WO2021039599A1 - 潜熱蓄熱材用マイクロカプセル及びその製造方法、並びに、潜熱蓄熱材用マイクロカプセルを含む粉末、及び当該粉末を含む蓄熱装置 - Google Patents

潜熱蓄熱材用マイクロカプセル及びその製造方法、並びに、潜熱蓄熱材用マイクロカプセルを含む粉末、及び当該粉末を含む蓄熱装置 Download PDF

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WO2021039599A1
WO2021039599A1 PCT/JP2020/031517 JP2020031517W WO2021039599A1 WO 2021039599 A1 WO2021039599 A1 WO 2021039599A1 JP 2020031517 W JP2020031517 W JP 2020031517W WO 2021039599 A1 WO2021039599 A1 WO 2021039599A1
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Prior art keywords
heat storage
latent heat
microcapsule
microcapsules
storage material
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PCT/JP2020/031517
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English (en)
French (fr)
Japanese (ja)
Inventor
貴宏 能村
貴大 川口
浩紀 坂井
俊介 長
康平 樫山
佐藤　賢次
和之 味谷
澁谷　義孝
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Hokkaido University NUC
JX Nippon Mining and Metals Corp
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Hokkaido University NUC
JX Nippon Mining and Metals Corp
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Priority to EP20856336.1A priority Critical patent/EP4019605B1/en
Priority to JP2021542820A priority patent/JP7471663B2/ja
Priority to US17/636,349 priority patent/US12617991B2/en
Publication of WO2021039599A1 publication Critical patent/WO2021039599A1/ja
Anticipated expiration legal-status Critical
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/09—Mixtures of metallic powders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the present invention relates to microcapsules for latent heat storage material and a method for producing the same, powder containing microcapsules for latent heat storage material, and a heat storage device containing the powder.
  • Examples of technologies for accumulating heat include sensible heat storage and latent heat storage.
  • the sensible heat storage utilizes the temperature change of the heat storage body.
  • the latent heat storage utilizes, for example, the phase change of the heat storage body from the solid phase to the liquid phase.
  • Patent Document 1 discloses a latent heat storage body, wherein the latent heat storage body is composed of core particles of an Al—Si alloy and a shell of an Al oxide film covering the core particles. With respect to the shell, Patent Document 1 discloses that the core particles are subjected to a chemical conversion film treatment, further a thermal oxidation treatment, and thereby an oxide film can be formed.
  • the core particles of the latent heat storage body are an alloy of at least one alloy component A selected from the following group A and at least one alloy component B selected from the following group B (AB). It is disclosed that it is an alloy).
  • Group A Ca, Si, Bi, Mg, Sb, In, Sn, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Ag, Au, Pb
  • Group B Al, Cr, Mn, Si, Mg, Co, Ni
  • Patent Document 2 discloses that the following relationship is satisfied.
  • Non-Patent Document 1 discloses the following three types of alloys. Zn 84 Al 8.7 Mg 7.3 , Zn 88.7 Al 11.3 , Zn 92.2 Mg 7.8 (Each number represents at.%) Then, Non-Patent Document 1 discloses that the possibility that these alloys can be used as a phase change material for latent heat storage has been evaluated. Furthermore, according to this document, a melting point of 344 ° C., respectively, 382 ° C., was 371 ° C., respectively heat of fusion 132Jg -1, 118Jg -1, it was 106Jg -1 it is described.
  • the present inventor considered using the above-mentioned core-shell type latent heat storage body for temperature control of automobile exhaust.
  • the temperature range of automobile exhaust is wide, for example, about 200 ° C. during idling and about 800 ° C. during full-load operation.
  • the exhaust system of an automobile is equipped with an exhaust purification catalyst.
  • the exhaust temperature is too high, it may cause deterioration and / or deterioration of the performance of the exhaust purification catalyst. Therefore, for the purpose of suppressing an excessive rise in the exhaust temperature, it is conceivable to install a latent heat storage body in the exhaust system of the automobile to exchange heat.
  • the exhaust temperature is too low, the performance of the exhaust purification catalyst will not be fully exhibited. From the above viewpoint, there is a possibility that excessive fluctuation of the exhaust temperature of the automobile can be suppressed by using a latent heat storage body having an appropriate operating temperature of about 300 to 550 ° C. and an excellent latent heat amount.
  • an object of the present invention is a latent heat storage body having a melting point of about 300 to 550 ° C. and less likely to leak phase change material. (For example, powder, heat storage device, etc.) to which the above is applied. Further, in another embodiment, an object of the present invention is to provide a method for producing such a latent heat storage body.
  • microcapsules containing a combination of Al and Zn have a suitable melting point and are advantageous in preventing leakage of phase change materials.
