NL2023239B1 - Flexible phase change material - Google Patents

Flexible phase change material Download PDF

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Publication number
NL2023239B1
NL2023239B1 NL2023239A NL2023239A NL2023239B1 NL 2023239 B1 NL2023239 B1 NL 2023239B1 NL 2023239 A NL2023239 A NL 2023239A NL 2023239 A NL2023239 A NL 2023239A NL 2023239 B1 NL2023239 B1 NL 2023239B1
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Netherlands
Prior art keywords
composition
magnesium
fatty acid
acid salt
water
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NL2023239A
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Dutch (nl)
Inventor
Ijsbrand Tiesnitsch Johannes
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Tiesnitsch Beheer B V
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Application filed by Tiesnitsch Beheer B V filed Critical Tiesnitsch Beheer B V
Priority to NL2023239A priority Critical patent/NL2023239B1/en
Priority to PCT/NL2020/050343 priority patent/WO2020242309A1/en
Application granted granted Critical
Publication of NL2023239B1 publication Critical patent/NL2023239B1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F7/00—Heating or cooling appliances for medical or therapeutic treatment of the human body
    • A61F7/02—Compresses or poultices for effecting heating or cooling
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F7/00—Heating or cooling appliances for medical or therapeutic treatment of the human body
    • A61F7/02—Compresses or poultices for effecting heating or cooling
    • A61F2007/0203—Cataplasms, poultices or compresses, characterised by their contents; Bags therefor
    • A61F2007/0215—Cataplasms, poultices or compresses, characterised by their contents; Bags therefor containing liquids other than water
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F7/00—Heating or cooling appliances for medical or therapeutic treatment of the human body
    • A61F7/02—Compresses or poultices for effecting heating or cooling
    • A61F2007/0292—Compresses or poultices for effecting heating or cooling using latent heat produced or absorbed during phase change of materials, e.g. of super-cooled solutions

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biomedical Technology (AREA)
  • Vascular Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention relates to a composition comprising 50—99 wt.% of Na2804-10H20 and 0.1—5.0 wt.% of a fatty acid salt that has a water solubility 5 at 25 °C of 75 mg/L or less. Such composition may advantageously be used as a phase change material since the composition (and a pouch comprising the composition) remains flexible during the phase change. This was also the case when subjected to a number of subsequent cycles of heating and cooHng.

