HYDRATED CALCIUM BROMIDE REVERSIBLE PHASE CHANGE COMPOSITION

Abstract: A reversible liquid/solid phase change compo­ sition comprising a eutectic composition of CaBr₂·6H₂O and CaBr₂·4H₂O, having more than 5.4 but less than 6.0 moles of H₂O per mole of CaBr₂. The composition optionally includes additives selected from KBr and NaBr to lower the melting point of the composition. The composition optionally also includes a nucleating agent selected from Ba and Sr salts to reduce supercooling of the composition to 5°C or less.

Description: The invention relates to reversible liquid/solid phase change compositions. More particularly, the invention relates to a eutectic composition of CaBr₂·6H₂O and CaBr₂·4H₂O, having more than 5.4 but less than 6.0 moles of H₂O per mole of CaBr₂. Numerous phase change materials which are capable of storing thermal energy as latent heat are identified in "Solar Heat Storage: Latent Heat Materials" Volume 1, by G. A. Lane; CRC Press, Inc., 1983. Among the phase change materials disclosed are several inorganic eutectics with transition temperatures ranging from 13°C to 61°C (pp 46 and 47). Eutectic systems are particularly described on pages 69 to 72 and 76 to 78. Definitions to phase transition temperature, heat of fusion, density, supercooling, and crystal growth are provided on pages 42 and 43. A definition of nucleation and nucleators is provided on pages 116 and 143. The aforementioned definitions are applicable to the present invention. Other publications, particularly as they relate to CaBr₂·6H₂O phase change materials, are Japanese publication 57-180684 (Matsushita Electric Works) describing a phase change material of CaBr₂·6H₂O having added thereto various Barium and/or Strontium salts to prevent supercooling of the phase change material; Japanese publications 51-070193 (Mitsubishi Electric Corp.) discloses a phase change material comprising CaBr₂·6H₂O containing a small amount of Sr(OH)₂·8H₂0 or Ba(OH)₂·8H₂O or the anhydride to prevent supercooling of the composition; and Japanese publication 57-096079 (Mitsubishi Electric Corp.) discloses a phase change composition of CaCl₂ and/or CaBr₂·6H₂O containing a small amount of Sr or Ba oxide to prevent supercooling of the phase change composition. Storage materials which undergo a change in phase have been employed as an attractive alternative to materials which store thermal energy as sensible heat such as, for example, by raising the temperature of water or rocks. In contrast, a phase change material (PCM) absorbs a large quantity of latent thermal energy during its phase change from a solid to a liquid state and releases such thermal energy at a constant temperature as the process is reversed. Several classes of phase change materials consisting of hydrated inorganic salts exist and can be generally divided into two groups: (1) salt hydrates that go through many cycles of freezing and thawing without an appreciable separation of their chemical components are classified as congruent melting and eutectic salt hydrates, and (2) salt hydrates which undergo an appreciable segregation of their chemical components during repeated cycles of freezing and thawing are generally classified as semi-congruent melting or incongruent melting. Salt hydrates of group (1) which are "congruent melting" are hydrated materials such as, for example, CaBr₂·6H₂O for which, at the melting point, with solid and liquid phases in stable equilibrium, the solid phase contains no hydrated CaBr₂ other than the hexahydrate and the liquid phase contains 6 moles of water for every mole of CaBr₂, plus sufficient water to form the stable hydrate of any additive materials in solution. Eutectic salt hydrates are mixtures of two or more components mixed in such a ratio that the melting point of the mixture is lower than that of any component and the entire mixture at one and the same temperature passes from a solid form (frozen) into a liquid form and vice versa. An example of a eutectic salt hydrate is one comprising 58.7 weight percent Mg(NO₃)₂·6H₂O and 41.3 weight percent MgCl₂·6H₂O. The salt hydrate of the type herein under consideration is a eutectic salt hydrate. Mixtures of components which form a eutectic other than the eutectic composition hereinbefore defined are included within the scope of the present invention and are classified as either "hyper-eutectic" or "hypo-eutectic" hydrated