  • the present invention completed based on this finding is exemplified below.
  • the shell of the microcapsule has an oxide film containing Zn and O and an oxide film containing Al and O adjacent to the inside of the oxide film.
  • XRD X-ray diffractometer
  • RIR Reference Integrity Ratio
  • (Invention 2) The microcapsule for a latent heat storage material according to Invention 1, wherein the total mass of Al and Zn in the microcapsule is 100 parts by mass, Zn is 60 to 95 parts by mass, and Al is 5 to 40 parts by mass.
  • (Invention 3) Microcapsules for latent heat storage material according to Invention 1 or 2, wherein the average thickness of the oxide film containing Al and O is 100 to 1000 nm.
  • (Invention 4) The microcapsule for a latent heat storage material according to any one of Inventions 1 to 3, wherein the oxide film containing Zn and O has an average thickness of 100 to 1000 nm.
  • invention 5 The microcapsule for a latent heat storage material according to any one of Inventions 1 to 4, wherein the microcapsule has a melting point of 300 to 550 ° C.
  • invention 6 The microcapsule for a latent heat storage material according to any one of Inventions 1 to 5, wherein the latent heat amount of the microcapsule is 0.3 to 1.2 GJm -3.
  • invention 7 The microcapsule for a latent heat storage material according to any one of Inventions 1 to 6, wherein the volume expansion coefficient of the core when the microcapsule is melted is 5 to 9%.
  • Invention 8) A powder containing a plurality of microcapsules for a latent heat storage material according to any one of the inventions 1 to 7.
  • invention 9 The powder of Invention 8 having an average particle size of 20 to 80 ⁇ m.
  • invention 10 The powder according to Invention 9, which has an average particle size of 20 to 38 ⁇ m.
  • invention 11 A heat storage device comprising the powder according to any one of the inventions 8 to 10.
  • invention 12 The heat storage device according to invention 11, which is installed on the outer periphery of an exhaust passage of an automobile.
  • invention 13 The Zn—Al alloy particles are subjected to a boehmite treatment and an oxidation treatment in order, and the oxidation treatment raises the temperature to a holding temperature at a temperature rising rate of 10 ° C./min or more, and the holding temperature and oxygen-containing atmosphere.
  • invention 14 The production method according to Invention 13, wherein the holding temperature is 700 ° C. to 910 ° C.
  • Invention 15 The production method according to the invention 13 or 14, wherein the rate of temperature rise to the holding temperature is 30 ° C./min or more.
  • the melting point can be easily adjusted in the range of about 300 to 550 ° C., and this melting point adjustment changes the content ratio of Al and Zn. It can be realized by. Moreover, since the phase change material (Al and Zn) inside the microcapsule is protected by the double oxide film, leakage of the phase change material is unlikely to occur. Furthermore, the mass ratio of ZnAl 2 O 4 is 4% or less, in other words, the oxide film is homogeneous and there are few surface defects. As a result, leakage of the phase change material is unlikely to occur. Therefore, the microcapsules for the latent heat storage material are expected to be used in a heat storage device. For example, it is expected that the heat storage device is installed in the exhaust system of an automobile to stabilize the exhaust temperature.
  • the microcapsules for latent heat storage material have a melting point of 300 to 550 ° C.
  • the latent heat storage material microcapsule can store not only the exhaust heat of the automobile but also various unused heat generated in the temperature range.
  • the microcapsules for latent heat storage material according to the preferred embodiment of the present invention have a shell with few surface defects. As a result, the oxide film constituting the shell is less likely to be damaged during repeated use, and therefore durability is expected to be improved.
  • the microcapsules for latent heat storage material there are few surface defects even if the shell is thin. Since the shell itself does not contribute to the latent heat storage effect, the thinner the shell, the relatively larger the volume of the core. Therefore, the amount of latent heat per unit volume of the microcapsules for latent heat storage material can be increased.
  • the volume expansion coefficient at the time of phase change from solid phase to liquid phase is small.
  • the oxide film constituting the shell is less likely to be damaged during repeated use, and therefore durability is expected to be improved.
  • 6 is an SEM image of a cross section of a microcapsule for a heat storage latent heat material according to Example 3.
  • 6 is an SEM image of the surface of microcapsules for heat storage latent heat material according to Examples 1 to 2, 4 and Comparative Example 1.
  • the latent heat storage material microcapsules according to the present invention contain Al and Zn.
  • the melting point of Al is 660.3 ° C, and the melting point of Zn is 419.5 ° C. Therefore, the melting point of the microcapsules can be lowered as the ratio of Zn to be combined with Al is increased. Further, even if the melting point is lowered, on the other hand, the microcapsules containing Al and Zn have a feature that the latent heat amount per volume at the time of melting is large.