Description

FLEXIBLE PHASE CHANGE MATERIAL The invention relates to a phase change material composition, to a container comprising such composition and to cooling garment comprising such container.
Latent heat storage has become increasingly important in recent years. Phase change materials (PCMs) fulfill an important role herein because of their effective way of storing thermal energy. They have the advantages of a high energy storage density and an isothermal energy storage process.
PCMs are advantageously applied in e.g. buildings, industry, spacecraft and apparel. They can be used for space heating and cooling, off-peak energy storage, heat exchanger improvements, cooling or heating a human or animal body, etc.
However, the application of PCMs may become restricted by disadvantages associated with phase changes exhibited by the PCMs. For example, in a PCM that exhibits a solid-liquid phase change, such change is accompanied by a change in mechanical properties such as brittleness/plasticity, hardness, viscosity and surface roughness. This is a disadvantage in applications where flexibility of the PCM is important, and where a user appreciates a nice look and feel of the product comprising the PCM.
This problem manifests in particular with apparel. For example, it is uncomfortable when a flexible garment becomes stiff and crispy once the PCM in its inside has changed from liquid to crystalline. Depending on how the PCM is incorporated in the garment, an undesired increase of the roughness of the garment’s surface may also occur.
Being relatively unhazardous and having a sharp phase change at a temperature of 32.4 °C, the compound Na>SO4 10H:20 finds useful application as a PCM in apparel. Effective application of this compound requires that its ten equivalents of water are maintained. To this end, it is usually packaged in a water-tight container (e.g. a pouch or pocket) to prevent evaporation of the water. The phase change on which the heat storage of Na2S0O::10H20 relies is a liquid- solid phase change, which gives rise to the problems outlined above when it is desired that a flexible pouch of Na2SO, 10H20 is being applied in apparel. The crystals that form upon phase change result in a solid and non-flexible pouch with a rough surface. When force is applied on the pouch, the sharp crystals inside the pouch press against the inner surface of the pouch and may so damage it (e.g. by puncturing).
There are at present however no satisfactory PCMs based on Na2SO4:10Hs0 that maintain their flexibility during the phase change. lt is further important that any modification of the Na2SOa4:10H20 does not have the side-effect that the heat storage capacity of the PCM is decreased and/or that the phase change is spread out over a temperature trajectory.
It is therefore an objective of the present invention to provide a PCM based on Na>SO4-10H20 that maintains its flexibility during phase change. In addition, it is aimed to provide a PCM based on Na2S0O::10H2O wherein no sharp (crystalline) material forms upon phase change that may e.g. damage the enclosing container. Further, it is an objective that phase change occurs at a single temperature, or at least that the temperature trajectory of the phase change is as short as possible.
It has now been found that one or more of these objectives can be reached by using a particular additive to the Na2SOa4:10H20. Accordingly, the present invention relates to a phase change material composition comprising - 50.0-99,9 wt.% of Na2SO4:10H20; and - 0.1-5.0 wt.% of a fatty acid salt that has a water solubility at 25 °C of 75 mg/L or less. A composition of the invention comprises 50.0-99.9 wt.% of NasSO:10Hs0, which is the actual phase change material in the composition. The content of Na2SO4-10H20 is usually in the range of 50.0-99.0 wt.%. It may also be in the range of 70-98 wt.%, in the range of 80-98 wt.% or in the range of 90-98 wt.%. It may also be in the range of 75-95 wt. %.
The higher the content of the Na=SO4:10H20 in the composition, the more effective the composition is in terms of the amount of energy that can be absorbed per kg of the total composition. Therefore, the content of Na2SO4:10H20 is preferably as high as possible. The addition of additives, on the other hand,
reduces the content of Na2SO4 10H20. Nevertheless, additives may be preferred for a number of reasons. The melting point of pure Na2SO4:10Hz0 is 32.4 °C. This point can be influenced by the presence of certain additives. For example, it is known that the presence of NaCl lowers the melting point. In a composition of the invention, a NaCl content of up to 20 wt.% may be present for tuning the melting point. The content of NaCl in a composition with Na2SO4:10H2O may also be 15 wt.% or less, wi.% or less, 8 wt.% or less or 5 wt.% or less. It may also be in range 0.1-15 wt.%, in particular in the range of 0.5-10 wi. %.
10 Also borax (Na2BsOs(OH)4-8 H2O} may be used to alter the melting point of the Na2SO: 10Hs0O. To this end, its content may be up to 10 wt.%, for example in the range of 0.1-8.0 wt.%, in the range of 2.0-6.0 wt.% or in the range of 0.54.0 wt. %.
Another optional additive is sodium carboxymethyl cellulose, which may be present in an amount of up to 10 wt.%. Usually, when present, its content is 5 wt.% or less. lt is for example in the range of 0.5-4.0 wt.%. The function of sodium carboxymethyl cellulose is to prevent separation of water from the composition.
In a composition of the invention, water may be present in addition to the water provided by the Na>SO4-10H20. This is useful for the following reason. Effective application of Na=SO4-10H20 as a phase change material requires that its ten equivalents of water are maintained. To this end, the Na2SO::10H20 is usually packaged in a water-tight container (such as a flexible pouch or sachet) to prevent evaporation of the water. A small amount of excess water may be present in such container to accommodate for an eventual escape of part of the water from the container. Such excess barely influences the heat storage capacity and the phase change temperature of the composition, while any shortage of water (i.e. when the total water content of the composition is below the ten equivalents) would have a strongly negative influence on the action of the composition in terms of the heat storage capacity and the phase change temperature. When an excess of water is included in the product upon its manufacturing, then this improves the long term stability of the product.
