(12) United States Patent
`Malach
`
`(10) Patent N0.:
`(45) Date of Patent:
`
`US 6,482,332 B1
`Nov. 19, 2002
`
`US006482332B1
`
`......... .. 62/457.2
`7/1997 Scaringe et al.
`5,647,226 A
`4/1998 Takei
`........................ .. 252/70
`5,744,054 A
`5/1999 Pnfdnnl
`--------- --
`62/371
`5,899,088 A
`* 1;/2333 at
`2:71/:2
`21127323:
`r um ......... ..
`,
`,
`A *
`Shang . . . . . . . . . . . . . . . . . . . . . . ..
`FOREIGN PATENT DOCUMENTS
`4108369
`*
`9/1992
`285213
`* 10/1988
`8451468
`*
`6/1996
`
`
`
`DE
`EP
`JP
`
`(54) PHASE CHANGE FORMULATION
`
`(76)
`
`(*) Notice:
`
`Inventor: Ted J. Malach, 105 Appleglen Pl. SE.,
`<69
`Subject to any disclaimer the term of
`patent issexgentded oir adjusted under 35
`U.S.C. 1 4
`0
`.
`( )
`y
`ays
`
`(21) Appl. No.: 09/523,570
`
`(22)
`
`(60)
`
`Filed:
`
`Mar. 10, 2000
`a a
`ea e
`.
`.
`ica ion
`RltdUSAppl't' Dt
`Provisional a
`lication No. 60/124,049, filed on Mar. 12,
`pp
`1999-
`
`* Cited by examiner
`reen
`.
`t on
`rzmar
`xammer
`P’
`yE
`'—Anh yJG
`ristensen
`Home ,
`em, or
`Lrm
`(74) A
`y Ag
`F’ —Ch'
`Johnson Kindness PLLC
`
`O’C
`
`onnor
`
`(57)
`
`ABSTRACT
`.
`.
`.
`A1heiina1 Packaging .SYS1ein.nSing a Singie Phase change
`materlal (PCM) part In hquld and part {I1 sohd form to
`confine the temperature of the product within a predeter-
`mined range. The temperature ranges are determined by the
`selection of PCM formulation. The phase change materials
`selected have hi h latent heats of fusion and maintain
`relatively constan% temperatures as they change phase. This
`Penniie right ‘Weight Packaging With the inainienance cf
`temperatures in narrow, preselected ranges over extended
`periods of time. A phase change formulation that can be
`adjusted to freeze at temperatures from +40° C. to below
`—30° C. is disclosed, comprising butanediol, selected per-
`centages of distilled water, and nucleating agents. The phase
`change occurs over a narrow temperature range making this
`~
`~
`~
`an “irear ienpfigiigj Control 1:91?‘ Nucrfarmg Or other
`age.“ 5 are rrre ‘r e
`e rrarrew e errrpera “re rarrge ever
`Which the Phase Change OCCHFS.
`
`20 Claims, 15 Drawing Sheets
`
`Int. Cl.7 ................................................ .. C09K 5/00
`(51)
`(52) U.S. Cl.
`........................... .. 252/70; 252/71; 252/73;
`252/74; 165/10; 165/104.19; 165/104.21
`(58) Field of Search ............................ .. 252/70, 71, 73,
`252/74; 165/104.19, 10, 104.21
`
`References Cited
`U-S- PATENT DOCUMENTS
`2,936,741 A *
`5/1960 Telkes ....................... .. 122/32
`4,403,645 A as
`9/1933 Maccracken .
`. 165/10
`9/1984 Morris ,,,,,,,,,,,,,, ,,
`4,470,264 A
`62/60
`.
`607/114
`4,596,250 A *
`6/1986 Beisang, III et al.
`
`------------- -- 165/10
`4,793,402 A * 12/1988 YaI10 6191-
`- - - -~ 428/76
`49319333 A
`6/1990 HeniY - - - - - ~ ~
`499719713 A * 11/1990 Arrres ‘ ‘ ‘ ‘ ‘ ‘ ‘ ‘ ‘ ‘ ‘ ‘ ‘ ‘ ‘
`‘ ‘ ‘ " 252/70
`5,072,596 A * 12/1991 Gilbertson et al.
`62/185
`..
`5,110,502 A *
`5/1992 Singh ..................
`252/319
`5,168,724 A * 12/1992 Gilbertson et al.
`62/430
`5,402,650 A *
`4/1995 Stewart, Jr. ............ .. 62/71
`5,417,082 A
`5/1995 Foster
`........ ..
`62/457.1
`5,478,988 A * 12/1995 Hughes et al.
`............ .. 219/730
`
`
`
`(56)
`
`O01
`
`MAZE INNOVATIONS, INC.
`
`EX. 1007
`
`001
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 1 of 15
`
`US 6,482,332 B1
`
`FIG.
`
`1
`
`h IIIIZIIIIIIIIIIIIIIIIIIIIIJ
`&\\\\\\\\\\\\\\\\\\\\\\\\\\V
`TIIIIIIIIIIIIIIIIIIIIIIIIIJQ
`
`TIIIIIIIIIIIIIIIIIIIIIIIIIZ
`
`FIG. 2
`
`045
`00fifii
`§»
`29
`
`0.
