper selectlon Or the liquid, be used to indicate exposure to a particular temperature and thus may be used with ad~antage ln comblnatlon wlth tempera-ture sensltlve items, s~ch as frozen foods, foods which require cooking, and the likeO
Various devices used to lndicate the passage of a predetermined lnterval o~ tlme are known in the prior artO
Some o~ the chemlcal tlmlng devlces which are known have lnvolved the exposure Or a wick material to a free liquid source such`as a pool Or llquid, and have proYided a chemical reagent in the wick at some predetermined point which reacted ~$
~ 5.~;3~Z ~
wlth the mlgrating liquid to change colorO The liquid, wick material, and length o~ the wick are selected so as to provide a desirable time interval before the color change oc curs .
U.S0 Patent 3,620,677 teaches an indicator device suitable for detecting the passa~e of a predetermined tlme interval. This device comprises a fluid chamber with fluld thereln, a wlck material exposed to the fluid and an lndicating means to detect the progress of the fluld along the wlck. In addltlon, the lndlcating devlce is intimately sheathed by, and laminated to, an impervious covering to mlnlmlze the effects of the environment to whlch the device i8 exposedO The fluids whlch are used are aqueous liqulds or waterO
Similar construotlons have been used as signal devices for determinin~ if frozen food packages have been sub~ected to defrostlng conditions prlor to reachlng the consumerO Devlces of thls type are shown by UOSo Patent
The present invention relates to an lmproved indlcating device adapted to measure the progress of rluid along.a wick material, which progress can be determined and relat;ed to a particular time interval, a particular tempera-~ure, or a particular t-ime-temp~ra~ure~-relationshlpO` The lnvention also relates to mean~ for controlling the selec-tlon of the time interval or the time-temperature interval W}~ch c-an be`indicatedO
Tn~se i~ndicating devices are use~ul for attaching bo periæhablè items to lndlcate the length of tlme they have been on the marketer's shelf. Aslde from the applicatlon to varlous food products, other perlshable or temperature sensltive ltems oan oarry the indicating device of the present inventionO Photographic materials which must be used withln a limited time after manufacture can have these chemical timers attached to the package and activated at the time Or manufactureO A readily visible signal will appear when the materials have been in commerce for a given perlod of tlmeO
. The devices may, by proper selectlon Or the liquid, be used to indicate exposure to a particular temperature and thus may be used with ad~antage ln comblnatlon wlth tempera-ture sensltlve items, s~ch as frozen foods, foods which require cooking, and the likeO
Various devices used to lndicate the passage of a predetermined lnterval o~ tlme are known in the prior artO
Some o~ the chemlcal tlmlng devlces which are known have lnvolved the exposure Or a wick material to a free liquid source such`as a pool Or llquid, and have proYided a chemical reagent in the wick at some predetermined point which reacted ~$
~ 5.~;3~Z ~
wlth the mlgrating liquid to change colorO The liquid, wick material, and length o~ the wick are selected so as to provide a desirable time interval before the color change oc curs .
U.S0 Patent 3,620,677 teaches an indicator device suitable for detecting the passa~e of a predetermined tlme interval. This device comprises a fluid chamber with fluld thereln, a wlck material exposed to the fluid and an lndicating means to detect the progress of the fluld along the wlck. In addltlon, the lndlcating devlce is intimately sheathed by, and laminated to, an impervious covering to mlnlmlze the effects of the environment to whlch the device i8 exposedO The fluids whlch are used are aqueous liqulds or waterO
Similar construotlons have been used as signal devices for determinin~ if frozen food packages have been sub~ected to defrostlng conditions prlor to reachlng the consumerO Devlces of thls type are shown by UOSo Patent
2,560,537 and U.S0 Patent 2,951,7640 In addltion UOSo Patent 3,243,303 teaches the use of an absorbent pad completely satura~ed with an aqueous, lmmoblllzed fluld as a fluid source ln a freeze-thaw indicatorO
Indlcating devlces whlch use pools Or free llquid as a fluld source have many disadvantagesO The use of a pool of free liquld lnherently creates problems related to devising means to securely contain the liquid pool and means to separate the liquid from the wick prior to "starting" the timerO In some cases, as in the frozen food indicators shown ln the aforementioned UOSo patents 2,560,537, 2,951,764 and 3,243,303, freezing the liquid 1~5'~3Z
has been expedient. However, this poses problems in the manufacture of the device in that the device must be immediatel~ frozen or the liquid introduced at some later time just prior to freezing. Moreover, this method is not con-venient for devices which are intended for room temperature operation. The use of a free pool of liquid also provides a constant driving force which cannot be controlled to provide slower or a ter liquid migration rates so that if a long time interval must be indicated, a very large wick is required.
This introduces further complications in the design of chemical timing devices.
The present invention provides an improved indicating device that can be handled, stored and used as simply as a compact pad of paper.
The invention provides a device for indicating the passage of a selected time interval comprising, in combination, a porous liquid source pad containing a liquifiable indicating material, an elongated wick capable of wicking liquid from said pad, migration of said indicating material from said source pad to said wick initially being selectivel~ prevented, said wick and said pad being arranged to direct migration of liquid indicating material once initiated along a major dimension of said wick to provide a visible migrating front of indicating liquid in said wick, said liquid source pad containing and presenting a controlled amount of liquid to said wick and thereb~ selectivel~ limiting the maximum migration rate for a given liquid below the migration rate provided b~ a free pool of said liquid.
As explained in greater detail hereinafter, migration between the fluid source and the wick can be selectively prevented in many ways. The porous pad and wick can be biased toward each other with a ba~rier layer inter-posed between them; the porous pad and wick can be spatiall~ separated and arranged to allow these elements to be subsequentl~ brought into contact; or alternativel~, the porous pad can contain a material which is solid at 105'~63'~:
the storage temperature and becomes fluid, eOgO melts~ at the operating temperatureO
In one presently preferred embodiment, the device is a dry appearlng, storage stable indicating device com-5 prising, in combination, a generally flat porous pad containing a liquid source, a flat wick, and a barrier layer adapted to prevent mlgration of liquid from the porous pad to the wick material, said barrier layer being impervlous to said liquid saturant and belng removably interposed between said wick and sald pad, and means interconnectingsaid pad, wick and barrier layer in layers and biasing sald pad and wick toward one another so that they contact one another upon removal of said barrier layer and whereln sald devlce further lncludes means for lndicating the presence of liquld saturant ln the wlcko In yet another preferred embodiment, the lndlcat-lng device comprises in combination a generally flat porous pad containing a liquid source, a flat wick, and means supporting sald wlck and said pad and adapted to maintain these elements in fixed spatlal relation such that nomigration o~ liquid from the pad to the wick wlll occur untll said supportlng means is deformed or acted upon so as to cause sald pad and said wlck to be brought lnto lntimate contact, said supporting means belng adapted to maintain sald pad and said wick in intimate contactO Said device further comprises means for indicating the presence - of li~uid saturant in the wicko A preferred means of indicating the presence of the fluid saturant in the wick comprises providing an
Indlcating devlces whlch use pools Or free llquid as a fluld source have many disadvantagesO The use of a pool of free liquld lnherently creates problems related to devising means to securely contain the liquid pool and means to separate the liquid from the wick prior to "starting" the timerO In some cases, as in the frozen food indicators shown ln the aforementioned UOSo patents 2,560,537, 2,951,764 and 3,243,303, freezing the liquid 1~5'~3Z
has been expedient. However, this poses problems in the manufacture of the device in that the device must be immediatel~ frozen or the liquid introduced at some later time just prior to freezing. Moreover, this method is not con-venient for devices which are intended for room temperature operation. The use of a free pool of liquid also provides a constant driving force which cannot be controlled to provide slower or a ter liquid migration rates so that if a long time interval must be indicated, a very large wick is required.
This introduces further complications in the design of chemical timing devices.
The present invention provides an improved indicating device that can be handled, stored and used as simply as a compact pad of paper.
The invention provides a device for indicating the passage of a selected time interval comprising, in combination, a porous liquid source pad containing a liquifiable indicating material, an elongated wick capable of wicking liquid from said pad, migration of said indicating material from said source pad to said wick initially being selectivel~ prevented, said wick and said pad being arranged to direct migration of liquid indicating material once initiated along a major dimension of said wick to provide a visible migrating front of indicating liquid in said wick, said liquid source pad containing and presenting a controlled amount of liquid to said wick and thereb~ selectivel~ limiting the maximum migration rate for a given liquid below the migration rate provided b~ a free pool of said liquid.
