Freeze indicators, flexible freeze indicators and manufacturing methods
View Patent ↗Freeze indicators providing a visual indication of exposure of the freeze indicator to a freezing or near-freezing temperature and their manufacture are disclosed. The freeze indicators employ colloidal dispersions as active elements and include flexible freeze indicators, freeze indicators protected against drying out and freeze indicators employing core shell composites, for example gold coated pigments as active indicator elements. Also disclosed are: a combination freeze indicator and threshold temperature indicator; a combination threshold indicator and cumulative temperature indicator; and three-way combination indicators that can provide indications of cumulative past temperature exposure, exposure to freezing temperatures and exposure to a temperature above a threshold.
1. A flexible freeze indicator comprising:
(a) an indicator volume;
(b) an active indicator element contained in the indicator volume and comprising an indicator dispersion of solid particles dispersed in a liquid medium, the indicator being capable of coagulating to provide an irreversible appearance change when subject to freezing; and
(c) at least one vapor block member extending around the indicator volume to prevent loss of vapor from the indicator dispersion, the vapor block member having a transparent portion for viewing the active indicator element;
wherein the freeze indicator is flexible and is conformable with a desired host product curved surface.
2. A flexible freeze indicator according to claim 1 wherein the vapor block member comprises a transparent polymeric vapor block layer and an adhesive-receptive layer to facilitate bonding of the vapor block layer to a support for the indicator volume.
3. A flexible freeze indicator according to claim 2 wherein the adhesive-receptive layer is the product of pretreating the surface of the transparent polymeric vapor block layer, the pretreatment optionally being effected by flame, corona or plasma.
4. A flexible freeze indicator according to claim 2 wherein the transparent polymeric vapor block layer has a thickness providing flexibility and comprises a polymer or polymer film selected from the group consisting of fluoropolymers, polychlorotrifluoroethylenes, ACLAR® (trademark) fluoropolymer film and ACLAR® Flex (trademark) fluoropolymer film.
5. A flexible freeze indicator according to claim 2 wherein the indicator volume has a capacity of not more than about 100 μl and optionally has a large dimension of from about Ito about 25 mm and a height of from about 0.5 to about 10 mm.
6. A flexible freeze indicator according to claim 2 wherein the liquid medium comprises water and the flexible freeze indicator comprises a support member to support the indicator volume and an aluminum vapor block member to prevent loss of vapor through the support member from the indicator volume and wherein the support member comprises a water barrier layer disposed between the aluminum layer and the liquid medium in the indicator volume to prevent exposure of the aluminum vapor block member to the water.
7. A flexible freeze indicator according to claim 2 wherein the active indicator element comprises a colloidal dispersion of coated pigment particles in a liquid medium, the coated pigment particles having a coating comprising a freeze-responsive colloid stabilizing material and optionally having a coating stabilizer layer between the pigment particles and the coating to stabilize the coating.
8. A flexible freeze indicator according to claim 7 wherein the coating material is selected from the group consisting of noble metals, precious metals, gold and silver and the freeze indicator wherein the freeze indicator has a green appearance before freezing and the pigment is selected from the group consisting of green pigments, green chromium oxide and phthalocyanine green G.
9. A flexible freeze indicator according to claim 2 in combination with a freeze-sensitive host product, the freeze indicator being associated with the host product to indicate past exposure of the host product to a freezing or near freezing temperature.
10. A flexible freeze indicator according to claim 9 wherein the host product is a freeze-sensitive product selected from the group consisting of vaccines; vials, syringes and biological containers containing freeze-sensitive biologicals; pharmaceuticals; medicaments; blood and perishable blood products; cultures; human and animal organs; diagnostic devices, kits and ingredients; health care products, foodstuffs; dairy products; vegetables; plants; flowers; plant bulbs; dairy products; baked goods; fresh, cooked, cured or smoked meats and fish; food service products; mail order supplied or public carrier delivery food products; animal foods; cut and uncut flowers; cosmetics; chemical or biological agent detection kits; chemicals; water-based chemicals; paints; and water-based adhesives and the freeze indicator is adhered to the host product.
11. A freeze indicator according to claim 2 in combination with a freeze-sensitive host product, the freeze indicator being associated with the host product to indicate past exposure of the host product to a freezing or near freezing temperature.
12. A freeze indicator comprising an active indicator element providing an irreversible appearance change in response to exposure to a predetermined low temperature, wherein the active indicator element comprises a colloidal dispersion of coated pigment particles in a liquid medium, the coated pigment particles having a coating comprising a freeze-responsive colloid stabilizing material and optionally having a coating stabilizer layer between the pigment particles and the coating to stabilize the coating.
13. A freeze indicator according to claim 12 wherein the coating material is selected from the group consisting of noble metals, precious metals, gold and silver.
14. A freeze indicator according to claim 13 wherein the freeze indicator has a green appearance before freezing the pigment is selected from the group consisting of green pigments, green chromium oxide and phthalocyanine green G.
15. A freeze indicator according to claim 14 having a white, black or red appearance after freezing and thawing.
16. A freeze indicator according to claim 13 wherein the pigment particles are selected from the group consisting of particles of silica, white and colored plastic microspheres, white and colored polymeric microspheres, white and colored hollow plastic microspheres and white and colored hollow polymeric microspheres and the coating material is a noble metal.
17. A freeze indicator according to claim 13 comprising at least one vapor block member of flexible polymeric vapor block material surrounding the active indicator element to prevent loss of liquid vapor from the colloidal dispersion wherein the freeze indicator is flexible and is conformable with a desired host product curved surface.