`
`9 0
`
`00%ééwfiq¢§0gap
`3»d%d%00dfifihfi000990fifififififi90
`
`O
`
`455009
`¢%%&§%%&&%g
`0000900099090
`o°3'3'3°3°3’3*3’3°3°3’3‘3"
`gahaggggggggg
`‘§o:‘%‘%
`0909000000090
`gfigaggggggggg
`éfifififififififififififi
`69
`@@®fi@%fifi%9’
`qgggfiggflp
`:3:3:3:3:=:3:3:¥
`o*3°3°3°3°3*o°
`§W&fi&%
`%%%%%%
`qgggggp
`
`0’:’:’:’: '°“
`fihflfifivb
`I
`Qfififlfifififi
`¢wygg¢¢
`
`002
`
`002
`
`

`
`9;at
`
`115%
`
`t11
`
`MW
`
`19’
`
`M¢0
`
`91%‘
`
`¢ 0
`
`15f
`
`{J
`
`5 6/6
`
`fly
`
`1j?¢99
`
`
`
`fig’
`
`5
`
`
`
` //I/I/I/I/I/I/I/I/I/I/I/I/I/I/I/I/I/I/I/I/I/I/I/454,
`'1
`
`1
`
`flfi
`
`fig
`
`46
`
`6?
`
`fig
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`11515355
`/IIIIIIII
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`115555555555” 11lllllllll/lllllllllll /IIIIIIIIIII111111111111/IIlI’I,IIIl/"IIIIIIlI111111111111111111111111/IIIIIIIIIII1/1/11/Inn/”IIIlII’I111111111111/lllllllllll1IIIIIIIIII1IIIIIIIIII
`
`
`
` /IIIIIIIIIIA/IIIIIIIIIII1IIIIIIIIII111111111111
`/IIIIIIIIIII
`/IIIIIIIII
`55555”
`$11
` IIIIIIIII IIIII III IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIlI5’III
`
` III]?IIIII
`II
`
`III
`1115
`555555:
`1515555555
`IIIIIIIIIIIIIII
`Illlllllllllllll
`r:55555555555555”
`
`
`IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII
`,,,;;%??‘??2??‘‘'‘
`Illllllllllll
`IIIIIIIIIIIIIII
`IIIIIIIIIIIIIII
`IIIIIIIIIIIIIII
`n5555555555555’5’
`lllllllllllllll/
`llllllllllllllg
`Vllllllllllll
`VIIIIIIIIIII
`5:555:55"
`Ilojll
`$11
`I/'
`,;
`I,
`
`/’,
`
`I I’II;IfI’/
`/I,
`If[f
`
`/’,
`
`fl’
`
`’/If,’
`
`I
`
` //1;/I/I/.1/I/I/I/I/I/I/I/I/I/I/I/I/I/1/I/I////1‘/VI
`
`I,
`//////////
`//////
`//
`,
`/
`,
`
`fly’
`
`1/
`
`009
`
`003
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 3 of 15
`
`US 6,482,332 B1
`
`
`
`270°C
`
`20.0°C
`
`15_o°c
`
`1o.0°C
`
`TEMPERATURE
`
`5.0°C
`
`0.0°C
`
`—5.0°C
`
`-10.0°C
`
`-15.o°c
`
`—19.o°c
`
`18:00
`
`21:00
`
`0:00
`
`3:00
`
`6:00
`
`9:00
`
`12:00
`
`TIME (HOURS)
`
`FIG. 6
`
`004
`
`004
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 4 of 15
`
`US 6,482,332 B1
`
`TEMPERATURE
`
`TIME
`
`FIG. 7
`
`TEMPERATURE
`
`TIME
`
`FIG. 8
`
`005
`
`005
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 5 of 15
`
`US 6,482,332 B1
`
`112°C
`
`~~
`
`-4.0%:
`
`8W0
`
`40°C
`
`00°C
`
`-8.000
`
`:iF.RE_EZE A
`
`A
`
`*———~
`
`—12.o°C
`
`-1e.o°c
`
`—19.7°c
`
`
`
`12:00
`
`15:00
`
`18:00
`
`TIME (HOURSIMINUTES)
`
`FIG. 9
`
`,_,,___,T_ l
`X NORMAL COOLING (SIMILAR TO GEL PACK)
` 2o.o° C
`
`27.0: C
`25.0 C
`
`15.o°c
`
`wfc —'——A
`
`TEMPERATURE
`
`TEMPERATURE
`
`5.o°c
`
`00°C
`
`—5.o° c
`
`_10_0°C
`-12.
`°0 C
`
`— PHASE CHANGE (FREEZING) —
`
`A
`
`———— — —
`
`A
`
`—— — — — — — A A — —
`o.oo
`
`12:00
`
`o.oo
`
`12:00
`
`TIME (HOURS)
`
`FIG.
`
`I0
`
`006
`
`006
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 6 of 15
`
`US 6,482,332 B1
`
`‘W40?-
`
`g Q A Q A Q A L.
`A
`'1Vi'I'I'IVIViV}"
`
`.
`
`.
`
`.
`
`.