As explained in greater detail hereinafter, migration between the fluid source and the wick can be selectively prevented in many ways. The porous pad and wick can be biased toward each other with a ba~rier layer inter-posed between them; the porous pad and wick can be spatiall~ separated and arranged to allow these elements to be subsequentl~ brought into contact; or alternativel~, the porous pad can contain a material which is solid at 105'~63'~:
the storage temperature and becomes fluid, eOgO melts~ at the operating temperatureO
In one presently preferred embodiment, the device is a dry appearlng, storage stable indicating device com-5 prising, in combination, a generally flat porous pad containing a liquid source, a flat wick, and a barrier layer adapted to prevent mlgration of liquid from the porous pad to the wick material, said barrier layer being impervlous to said liquid saturant and belng removably interposed between said wick and sald pad, and means interconnectingsaid pad, wick and barrier layer in layers and biasing sald pad and wick toward one another so that they contact one another upon removal of said barrier layer and whereln sald devlce further lncludes means for lndicating the presence of liquld saturant ln the wlcko In yet another preferred embodiment, the lndlcat-lng device comprises in combination a generally flat porous pad containing a liquid source, a flat wick, and means supporting sald wlck and said pad and adapted to maintain these elements in fixed spatlal relation such that nomigration o~ liquid from the pad to the wick wlll occur untll said supportlng means is deformed or acted upon so as to cause sald pad and said wlck to be brought lnto lntimate contact, said supporting means belng adapted to maintain sald pad and said wick in intimate contactO Said device further comprises means for indicating the presence - of li~uid saturant in the wicko A preferred means of indicating the presence of the fluid saturant in the wick comprises providing an
3~ indicating means along the wlck so as to detect the presence lQ5'~32 Or the migrating fluld saturant along the wick or at such place or places on the wlck provlded wlth sald indicating means. Thi~ may be done by means of a chemical reactant whlch reacts with the fluid saturant to produce a vislble color change in or on the wlc~. Alternatlvely, the fluid saturant may have a coloring component dissolved therein so that the progress o~ the colored fluid saturant along the wick can be ob~ervedO The wick may have lndicla marked :
at predetermined lntervals along lts length to aid ln -~
observing the progress of the fluld saturant.
The lnvention will now be described in greater detall with reference to the accompanylng drawings wherein FIGURE 1 ls an isometric exploded view of the elements of an indicator devlce;
FIGURE 2 is a top view of an assembled indlcator device;
. FIGURE 3 is a cross-sectional view along line 3-3 Or the assembled indicator device shown in FIGURE 2;
FIGURE 4 is an isometric exploded view of an alternative embodiment Or an indicator device;
FIGURE ~ is a cross sectional end view Or the assembled indicator device shown in FIGURE 4;
FIGURE 6 is an exploded top view of a time-temperature indicatlng devlce;
FIGURE ? is a top view of the assembled devlce shown in FIGURE 6;
FIGURE 8 is a cross sectional vlew taken along line 8-8 of FIGURE 7;
FIGURE 9 is an exploded view of an additional 3~ embodiment of an indicating device; and il~5'~t;32 FIGURE 10 is a transfer section of the assembled indicatlng device shown in FIGURE 90 To more clearly illustrate the invention, reference is made to the selected embodlment shown in FIGURES 1, 2 and 3 wherein device 10 has a lower cover means 14 comprising a paperboard cover 16 provided with an impervlous cover liner 18. Overl~ylng ~nd adhered to cover 14 is wick 20 having coated on a portion thereof a chemical reactant layer or impregnant 22. A transparent plastic separator sheet 24 overlies wick 20 and is interposed between wick 20 and fluid source pad 26 containing a liquld saturant so as to prevent the migration of liquid ~rom pad 26 lnto and along wlck 200 Upper cover means 28 comprises paperboard cover 30 and impervious cover liner 32 and overlles and is substantially in register with lower cover means 140 Attaching means 34 is shown adhered to the autslde of lower cover means 14 and comprises a pressure-sensitive adhesive layer 36 and removable protec-tive liner 38. Retaining clip 40 fits over upper and lower cover means 28 and 14 to maintain the elements of the device in flxed relatlon and biases the fluid pad 26 toward wick 20 so that they contact one another upon removal of separator sheet 240 In the alternate embodiment `shown in FIGURE 4 device 50 comprises a pair of flexible transparent cover means 52 substantially in registerO Located between - covers 52 are fluid source pad 54 carrying a liquid saturant material and wick 56 having chemical reactant layer 580 Interposed between said wick 56 and fluid source pad 54 is an imperv~ous separator sheet 60 which iOS'~f~3A~
can be removed to allow contact between pad 54 and wick 560 As ls shown in the sectional end view in FIGURE 5, a ~astening means such as staples 62 are used to hold the elements 54, 56 and 60 in fixed relation between covers 52, and also causes fluid source pad 54 and wick 56 to be biased toward one another so that on removal of separator sheet 60 the pad 54 and wick 56 will be brought into contact with one anotherO Attaching means 64 is shown adhered to cover 52 and comprises pressure-sensitive adhesive layer 66 and removable protective liner 680 Yet another embodiment of the present invention is shown in Figures 6, 7 and 80 Figure 6 shows a top view of the elements of a time-temperature indicating device 70 which comprises a plastic coated paperboard lower cover 720 Overlying said lower cover 72 and adhered thereto are a plurality of fluid source pads 74(a), 74(b), 74(c) and 74(d) carrying liquid saturant materials having differing melting points such that for example the liquid saturant in pad 74(d) is liquid at room temperature, while the liquid saturants in pads 74(a-b~ are solid at room temperature having melting points at differing elevated temperatures.
qverlying said pads and in register with lower cover 72 is impervious separator sheet 760 A plastic coated paperboard ; upper cover 76 has adhered to the underside thereof a wick designated generally as 800 Wick 80 comprises a plurallty of paths or branches leading from a common lndicating portion 82 having a chemical reactant layer or impregnant 7 portion 840 The wick paths or branches terminate in fluid pad contacting means 86 (a-d)O The wick 80 is adhered to the underside of upper cover 78 su h that the indicating iOS'~632 portion 82 Or wick 80 i8 in registry and vlsible through wlndow 88 of cover 78. Cover 78 and wick 80 are then ~uxtaposed over lower cover 72 and separator sheet 76 such that pad contacting means 86a, 86b, 86c and 86d are in register with fluld source pads 74a, 74b, 74c and 74d, respectlvely. Steel pressure plates 9Q overlay the outer surface of covers 72 and 78 and in combination with a metal tlghtening strap 92 and screw 94 as shown in FIGURES 7 and 8 are used to maintain the elements of device 70 in fixed relatlon and serve to bias pads 74 a-d toward wick 80, such that removal of separator sheet 76 causes wick portions 86 a, b, c, and d, to contact pads 74 a, b, c and d, respectively.
An additional embodiment is shown in Figures 9 and 10. FIGURE 9 shows an exploded vlew of an indicating device 100 comprising a channel shaped carrier 102 which comprises a base 104 and upwardly extending side walls 106 disposed along opposite edges of said baseO m e walls have an undulating shape defining upper grooves 108, extended central portions 110, and lower grooves 112O The carrier 102 is preferably constructed of a stiff material havlng sufficient flexibility so that walls 106 can be de~lected outward with moderate hand pressureO Wick 114 is seated on base 104 and is generally cut from blotter paper stock having a straight or tortuous path and an indicating area 116 located so that the presence of fluid saturant thereln is indlcative o~ the passage o~ a predetermined time intervalO A porous matrix 118 carrying a fluid saturant absor~ed therein (not shown) ls associated with matrix holder 1200 ~atrix holder 120 comprlses upper protective ~OS'~ti3'~
cover portlon 122 and enlarged end portion 124 includlng slot 126 into wh~ch porous matrlx 118 can be inserted and retalned in underlylng relation to cover portion 122.
FIGURE 10 shows a tran~fer section of the assembled device shown in FIGURE 9 with the additlon of attaching means 128 which comprlses pressure sensitlve adhesive layer 130 and removable protective liner 132.
The operation of the indicating device of the present invention can be most clearly understood by refer-ence to the drawingsO FIGURE 1 shows the ma~or componentsof a chemical indicating deviceO The devlce ls assembled as in FIGURE 3 after a liquid saturant containing a color-forming coreactant ohemical dissolved therein is added to porous pad 260 Clip 40 holds the elements tightly together. When the device is to be activated,`separator sheet 24 is pulled free of the assembly, thus allowing porous pad 26 to contact wick 200 Clip 40 aids in main-taining firm and intimate contact between pad 26 and wick 20 so that the liquid saturant in pad 26 can migrate into and along the wick 200 After a period of tlme, the liquid saturant reaches the chemical coreactant portion 22 of the wick 20 and the chemical reactant dissolved in the liquid sa~urant reacts with chemical portion 22 to produce a colored material indicating the passage of a predetermined interval of timeO
In the alternative embodiment shown in FIGURES 4 and 5, porous pad 54 is allowed to absorb a liquid saturant containing a color forming coreactant chemical dissolved therein, and the components are then sandwlched between protectlve transparent covers 52, as shown in 1(~5'~;3Z
FIGURE 5, such as by stapling the covers tightly together at the~r edges with staples 620 When the devlce i8 to be actlvated, separator sheet 60 i9 pulled free of the assembly, thus bringlng the porous pad 54 carrying the liquid saturant into intimate contact wlth wlck materlal 560 The liquid ~aturant is thereby caused to mlgrate through porous wlck material 56 and eventually contacts layer 58, whereby a colored material is formed whlch i8 visible through transparent cover liner 520 The appearance of the colored materlal indicate~ the passage Or a predetermined time intervalO
Indicating devlces Or the structure shown in FIGURES 4 and 5 are also partlcularly useful for indicating exposure to a particular temperatureO Thu~, by chooslng a liquld saturant material whlch i5 solld at temperatures at which frozen ~oods are stored but becomes liquid at temperatures at which the rood is thawed, eOg. room tempera-ture, a device which indicates when a frozen rood is thawed can be providedO The device can be attached to the packaged food and after the food is frozen, the separator sheet 60 i~ removedO When the rood thaws, the saturant material becomes liquld, rlows through wick 56 and reacts wlth layer 58 to form a colored material, thus indicating the food has been thawedO If the food i~ refrozen, the color remains to ~arn the consumer that the food has been thawedO By choos-ing saturant materials having suitably difrerent melting points, the devlce can éffectively-operate as a temperature lndicator for variou~ temperaturesO Proper selection Or wick dimensions, especially thickness, can in~luence the time interval indicated and thus the device can be used to 1~5'~;3'~
indicate a heat history, i.el whether or not an article has been exposed to a given minimum temperature for a glven perlod of tlme.