The content of any additional water (i.e. water in excess to the ten water equivalents in Na2SO4:10H20) in a composition of the invention may be up to
4.0 wt.% or up to 6.0 wt.%, for example in the range of 0.5-5.0 wt.% or in the range of 1.0-3.0 wt.%.
Alternatively, the content of the additional water may be in the range of
0.10-10.0 mol% of the amount of Na2SO4: 10H20 (i.e. the molar ratio of the additional water to the Na2S04*10H20 is in the range of 0.10 : 1.0 to 10.0 : 1.0). The content of the additional water may in particular be in the range of 0.20 : 1.0 to
6.0 : 1.0, more in particular in the range of 0.40 : 1.0 to 4.0 : 1.0.
A composition of the invention comprises a fatty acid salt, i.e. a salt of a fatty acid. By a fatty acid is meant a carboxylic acid with a long aliphatic chain (e.g. 6-30 carbon atoms), which is either saturated or unsaturated. The fatty acid salt in a composition of the invention may in principle be any fatty acid salt as long as it has a water solubility at 25 °C of 75 mg/L or less. Preferably, the fatty acid salt is a saturated fatty acid salt, i.e. it comprises a saturated alkyl chain.
Usually, the fatty acid salt comprises 10-30 carbon atoms, in particular it comprises a chain of 10-30 carbon atoms (i.e. it is a salt of a C10-C30 fatty acid). Such chain may be branched, for example with one or more methyl groups. Usually, however, such chain is linear (i.e. unbranched).
Preferably, the fatty acid salt comprises a fatty acid carboxylate selected from the group of caprylate, caprate, laurate, myristate, palmitate, stearate, arachidate, behenate and lignocerate.
A fatty acid salt in a composition of the invention is usually the salt of a metal (Le. it is a metal carboxylate). The metal is then usually a divalent metal, in particular one selected from the group of magnesium, calcium, manganese, zinc, tin and lead. Accordingly, such divalent metal carboxylate is typically of the formula M(C,H21COO)2z, wherein M is the divalent metal. In the formula, x is usually in the range of 7-25, in particular in the range of 9-13.
Preferably, the fatty acid salt in a mixture of the invention is selected from the group of magnesium caprylate, magnesium caprate, magnesium laurate, magnesium myristate, magnesium palmitate, magnesium stearate, magnesium arachidate, magnesium behenate and magnesium lignocerate.
A composition of the invention may comprise more than one fatty acid salt, for example two, three or four. In particular, they are independently from one another selected from the group of magnesium caprylate, magnesium caprate, magnesium laurate, magnesium myristate, magnesium palmitate, magnesium 5 stearate, magnesium arachidate, magnesium behenate and magnesium lignocerate.
The solubility of the fatty acid salt in water at 25 °C is 75 mg/L or less. Usually, it is 60 mg/L or less. It may also be 50 mg/L or less, 40 mg/L or less or 30 mg/L or less. lt is typically in the range of 1-50 mg/L. It may also be in the range of 5-40 mg/L.
The invention further relates to a method for preparing a composition as described above, comprising the mixing of Na2SO4:10H20 with a fatty acid salt, in particular a fatty acid salt such as magnesium stearate.
When the composition of the invention is applied as a phase change material, the composition is usually present in a container. For application in apparel, a flexible container is preferred, e.g. a pouch or a pocket. Such container is preferably impermeable to water to prevent the escape of water that is required for the phase change of the composition. Accordingly, the invention further relates to a container comprising a composition as described above, wherein the container is impermeable to water.
A composition of the invention (for example when present in a pouch) remained flexible when subjected to a number of subsequent cycles of heating and cooling. The thermal characteristics of the composition in the container were measured by monitoring the temperature during the cycles, which confirmed that a phase change occurred in each cycle.
A composition of the invention finds advantageous application in apparel. Accordingly, the invention further relates to a garment (such as a jacket, coat, trousers or headgear), comprising a composition as described above, in particular a container comprising such composition.
The invention further relates to a method for cooling a body or an item, comprising the use of a container as described above, or a garment such as a jacket, trousers or headgear comprising such container.
EXAMPLE The following composition was prepared and put into a pouch of aluminum foil that was sealed afterwards to yield a water-tight container: - 84.8 wt.% of NasSO4: 10H20 - 1.6 wi.% of sodium carboxymethyl cellulose - 1.6 % wt.% of borax - 2.1 wt.% of water - 8.3 wt.% of sodium chloride - 1.6 % wt.% of magnesium stearate The pouch was warmed in a water bath of 50 °C and left at that temperature during 15 minutes.
The pouch was then flexible and could easily be deformed manually.
Thereafter, it was allowed to cool down to 5 °C in a refrigerator and left at that temperature during 15 minutes.
The pouch was stil! flexible and no solid particles could be felt in the pouch.
The only difference with the warm pouch was the ductility: the warm pouch was easier to deform than the cold pouch.
Such warming and cooling sequence is regarded as one heating cycle.
The pouch was subjected to ten heating cycles and weighed before and after each cycle. lt appeared that the weight of the pouch had not changed over time, and that the pouch had the same flexibility after each cycle.
Monitoring of the temperature during the cycles demonstrated that a phase change occurred at 24 °C.