`
`44
`
`*1*1*1*1*3*3'1*3‘4 -------------'
`. g A 4 A A A 4. A 4 . . . .
`.
`. . .
`IIIILTIIIIIIITITI .............5
`
`FIG.
`
`11
`
`007
`
`007
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 7 of 15
`
`US 6,482,332 B1
`
`_
`
`20°C TO 14°C IN
`7 HOURS, 20 MINUTES
`
`+2°C AMBIENT
`
`
`
`15:00
`
`18:00
`
`21:00
`
`TIME (HOURS)
`
`FIG. 12
`
`~— ~ ~
`~
`i 14°C TO 20°CIN
`42 HOURS, 50 MINUTES
`
`0:00
`
`12:00
`
`0:00
`
`12:00
`
`TIME (HOURS)
`
`FIG. 13
`
`008
`
`21.7°C
`
`0
`20.0 C
`
`180°C
`
`0
`16.0 C
`
`14.0°C
`
`13.3°C
`
`27.1°C
`
`24.0°C
`
`200°C
`
`0
`16.0 C
`
`12.0°C
`
`7.8°C
`
`UJ
`0:
`
`E<
`
`35
`GEL
`‘L3
`
`UJ
`9,‘
`I-
`
`< E
`
`EL
`2
`LU
`
`*‘
`
`,
`
`008
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 8 0f 15
`
`US 6,482,332 B1
`
`
`
`I
`14°C TO 20°C IN
`HOURS 58 MINUTES
`~
`»:
`
`I
`}
`
`.
`I
`I
`+37°c AMBIENT
`I
`
`
`
`24.3°C
`
`200°C
`
`160°C
`
`Lu
`D!
`
`3 L
`
`T:
`0:
`IJJ
`E
`UJ
`
`I I I
`
`
`
`‘
`
`—
`
`21:00
`
`0:00
`
`3:00
`
`6:00
`
`TIME (HOURS)
`
`FIG. 14
`
`"
`
`12.0°C
`
`7.9%;
`
`12.8°C :
`12.0°C
`
`I-
`
`Q EU
`
`J
`
`10-000
`g 80°C
`‘
`
`LU
`
`0
`0
`———— ———v——
`~~—»»—— 10 CTO2 CIN
`21 HOURS, 43 MINUTES ‘Ti’
`8°CTO2°C|N
`”’—_'
`_ _ E E E _ 20 HOURS, 53 MINUTES
`I
`
`’
`
`18:00
`
`0:00
`
`6:00
`
`12:00
`
`TIME (HOURS)
`
`FIG.
`
`1 5
`
`009
`
`009
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 9 of 15
`
`US 6,482,332 B1
`
`I
`
`I
`
`I
`
`%
`
`
`
`
`I
`10°CTo2°CIN E :1
`5HOURS, 30 MINUTES
`
`8°C TO 2°C IN
`4 HOURS, 28 MINUTES
`I—
`I~:
`
`~—:
`-21’ C AMBIENT
`
`;::——
`
`19:00
`
`20:00
`
`21:00
`
`22:00
`
`23:00
`
`0:00
`
`TIME (HOURS)
`
`FIG. 16
`
`I
`
`
`2°CTo 10°C IN
`
`
`— 6 HOURS, 57 MINUTES
`
`
`2°CTo a°CIN
`10 HOURS, 40 MINUTES
`hfl
`
`
`
`0:00
`
`6:00
`
`12:00
`
`18:00
`
`0:00
`
`TIME (HOURS)
`
`FIG.
`
`I7
`
`010
`
`LI.l
`gt,
`E
`E
`E
`,U_J
`
`13.7°C
`12_0oC
`
`100°C
`
`8.0°C
`60°C
`0
`4.0 C
`
`20°C
`
`-0.4°C
`
`19.7°C
`
`160°C
`
`E 12000
`E
`'
`8.0°C
`
`<3
`
`CL
`
`5
`,_
`
`0
`4.0 C
`
`0.0°C
`
`—3.1°C
`
`010
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 10 of 15
`
`US 6,482,332 B1
`
`
`
`HOURS, 43 MINUTES
`I
`1
`
`
`
`E
`———>———- 2°C TO 10°C
`IN
`
`
`}
`6 HOURS, 28 MINUTES
`2°C TO 8°C IN
`
` _ 4
`#1
`
`
`142°C
`
`12.0°C
`
`100°C
`
`80°C
`
`6.0°C
`
`4.0°C
`
`TEMPERATURE
`
`0.1°C
`
`27.0°C
`25.o°c
`
`20.0%:
`
`15.0%:
`
`10.0°C
`
`O01'%'°oO0
`
`-5.0°C
`
`-10.0°C
`—12.o°c
`
`TEMPERATURE
`
`
`
`1 1
`
`2.o°c 0
`
`3:00
`
`4:00
`
`5:00
`
`6:00
`
`7:00
`
`8:00
`
`9:00
`
`10:00
`
`TIME (HOURS)
`
`FIG. 18
`
`I
`
`T
`
`1
`
`0’
`
`“T
`
`11
`
`T
`
`PRODUCT TEMPERATURE
`ABOVE +1° C FOR 23 HOURS
`
`/
`
`
`
`12:00
`
`18:00
`
`0:00
`
`6:00
`
`TIME (HOURS)
`
`FIG.