Devlces of the type shown ln FIGURES 6-8 are 5 particularly suited for attaching to articles which are sensltlve to elevated temperatures or room temperature, and whlch sensltlvity increases with increasing temperature such as photographlc film and the llkeO For example, an article may be able to tolerate 72 hours exposure to room lO temperature before deteriorating, but may only be able to tolerate 48 hours at 32 CO or 8 hours at 38 C0 A device as shown ln FIGURES 6-8 can indicate whether an article of chis type has been exposed to a debilitating heat historyO
mis is accomp~ished by selecting the llquld saturant 15 materlals carrled ln the porous fluld source pads 74 a, b, c and d, such that each has a different meltlng polnt, for example 66 C., 38 C0, 32 C~, and 10 CO The path length for each branch Or wick 80 is chosen such that the time taken for the liquld to travel along a given branch of the 20 wick at a given temperature is the same as the time the article can withstand that temperatureO For example, uslng liquid saturants havlng the above noted melting points ln pads 74 a, b, c, and d, re~pectlvely lf the timer is -aotivated at 0 CO~ no liquid migration occursO If the 25 temperature reaches 24 C0 the first materlal becomes liquid and migrates into portion 86 d of wick 80 and reaches lndicator portion 82 in 72 hoursO If the tempera-ture reaches 35 C0, the saturant ln pad 74 c becomes llquid, mlgrates through 86 c of wick 80, and reaches ~
30 indicator portion 82 in 48 hoursO Even higher temperatures _ 11 --105'~3Z
will cause indicator portion 82 to change color in a shorter time intervalO
The device ~hown in FIGURES 9 and 10 is a partic-ularly slmple and convenient device. When assembled as shown in FIGURE 10, the device is inactive and can be easily store~ and handled~ When it is deslred to activate the device, top cover 122 and lower carrier means 102 are squeezed together, forctng walls 106 to flex outwardly and allow the movement of cover 122 toward wick 114, thereby con~actlng wick 114 with matrix 118. Matri~ 118 and over-lying top cover 122 are biased toward wick 114 by pressure exerted by groove 112 in resilient wall 1060 Alternatively, tQp cover means 122 and underlying matrix 118 can be removed from upper groove 108 and inserted ln lower groove 112 whérein the matrix and wick are brought into intimate contact and maintained therein ~y pressure from the resilient walls 1060 The intimate contact between matrix 118 and wick 114 allows mlgration of the fluid from matrix 118 into and along wick 1140 The fluid generally is vlslbly colored by a dye contalned thereln, and thus the progress of the migratlng fluid front can be observedO The time-dlstance relationshlp ror a given liquid and wick combinatlon can be determined and can be used to design devices which correlate the passage of a-given time interval with a particular location of the fluid front along the wicko The indicating devlces of the present invention are pa~ticularly adapted to measure the passage of a given interval of time or a given interval of time at or above a minimum temperature or exposure to a glven temperatureO
16~5;~ Z
This is accomplished in the present inventlon by providlng a unlque combination of elements comprlsing a source of fluid ln contact with a wick material and by measuring the progress of liquld migrating along the wick and correlating this progress wlth the passage of timeO
The rluid in the fluid source, by virtue of the fluid concentration gradient between the source and the wick, will be cauYed to migrate along and through the wick progressively with timeO The time the fluld takes to travel a given distance will vary, dependlng on varlous influenclng factors, eOg. temperature, fluld concentration in source, wick material, properties of fluid, etcO This tlme-dlstance relatlonshlp can be determined for a given set of materials and conditions and can be used to design and calibrate devlces whlch will perform the functlon Or a chemical tlmer~
In order to detect the presence Or the liquid in the wick, an lndlcatlng means is necessaryO In one preferred embodi-ment this indicatlng means may be an element located at a given distance along the wlck to detect the presence of ~0 fluid, pre~erably by some visible meansO A preferred lndlcating means i8 a chemical whlch 18 reactive wlth the migratlng fluid or component thereor to form a visibly colored materialO This reactive indicating component may be a separate element or may be a portlon of the wick itself which has been lmpregnated or coated with the color-reactive componentO Alternatlvely, the lndlcatlng means may be simply a visible dye dissolved in or carried by the mlgratlng ~luido The dye preferably lmparts a color to the fluld which contrasts with the color of the wick material so that the fluid front is readlly visible.
i~s;~
The devlce ls adapted to regulate or prevent migratlon o~ ~luid rrom the ~luld ~ource to the wick during storage o~ the device prlor to use. This can be accomplished by provlding a removable lmpervlous physical barrler between the fluid source and the wick. At the beglnning of the time interval to be indicated, the barrier ls removed and the rluid source brought into contact with the wick~ This induces migratlon of the fluld along the wlck and, ln ef~ect, "starts" the chemical tlmer. Alternatlvely, the wlck and ~luld source can be spaced apart rrom one another during storage, but arranged to allow these elements to subsequently be brought into contact, and maintained in said contact.
The device shown ln FIGURES 9 and lO exempll~les thls latter method o~ constructlonO
me comhination of elements which comprise the indlcators Or the present invention can be held and main-tained ln fixed relationshlp by binding means such as by sandwlchlng sald elements between covers Or stirr paper-board or plastlc sheets or other binding or supportlng mean~0 A ~heet o~ pressure-sensitive adhesive having a removable llner thereon can be affixed to the outside Or one of the coversO This allows attaching the devlce to a surface such a~ an artlcle of commerce so that the device wlll ~ollow and be exposed to whatever envlronmental history, such as temperature, that the artlcle ls exposed toO In additlon, thls allows attachlng the devlce to a location convenient to the eye as a visible reminder Or the paæsa~e of a preselected interval of tlmeO
Legends can also be printed on the sur~ace of the device to denote the time lnterval which the devlce 1~5;~f~32 lndicates or to convey advertlslng, lnstructlon and the llkeO
By varylng the shape and materlals o~ construc-tlon Or the indicatlng devlce, the tlme lnterval whlch i8 5 lndlcated by the devlce can be varled as deslréd as wlll be ~-more fully detailed hereinafter~
The fluid source in the present lnvention may be any source or material which presents a fluld front at the operating temperatures and whlch i9 free to migrate as by a wlcklng mechanism at the desired temperature, but which ls retained in the fluld source such that it will not pour, run, drip or otherwlse rlow as would a pool of rree liquld~
The preferred source comprlses a porous wettable matrlx carrylng a fluid saturant. As used hereln the term saturant 15 merely rerers to an absorbed or contained llquld and does ~-not lmply that the matrlx ls necessarlly saturated wlth ~luld since the present invention contemplates both satur-ated and unsaturated matrices as will be described herein-arterO The use of a fluid saturant carried ln a porous matrix overcomes many o~ the dlrricultles Or the prlor art devices using a pool Or free liquidO The use Or a porous matrlx carrying a fluid saturant allows construction Or a devlce whlch ls substantially flat and easily handled and stored without fear of leakage or splllageO The problem Or de~lgnlng a means to prevent or regulate migration Or the -uid from the matrlx to the wick prior to use ls simpllfledO
me use of the fluld source o~ the present invention of~ers other advantages over a pool Or ~ree liquidO The driving force for the fluid to migrate along 1~5'~3Z
the caplllary materlal or wlck ls a function Or concentra-tlonO For a pool of free llquld the concentratlon is constant and is flxed. In contrast to devlces using a rree pool of liquid, the fluld source of the present lnvention has the capabllity Or provlding a varlable drlvlng force slnce in efrect the porous matrix materlal "dilutes" the fluid saturant contained ln the matrix. By increasing the amount of fluid carried in the matrix, the driving force lnfluencing the migration Or the rluld lnto and along the wick ls lncreased and the fluid wlll migrate along the wlck at a faster rate than lf the matrlx contained relatlvely less fluid.
As the fluid mlgrates into and along the wlck material, the concentration Or the fluid in the matrix will decrease. This in turn results in a decrease of the drlv-ing forceO The u~e Or a relatively large fluid source with large amounts Or fluid carrled therein wlll minimize the variation of driving force with time, while the use Or a smaller matrix having relatlvely small amounts Or fluid carried thereln will result in greater variation of drlving force with time~
In any event, this phenomenon can be used to advantage to vary the tlme lnterval which is to be measuredO Depletion of fluid in the matrix due to migration into the wick can be used to make a compact deslgn which slows down wlth time due to this depletion effectO m us, relatively small devices which measure long time intervals can be constructed; whereas, prior art devi¢es using free fluid as a liquid source generally require unusually long or bulky wicks to measure long time l()S;~32 lntervals, since they must absorb greater amounts of llquld over the same tlme lnterval.
The fluld saturant portion Or the rluid source can be any materlal which is a fluid or becomes a fluid at the temperatures at which the tlmlng device is to be operatlve and which can dissolve or carry a colored sub-stance, a color-fo~mlng chemical substance, or be colored itself. Preferred rlulds are non-aqueous materials which are liquid at temperatures at which the lndicating device ls to operate. In additlon, the liquid preferably is one whlch has a relatively low vapor pressure at the operating temperatures in order to minimize evaporation before and durlng useO As a general rule liquids havlng a boiling polnt above that Or water are most desirable; however, liquids with hlgher vapor pressures can prove useful under certain conditionsO ~specially preferred liquids are liquld organlc phosphate esters or mixtures thereofO A
particularly preferred liquld system is a 50:50 mixture of tributyl phosphate and trloctyl phosphate.