salt mixtures. The hyper-eutectics contain more and the hypo-eutectics contain less of the principle component than the eutectic composition. Calcium bromide hexahydrate, CaBr₂·6H₂O, contains 64.90 weight percent CaBr₂ and melts at a temperature of 34.3°C. The hexahydrate is congruent-melting, and forms a eutectic with the tetrahydrate containing 66.95 weight percent CaBr₂ which melts at a temperature of 33.8°C, with a 5.57 degree of hydration. While the heat of fusion for CaBr₂·.6H₂O is lower than for some other salt hydrates, a significant property is its very high density. On a volumetric basis, the heat of fusion of 54 cal/cm³ is high relative to many other hydrated inorganic salts. On a weight basis, the heat of fusion for CaBr₂·.6H₂O is 27.6 cal/g. For applications where space is at a premium, CaBr₂·6H₂O is thus a very desirable phase change material. The term "supercooling" herein refers to a discrepancy between the temperature at which freezing initiates and the melting temperature of a given hydrated salt when cooled and heated under quiescent conditions. The terms "nucleator" and "nucleating agent" refer to small "seed" crystals which initiate crystallization. In order for any nucleation and crystal growth to occur, the melted phase change material must be supersaturated or supercooled. If the phase change material is below its melting point, the addition of nucleating crystals tends to initiate crystallization. A eutectic phase change material freezes to a polycrystalline mixture of the separate components of the eutectic. Nucleation is possible by initiating freezing of one of these phases. If only one phase begins to freeze, depletion in the remaining liquid of the composition raises the liquidus temperature of the other phase until critical supercooling is obtained. At this point, the second phase nucleates and begins to freeze. The term "additive" includes, in addition to nucleators or nucleating agents, KBr and/or NaBr to effect a lowering of the melting point of the phase change material. Phase change materials are ideally packaged in individual encapsulating means for use in conjunction with solar heating systems for commercial or residential buildings, for use in heat exchange systems in which heat exchange coils or plates are positioned within bulk containers containing the phase change material, and the like. Exemplary of suitable known encapsulating means for heat storage materials may also be included water impervious films or foils of plastic/metal laminates. Other useful encapsulating means are concrete, metal or plastic containers, pipes, and the like. The invention particularly resides in a reversible liquid/solid phase change composition comprising a eutectic of CaBr₂·6H₂O and CaBr₂·4H₂O having more than 5.4 but less than 6.0 moles of H₂O per mole of CaBr₂. The invention also resides in a heat storage device comprising an encapsulating means having a reversible liquid/solid phase change composition hermetically sealed in said encapsulating means to prevent evaporation of water from the composition, said composition comprising a eutectic of CaBr₂·6H₂O and CaBr₂·4H₂O having more than 5.4 but less than 6.0 moles of H₂O per mole of CaBr₂. The invention further resides in a method of storing heat, comprising the steps of preparing a reversible liquid/solid phase change composition by admixing CaBr₂ and water to form a eutectic having more than 5.4 but less than 6.0 moles of H₂O per mole of CaBr₂, introducing the composition into an encapsulating means, and hermetically sealing the encapsulating means to prevent evaporation of water from the composition. Preferably, the composition includes a specified nucleating agent or a mixture of such nucleating agents in order to effectively reduce super-cooling of the hydrated eutectic composition. Optionally, the phase change composition of the invention also includes, as an additive, KBr and/or NaBr in an amount effective to lower the melting point of the composition. The present invention represents a significant improvement in the development of a eutectic composition of CaBr₂·6H₂O and CaBr₂·4H₂O which melts and freezes completely and reversibly at a temperature of 33.4°C and to which water of varying amounts can be added without causing a segregation of the hexahydrate and tetrahydrate phases. Even with varying amounts of water in the composition, the