`
`19
`
`011
`
`011
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 11 of 15
`
`US 6,482,332 B1
`
`35.9°C
`
`30.0°C
`
`*
`
`;
`‘
`/1
`1
`—
`AMBIENT TEMPERATURE
`
`PRODUCT TEMPERATURE
`,
`/
`1
`1
`
`1
`
`Lu
`II 20.0°C —~ --
`D
`1
`|._
`1
`E
`LU
`2
`n.
`LL]
`
`0
`10.0 C
`
`1
`;
`
`A
`
`"
`
`0.0°C
`
`—»~«-
`
`-12.O°C
`
`*
`
`18:00
`
`0:00
`
`6:00
`
`12:00
`
`18:00
`
`T|ME(HOURS)
`
`FIG. 20
`
`26.0°C
`
`:: 0,, ,
`
`,
`
`:
`
`0
`
`:_
`
`1
`
`~
`
`——
`
`-21°CAMBlENT
`
`+20°CAMBIENT
`
`
`
`6:00
`
`12:00
`
`18:00
`
`0:00
`
`6:00
`
`20.0°C
`
`0
`Lu
`§ 15-0 C
`I-
`§ 10.0°C
`‘cf
`5.0°C
`
`0.0°C
`
`—5.0°C
`
`-12.0°C
`
`E1
`
`-
`
`TIME (HOURS)
`
`FIG. 21
`
`012
`
`012
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 12 of 15
`
`US 6,482,332 B1
`
`
`
`0:00
`
`1:00
`
`2:00
`
`TIME (HOURS)
`
`FIG. 22
`
`/ NORMAL COOLING
`5
`
`FREEZING TEMPERATU RE
`/:
`
`
`
`
`11:15
`
`11:30
`
`11:45
`
`12:00
`
`12:15
`
`12:30
`
`TIME (HOURS:M|NUTES)
`
`FIG. 23
`
`013
`
`TEMPERATURE
`
`TEMPERATURE
`
`18.3°C
`
`16.0°C
`
`120°C
`
`80°C
`
`40°C
`
`0.0°C
`
`-1.8°C
`
`19.8°C
`
`16.0°C
`
`120°C
`
`80°C
`
`40°C
`
`00°C
`
`-4.0°C
`
`—s.2°c
`
`013
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 13 of 15
`
`US 6,482,332 B1
`
`/ NORMAL COOLING
`
`TEMPERATURE
`
`TEMPERATURE
`
`72.8°F
`70.0°F
`
`65.0°F
`
`60.0°F
`
`55.0°F
`
`50.0°F
`
`45.0°F
`
`40.0°F
`
`35.0°F
`
`29.5°F
`
`41.4°F
`
`40.0°F
`
`38.0°F
`
`36.0°F
`
`34.0°F
`
`32.8°F
`
`PHASE CHANGE ’ ’ ’ ” ”
`
`(SOLIDIFICATION)
`
`/
`
`
`
`
`
`10:00
`
`16:30
`
`17:00
`
`17:30
`
`13:00
`
`18:30
`
`19:00
`
`T|ME(HOURS)
`
`FIG. 24
`
`
`
`1:30
`
`2:00
`
`2:30
`
`3:00
`
`3:30
`
`4:00
`
`TIME (HOURS)
`
`FIG. 25
`
`014
`
`014
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 14 of 15
`
`US 6,482,332 B1
`
`12.2°C
`
`8.0°C
`
`4.0°C
`
`0.0°C
`
`TEMPERATURE —4.0°C
`
`-5.5°C
`
`22:30
`
`23:00
`
`23:30
`
`0:00
`
`0:30
`
`1:00
`
`T|ME(HOURS)
`
`FIG. 26
`
`16.9°C
`
`100°C
`
`5.0°C
`
`0.0°C
`
`-5.0°C
`
`TEMPERATURE
`
`-10.0°C
`
`-15.0°C
`
`-21.1°C
`
`14:00
`
`15:00
`
`16:00
`
`17:00
`
`18:00
`
`TIME (HOURS)
`
`FIG. 27
`
`015
`
`015
`
`

`
`U.S. Patent
`
`Nov. 19, 2002
`
`Sheet 15 of 15
`
`US 6,482,332 B1
`
`55.0°F
`
`50.0°F
`
`45.0°F
`
`40.0°F
`
`35.0°F
`
`30.0 F
`
`TEMPERATURE
`
`25.o°F
`
`20.0°F
`
`15.o°F
`
`10.9°F
`
`0:00
`
`3:00
`
`6:00
`
`9:00
`
`TIME (HOURS)
`
`FIG. 28
`
`26.000
`
`200°C
`
`15.0°C
`
`10.0°C
`
`TEMPERATURE
`
`50°C
`
`00°C
`
`-5 0°C
`
`-10.0°C
`-12.0°C
`
`0:00
`
`12:00
`
`0:00
`
`12:00
`
`o;oo
`
`TIME (HOURS)
`
`FIG. 29
`
`016
`
`016
`
`

`
`US 6,482,332 B1
`
`1
`PHASE CHANGE FORMULATION
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`
`This application claims the benefit of U.S. provisional
`application Serial No. 60/124,049 filed Mar. 12, 1999.