The porous matrix material employed in the fluld source can be any porous matrix materlal which can absorb or entrap the liquid and which will allow the liquid to migrate into the wick when contacted by the wicko The preferred matrices of the present invention are fibrous materia}s made from woven or non-woven natural or synthetic fibersO Cellulosic materials, as for example Krart blotter papers, are particularly desirableO Ordinary bond paper may be used for many applicatlons as may be films or papers or nonwoven fabrics made from synthetic fibersO The physical dimensions of the matrix material can be varied as ~V5'~
deslred to conform to a part~cular design requlrement or to provlde a partlcular amount or concentratlon of fluld in the matrlx.
Generally the same materlals whlch are sultable for use as the porous matrlx are sultable for use as the wlck material. It is preferred that the material be self-supporting so as to maintain a fixed geometric shape in order that polnts on the wlck remain ln flxed relationshlpO
An indicating means is necessary to determlne whether, or to what extent, migration of the liquid saturant has taken place. A suitable indicating means is a dye dissolved in or carrled by the fluid saturant in the matrlx. By appropriate selectlon of a contrasting dye color the progress of fluld migrating from the porous matrix into the wick can be visibly notedO If desired, the wick can have prlnted thereon lndlcia to aid ln viaibly indicating the progress of the fluid and the correlative passage of time.
Alternatively, a color producing chemical co-reaotant system may be employed as the indicatlng means in the present inventionO This can be accomplished, for example, by dissolving one o~ the coreactant pair in the fluid saturant contained in the porous matrix and addltlon-coating or impregnating the wick material at a predetermined dlstance from the porous matrix with the second color producing coreactant chemicalO When the liquid saturant has migrated the predeterm~ned distance along the wick, the chemicals react to produce a visible color, indicating the passage of a given time intervalO Chemical coreactant systems which form colored chemical complexes are well l~S'~3'~
knownO A userul system comprlses dithlooxamide or N,N'-diorgano substltuted derlvatlves Or dlthlooxamides as one Or the chemlcal coreactants and a metal salt such as nlckel roslnate as the other coreactantO These materlals react to provlde a characterlstic purple colored complex. A pre-rerred coreactant system comprlses N,N'-bis-(2-octanoyloxy-ethyl) dlthlooxamlde as the flrst coreactant ~generally dissolved ln the llquld saturant), and nlckel roslnate as the second coreactant chemical (generally applled to the wlck). As noted previously, the second chemlcal can be located at a predetermined polnt on the wlck such that the ~-~
presence o~ the migratlng llquld at said point, and the simultaneous color rormatlon, indlcates the passage of a given lnterval of tlme.
In one embodlment, the tlmer comprlses a porous matrlx prepared from a piece Or 20 mil (O05 cm) thlck ''Blueblrd Blotting Paper" (Sorg Paper Co.) havlng absorbed thereln a 6% solution Or N,N'-bis-(2-octanoyloxyethyl) dithlooxamide (DOEDTO) disaolved in a 50:50 mixture Or trl-butyl phosphate (TBP):trioctyl phosphate (TOP)o The wick is a 1/2" (1025 cm) wide strip Or 20 mil (O05 om) "Bluebird Blotting Paper"O On removal Or the separating sheet, the llquld migrates along the wicko Table I show~ the efrect Or concentration Or llquid ln the matrix on the mlgration rate along the wlck meaaured at room temperature (24 C.)O
.
105;~3Z
TABLE I
CONCENTRATION OF FLUID IN THE SOURCE PAD o _ AT S~ART OF TEST AND (AT FINAL READING) o , Parts Liquid/Parts Pad _ .. _--.
. _ _ ~ _ ~ _ _ __ t' "u:~l~ ,_,_ ,_~ ~ ~W WW W~ .P~ .~ C :C
o IP ~JI U~ O W Ul 00 O 1~ Ul ~1 0 ~ Ul . 0~ ~D H O
Ct>~ . ~ ~ . ~ . ~ ~ ~ ~ ~ C~ C
. ~ ~D ~ CD IJ a~ _l ~I 1~ ~I ~ o~ o~ Ul ~11 Ul Ul ~ o ~ ~ ~ ~ ~n ~ O co ~ w o co ~n , ~ I_ l U~
O CO CO ~I ~ _ _ _ Ul O O~ I_ O
_ ~ ~O W ~C __ ~
' l _ ~ LO ~ 'w w æ
~ IJ l_ l_ ~ O~ ~ l- i_ ~O- ~
_ w ~n w I_ ~n ~ .P ~
_ __ _ . ~ W O ~ , =--__ ~ ~ ~--~ ~ ~- ~¦r~
w ~ ~ ~ w -- b~H
t' ~ c~ t~ ~n ~ ~D ,~11- t~ I -Ul ~ ~ W . . ~__ W H ~ .
_ W O ~1 D ~I V~ ~~1 O ~ SZ
~0 O~ 1- 1- lwv W ~1~ _ _ o .~ , .`
~) P I_ ~I t~) ~_` O O 0 C~
w w ~ ~ ~ w.. ~ ,_ __ ~n W P` ~1 . O _ H
co , I_ ~ ~ ~ ~ I_ _ _ ~D zO
. w ~n ~n I_ ~I ~ u~ o ~
O O
_ ~ U~ ~ _ U~
~r ~ W ~ ~n ., w a~ a~ ~ o o ~ o ~
., cr _ ~ ~.Q ~n _ ~ c~ _ ~3 I_ ~ w ~ ~n _ P~
~W ~1 ~ ,p ~ w ~n o o~ ~ ~ ~ c~ a~ _ _ _ _ :: - w ~I co ~n ~ ~F _ CO ~D . ~ a~ w ~ _ ~ ~
.P CO ID cn o~ _J o _ l_ ~_ ~ ~ o~ ~ _ . _ o ~ OD O C~ CD ~ O
~~ a~ I_ ~ I_ ~n o . . _ _ _ _ _ ~ ~ w ~ l_ ~ CO O ~D D 1~ O
w ~o aoUl a) o . . _ . - w _ _ _ _ l_ o l_ ~ o a~ ~ ~ ~n I~ o~ o _ w _ __ ~ ~ .~ I_ ~ . o a~, o~ I~ , Ul _I _._ _ _ _ O
105;~;32 ` ~`
It can be seen from the a~ove T~ble that tlme .lntervals Or varylng length can be equated to the distance along the wick through whlch the fluid has migrated and used to design timers ror indicating various time intervalsO
The efrect of temperature on a system slmilar to that shown above whereln the fluld concentratlon ln the source pad ls about 45% by welght ls shown ln Table IIo ~OSi~32 TABLE I I
TEMPE RATURE C .
.__ :__ _ _ ~ C ~j o~ o~ _ ~
a~ ~ I_ I_ . ~ ~.
W ~ I o~ ~ t' ~ ~ ~ 1' ~ :' In ~P ~ ~n tl , . ~ _ _ Ul H
l_ ~ ~ - ~ ~
D ~.
~I ~O ~ O ~ ~3 .~ W C
~ ,o ~ o o ~, = = ~
_ ~ ~o . . ~- ~ ~o === o ... ~ . , .
.. . .
105 ;~ ~; 3 Z
In addltion to the TBP:TQP system shown ahffove, a llquid comprlsing one part DOEDTO to 4 parts o~ the ~ollow- ~ :
lng compounds were found to be acceptableO These compounds i provlde no migratlon below the temperatures shown and thus provlde temperature sensltive lndlcating device~O
Methyl Stearate 34 C
Methyl Palmltate 27 C
Ethyl Stearate 21 C
Methyl Myristate 14 C~
10 Butyl Stearate 12 C.
Dimethyl Phthalate - 1 CO
Table III below shows migratlon rates wlth systems employing pads Or 20 mil (O05 cm) "Bluebird Blotting Paper"
as the porow matrix and a.liquid comprising DO~DTO in methyl stearate and DOEDTO in ethyl stearateO The concen-tration of liqùid in the porous matrix is about 45% by weight based on the combined weight of the matrix and liquid ln both casesO
TABL~ III
CM PENETRATION FROM FLUID SOURCE PAD
Methyl 3O8 5O1 7 ol 809 : Stearate at 38 CO
: 25 Ethyl 106 204 3O3 3O9 406 5O3 7O4 Stearate at 26 CO
The following example illustrates particularconditions, steps, and materlals within the scope of the present inventionO. However, this example is given only for the purpose of illustration and not limitationO
~1)5;~32 Example An lndicator device was con~tructed substantially as shown in FIGURE lo Covers 16 and 30 were cut to size from 20 mil (005 cm) white card stock and laid end to endO
A strip Or clear plastic film was cut to size and heat sealed to the covers with a hand held electrically heated platen to form cover liners 18 and 320 The rilm prevents liquid saturant from soaklng into the card stock covers and also forms a hinge holding covers 16 and 30 togetherO
A porous fluid source pad 26 was prepared by cutting to size a piece Or 20 mil (005 cm) blotting paperO
m e paper pad was weighed and a liquid comprising (a) 94% of a 50:50 mixture of tributyl phosphate and trioctyl phosphate, and (b) a 6% solution Or N,N'-bis-t2 octanoyloxy-ethyl)dithiooxamide (DOEDTO) was added to the paper pad to provide a fluid source having 45% liquid saturant based on the combined weight of the pad and the liquid, iOeO 45 parts liquid/55 parts padO The liquid was placed dropwise on the paper pad and migration of the liquid within the pad quickly provlded a uniform distribution Or liquid saturant within the padO The pad 26 was adhered with liquid cement to cover 28 in the position shown in FIGURES 1 and 20 A wick 20 was cut from 20 mil (.~5 cm) Bluebird Blotting Paper in substantially the shape shown in FIGURE lo A solution of nickel rosinate was applied by spraying the end of the wick to form layer 22, the rest of the wick being shielded 80 as to prevent applicatlon of the nlckel rosinate to the remainlng areasO When dried, the nlckel rosinate layer 22 was eæsentially the same white color as the untreated areaO
- 24 _ 105i~632 The wick 20 was adhered with liquid cement to cover 14 in the posltlon shown in FIGURE 1~ A separator sheet 24 was cut to size from a sheet of transparent poly- -ester film and positloned over wlck 20 as shown in FIGURE 1 ~o as to prevent the contact of pad 26 with wick 200 The covers 14 and 28 were then folded together, sandwiching the separator sheet 24 between pad 26 and wick 20 and a clip 40 sllpped over the hinged end of the covers to hold the combination Or elements in flxed relatlonshipO
A strip of pressure-sensitlve adhesive transfer film 36 having removable protective liner 38 was applied to the outside of cover 14 to allow easy attachment to a surface.