composition still melts and freezes nearly isothermally, i.e. at a constant temperature. The isothermal freezing process which takes place is sometimes referred to as a "phase reaction" in which the liquid phase is disappearing, while the two solid phases of the eutectic composition are growing. It should be noted that segregation of the material formed by the phase reaction during freezing or by the opposite reaction during melting will not likely take place. Since both solids are forming together, they will remain intimately mixed. In a congruent melting phase change material, such as CaBr₂·6H₂O, the phase change material does not segregate during melting and freezing. The material stores heat isothermally, completely melting at a temperature of 34.3°C and reversibly freezing at the same temperature (at equilibrium). However, in industrial scale manufacturing plants, where phase change materials are employed in bulk quantity, it may require great care and close control of process parameters to assure that the CaBr₂ salt contains exactly 6.0 moles of H₂O per mole of CaBr₂. Any excess H₂O which may be present in the composition is highly detrimental because, during freezing, crystalline CaBr₂·6H₂O is formed, leaving behind a saturated solution of CaBr₂ in the excess H₂O. If the temperature is lowered, additional hexahydrate crystallizes but complete freezing is not achieved until the cryohydric point (the temperature at which a cryohydrate crystallizes from a freezing mixture) is reached at a temperature well below 0°C. A eutectic composition of the present invention has the advantage that any extra water which may be present in varying amounts will still melt and freeze the composition nearly isothermally. The melting range of the composition remains within a temperature range of only 0.4 to 0.8°C. In the phase change composition of the invention, the CaBr₂·4H₂O is present in the composition in an amount of greater than 0 weight percent but less than 30 weight percent, and the CaBr₂·6H₂O is present in an amount of less than 100 weight percent but greater than 70 weight percent. More particularly, if the composition contains more than 5.4 moles of water per mole of CaBr₂ the CaBr₂·4H₂O is present in the composition in an amount of less than 30 weight percent while the CaBr₂·6H₂O is present in the composition in an amount greater than 70 weight percent. When the composition contains 5.6 moles of H₂O per mole of CaBr₂, the composition contains 20 weight percent CaBr₂·4H₂O and 80 weight percent CaBr₂·6H₂O. At 5.8 moles of H₂O per mole of CaBr₂, the composition contains 10 weight percent of CaBr₂·4H₂O and 90 weight percent CaBr₂·6H₂O. When the composition contains less than 6.0 moles water per mole of CaBr₂, the CaBr₂·4H₂O is present in the composition in an amount greater than 0 weight percent while the CaBr₂·6H₂O is present in the composition in an amount of less than 100 weight percent. Preferably, the eutectic composition contains from 5.5 to 5.8 moles of H₂O per mole of CaBr₂. Most preferably, the composition contains about 5.6 moles of H₂O per mole of CaBr₂. The composition preferably includes a nucleating agent selected from BaO, Ba(OH)₂, Ba(OH)₂·8H₂O, BaCO₃, BaSO₄, BaCl₂, BaCl₂·2H₂O, BaBr₂, BaBr₂·2H₂O, BaI₂, BaI₂·6H₂O, SrO, Sr(OH)₂, SrCO₃, SrSO₄, SrCl₂, SrCl₂·6H₂O, SrBr₂, SrBr₂·6H₂O, SrI₂, FeF₂, and mixtures thereof. Preferred nucleators are BaO, Ba(OH)₂, Ba(OH)₂·8H₂O, BaCl₂, BaCl₂·2H₂O, BaI₂·6H₂O, SrBr₂, and SrBr₂·6H₂O and mixtures thereof. A nucleator is added to the composition in an amount effective to supress the supercooling properties of the hydrated CaBr₂ liquid phase. Effective amounts of a selected nucleator for the hydrated CaBr₂ salt of the invention are determined by testing a given composition over repetitive phase change cycles in a manner similar to the procedure employed in U.S. Patent No. 4,613,444, issued Sept. 23, 1986. A nucleator in an amount in excess of about 2.0 weight percent of the weight of the composition is generally not detrimental to the performance of the phase change composition and, by the same token, does not provide any increase in benefit. Accordingly, the nucleator is preferably present in an amount of from about 0.005 to about 2.0 weight percent based on the total weight of the composition. The composition of the present invention optionally also includes KBr and/or NaBr which act as