`
`FIELD OF THE INVENTION
`
`This invention relates to packaging systems, and phase
`change formulations.
`
`BACKGROUND OF THE INVENTION
`
`In the art of packaging systems, it is known to provide an
`insulated chamber with a heat sink formed of dry ice on one
`upper side of the chamber, and a heat source formed of water
`ice on a lower side of the chamber. Such designs do not
`provide for precise temperature control over a wide variety
`of temperature ranges. It is an object of this invention to
`provide a packaging system with good temperature control
`over a a wide temperature range.
`Glycols are known in the art as being suitable phase
`change materials for controlling temperature of products.
`Glycols, however, tend to undercool before freezing due to
`trace amounts of contaminants, and it is an objective of this
`invention to overcome problems of undercooling of glycols.
`In addition, while providing phase change materials
`within containers is known,
`these materials tend to be
`arranged in a single layer of pockets sandwiched between
`two sheets. The present invention provides an improvement
`on such devices.
`
`SUMMARY OF THE INVENTION
`
`According to an aspect of the invention, there is provided
`a packaging system comprising an insulated container hav-
`ing a chamber for receiving product, product in the chamber,
`and plural layers of phase change material on at least one
`side of the product,
`the layers of phase change material
`comprising at least one liquid layer and one solid layer.
`According to a further aspect of the invention, the layers
`are formed of the same phase change material.
`According to a further aspect of the invention, there are
`plural layers on one side of the product and at least one layer
`of phase change material on another side of the product.
`According to a further aspect of the invention,
`there is
`provided plural layers of phase change material above and
`below the product, including both solid and liquid phase
`change material above and below the product.
`According to a further aspect of the invention, the product
`is wrapped in a blanket of phase change material. According
`to a further aspect of the invention, the product is wrapped
`in a foil.
`
`there
`According to a further aspect of the invention,
`insulated chamber comprises an inner wall, an outer wall
`and phase change material disposed between the inner and
`outer walls.
`
`According to a further aspect of the invention, there is
`provided a phase change formulation comprising 1—99.5%
`by weight polyol, 0.5—99% water, and nucleating agent. The
`polyol may be a glycol, which may itself be 1,4-butanediol,
`1,2-butanediol, 2,3-butanediol or a mixture thereof. The
`phase change formulation may further comprise glycerol in
`the range of 0.5 to 15%.
`According to a further aspect of the invention, the polyol
`is a triol, which may be glycerol.
`
`2
`According to a further aspect of the invention, the nucle-
`ating agent is selected from the group consisting of talc and
`an alkaline earth metal salt.
`
`Thickening agent may be added to the phase change
`formulation, such as kaolin clay or talc.
`According to a further aspect of the invention, there is
`provided a thermal stabilizer, comprising, a fluid, an imper-
`meable envelope that is impermeable to the fluid, the imper-
`meable envelope having an interior, a permeable mat con-
`fined within the impermeable envelope, the permeable mat
`being commensurate in size with the interior of the enve-
`lope; and the permeable mat being impregnated with the
`fluid.
`
`According to a further aspect of the invention, the fluid is
`a gellable fluid and the permeable mat is impregnated with
`a gelling agent. The permeable mat may be a fibrous mat.
`The fluid may be a phase change material. The envelope may
`have a height, width and length, and the height is less than
`1/5 of the width and less than 1/5 of the length. The envelope
`may have a height, width and length, and the height is less
`than 1/5 of the width and less than 1/10 of the length.
`According to a further aspect of the invention, there is
`provided Amethod of making a thermal stabilizer, compris-
`ing the steps of inserting the permeable mat into an enve-
`lope; and impregnating the permeable mat with a fluid. The
`method may further comprise impregnating the permeable
`mat with a gelling agent, before impregnating the permeable
`mat with a fluid, the fluid being a gellable fluid. The fluid
`may be a phase change material.
`Further aspects of the invention are set forth in the claims
`and other aspects of the invention are described in the
`detailed description. Particularly, several novel phase
`change formations are disclosed.