The device was activated at 75 Fo (25 C) by removlng the separator sheetO After 72 hours the character-istic purple color Or the DOEDTO - nickel complex began to appear in layer 22~ By the end of 98 hours about one-half of the area of layer 22 had turned purpleO
at predetermined lntervals along lts length to aid ln -~
observing the progress of the fluld saturant.
The lnvention will now be described in greater detall with reference to the accompanylng drawings wherein FIGURE 1 ls an isometric exploded view of the elements of an indicator devlce;
FIGURE 2 is a top view of an assembled indlcator device;
. FIGURE 3 is a cross-sectional view along line 3-3 Or the assembled indicator device shown in FIGURE 2;
FIGURE 4 is an isometric exploded view of an alternative embodiment Or an indicator device;
FIGURE ~ is a cross sectional end view Or the assembled indicator device shown in FIGURE 4;
FIGURE 6 is an exploded top view of a time-temperature indicatlng devlce;
FIGURE ? is a top view of the assembled devlce shown in FIGURE 6;
FIGURE 8 is a cross sectional vlew taken along line 8-8 of FIGURE 7;
FIGURE 9 is an exploded view of an additional 3~ embodiment of an indicating device; and il~5'~t;32 FIGURE 10 is a transfer section of the assembled indicatlng device shown in FIGURE 90 To more clearly illustrate the invention, reference is made to the selected embodlment shown in FIGURES 1, 2 and 3 wherein device 10 has a lower cover means 14 comprising a paperboard cover 16 provided with an impervlous cover liner 18. Overl~ylng ~nd adhered to cover 14 is wick 20 having coated on a portion thereof a chemical reactant layer or impregnant 22. A transparent plastic separator sheet 24 overlies wick 20 and is interposed between wick 20 and fluid source pad 26 containing a liquld saturant so as to prevent the migration of liquid ~rom pad 26 lnto and along wlck 200 Upper cover means 28 comprises paperboard cover 30 and impervious cover liner 32 and overlles and is substantially in register with lower cover means 140 Attaching means 34 is shown adhered to the autslde of lower cover means 14 and comprises a pressure-sensitive adhesive layer 36 and removable protec-tive liner 38. Retaining clip 40 fits over upper and lower cover means 28 and 14 to maintain the elements of the device in flxed relatlon and biases the fluid pad 26 toward wick 20 so that they contact one another upon removal of separator sheet 240 In the alternate embodiment `shown in FIGURE 4 device 50 comprises a pair of flexible transparent cover means 52 substantially in registerO Located between - covers 52 are fluid source pad 54 carrying a liquid saturant material and wick 56 having chemical reactant layer 580 Interposed between said wick 56 and fluid source pad 54 is an imperv~ous separator sheet 60 which iOS'~f~3A~
can be removed to allow contact between pad 54 and wick 560 As ls shown in the sectional end view in FIGURE 5, a ~astening means such as staples 62 are used to hold the elements 54, 56 and 60 in fixed relation between covers 52, and also causes fluid source pad 54 and wick 56 to be biased toward one another so that on removal of separator sheet 60 the pad 54 and wick 56 will be brought into contact with one anotherO Attaching means 64 is shown adhered to cover 52 and comprises pressure-sensitive adhesive layer 66 and removable protective liner 680 Yet another embodiment of the present invention is shown in Figures 6, 7 and 80 Figure 6 shows a top view of the elements of a time-temperature indicating device 70 which comprises a plastic coated paperboard lower cover 720 Overlying said lower cover 72 and adhered thereto are a plurality of fluid source pads 74(a), 74(b), 74(c) and 74(d) carrying liquid saturant materials having differing melting points such that for example the liquid saturant in pad 74(d) is liquid at room temperature, while the liquid saturants in pads 74(a-b~ are solid at room temperature having melting points at differing elevated temperatures.
qverlying said pads and in register with lower cover 72 is impervious separator sheet 760 A plastic coated paperboard ; upper cover 76 has adhered to the underside thereof a wick designated generally as 800 Wick 80 comprises a plurallty of paths or branches leading from a common lndicating portion 82 having a chemical reactant layer or impregnant 7 portion 840 The wick paths or branches terminate in fluid pad contacting means 86 (a-d)O The wick 80 is adhered to the underside of upper cover 78 su h that the indicating iOS'~632 portion 82 Or wick 80 i8 in registry and vlsible through wlndow 88 of cover 78. Cover 78 and wick 80 are then ~uxtaposed over lower cover 72 and separator sheet 76 such that pad contacting means 86a, 86b, 86c and 86d are in register with fluld source pads 74a, 74b, 74c and 74d, respectlvely. Steel pressure plates 9Q overlay the outer surface of covers 72 and 78 and in combination with a metal tlghtening strap 92 and screw 94 as shown in FIGURES 7 and 8 are used to maintain the elements of device 70 in fixed relatlon and serve to bias pads 74 a-d toward wick 80, such that removal of separator sheet 76 causes wick portions 86 a, b, c, and d, to contact pads 74 a, b, c and d, respectively.
An additional embodiment is shown in Figures 9 and 10. FIGURE 9 shows an exploded vlew of an indicating device 100 comprising a channel shaped carrier 102 which comprises a base 104 and upwardly extending side walls 106 disposed along opposite edges of said baseO m e walls have an undulating shape defining upper grooves 108, extended central portions 110, and lower grooves 112O The carrier 102 is preferably constructed of a stiff material havlng sufficient flexibility so that walls 106 can be de~lected outward with moderate hand pressureO Wick 114 is seated on base 104 and is generally cut from blotter paper stock having a straight or tortuous path and an indicating area 116 located so that the presence of fluid saturant thereln is indlcative o~ the passage o~ a predetermined time intervalO A porous matrix 118 carrying a fluid saturant absor~ed therein (not shown) ls associated with matrix holder 1200 ~atrix holder 120 comprlses upper protective ~OS'~ti3'~
cover portlon 122 and enlarged end portion 124 includlng slot 126 into wh~ch porous matrlx 118 can be inserted and retalned in underlylng relation to cover portion 122.
FIGURE 10 shows a tran~fer section of the assembled device shown in FIGURE 9 with the additlon of attaching means 128 which comprlses pressure sensitlve adhesive layer 130 and removable protective liner 132.
The operation of the indicating device of the present invention can be most clearly understood by refer-ence to the drawingsO FIGURE 1 shows the ma~or componentsof a chemical indicating deviceO The devlce ls assembled as in FIGURE 3 after a liquid saturant containing a color-forming coreactant ohemical dissolved therein is added to porous pad 260 Clip 40 holds the elements tightly together. When the device is to be activated,`separator sheet 24 is pulled free of the assembly, thus allowing porous pad 26 to contact wick 200 Clip 40 aids in main-taining firm and intimate contact between pad 26 and wick 20 so that the liquid saturant in pad 26 can migrate into and along the wick 200 After a period of tlme, the liquid saturant reaches the chemical coreactant portion 22 of the wick 20 and the chemical reactant dissolved in the liquid sa~urant reacts with chemical portion 22 to produce a colored material indicating the passage of a predetermined interval of timeO
In the alternative embodiment shown in FIGURES 4 and 5, porous pad 54 is allowed to absorb a liquid saturant containing a color forming coreactant chemical dissolved therein, and the components are then sandwlched between protectlve transparent covers 52, as shown in 1(~5'~;3Z
FIGURE 5, such as by stapling the covers tightly together at the~r edges with staples 620 When the devlce i8 to be actlvated, separator sheet 60 i9 pulled free of the assembly, thus bringlng the porous pad 54 carrying the liquid saturant into intimate contact wlth wlck materlal 560 The liquid ~aturant is thereby caused to mlgrate through porous wlck material 56 and eventually contacts layer 58, whereby a colored material is formed whlch i8 visible through transparent cover liner 520 The appearance of the colored materlal indicate~ the passage Or a predetermined time intervalO
Indicating devlces Or the structure shown in FIGURES 4 and 5 are also partlcularly useful for indicating exposure to a particular temperatureO Thu~, by chooslng a liquld saturant material whlch i5 solld at temperatures at which frozen ~oods are stored but becomes liquid at temperatures at which the rood is thawed, eOg. room tempera-ture, a device which indicates when a frozen rood is thawed can be providedO The device can be attached to the packaged food and after the food is frozen, the separator sheet 60 i~ removedO When the rood thaws, the saturant material becomes liquld, rlows through wick 56 and reacts wlth layer 58 to form a colored material, thus indicating the food has been thawedO If the food i~ refrozen, the color remains to ~arn the consumer that the food has been thawedO By choos-ing saturant materials having suitably difrerent melting points, the devlce can éffectively-operate as a temperature lndicator for variou~ temperaturesO Proper selection Or wick dimensions, especially thickness, can in~luence the time interval indicated and thus the device can be used to 1~5'~;3'~
indicate a heat history, i.el whether or not an article has been exposed to a given minimum temperature for a glven perlod of tlme.
