Encapsulated phase change thermal energy storage materials and process

• US 4,513,053 A
• Filed: 05/14/1984
• Issued: 04/23/1985
• Est. Priority Date: 06/13/1983
• Status: Expired due to Term

• Current Assignee: Elf Atochem North America, Inc. (Totalenergies Se)
• Original Assignee: Pennwalt Corporation (Arkema)
• Inventors: Chen, Johnson C. H., Eichelberger, John L.
• Primary Examiner(s): Lusignan, Michael R.
• Application Number:
  US06/609,672
• Time in Patent Office: 344 Days
• Field of Search: 252/70, 427/3, 427/213, 427/214, 427/221, 264/7, 428/304.4, 428/403, 428/407, 428/221, 523/200, 523/207, 523/210, 523/211, 165/53, 165/104.17
• US Class Current: 428/221
• CPC Class Codes: F28D 20/023 the latent heat storage material being enclosed in granular particles or dispersed in a porous, fibrous or cellular structure
• CPC Class Codes: Y02E 60/14 Thermal energy storage
• CPC Class Codes: Y10S 106/03 Mica
• CPC Class Codes: Y10T 428/249921 Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/249953 Composite having voids in a component [e.g., porous, cellular, etc.]

Abstract

A thermal energy storage composite pellet-shaped product of about 1/8 inch to 1 inch in size, formed of an outer seamless shell member which defines a cavity that permanently encases a phase-change composition, the composition being present in a quantity such that the total volume of the composition, whether in its solid form, liquid form, or both forms as in its transition state, never exceeds the volume of the cavity; and a process for making the product which includes using the phase-change composition in a compacted powder form as cast about which the shell member is formed by roll-coating steps.

Claims

1. A concrete or gypsum building construction component having dispersed within the component less than about 75% by weight of a thermal energy storage composite product capable of incorporation within rigid building construction components without causing fracture or damage to the components or product after the product undergoes repeated thermal change cycles, said product comprising:

(a) an outer shell member having a longest dimension of from about 1/8 inch to about 1 inch and having interior surfaces defining an internal cavity that is adapted to permanently encase a thermal energy storage phase-change composition, said shell being comprised of at least one seamless layer of a wall-forming material that is substantially impermeable to and non-reactive with said phase-change composition or water, the total volume of the wall-forming material being from about 5% to 30% of the volume of said cavity; and

(b) a thermal energy storage phase-change composition permanently disposed within the cavity of the shell, said phase-change composition being capable of existing in solid form, a melted liquid form, or a transition state that includes both the liquid and the solid forms, the composition being present in a quantity such that the total volume of composition whether in the solid form, the liquid form, or the transition state does not exceed the volume of the cavity.

2. The construction component as defined in claim 1 wherein the shell member of (a) is comprised of multiple seamless coatings of the wall-forming material.

3. The construction component as defined in claim 1 wherein the outer shell member of (a) has convex shaped outer surfaces with rounded edges.

4. The construction component as defined in claim 1 wherein the wall-forming material of (a) is a material selected from the group consisting of a copolymer latex of butadieneacrylonitrile, a copolymer of vinylidene chloride-acrylic, resinous latexes, rubber latexes, epoxy polymers, polyurethane polymers, acrylic polymers, cellulose acetate and polyamides.

5. The construction component as defined in claim 1 wherein the interior surfaces of shell member of (a) are coated with a primer substance.

6. The construction component as defined in claim 5 wherein the primer coating is a water-resistant primer substance.

7. The construction component as defined in claim 6 wherein the water-resistant primer coating is comprised of asphalt or acrylic polymer.

8. The construction component as defined in claim 5 wherein the primer coating is present in a volumetric amount that is less than about 5% of the volume of the cavity.

9. The construction component as defined in claim 2 wherein mica is dispersed onto at least one of the coatings comprising the shell member.

10. The construction component as defined in claim 1 wherein the thermal energy phase-change composition of (b) has a liquid density that is at least 85% but less than 100% of the solid density of the composition.

11. The construction component as defined in claim 1 wherein the thermal energy phase-change composition of (b) has a phase change transition temperature within the range of about 7°

C. to about 90°

C.

12. The construction component as defined in claim 1 wherein the thermal energy phase-change composition of (b) is selected from the group consisting of a Glauber salt eutectic mixture, sodium hydroxide, polyethylene, sodium sulfate decahydrate, sodium thiosulfate pentahydrate, calcium chloride hexahydrate, magnesium nitrate hexahydrate, the eutectic of magnesium nitrate hexahydrate and ammonium nitrate, potassium fluoride tetrahydrate, sodium acetate trihydrate, stearic acid, the eutectic of naphthalene and benzoic acid and paraffinic hydrocarbons.