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`There will now be described preferred embodiments of
`the invention, with reference to the drawings, by way of
`illustration only and not with the intention of limiting the
`scope of the invention, in which like numerals denote like
`elements and in which:
`
`FIG. 1 shows a top view of a first embodiment of a
`constant temperature packing arrangement according to the
`invention;
`FIG. 2 shows a side view section through the embodiment
`of a constant temperature packing arrangement according to
`the invention of FIG. 1;
`FIG. 3 shows section through a wall of a container
`according to an aspect of the invention;
`FIG. 4 shows a side view section through a second
`embodiment of the packaging system of the invention;
`FIG. 5 shows a cross section through an aspect of the
`invention comprising a laminate style container for phase
`change material;
`FIG. 6 is a graph showing freeze and thaw characteristic
`of a glycerol (10%)/water (90%)/talc (0.05%) formulation
`according to the invention;
`FIG. 7 is a graph showing freeze characteristic of
`butanediol/water formulation;
`FIG. 8 is a graph showing melt characteristic of
`butanediol/water formulation;
`FIG. 9 is a graph showing an example of freeze and thaw
`hysteresis;
`FIG. 10 is a graph showing cooling and freeze character-
`istic of Red PCM, which comprises 1,4 butanediol with a
`talc nucleating agent, a formulation according to the inven-
`tion;
`
`5
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`017
`
`017
`
`

`
`US 6,482,332 B1
`
`3
`FIG. 11 is a side View cross section of an insulating box
`and configuration used to test phase change material cooling
`and warming;
`FIG. 12 is a graph showing cooling characteristic for
`ICE-PAK water based gel packs (ICE-PAK is a company in
`Montreal, Canada);
`FIG. 13 is a graph showing warming and thaw charac-
`teristic for Red PCM;
`FIG. 14 is a graph showing warming characteristic for
`ICE-PAK water based gel packs;
`FIG. 15 is a graph showing cooling and freezing charac-
`teristic for Blue PCM, which comprises 94.3% butanediol,
`5.7% water and about 0.01% talc;
`FIG. 16 is a graph showing cooling characteristic for
`ICE-PAK water based gel packs;
`FIG. 17 is a graph showing warming and thawing char-
`acteristic for Blue PCM;
`FIG. 18 is a graph showing warming characteristic for
`ICE-PAK water based gel packs;
`FIG. 19 is a graph showing product temperature history
`for a blood shipping package test in cold ambient;
`FIG. 20 is a graph showing product temperature history
`for a blood shipping package test in warm ambient;
`FIG. 21 is a graph showing product temperature history
`for a blood shipping package test in cold and hot ambient;
`FIG. 22 is a graph showing cooling and freezing charac-
`teristic of a 94.5% 1,4-butanediol 5.5% water formulation
`with 0.05% talc;
`FIG. 23 is a graph showing cooling and freezing charac-
`teristic of a 94% 1,4 butanediol and 6% water formulation;
`FIG. 24 is a graph showing cooling and freezing charac-
`teristic of a formulation which comprises 93.8% butanediol,
`6.2% purified water, and 0.01% N660 Talc;
`FIG. 25 is a graph showing thawing characteristic of the
`formulation of FIG. 24;
`FIG. 26 is a graph showing cooling and freezing charac-
`teristic of a formulation comprising 5% water 95% 1,4
`butanediol and 0.05% Barium Sulfate as a nucleating agent;
`FIG. 27 is a graph showing cooling and freezing charac-
`teristic of a formulation which comprises comprises 98%
`purified water, 2% Sentry Grade Polyethylene Glycol 400 by
`Union Carbide and 0.01% Altalc 500V USP by Luzenac
`America Inc. as a nucleating agent;
`FIG. 28 is a graph showing warming and thawing char-
`acteristic of the formulation of FIG. 27; and
`FIG. 29 is a graph showing cooling and freezing charac-
`teristic of CryomatTM, which is a commercially available
`product comprising 3% Polyethylene Glycol and 97% water.
`
`DETAILED DESCRIPTION OF PREFERRED
`EMBODIMENTS
`
`In this patent document, “comprising” means “including”.
`In addition, a reference to an element by the indefinite article
`“a” does not exclude the possibility that more than one of the
`element is present.
`The packaging system was developed for shipments of
`goods which must be kept within narrow temperature ranges
`over a period of days under uncontrolled ambient tempera-
`ture conditions. Such goods include biological products,
`blood products, vaccines, pharmaceuticals, chocolate
`products, latex paints, etc. Examples include whole blood 1
`to 10° C., Factor VIII (used by hemophiliacs) 2 to 8° C.,
`diagnostic blood samples 1 to 10° C., some vaccines 2 to 10°
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`4
`
`C., blood platelets 20 to 24° C., and chocolate approximately
`10° C. The system described here can maintain controlled
`product
`temperatures under both high and low ambient
`temperature conditions.
`This system uses phase change materials for tight tem-
`perature control and minimum shipping weight and volume.
`For example, the formulation that changes phase at between
`15 and 20° C. has a latent heat of fusion of approximately
`50 cal/g. Common gel packs and water have specific heats
`of about 1 cal/g/° C. at that temperature. If this formulation
`was used to control temperature within a 5° C. range (+15°
`C. to 20° C.), it would have the equivalent thermal energy
`of ten times its weight in gel packs.
`These phase change materials are reusable, and can save
`significantly on shipping costs. Particularly, 1,4 butanediol,
`glycerol, polyethylene glycols (PEGs) and 1,6 hexanediol
`are inexpensive and widely available.
`All of the material compositions of liquids described
`below are by volume percent, unless otherwise stated. The
`amount of nucleating agent
`is also specified as volume
`percent. The percentages given are the percentage of the
`total product. In some cases, the totals do not add up to 100%
`since the amount of nucleating agent is within the error
`bounds on the measurement of the liquid.
`FIGS. 1-4 show a packaging system that may be used in
`conjunction with the phase change materials described here.