Devlces of the type shown ln FIGURES 6-8 are 5 particularly suited for attaching to articles which are sensltlve to elevated temperatures or room temperature, and whlch sensltlvity increases with increasing temperature such as photographlc film and the llkeO For example, an article may be able to tolerate 72 hours exposure to room lO temperature before deteriorating, but may only be able to tolerate 48 hours at 32 CO or 8 hours at 38 C0 A device as shown ln FIGURES 6-8 can indicate whether an article of chis type has been exposed to a debilitating heat historyO
mis is accomp~ished by selecting the llquld saturant 15 materlals carrled ln the porous fluld source pads 74 a, b, c and d, such that each has a different meltlng polnt, for example 66 C., 38 C0, 32 C~, and 10 CO The path length for each branch Or wick 80 is chosen such that the time taken for the liquld to travel along a given branch of the 20 wick at a given temperature is the same as the time the article can withstand that temperatureO For example, uslng liquid saturants havlng the above noted melting points ln pads 74 a, b, c, and d, re~pectlvely lf the timer is -aotivated at 0 CO~ no liquid migration occursO If the 25 temperature reaches 24 C0 the first materlal becomes liquid and migrates into portion 86 d of wick 80 and reaches lndicator portion 82 in 72 hoursO If the tempera-ture reaches 35 C0, the saturant ln pad 74 c becomes llquid, mlgrates through 86 c of wick 80, and reaches ~
30 indicator portion 82 in 48 hoursO Even higher temperatures _ 11 --105'~3Z
will cause indicator portion 82 to change color in a shorter time intervalO
The device ~hown in FIGURES 9 and 10 is a partic-ularly slmple and convenient device. When assembled as shown in FIGURE 10, the device is inactive and can be easily store~ and handled~ When it is deslred to activate the device, top cover 122 and lower carrier means 102 are squeezed together, forctng walls 106 to flex outwardly and allow the movement of cover 122 toward wick 114, thereby con~actlng wick 114 with matrix 118. Matri~ 118 and over-lying top cover 122 are biased toward wick 114 by pressure exerted by groove 112 in resilient wall 1060 Alternatively, tQp cover means 122 and underlying matrix 118 can be removed from upper groove 108 and inserted ln lower groove 112 whérein the matrix and wick are brought into intimate contact and maintained therein ~y pressure from the resilient walls 1060 The intimate contact between matrix 118 and wick 114 allows mlgration of the fluid from matrix 118 into and along wick 1140 The fluid generally is vlslbly colored by a dye contalned thereln, and thus the progress of the migratlng fluid front can be observedO The time-dlstance relationshlp ror a given liquid and wick combinatlon can be determined and can be used to design devices which correlate the passage of a-given time interval with a particular location of the fluid front along the wicko The indicating devlces of the present invention are pa~ticularly adapted to measure the passage of a given interval of time or a given interval of time at or above a minimum temperature or exposure to a glven temperatureO
16~5;~ Z
This is accomplished in the present inventlon by providlng a unlque combination of elements comprlsing a source of fluid ln contact with a wick material and by measuring the progress of liquld migrating along the wick and correlating this progress wlth the passage of timeO
The rluid in the fluid source, by virtue of the fluid concentration gradient between the source and the wick, will be cauYed to migrate along and through the wick progressively with timeO The time the fluld takes to travel a given distance will vary, dependlng on varlous influenclng factors, eOg. temperature, fluld concentration in source, wick material, properties of fluid, etcO This tlme-dlstance relatlonshlp can be determined for a given set of materials and conditions and can be used to design and calibrate devlces whlch will perform the functlon Or a chemical tlmer~
In order to detect the presence Or the liquid in the wick, an lndlcatlng means is necessaryO In one preferred embodi-ment this indicatlng means may be an element located at a given distance along the wlck to detect the presence of ~0 fluid, pre~erably by some visible meansO A preferred lndlcating means i8 a chemical whlch 18 reactive wlth the migratlng fluid or component thereor to form a visibly colored materialO This reactive indicating component may be a separate element or may be a portlon of the wick itself which has been lmpregnated or coated with the color-reactive componentO Alternatlvely, the lndlcatlng means may be simply a visible dye dissolved in or carried by the mlgratlng ~luido The dye preferably lmparts a color to the fluld which contrasts with the color of the wick material so that the fluid front is readlly visible.
i~s;~
The devlce ls adapted to regulate or prevent migratlon o~ ~luid rrom the ~luld ~ource to the wick during storage o~ the device prlor to use. This can be accomplished by provlding a removable lmpervlous physical barrler between the fluid source and the wick. At the beglnning of the time interval to be indicated, the barrier ls removed and the rluid source brought into contact with the wick~ This induces migratlon of the fluld along the wlck and, ln ef~ect, "starts" the chemical tlmer. Alternatlvely, the wlck and ~luld source can be spaced apart rrom one another during storage, but arranged to allow these elements to subsequently be brought into contact, and maintained in said contact.
The device shown ln FIGURES 9 and lO exempll~les thls latter method o~ constructlonO
me comhination of elements which comprise the indlcators Or the present invention can be held and main-tained ln fixed relationshlp by binding means such as by sandwlchlng sald elements between covers Or stirr paper-board or plastlc sheets or other binding or supportlng mean~0 A ~heet o~ pressure-sensitive adhesive having a removable llner thereon can be affixed to the outside Or one of the coversO This allows attaching the devlce to a surface such a~ an artlcle of commerce so that the device wlll ~ollow and be exposed to whatever envlronmental history, such as temperature, that the artlcle ls exposed toO In additlon, thls allows attachlng the devlce to a location convenient to the eye as a visible reminder Or the paæsa~e of a preselected interval of tlmeO
Legends can also be printed on the sur~ace of the device to denote the time lnterval which the devlce 1~5;~f~32 lndicates or to convey advertlslng, lnstructlon and the llkeO
By varylng the shape and materlals o~ construc-tlon Or the indicatlng devlce, the tlme lnterval whlch i8 5 lndlcated by the devlce can be varled as deslréd as wlll be ~-more fully detailed hereinafter~
The fluid source in the present lnvention may be any source or material which presents a fluld front at the operating temperatures and whlch i9 free to migrate as by a wlcklng mechanism at the desired temperature, but which ls retained in the fluld source such that it will not pour, run, drip or otherwlse rlow as would a pool of rree liquld~
The preferred source comprlses a porous wettable matrlx carrylng a fluid saturant. As used hereln the term saturant 15 merely rerers to an absorbed or contained llquld and does ~-not lmply that the matrlx ls necessarlly saturated wlth ~luld since the present invention contemplates both satur-ated and unsaturated matrices as will be described herein-arterO The use of a fluid saturant carried ln a porous matrix overcomes many o~ the dlrricultles Or the prlor art devices using a pool Or free liquidO The use Or a porous matrlx carrying a fluid saturant allows construction Or a devlce whlch ls substantially flat and easily handled and stored without fear of leakage or splllageO The problem Or de~lgnlng a means to prevent or regulate migration Or the -uid from the matrlx to the wick prior to use ls simpllfledO
me use of the fluld source o~ the present invention of~ers other advantages over a pool Or ~ree liquidO The driving force for the fluid to migrate along 1~5'~3Z
the caplllary materlal or wlck ls a function Or concentra-tlonO For a pool of free llquld the concentratlon is constant and is flxed. In contrast to devlces using a rree pool of liquid, the fluld source of the present lnvention has the capabllity Or provlding a varlable drlvlng force slnce in efrect the porous matrix materlal "dilutes" the fluid saturant contained ln the matrix. By increasing the amount of fluid carried in the matrix, the driving force lnfluencing the migration Or the rluld lnto and along the wick ls lncreased and the fluid wlll migrate along the wlck at a faster rate than lf the matrlx contained relatlvely less fluid.
As the fluid mlgrates into and along the wlck material, the concentration Or the fluid in the matrix will decrease. This in turn results in a decrease of the drlv-ing forceO The u~e Or a relatively large fluid source with large amounts Or fluid carrled therein wlll minimize the variation of driving force with time, while the use Or a smaller matrix having relatlvely small amounts Or fluid carried thereln will result in greater variation of drlving force with time~
In any event, this phenomenon can be used to advantage to vary the tlme lnterval which is to be measuredO Depletion of fluid in the matrix due to migration into the wick can be used to make a compact deslgn which slows down wlth time due to this depletion effectO m us, relatively small devices which measure long time intervals can be constructed; whereas, prior art devi¢es using free fluid as a liquid source generally require unusually long or bulky wicks to measure long time l()S;~32 lntervals, since they must absorb greater amounts of llquld over the same tlme lnterval.