13. The construction component as defined in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 in which the component comprises a wall of a building and the product is present in an amount within the range of about 20% to 75% by weight.

14. The construction component as defined in claim 13 wherein the concrete is selected from the group of concretes comprising conventional concrete mixtures, polymer concrete, epoxy concrete, or polyester concrete.

15. A floor or ceiling building construction component having dispersed therein a thermal energy storage composite product capable of incorporation within rigid building construction components without causing fracture or damage to the components or product after the product undergoes repeated thermal change cycles, said product comprising:

(a) an outer shell member having a longest dimension of from about 1/8 inch to about 1 inch and having interior surfaces defining an internal cavity that is adapted to permanently encase a thermal energy storage phase-change composition, said shell being comprised of at least one seamless layer of a wall-forming material that is substantially impermeable to and non-reactive with said phase-change composition or water, the total volume of the wall-forming material being from about 5% to 30% of the volume of said cavity; and

(b) a thermal energy storage phase-change composition permanently disposed within the cavity of the shell, said phase-change composition being capable of existing in solid form, a melted liquid form, or a transition state that includes both the liquid and the solid forms, the composition being present in a quantity such that the total volume of composition whether in the solid form, the liquid form, or the transition state does not exceed the volume of the cavity.

16. The construction component as defined in claim 15 wherein the shell member of (a) is comprised of multiple seamless coatings of the wall-forming material.

17. The construction component as defined in claim 15 wherein the outer shell member of (a) has convex shaped outer surfaces with rounded edges.

18. The construction component as defined in claim 15 wherein the wall-forming material of (a) is a material selected from the group consisting of a copolymer latex of butadieneacrylonitrile, a copolymer of vinylidene chloride-acrylic, resinous latexes, rubber latexes, epoxy polymers, polyurethane polymers, acrylic polymers, cellulose acetate and polyamides.

19. The construction component as defined in claim 15 wherein the interior surfaces of shell member of (a) are coated with a primer substance.

20. The construction component as in claim 19 wherein the primer coating is a water-resistant primer substance.

21. The construction component as in claim 20 wherein the water-resistant primer coating is comprised of asphalt or acrylic polymer.

22. The construction component as in claim 19 wherein the primer coating is present in a volumetric amount that is less than about 5% of the volume of the cavity.

23. The construction component as in claim 16 wherein mica is dispersed onto at least one of the coatings comprising the shell member.

24. The construction component as in claim 15 wherein the thermal energy phase-change composition of (b) has a liquid density that is at least 85% but less than 100% of the solid density of the composition.

25. The construction component as in claim 15 wherein the thermal energy phase-change composition of (b) has a phase change transition temperature within the range of about 7°

C. to about 90°

C.

26. The construction component as in claim 15 wherein the thermal energy phase-change composition of (b) is selected from the group consisting of a Glauber salt eutectic mixture, sodium hydroxide, polyethylene, sodium sulfate decahydrate, sodium thiosulfate pentahydrate, calcium chloride hexahydrate, magnesium nitrate hexahydrate, the eutectic of magnesium nitrate hexahydrate and ammonium nitrate, potassium fluoride tetrahydrate, sodium acetate trihydrate, stearic acid, the eutectic of naphthalene and benzoic acid and paraffinic hydrocarbons.

27. A process for manufacturing a thermal energy storage phase-change composite product and a construction component therefrom, comprising:

(a) selecting a thermal energy storage phase-change composition having a phase-change transition temperature within the temperature range of the contemplated environment in which the product is to be used, and maintaining the temperature of the composition below the melting point of the composition, after the composition has been first melted, to provide a solidified thermal energy phase-change composition;

(b) converting the solidified thermal energy storage phase-change composition of (a) to a flowable powder to provide a flowable powder composition while maintaining the composition at a temperature below its melting point;

(c) compacting and pelletizing the flowable powder composition of (b) to form discrete pellet-shaped compacted powder structures having a longest dimension of from about 1/8 inch to about 1 inch and a shortest dimension of at least about 1/8 inch while maintaining a temperature below the melting point of the composition, the degree of compacting being controlled to provide compacted powder structures of sufficient integrity to withstand coating with a wall-forming material as well as an apparent solid density that is less than or equal to the liquid density of the phase-change composition;