`An insulated outer container 10 includes a top wall 12,
`bottom wall 14 and identical side walls 16. Each wall 12, 14,
`16 may be constructed as shown in FIG. 3 in which an inner
`wall 18 and outer wall 20 sandwich a layer of phase change
`material (PCM) 22. In the embodiment of FIG. 3, the walls
`16 of the container 10 comprise 3 layers: an outer and inner
`insulation material layer, between which is a PCM 22 in
`plastic containers. This embodiment would provide a more
`even temperature in the product. Until
`the PCM in the
`middle layer has all melted or frozen, the temperature would
`be nearly uniform everywhere at the container’s inner sur-
`face.
`
`Alternatively, the inner wall 18 and outer wall 20 may
`sandwich insulation in various forms such as a sheet. The
`
`phase change material 22 may be retained in plural pockets
`23 arranged in a grid fashion between two sheets of liquid
`impermeable material. The outer container 10 may be used
`to contain a variety of shapes and sizes of product 24, and
`may itself have various shapes. The higher the insulation or
`R-Factor,
`the better the performance of the system. The
`insulated container 10 should completely enclose the prod-
`uct 24 except for the opening for the top wall 12. The top
`wall 12 preferably has the form of a plug, with a relatively
`tight and air proof fit with the side walls 16. The top wall 12
`may be made from insulating foam or other insulating
`material, and may take the form of an insulated lid rather
`than a plug. Alid may be made of insulated walls that fasten
`together. An insulated blanket may be wrapped around the
`insulated container instead of a plug or lid. The insulated
`blanket than becomes the top wall 12.
`Phase change material 26 is provided inside the container
`10 in plural layers, on one side of the product 24 as shown
`in FIG. 2 or on both sides as shown in FIG. 4. Each layer 26
`may be made from a grid of pockets, or may be formed of
`a thin laminate (for example a fiber mat) of inert permeable
`material 28 impregnated with phase change material and
`then enclosed within an impermeable envelope 30, as illus-
`trated in FIG. 5. Possible inert permeable materials include
`air laid materials such as air laid cellulose fibres or any
`fibrous permeable mat.
`Inert means that
`the permeable
`
`018
`
`018
`
`

`
`US 6,482,332 B1
`
`5
`material does not react with the phase change material to
`destroy its desirable phase change properties. The envelope
`30 is impermeable to the phase change material. By imper-
`meable is not intended absolute impermeability, but suffi-
`cient
`impermeability that
`the product may be used for
`practical purposes without leakage. Appropriate materials
`are well known in the art such as nylon outer with polypro-
`pylene inner welded together. Plastics that are inadequately
`impermeable in themselves may have aluminum facings to
`enhance impermeability. The envelope 30 has an interior
`that confines the permeable fiber mat, with the permeable
`fiber mat being commensurate in size with the interior of the
`envelope. Preferably, the height of the envelope is less than
`1/5 its width, and the height is less than 1/5 is length, and even
`more preferably, less than 1/10 for each ratio. For example,
`the envelope should not be more than about 1/2 inch thick,
`and the length and width may each be 5 inches or more and
`need not be equal.
`The plural layers 26 or laminate may be formed of a single
`phase change material, with alternating layers of liquid and
`solid (eg solid-liquid-solid above and below the product 24
`in FIG. 4), to thus maintain a single temperature, or may be
`made of different phase change materials, each having a
`different freezing point, to thus maintain the product within
`a range of temperature bounded by the freezing points of the
`two phase change materials. Thus, the layers 26 in FIGS. 2
`and 4 may be arranged with phase change material A, then
`phase change material B on top, and then another layer of
`phase change material A. Multiple layers may be used, for
`example 2-10 layers. The layers 26 are preferably slab
`shaped, in that they should be thin in relation to their width
`and length, as for example the depth or thickness being at
`least less than 1/5 of both the width and length. A divider 32
`may be used to separate product 24 from phase change
`material. Dividers 32 reduce product temperature gradients
`if they are constructed of a thermally conductive material
`such as light gauge aluminum sheets. Plastic dividers cov-
`ered with aluminum foil on one or both sides may also be
`used. They also can serve as a mechanical protective barrier
`for the product.
`In the case of use of the same phase change material in all
`layers 26, the phase change material 26 whether liquid or
`solid is set close to the freezing point, and is placed in the
`container in a ratio of solid to liquid that is determined by
`whether protection against cold is required or protection
`against heat is required. Various numbers of layers of phase
`change material 26 may be used based upon time
`requirements, ambient temperature requirements,
`thermal
`insulation factor of the outer container, and the degree of
`temperature control required for the product. The precision
`of the preconditioning temperature is not so critical when the
`solid and liquid phase packages are placed together they will
`automatically stabilize within the phase transition tempera-
`ture range. The stabilization temperature will depend mostly
`upon the amount of solid and liquid phase change material,
`as the latent heats of fusion or melting are much larger than
`the specific heats.
`The product 24 may be wrapped in thermally conductive
`material 34 (eg. thermally conductive metal foil such as
`aluminum foil) to further reduce thermal gradients. House-
`hold grade of aluminum foil may be used, in which the
`thickness in the order of a few thousandths of an inch thick.
`
`As an alternate, a product enclosure constructed of thermally
`conductive material may be used. It should be noted that
`although aluminum foil may not seem like such a good
`thermal conductor, in an insulated container it is compara-
`tively a very good conductor.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`6
`With packages of solid PCM, 26 liquid PCM 26 and
`product 24 in place,
`the product chamber will be at a
`temperature between those given by the melting temperature
`curve and the freezing temperature curve for the PCM
`formulation selected. An exemplary curve is shown in FIG.