The fluld saturant portion Or the rluid source can be any materlal which is a fluid or becomes a fluid at the temperatures at which the tlmlng device is to be operatlve and which can dissolve or carry a colored sub-stance, a color-fo~mlng chemical substance, or be colored itself. Preferred rlulds are non-aqueous materials which are liquid at temperatures at which the lndicating device ls to operate. In additlon, the liquid preferably is one whlch has a relatively low vapor pressure at the operating temperatures in order to minimize evaporation before and durlng useO As a general rule liquids havlng a boiling polnt above that Or water are most desirable; however, liquids with hlgher vapor pressures can prove useful under certain conditionsO ~specially preferred liquids are liquld organlc phosphate esters or mixtures thereofO A
particularly preferred liquld system is a 50:50 mixture of tributyl phosphate and trloctyl phosphate.
The porous matrix material employed in the fluld source can be any porous matrix materlal which can absorb or entrap the liquid and which will allow the liquid to migrate into the wick when contacted by the wicko The preferred matrices of the present invention are fibrous materia}s made from woven or non-woven natural or synthetic fibersO Cellulosic materials, as for example Krart blotter papers, are particularly desirableO Ordinary bond paper may be used for many applicatlons as may be films or papers or nonwoven fabrics made from synthetic fibersO The physical dimensions of the matrix material can be varied as ~V5'~
deslred to conform to a part~cular design requlrement or to provlde a partlcular amount or concentratlon of fluld in the matrlx.
Generally the same materlals whlch are sultable for use as the porous matrlx are sultable for use as the wlck material. It is preferred that the material be self-supporting so as to maintain a fixed geometric shape in order that polnts on the wlck remain ln flxed relationshlpO
An indicating means is necessary to determlne whether, or to what extent, migration of the liquid saturant has taken place. A suitable indicating means is a dye dissolved in or carrled by the fluid saturant in the matrlx. By appropriate selectlon of a contrasting dye color the progress of fluld migrating from the porous matrix into the wick can be visibly notedO If desired, the wick can have prlnted thereon lndlcia to aid ln viaibly indicating the progress of the fluid and the correlative passage of time.
Alternatively, a color producing chemical co-reaotant system may be employed as the indicatlng means in the present inventionO This can be accomplished, for example, by dissolving one o~ the coreactant pair in the fluid saturant contained in the porous matrix and addltlon-coating or impregnating the wick material at a predetermined dlstance from the porous matrix with the second color producing coreactant chemicalO When the liquid saturant has migrated the predeterm~ned distance along the wick, the chemicals react to produce a visible color, indicating the passage of a given time intervalO Chemical coreactant systems which form colored chemical complexes are well l~S'~3'~
knownO A userul system comprlses dithlooxamide or N,N'-diorgano substltuted derlvatlves Or dlthlooxamides as one Or the chemlcal coreactants and a metal salt such as nlckel roslnate as the other coreactantO These materlals react to provlde a characterlstic purple colored complex. A pre-rerred coreactant system comprlses N,N'-bis-(2-octanoyloxy-ethyl) dlthlooxamlde as the flrst coreactant ~generally dissolved ln the llquld saturant), and nlckel roslnate as the second coreactant chemical (generally applled to the wlck). As noted previously, the second chemlcal can be located at a predetermined polnt on the wlck such that the ~-~
presence o~ the migratlng llquld at said point, and the simultaneous color rormatlon, indlcates the passage of a given lnterval of tlme.
In one embodlment, the tlmer comprlses a porous matrlx prepared from a piece Or 20 mil (O05 cm) thlck ''Blueblrd Blotting Paper" (Sorg Paper Co.) havlng absorbed thereln a 6% solution Or N,N'-bis-(2-octanoyloxyethyl) dithlooxamide (DOEDTO) disaolved in a 50:50 mixture Or trl-butyl phosphate (TBP):trioctyl phosphate (TOP)o The wick is a 1/2" (1025 cm) wide strip Or 20 mil (O05 om) "Bluebird Blotting Paper"O On removal Or the separating sheet, the llquld migrates along the wicko Table I show~ the efrect Or concentration Or llquid ln the matrix on the mlgration rate along the wlck meaaured at room temperature (24 C.)O
.
105;~3Z
TABLE I
CONCENTRATION OF FLUID IN THE SOURCE PAD o _ AT S~ART OF TEST AND (AT FINAL READING) o , Parts Liquid/Parts Pad _ .. _--.
. _ _ ~ _ ~ _ _ __ t' "u:~l~ ,_,_ ,_~ ~ ~W WW W~ .P~ .~ C :C
o IP ~JI U~ O W Ul 00 O 1~ Ul ~1 0 ~ Ul . 0~ ~D H O
Ct>~ . ~ ~ . ~ . ~ ~ ~ ~ ~ C~ C
. ~ ~D ~ CD IJ a~ _l ~I 1~ ~I ~ o~ o~ Ul ~11 Ul Ul ~ o ~ ~ ~ ~ ~n ~ O co ~ w o co ~n , ~ I_ l U~
O CO CO ~I ~ _ _ _ Ul O O~ I_ O
_ ~ ~O W ~C __ ~
' l _ ~ LO ~ 'w w æ
~ IJ l_ l_ ~ O~ ~ l- i_ ~O- ~
_ w ~n w I_ ~n ~ .P ~
_ __ _ . ~ W O ~ , =--__ ~ ~ ~--~ ~ ~- ~¦r~
w ~ ~ ~ w -- b~H
t' ~ c~ t~ ~n ~ ~D ,~11- t~ I -Ul ~ ~ W . . ~__ W H ~ .
_ W O ~1 D ~I V~ ~~1 O ~ SZ
~0 O~ 1- 1- lwv W ~1~ _ _ o .~ , .`
~) P I_ ~I t~) ~_` O O 0 C~
w w ~ ~ ~ w.. ~ ,_ __ ~n W P` ~1 . O _ H
co , I_ ~ ~ ~ ~ I_ _ _ ~D zO
. w ~n ~n I_ ~I ~ u~ o ~
O O
_ ~ U~ ~ _ U~
~r ~ W ~ ~n ., w a~ a~ ~ o o ~ o ~
., cr _ ~ ~.Q ~n _ ~ c~ _ ~3 I_ ~ w ~ ~n _ P~
~W ~1 ~ ,p ~ w ~n o o~ ~ ~ ~ c~ a~ _ _ _ _ :: - w ~I co ~n ~ ~F _ CO ~D . ~ a~ w ~ _ ~ ~
.P CO ID cn o~ _J o _ l_ ~_ ~ ~ o~ ~ _ . _ o ~ OD O C~ CD ~ O
~~ a~ I_ ~ I_ ~n o . . _ _ _ _ _ ~ ~ w ~ l_ ~ CO O ~D D 1~ O
w ~o aoUl a) o . . _ . - w _ _ _ _ l_ o l_ ~ o a~ ~ ~ ~n I~ o~ o _ w _ __ ~ ~ .~ I_ ~ . o a~, o~ I~ , Ul _I _._ _ _ _ O
105;~;32 ` ~`
It can be seen from the a~ove T~ble that tlme .lntervals Or varylng length can be equated to the distance along the wick through whlch the fluid has migrated and used to design timers ror indicating various time intervalsO
The efrect of temperature on a system slmilar to that shown above whereln the fluld concentratlon ln the source pad ls about 45% by welght ls shown ln Table IIo ~OSi~32 TABLE I I
TEMPE RATURE C .
.__ :__ _ _ ~ C ~j o~ o~ _ ~
a~ ~ I_ I_ . ~ ~.
W ~ I o~ ~ t' ~ ~ ~ 1' ~ :' In ~P ~ ~n tl , . ~ _ _ Ul H
l_ ~ ~ - ~ ~
D ~.
~I ~O ~ O ~ ~3 .~ W C
~ ,o ~ o o ~, = = ~
_ ~ ~o . . ~- ~ ~o === o ... ~ . , .
.. . .
105 ;~ ~; 3 Z
In addltion to the TBP:TQP system shown ahffove, a llquid comprlsing one part DOEDTO to 4 parts o~ the ~ollow- ~ :
lng compounds were found to be acceptableO These compounds i provlde no migratlon below the temperatures shown and thus provlde temperature sensltive lndlcating device~O