a modifier to vary the freezing point of the basic phase change composition. The modifier is present in the compositon in an amount of greater than 0 weight percent up to about 5.0 weight percent based on the total weight of the composition. An amount larger than about 5.0 weight percent is generally not detrimental to the performance of the phase change composition and, by the same token, does not provide any increase in benefit in varying the freezing point of the composition. The effect of adding KBr and/or NaBr to the composition is to lower the freezing point of the composition by as much as 3°C. Impurities may also be present in the phase change composition in minor amounts of less than about 3.0 weight percent and provided that such impurities do not detrimentally affect the function of the basic composition of the invention which may include the hereinbefore specified nucleating agents and modifying additives. Impurities may include, for example, LiBr, MgBr₂, CaCl₂, CaI₂, and mixtures thereof. The following examples illustrate the effectiveness of the eutectic composition of the invention in which extra water of varying amounts is introduced into the hydrated calcium bromide composition which still melts and freezes nearly isothermally and within a range of 0.4 to 0.8°C. Comparative Example 1 CaBr₂·6H₂O is prepared by mixing water and hydrated CaBr₂. The mixture is brought to an equilibrium at the melting point so that both solid and liquid CaBr₂·6H₂O are present. The hexahydrate contains 64.90 percent by weight of CaBr₂ and has a melting point at 34.3°C. At equilibrium, the composition freezes completely at this temperature to form 100 mole percent CaBr₂·6H₂O. This exemple shows that the congruent melting phase change material of CaBr₂·6H₂O is very satisfactory and does not segregate during melting and freezing. The composition stores thermal energy isothermally and completely melts at a temperature of 34.3°C and reversibly freezes at the same temperature at equilibrium. Although the composition performs very satisfactorily, great care and close control of process parameters have to be excercised in the use of this material in an industrial manufacturing plant to assure that the phase change material contains exactly 6.0 moles of H₂O per mole of CaBr₂. Comparative Example 2 In the same manner as in Example 1, a hydrated CaBr₂ phase change material is prepared except that an excess of water is used to prepare a composition having 6.4 moles of water per mole of CaBr₂. This phase change material has a melting temperature below 32.6°C. The composition melts completely at 32.6°C but freezing occurs over a temperature range, and is not absolutely complete until the composition reaches a temperature well below 0°C. This example shows the effect of having an excess of water, i.e. 6.4 moles in the composition. During freezing, crystalline CaBr₂·6H₂O is formed leaving behind a saturated solution of CaBr₂ in the extra water. If the temperature is lowered, more hexahydrate crystallizes but complete freezing is not achieved until the cryohydric point (the temperature at which a cryohydrate crystallizes from a freezing mixture), well below 0°C, is reached. Example 3 In the same manner as in Example 1, a phase change material is prepared containing 5.6 moles of water per mole of CaBr₂. The eutectic composition has a melting point of 33.4°C. The material freezes completely at 33.4°C and forms an intimate mixture of 80 mole percent CaBr₂·6H₂O/20 mol percent CaBr₂·4H₂O with no liquid remaining in the composition. This example describes a eutectic composition of the invention containing 5.6 moles of water which melts and freezes completely and reversibly at equilibrium, i.e. at a temperature of 33.4°C. Example 4 Three samples are prepared in the same manner as in Example 1 except that the eutectic compositions contain 5.7, 5.8, and 5.9 moles of water per mole of CaBr₂. The three (3) compositions have a melting range of from 33.4°C to 33.8°C, from 33.4°C to 34.0°C, and from 33.4°C to 34.2°C, respectively. Each of these samples freeze completely at a temperature of 33.4°C to form an intimate mixture containing an amount of greater than 80 mole percent CaBr₂·6H₂O and less than 20 mole percent CaBr₂·4H₂O. Each of the compositions melt and freeze nearly isothermally with the melting range being within the narrow temperature range of from 0.4 