Claims (15)

ConclusiesConclusions 1. Samenstelling omvattende - 50-99 gew.% Na2S0:4:10H20; en - 0.1-5.0 gew.% van een vetzuurzout met een wateroplosbaarheid bij 25 °C van 75 mg/L of minder.A composition comprising - 50-99 wt.% Na 2 SO: 4: 10H 2 O; and - 0.1-5.0% by weight of a fatty acid salt with a water solubility at 25 ° C of 75 mg / L or less. 2. Samenstelling volgens conclusie 1, waarin het vetzuurzout een zout is van een C10-C30 vetzuur met een lineaire alkylketen of een vertakte alkylketen.The composition of claim 1, wherein the fatty acid salt is a salt of a C10-C30 fatty acid having a linear alkyl chain or a branched alkyl chain. 3. Samenstelling volgens conclusie 1 of 2, waarin het vetzuurzout een verzadigde alkylketen heeft.The composition of claim 1 or 2, wherein the fatty acid salt has a saturated alkyl chain. 4. Samenstelling volgens conclusie 3, waarin het vetzuurzout een carboxylaat omvat gekozen uit de groep van caprylaat, capraat, lauraat, myristaat, palmitaat, stearaat, arachidaat, behenaat en lignoceraat.The composition of claim 3, wherein the fatty acid salt comprises a carboxylate selected from the group consisting of caprylate, caprate, laurate, myristate, palmitate, stearate, arachidate, behenate and lignocerate. 5. Samenstelling volgens een der conclusies 1-4, waarin het vetzuurzout een tweewaardig metaaldicarboxylaat is met de formule M(CxH2x1COO)2.A composition according to any one of claims 1-4, wherein the fatty acid salt is a divalent metal dicarboxylate of formula M (CxH2x1COO) 2. 6. Samenstelling volgens conclusie 5, waarin het tweewaardig metaal gekozen is uit de groep van magnesium, calcium, mangaan, zink, tin en Jood.The composition of claim 5, wherein the divalent metal is selected from the group of magnesium, calcium, manganese, zinc, tin and iodine. 7. Samenstelling volgens conclusie 1, waarin het vetzuurzout gekozen is uit de groep van magnesiumcaprylaat, magnesiumcapraat, magnesiumlauraat, magnesiummyristaat, magnesiumpalmitaat, magnesiumstearaat, magnesiumarachidaat, magnesiumbehenaat en magnesiumlignoceraat.The composition of claim 1, wherein the fatty acid salt is selected from the group of magnesium caprylate, magnesium caprate, magnesium laurate, magnesium myristate, magnesium palmitate, magnesium stearate, magnesium arachidate, magnesium behenate and magnesium lignocerate. 8. Samenstelling volgens een der conclusies 1-7, waarin het vetzuurzout een wateroplosbaarheid heeft bij 25 °C in het bereik van 1-50 mg/L.Composition according to any one of claims 1-7, wherein the fatty acid salt has a water solubility at 25 ° C in the range of 1-50 mg / L. 9. Samenstelling volgens een der conclusies 1-8, verder omvattende 0.5-4.0 gew.% borax.A composition according to any of claims 1-8, further comprising 0.5-4.0 wt% borax. 10. Samenstelling volgens een der conclusies 1-9, verder omvattende 0.54.0 gew.% natriumcarboxymethylcellulose.A composition according to any one of claims 1-9, further comprising 0.54.0 wt% sodium carboxymethyl cellulose. 11.Samenstelling volgens een der conclusies 1-10, verder omvattende 0.15-15.0 gew.% NaCl.A composition according to any of claims 1-10, further comprising 0.15-15.0 wt% NaCl. 12.Samenstelling volgens een der conclusies 1-11, verder omvattende 0.1-5.0 gew.% water.A composition according to any of claims 1-11, further comprising 0.1-5.0% by weight water. 13. Houder omvattende een samenstelling volgens een der conclusies 1-12, waarin de houder impermeabel is voor water.A container comprising a composition according to any of claims 1-12, wherein the container is impermeable to water. 14. Koelvest omvattende een samenstelling volgens een der conclusies 1-12, in het bijzonder een houder volgens conclusie 13.Cooling vest comprising a composition according to any one of claims 1-12, in particular a container according to claim 13. 15. Werkwijze voor het koelen van een lichaam of een voorwerp, omvattende het gebruik van een houder volgens conclusie 13 of een koelvest volgens conclusie 14.A method of cooling a body or an object, comprising the use of a container according to claim 13 or a cooling vest according to claim 14.
NL2023239A 2019-05-29 2019-05-29 Flexible phase change material NL2023239B1 (en)

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NL2023239A NL2023239B1 (en) 2019-05-29 2019-05-29 Flexible phase change material
PCT/NL2020/050343 WO2020242309A1 (en) 2019-05-29 2020-05-28 Flexible phase change material

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5785885A (en) * 1995-07-12 1998-07-28 Mitsubishi Chemical Corporation Heat storage material composition
US20080168595A1 (en) * 2004-07-02 2008-07-17 Createc Consulting, Llc Cooling Garment Having Phase Change Material In Its Extremity Portions
US7943056B2 (en) * 2009-04-22 2011-05-17 Zhao Joe R H Temperature control materials (TCM)

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5785885A (en) * 1995-07-12 1998-07-28 Mitsubishi Chemical Corporation Heat storage material composition
US20080168595A1 (en) * 2004-07-02 2008-07-17 Createc Consulting, Llc Cooling Garment Having Phase Change Material In Its Extremity Portions
US7943056B2 (en) * 2009-04-22 2011-05-17 Zhao Joe R H Temperature control materials (TCM)

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