(d) coating each of the compacted powder compositions with a curable liquid wall-forming material comprising from about 5% to 30% by weight of the product based upon the final cured weight of the wall-forming material, while maintaining a temperature below the melting point of the composition, said wall-forming material when in a cured state being nonreactive with and substantially impermeable to both the phase-change composition and water;

(e) curing the liquid wall-forming material on each of the compacted powder compositions to form a permanent seamless shell, that is substantially impermeable to and non-reactive with both the phase-change composition and water, which encapsulates each of the compacted powder compositions to provide the product;

said product being capable of dispersion throughout rigid building construction components without causing fracture or damage to the components or product upon repeated thermal change cycles of the encapsulated thermal phase-change storage composition; and

then

(f) incorporating the encapsulated powder composition product of step (e) within a concrete or gypsum building construction component to provide a component of improved thermal mass that can withstand repeated thermal cycles without causing damage or fracture to the product or component.

28. The process as defined in claim 27 wherein in (d) multiple coats of the liquid wall-forming material are applied.

29. The process as defined in claim 27 wherein in (c) the outer surfaces of the structures are convex shaped with rounded edges.

30. The process as defined in claim 27 wherein in (d) the wall-forming material is selected from the group consisting of a copolymer latex of butadiene-acrylonitrile, a copolymer of vinylidene chloride-acrylic, resinous latexes, rubber latexes, epoxy polymers, polyurethane polymers, acrylic polymers, cellulose acetate and polyamides.

31. The process as defined in claim 27 wherein in (d) the compacted powder structures are first coated with a water-resistant primer substance.

32. The process as defined in claim 27 wherein in (d) the compacted powder structures are first coated with a water-resistant primer substance selected from the group consisting of asphaltic material or an acrylic polymer or copolymer material.

33. The process as defined in claim 27 wherein in (d) the compacted structures are first coated with a water-resistant primer substance comprising less than about 5% by weight of the structure.

34. The process as defined in claim 28 wherein mica or similar material is coated onto at least one of the coatings of the structure.

35. The process as defined in claim 27 wherein in (a) the phase-change composition has a liquid density that is at least 85% but less than 100% of the solid density of the composition.

36. The process as defined in claim 35 wherein in (a) the composition has a phase-change transition temperature within the range of about 7°

C. to 90°

C.

37. The process as defined in claim 27 wherein in (a) the phase-change composition is selected from the group consisting of Glauber salt eutectic mixture, sodium hydroxide, polyethylene, sodium sulfate decahydrate, sodium thiosulfate pentahydrate, calcium chloride hexahydrate, magnesium nitrate hexahydrate, the eutectic of magnesium nitrate hexahydrate and ammonium nitrate, potassium fluoride tetrahydrate, sodium acetate trihydrate, stearic acid, the eutectic of naphthalene and benzoic acid and paraffinic hydrocarbons.

38. The process as defined in claim 27 wherein in (b) a binder material is added to the flowable powder composition to improve integrity in subsequent pelletizing in step (c).

39. The process as defined in claim 27 wherein in (b) fillers are added to the flowable powder composition to provide an apparent solid density after pelletizing in (c) that is less than or equal to the liquid density of the phase-change composition of (a).

40. The process as defined in claim 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, or 39 wherein the component is a wall of a building and the product comprises less than about 75% by weight of the component.

41. The process as defined in claim 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, or 39 wherein the concrete is selected from the group of concrete comprising conventional concrete mixtures, polymer concrete, epoxy concrete, or polyester concrete.

42. The process as defined in claim 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, or 39 wherein the encapsulated powder composition product of step (e) is then incorporated within a floor or ceiling building construction component.

43. A process for manufacturing a thermal energy storage phase-change composite product and a construction component of improved thermal mass therefrom, comprising

(a) selecting a thermal energy storage phase-change composition having a phase-change transition temperature within the temperature range of the contemplated environment in which the product is to be used;

(b) melting the composition to provide a liquid composition;

(c) maintaining the temperature of the liquid composition at a temperature just above the composition melting point and then forming discrete shaped structures of the composition by agglomerating the composition with agglomerator means to provide structures having a longest dimension of from about 1/8 inch to about 1 inch and a shortest dimension of at least about 1/8 inch and then maintaining the temperature of the structures at a temperature below the melting point of the composition, said agglomerating being controlled to provide structures having an apparent solid density that does not exceed the liquid density of the phase-change composition;