to 0.8° C. Example 5 A sample is prepared similar to that of Example 3 except that the hydrated composition is saturated with 2.6 weight percent potassium bromide. The eutectic composition contains 5.5 moles of water per mole of CaBr₂ and has a melting point of 31.9°C. The composition freezes completely at this temperature. This example illustrates that it is possible to vary the freezing point of the eutectic composition by adding KBr to lower the melting point by 2.4°C. Example 6 A sample is prepared as in Example 5 except that NaBr is added to the eutectic composition in place of KBr. The eutectic composition contains 5.6 moles of water per mole of CaBr₂ and 0.4 weight percent NaBr. The composition has a melting point of 33.1°C and freezes completely at this temperature. Example 6 shows that it is possible to vary the freezing point of the composition by 1.2°C by the addition of NaBr. Example 7 A sample of a phase change material is prepared from 64.9 weight percent CaBr₂ and 35.1 weight percent water. Freeze-thaw tests are conducted using aliquots of the CaBr₂ composition, each having a weight of 65 g. Ten successive freeze-thaw cycles are conducted by alternately freezing each aliquot in a water bath at a temperature of about 10°C and then melting the aliquot in an oven at a temperature of 40°C. Out of ten successive freeze-thaw cycles, the CaBr₂ composition fails to crystallize nine times and has to be seeded with frozen CaBr₂ hexahydrate in order to crystallize. On the third cycle, the material freezes spontaneously at a temperature of 22°C, with 12°C supercooling. This example indicates the need for the addition of a nucleating agent in order to obtain supercooling of the CaBr₂ composition. Example 8 To another aliquot of the same CaBr₂ composition of Example 7, a sufficient amount of BaCl₂·2H₂O is added as a nucleator to provide a phase change composition containing 0.5 weight percent BaCl₂. Under the same procedure of freeze-thaw cycling as in Example 7, the sample freezes spontaneously ten times out of ten, with an average supercooling of 8°C. This example indicates that BaCl₂ is effective as a nucleator in the CaBr₂ composition of the invention. However, in this example, a greater amount of the nucleator is desirable, i.e., above 0.5 weight percent, in order to control supercooling of the composition to less than about 5°C. When 0.5 weight percent BaO is substituted for BaCl₂ as a nucleator, the sample freezes spontaneously ten out of ten cycles with an average supercooling of 1°C. This example shows that BaO is an excellent nucleator for the CaBr₂ phase change composition of the invention. Example 9 Further tests are conducted with 50 g aliquots of the phase change composition of Example 7. The aliquots are again subjected to ten cycles of freezing at room temperature and melting in an oven at a temperature of 50°C. With three nucleators selected from BaI₂ (from the hexahydrate), Ba(OH)₂ (from the octahydrate), and SrBr₂ (from the hexahydrate), ten out of ten samples freeze spontaneously with an average supercooling of 7°C, 4°C, and 10°C, respectively. These tests show that the three nucleators are effective. However, in order to control supercooling to less than 5°C, especially in the case of BaI₂ and SrBr₂, an additional amount of the nucleator, i.e., above 0.5 weight percent, is preferred. Several other nucleators show nucleation activity but are somewhat less effective, with the nucleator freezing spontaneously on some cycles and not freezing on other cycles until the sample is placed in an ice bath. The addition of Sr(OH)₂ as a nucleator causes freezing spontaneously in three out of ten cycles. The addition of SrI₂ to the phase change composition causes freezing of the composition in two out of ten cycles. The addition of barium sulfate as a nucleator to the composition causes freezing of the composition in four out of ten cycles. The experiments show an average supercooling of 7°C, 2°C, and 11°C, respectively, for the Sr(OH)₂, SrI₂, and barium sulfate nucleators. A greater amount of the nucleators, i.e., greater than 0.5 weight percent, would be required in each case in order to reduce supercooling to less than 5°C. From Examples 8 and 9, it can be concluded that the preferred nucleators, in the order of effectiveness, are BaO, Ba(OH)₂, Ba(OH)₂·8H₂O, BaI₂, BaI₂·6H₂O, BaCl₂, BaCl₂·2H₂O, SrBr₂, and SrBr₂·6H₂O.