`6 for a mixture of glycerol 10%, water 90% and talc 0.05%,
`wherein the mixture freezes at about —5° C. and melts at
`
`about —2° C. The PCM’s will provide resistance to tempera-
`ture swings above and below the temperature boundaries as
`defined by the melting and freezing curves mentioned
`above. This will effectively lock the temperature into a
`pre-selected range. The use of dividers (optional) that are
`relatively conductive to heat will reduce thermal gradients
`within the product chamber. Wrapping the product in ther-
`mally conductive material (eg. aluminum foil) or having a
`thermally conductive product chamber will further reduce
`product temperature gradients. The product chamber tem-
`perature set point is determined by the PCM formulation
`selected.
`
`The PCM in liquid and solid phase as described above
`effectively acts as a PCM at an intermediate stage of phase
`change. By varying the ratio of solid phase PCM containers
`to liquid phase containers, protection can be tailored to
`ambient temperatures mostly above or below the required
`product temperature range. For example,
`if a product is
`required to be kept within a range of +2 to +8° C., and it is
`being shipped in ambient conditions of +30° C., more solid
`than liquid phase PCM could be employed. By the nature of
`this system, it still will provide protection against —20° C.
`but not for as long as against higher ambient temperatures.
`This can be important when shipping in aircraft with
`unheated cargo areas.
`Two PCMs can be used to more closely customize the
`temperature range and other properties of the shipment. For
`example, for food product to be kept anywhere between 0°
`C. and 17° C., liquid PCM that freezes at 2° C. and solid
`PCM that freezes at 15° C. could be used. Two PCMs could
`
`also be combined so as to achieve required temperature
`protection with minimum PCM. For example water ice and
`Blue PCM can be used to keep a product between 2 and 8°
`C. Blue PCM comprises 94.7% butanediol, 5.3% water and
`about 0.01% talc, and freezes at about 5° C. It is discussed
`in greater detail below. The water ice has a high heat
`capacity and therefore less of it is needed to keep the product
`below 8° C. However the PCM is needed as water alone will
`
`freeze near 0° C. and the product would therefore have
`insufficient protection against low temperature.
`PCMs with high freezing temperatures have the advan-
`tage of being rechargeable in commonly encountered ambi-
`ent temperatures. For example, Red PCM freezes at about
`16° C. If it is used as solid PCM in a shipment to protect
`against both high and low ambient temperatures,
`it will
`freeze again when the ambient temperature drops below 16°
`C., after which the shipping package will have the same
`capacity for protecting against high temperatures that it had
`at the start of shipping. Red PCM is discussed in detail
`below.
`
`Test results have demonstrated that this system can main-
`tain tight temperature ranges over a period of days under
`adverse ambient temperature conditions.
`This system can meet many of the most demanding
`temperature control requirements of biologics and pharma-
`ceutical shippers. Protection against high and low tempera-
`tures is provided simultaneously. Shipments will not have to
`be delayed due to unfavorable ambient temperature condi-
`tions. Shipments will not have to be met at intermediate
`
`019
`
`019
`
`

`
`US 6,482,332 B1
`
`7
`destinations to “recharge” the temperature regulating media.
`The system is economical to operate, all parts are reusable.
`The inherent lighter weight of this system will pay for itself
`many times over in reduced shipping costs. The biggest
`payback results from the reduction in spoiled shipments of
`expensive product. This packaging system provides addi-
`tional mechanical protection to product as both the dividers
`and the phase change material packages provide cushioning.
`An exemplary preferred phase change material is a butane-
`diol formulation disclosed below which is non-toxic and
`
`non-irritating. Butanediol has been accepted by a govern-
`ment regulatory body for use with blood products.
`(Butanediol has been used in its pure form, frozen state, to
`control the temperature of blood and platelets).
`The phase change material may be placed in blankets
`made up of pouches of phase change material. The blankets
`may also be thin, flat sheets using permeable mats 28,
`encased in plastic wrapping as illustrated in FIG. 5 The
`permeable mats 28 may be cellulose fibre or other absorbent
`material that does not deleteriously react with the PCM. The
`permeable material 28 preferably absorbs and holds the
`PCM in place, minimizing leakage in the event of a puncture
`as well as providing dimensional stability. As many of the
`PCMs disclosed here are still pliable when frozen, these
`sheets may be bent to conform to product when shipping.
`Such fibrous sheet blankets have less dead air space in
`packing, compared to a pouches-style blanket. Less dead air
`space makes packaging less voluminous and makes it more
`thermally efficient by reducing thermal leakage. Fibrous
`sheet blankets may be made thinner than a pouches-style
`blanket, and so provide quicker thermal equilibrium when
`frozen and liquid sheets are interleaved. There would also be
`more contact area between PCM sheets, and between PCM
`sheets and product, providing better temperature control.
`Blankets of PCM may be used to enclose entire pallets of
`product. The blankets may be layered as shown in FIGS. 2
`and 4, with alternate solid and liquid phase material used to
`protect product from both hot and cold conditions. The
`