Methyl Stearate 34 C
Methyl Palmltate 27 C
Ethyl Stearate 21 C
Methyl Myristate 14 C~
10 Butyl Stearate 12 C.
Dimethyl Phthalate - 1 CO
Table III below shows migratlon rates wlth systems employing pads Or 20 mil (O05 cm) "Bluebird Blotting Paper"
as the porow matrix and a.liquid comprising DO~DTO in methyl stearate and DOEDTO in ethyl stearateO The concen-tration of liqùid in the porous matrix is about 45% by weight based on the combined weight of the matrix and liquid ln both casesO
TABL~ III
CM PENETRATION FROM FLUID SOURCE PAD
Methyl 3O8 5O1 7 ol 809 : Stearate at 38 CO
: 25 Ethyl 106 204 3O3 3O9 406 5O3 7O4 Stearate at 26 CO
The following example illustrates particularconditions, steps, and materlals within the scope of the present inventionO. However, this example is given only for the purpose of illustration and not limitationO
~1)5;~32 Example An lndicator device was con~tructed substantially as shown in FIGURE lo Covers 16 and 30 were cut to size from 20 mil (005 cm) white card stock and laid end to endO
A strip Or clear plastic film was cut to size and heat sealed to the covers with a hand held electrically heated platen to form cover liners 18 and 320 The rilm prevents liquid saturant from soaklng into the card stock covers and also forms a hinge holding covers 16 and 30 togetherO
A porous fluid source pad 26 was prepared by cutting to size a piece Or 20 mil (005 cm) blotting paperO
m e paper pad was weighed and a liquid comprising (a) 94% of a 50:50 mixture of tributyl phosphate and trioctyl phosphate, and (b) a 6% solution Or N,N'-bis-t2 octanoyloxy-ethyl)dithiooxamide (DOEDTO) was added to the paper pad to provide a fluid source having 45% liquid saturant based on the combined weight of the pad and the liquid, iOeO 45 parts liquid/55 parts padO The liquid was placed dropwise on the paper pad and migration of the liquid within the pad quickly provlded a uniform distribution Or liquid saturant within the padO The pad 26 was adhered with liquid cement to cover 28 in the position shown in FIGURES 1 and 20 A wick 20 was cut from 20 mil (.~5 cm) Bluebird Blotting Paper in substantially the shape shown in FIGURE lo A solution of nickel rosinate was applied by spraying the end of the wick to form layer 22, the rest of the wick being shielded 80 as to prevent applicatlon of the nlckel rosinate to the remainlng areasO When dried, the nlckel rosinate layer 22 was eæsentially the same white color as the untreated areaO
- 24 _ 105i~632 The wick 20 was adhered with liquid cement to cover 14 in the posltlon shown in FIGURE 1~ A separator sheet 24 was cut to size from a sheet of transparent poly- -ester film and positloned over wlck 20 as shown in FIGURE 1 ~o as to prevent the contact of pad 26 with wick 200 The covers 14 and 28 were then folded together, sandwiching the separator sheet 24 between pad 26 and wick 20 and a clip 40 sllpped over the hinged end of the covers to hold the combination Or elements in flxed relatlonshipO
A strip of pressure-sensitlve adhesive transfer film 36 having removable protective liner 38 was applied to the outside of cover 14 to allow easy attachment to a surface.
The device was activated at 75 Fo (25 C) by removlng the separator sheetO After 72 hours the character-istic purple color Or the DOEDTO - nickel complex began to appear in layer 22~ By the end of 98 hours about one-half of the area of layer 22 had turned purpleO
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A device for indicating the passage of a selected time interval comprising, in combination, a porous liquid source pad containing a liquifi-able indicating material, an elongated wick capable of wicking liquid from said pad, migration of said indicating material from said source pad to said wick initially being selectively prevented, said wick and said pad being arranged to direct migration of liquid indicating material once initiated along a major dimension of said wick to provide a visible migrating front of indicating liquid in said wick, said liquid source pad containing and pre-senting a controlled amount of liquid to said wick and thereby selectively limiting the maximum migration rate for a given liquid below the migration rate provided by a free pool of said liquid.
2. A device according to claim 1 wherein said indicating material has a melting point at or below room temperature, said device including a barrier for temporarily preventing migration of liquid from said pad to said wick.
3. A device according to claim 1 wherein said indicating material has a melting point above room temperature.
4. A device according to claim 1, 2 or 3 wherein said source pad and said wick are absorbent paper.
5. A device according to claim 2 wherein said indicating material comprises a non-aqueous liquid.
6. A device according to claim 5 wherein said non-aqueous liquid comprises tributylphosphate.
7. An indicating device according to claim 1,2 or 3 wherein said wick is a branched wick, the branches of said wick terminating at a common point, said device including additional source pads associated with each of said branches and wherein each of said source pads contains a different liquefiable indicating material each having a different melting point.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40004473A | 1973-09-24 | 1973-09-24 | |
| US05/404,891 US3954011A (en) | 1973-09-24 | 1973-10-10 | Selected time interval indicating device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1052632A true CA1052632A (en) | 1979-04-17 |
Family
ID=27016879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA208,819A Expired CA1052632A (en) | 1973-09-24 | 1974-09-10 | Indicating device |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3954011A (en) |
| JP (1) | JPS5810709B2 (en) |
| CA (1) | CA1052632A (en) |
| DE (1) | DE2445379C2 (en) |
| FR (1) | FR2244984B1 (en) |
| GB (1) | GB1481100A (en) |
| IT (1) | IT1021661B (en) |
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| CN102203575B (en) * | 2008-10-24 | 2014-02-12 | 智力发现股份有限公司 | Precise critical temperature indicator |
| CN102326061B (en) * | 2008-12-24 | 2014-05-28 | 智力发现股份有限公司 | Precise critical temperature indicator and manufacturing method thereof |
| JP4904371B2 (en) * | 2009-01-29 | 2012-03-28 | 日本サーモスタット株式会社 | Temperature sensitive indicator |
| US8091503B2 (en) * | 2009-08-27 | 2012-01-10 | Xerox Corporation | Label configured to indicate an object reaching a predetermined temperature |
| GB201001235D0 (en) * | 2010-01-26 | 2010-03-10 | Uwl Technology Ltd | Elapsed time indicator |
| GB2485420A (en) | 2010-11-15 | 2012-05-16 | Pirtsemit Ltd | Lower threshold temperature indicator device |
| CA2834221C (en) | 2011-04-29 | 2015-12-22 | Colgate-Palmolive Company | Oral care implement having visual indicator of depletion of a fluid |
| US20130014676A1 (en) | 2011-07-15 | 2013-01-17 | Airdex International, Inc. | Load bearing structure having antimicrobial properties |
| US8979361B2 (en) * | 2012-04-30 | 2015-03-17 | Innosense Llc | Time-temperature dosimeter |
| US9310311B2 (en) | 2013-06-13 | 2016-04-12 | Performance Indicator, Llc | Time validation indicator |
| US9689849B2 (en) * | 2013-08-14 | 2017-06-27 | General Electric Company | Colorimetric indicators for use in medical devices |
| WO2015112679A1 (en) | 2014-01-27 | 2015-07-30 | Jp Laboratories, Inc | Indicating devices based on lateral diffusion of a mobile phase through a non-porous stationary phase |
| US10006816B2 (en) * | 2014-10-06 | 2018-06-26 | Temptine Corporation | Activatable temperature indicator |
| JP6383694B2 (en) * | 2015-03-30 | 2018-08-29 | 株式会社日立産機システム | Temperature history display body and manufacturing method thereof |
| DE102015218237A1 (en) * | 2015-09-23 | 2017-03-23 | Robert Bosch Gmbh | Timepiece and a method for determining a time span |
| US10408686B2 (en) | 2016-01-15 | 2019-09-10 | Temptime Corporation | Gel-based temperature indicators |
| JP6511408B2 (en) * | 2016-03-15 | 2019-05-15 | 株式会社日立産機システム | Temperature history indicator, method of manufacturing the same, and method of using the same |
| US10119946B2 (en) * | 2016-04-22 | 2018-11-06 | American Sterilizer Company | Sterilization test strip |
| KR101896155B1 (en) * | 2016-09-19 | 2018-09-07 | 성균관대학교산학협력단 | Indicator |
| DE102018107694B4 (en) * | 2018-03-29 | 2023-03-16 | T-TIMR GmbH | Timing device, timing system, timing method and manufacturing method for a timing device |
| US20240094679A1 (en) | 2022-09-15 | 2024-03-21 | Carefusion 303, Inc | Single use disposable elapsed time indicator with absorbable material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3006313A (en) * | 1959-12-14 | 1961-10-31 | Aseptic Thermo Indicator Compa | Telltale for overheated blood storage containers and the like |
| NL286850A (en) * | 1961-12-18 | 1900-01-01 | ||
| US3243303A (en) * | 1962-06-27 | 1966-03-29 | Leighton C Johnson | Temperature monitor employing a flowable aqueous composition containing dispersed polyvinyl acetate as a flow retardant |
| US3420205A (en) * | 1966-03-23 | 1969-01-07 | Miles Lab | Indicating device |
| US3521489A (en) * | 1968-01-22 | 1970-07-21 | Gillette Co | Disposable thermometer |
| US3479877A (en) * | 1968-08-28 | 1969-11-25 | Minnesota Mining & Mfg | Time-temperature indicator |
| US3520124A (en) * | 1969-02-13 | 1970-07-14 | Sumner Myers | Timer device |
| US3684737A (en) * | 1969-08-25 | 1972-08-15 | Mask Off Co | Coating composition for indicating sterilization |
| US3665770A (en) * | 1970-07-24 | 1972-05-30 | Bio Medical Sciences Inc | Temperature indicator |
-
1973
- 1973-10-10 US US05/404,891 patent/US3954011A/en not_active Expired - Lifetime
-
1974
- 1974-09-10 CA CA208,819A patent/CA1052632A/en not_active Expired
- 1974-09-20 JP JP49108662A patent/JPS5810709B2/en not_active Expired
- 1974-09-23 FR FR7432004A patent/FR2244984B1/fr not_active Expired
- 1974-09-23 DE DE2445379A patent/DE2445379C2/en not_active Expired
- 1974-09-23 GB GB41357/74A patent/GB1481100A/en not_active Expired
- 1974-09-23 IT IT53154/74A patent/IT1021661B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| US3954011A (en) | 1976-05-04 |
| FR2244984A1 (en) | 1975-04-18 |
| JPS5060262A (en) | 1975-05-24 |
| JPS5810709B2 (en) | 1983-02-26 |
| DE2445379C2 (en) | 1985-12-05 |
| IT1021661B (en) | 1978-02-20 |
| GB1481100A (en) | 1977-07-27 |
| DE2445379A1 (en) | 1975-04-17 |
| FR2244984B1 (en) | 1980-12-19 |
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