Claims: A reversible liquid/solid phase change composition comprising a eutectic composition of CaBr₂·6H₂O and CaBr₂·4H₂O having more than 5.4 but less than 6.0 moles of water per mole of CaBr₂. The composition of Claim 1, having from 5.5 to 5.8 moles of water per mole of CaBr₂. The composition of Claim 1 or 2, wherein the CaBr₂·4H₂O is present in the eutectic composition in an amount greater than 0 weight percent but less than 30 weight percent, and wherein said CaBr₂·6H₂O is present in an amount of less than 100 weight percent but greater than 70 weight percent. The composition of Claim 1, including a modifying additive selected from KBr and NaBr, said additive being present in an amount sufficient to lower the melting point of the eutectic composition. The composition of Claim 4, wherein said modifying additive is present in an amount of from 0.5 to 8.0 weight percent. The composition of Claim 1 or 4, including a nucleating agent in an amount sufficient to reduce supercooling of the eutectic composition to 5°C or less during retrieval of stored thermal energy upon crystallization of the eutectic composition. The composition of Claim 6, wherein the nucleating agent is present in an amount of from 0.005 to 2.0 weight percent. The composition of Claim 6, wherein the nucleating agent is selected from BaO, Ba(OH)₂, Ba(OH)₂·8H₂O, BaCO₃, BaSO₄, BaCl₂, BaCl₂·2H₂O, BaBr₂, BaBr₂·2H₂O, BaI₂, BaI₂·6H₂O, SrO, Sr(OH)₂, SrCO₃, SrSO₄, SrCl₂, SrCl₂·6H₂O, SrBr₂, SrBr·6H₂O, SrI₂, FeF₂, and mixtures thereof. The composition of Claim 7, wherein said nucleating agent is selected from BaO, Ba(OH)₂, Ba(OH)₂·8H₂O, SrBr₂, SrBr₂·6H₂O, BaI₂, BaI₂·6H₂O, BaCl₂, BaCl₂·2H₂O, and mixtures thereof. A heat storage device comprising an encapsulating means having a reversible liquid/solid phase change composition hermetically sealed in said encapsulating means to prevent evaporation of water from the composition, said composition comprising a eutectic composition of CaBr₂·6H₂O and CaBr₂·4H₂O having more than 5.4 but less than 6.0 moles of water per mole of CaBr₂. The storage device of Claim 10, wherein said eutectic composition includes from 0.5 to 8.0 weight percent of a modifier selected from KBr and NaBr for lowering the melting point of the composition by less than 3°C. The storage device of Claim 10, wherein said eutectic composition includes a nucleating agent in an amount of from 0.005 to 2.0 weight percent, wherein said nucleating agent is selected from BaO, Ba(OH)₂, Ba(OH)₂·8H₂O, BaCO₃, BaSO₄, BaCl₃, BaCl₂·2H₂O, BaBr₂, BaBr₂·2H₂O, BaI₂, BaI₂·6H₂O, SrO, Sr(OH)₂, SrCO₃, SrSO₄, SrCl₂, SrCl₂·6H₂O, SrBr₂, SrBr₂·6H₂O, SrI₂, FeF₂, and mixtures thereof. A method of storing thermal energy, comprising the steps of preparing a reversible liquid/solid phase change composition by admixing CaBr₂ and water to form a eutectic composition of CaBr₂·6H₂O and CaBr₂·4H₂O having more than 5.4 but less than 6.0 moles of water per mole of CaBr₂, introducing the composition into an encapsulating means for use as a heat storage device, and hermetically sealing the encapsulating means to prevent evaporation of water from the composition. The method of Claim 13 wherein said eutectic composition includes from 0.5 to 5.0 weight percent of a modifier for lowering the melting point of the composition, said modifier being selected from KBr and NaBr. The method of Claim 13, wherein said eutectic composition includes a nucleating agent in an amount of from 0.005 to 2.0 weight percent, wherein said nucleating agent is selected from BaO, Ba(OH)₂, Ba(OH)₂·8H₂O, BaCO₃, BaSO₄, BaCl₂, BaCl₂·2H₂O, BaBr₂, BaBr₂·2H₂O, BaI₂, BaI₂·6H₂O, SrO, Sr(OH)₂, SrCO₃, SrSO₄, SrCl₂, SrCl₂·6H₂O, SrBr₂, SrBr₂·6H₂O, SrI₂, FeF₂ and mixtures thereof.

Inventors: LANE, GEORGE A., ROSSOW, HAROLD E.
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1987
Main classification: C09K5
IPC codes: C09K5