(d) coating each of the structures with a curable liquid wall-forming material comprising from about 5% to 30% by weight of the product based upon the final cured weight of the wall-forming material, while maintaining a temperature below the melting point of the composition, said wall-forming material when in a cured state being nonreactive with and impermeable to both the phase-change composition and water;

(e) curing the liquid wall-forming material on each of the structures to form a seamless shell, that is substantially impermeable to and non-reactive with both the phase-change composition and water, which encapsulates each of the compacted powder compositions to provide the product;

said product being capable of dispersion throughout rigid building construction components without causing fracture or damage to the components or product upon repeated thermal change cycles of the encapsulated thermal phase-change storage composition; and

then

(f) incorporating the encapsulated structure product of step (e) within a concrete or gypsum building construction component to provide a component of improved thermal mass that can withstand repeated thermal cycles without causing damage or fracture to the product or component.

44. The process as defined in claim 43 wherein the component is a wall of a building and the product comprises less than about 75% by weight of the component.

45. A process for manufacturing a thermal energy storage phase-change composite product and a floor or ceiling construction component therefrom, comprising

(a) selecting a thermal energy storage phase-change composition having a phase-change transition temperature within the temperature range of the contemplated environment in which the product is to be used;

(b) melting the composition to provide a liquid composition;

(c) maintaining the temperature of the liquid composition at a temperature just above the composition melting point and then forming discrete shaped structures of the composition by agglomerating the composition with agglomerator means to provide structures having a longest dimension of from about 1/8 inch to about 1 inch and a shortest dimension of at least about 1/8 inch and then maintaining the temperature of the structures at a temperature below the melting point of the composition, said agglomerating being controlled to provide structures having an apparent solid density that does not exceed the liquid density of the phase-change composition;

(d) coating each of the structures with a curable liquid wall-forming material comprising from about 5% to 30% by weight of the product based upon the final cured weight of the wall-forming material, while maintaining a temperature below the melting point of the composition, said wall-forming material when in a cured state being nonreactive with and impermeable to both the phase-change composition and water;

(e) curing the liquid wall-forming material on each of the structures to form a seamless shell, that is substantially impermeable to and non-reactive with both the phase-change composition and water, which encapsulates each of the compacted powder compositions to provide the product;

said product being capable of dispersion throughout rigid building construction components without causing fracture or damage to the components or product upon repeated thermal change cycles of the encapsulated thermal phase-change storage composition; and

then

(f) incorporating the encapsulated structure product of step (e) within a floor or ceiling building construction component to provide a component having up to 75% by weight of the product.

46. The process as defined in claim 45 wherein in (d) multiple coats of a liquid wall-forming material are applied.

47. The process as defined in claim 45 wherein in (c) the outer surfaces of the structures are convex shaped with rounded edges.

48. The process as defined in claim 45 wherein in (d) the wall-forming material is selected from the group consisting of a copolymer latex of butadiene-acrylonitrile, a copolymer of vinylidene chloride-acrylic, resinous latexes, rubber latexes, epoxy polymers, polyurethane polymers, acrylic polymers, cellulose acetate and polyamides.

49. The process as defined in claim 45 wherein in (d) the structures are first coated with a water-resistant primer substance.

50. The process as defined in claim 45 wherein in (d) the structures are first coated with a water-resistant primer substance selected from the group consisting of asphaltic material or an acrylic polymer or copolymer material.

51. The process as defined in claim 46 wherein mica is coated onto at least one of the coatings of the structure.

52. The process as defined in claim 45 wherein in (a) the phase-change composition has a liquid density that is at least 85% of the solid density of the composition.

53. The process as defined in claim 45 wherein in (a) the phase-change composition is selected from the group consisting of Glauber salt eutectic mixture, sodium hydroxide, polyethylene, sodium sulfate decahydrate, sodium thiosulfate pentahydrate, calcium chloride hexahydrate, magnesium nitrate hexahydrate, the eutectic of magnesium nitrate hexahydrate and ammonium nitrate, potassium fluoride tetrahydrate, sodium acetate trihydrate, stearic acid, the eutectic of naphthalene and benzoic acid and paraffinic hydrocarbons.

54. The process as defined in claim 45 wherein in (c) the agglomerating means are selected from the group of agglomerating means consisting of rotating pan agglomerator, fluidized bed agglomerator, or a combination of a rotating pan and fluidized bed agglomerator.