  • the Zn content is 60 to 95 parts by mass and the Al content is 5 to 40 parts by mass (here, the microcapsules).
  • the total mass of Al and Zn in the mixture is 100 parts by mass).
  • the Zn content is 60 to 90 parts by mass and the Al content is 10 to 40 parts by mass (here, in the microcapsules).
  • the total mass of Al and Zn is 100 parts by mass).
  • the Zn content is 70 to 80 parts by mass and the Al content is 20 to 30 parts by mass (here, the microcapsules).
  • the total mass of Al and Zn in the mixture is 100 parts by mass).
  • each mass part of Al and Zn in the microcapsule is the total mass of Al atom and Zn atom contained in both the metal core and the shell described later. It means a value based on, and each mass part of Al and Zn substantially corresponds to the mass ratio of Al atom and Zn atom in the raw material powder.
  • the metal core may contain one or more third elements (for example, Sn, Bi, Cu, In, Ni, etc.).
  • the microcapsules preferably contain Zn and Al in a total amount of 70% by mass or more, and 90% by mass or more, based on the total mass of the microcapsules. Is more preferable, and it is even more preferable that the content is 95% by mass or more.
  • the microcapsules may be composed only of Zn and Al, excluding oxygen (O) and unavoidable impurities.
  • the latent heat storage material microcapsule according to the present invention has a metal core containing Zn and Al, and a shell covering the metal core.
  • the metal core contains Zn and Al.
  • Zn and Al in the metal core can exist in the form of a Zn—Al alloy (eg, a binary alloy of Zn—Al).
  • the metal core can contain Zn and Al in a total amount of 70% by mass or more, preferably 90% by mass or more, and preferably 95% by mass or more. It is more preferable to contain it.
  • the metal core may be composed of only Zn and Al, excluding unavoidable impurities.
  • the shell has at least two membranes (eg, a double membrane).
  • These films include an oxide film containing Zn and O (for example, an oxide film containing ZnO, an oxide film containing Al, Zn and O, etc.) and an oxide film containing Al and O adjacent to the inside of the oxide film. (For example, an oxide film containing Al 2 O 3 , an oxide film containing Al and O and not containing Zn, etc.) may be used.
  • AES Alger electron spectroscopy
  • an oxide film containing Zn and O and an oxide film containing Al and O adjacent to the inside of the oxide film are detected.
  • the metal core is doubly protected by the shell having a double membrane. Therefore, leakage of phase change substances such as Zn and Al in the metal core is prevented.
  • the mass ratio of ZnAl 2 O 4 is small.
  • the mass ratio of ZnAl 2 O 4 is obtained by analyzing it with an XRD (X-ray diffractometer) and quantitatively analyzing the result using the RIR (Reference Integrity Ratio) method. Specifically, in microcapsules in which the total mass of each crystal phase present in the microcapsules is 100% and the mass ratio of ZnAl 2 O 4 is 4% or less when quantitative analysis is performed using the RIR method. It is preferable to have. Most preferably, the mass ratio of ZnAl 2 O 4 is as close to 0% as possible.
  • the mass ratio of ZnAl 2 O 4 there is a deep relationship between the mass ratio of ZnAl 2 O 4 and the amount of oxide film damage (or the amount of surface defects). More specifically, when the mass ratio of ZnAl 2 O 4 is small, the oxide film tends to be less damaged. If the oxide film is less damaged, it is expected that the durability during repeated use will be improved.
  • the RIR (Reference Integrity Ratio) method is a method of obtaining the mass ratio of the crystal phase from the ratio of the RIR value and the value of the strongest peak intensity of each crystal phase obtained from the XRD (X-ray diffractometer) result. is there. When the microcapsules contain crystal phases A, B, C, ..., The mass ratio X A of the crystal phase A is calculated by the following formula.
  • X A I A k A / (I A k A + I B k B + I C k C + 8)
  • I indicates the intensity of the strongest peak of X-rays of each crystal phase
  • k indicates the RIR value of each crystal phase.
  • the RIR value the value described in the powder diffraction file (PDF) database of the International Center for Diffraction Data can be used.
  • the average thickness of the oxide film containing Al and O can be, for example, 100 to 1000 nm, more preferably 200 to 500 nm, and typically 200 to 300 nm.
  • the average thickness of the oxide film containing Zn and O can be, for example, 100 to 1000 nm, and typically 500 to 600 nm.
  • the average thickness constituting the shell (specifically, the average thickness of the oxide film containing Al and O and the average thickness of the oxide film containing Zn and O) is measured by the following methods, respectively. ..
  • the cross section of the microcapsules is observed by SEM, the thickness of the oxide film is measured at three or more points for one microcapsule, and the average value of these measured values is calculated.
  • the same operation is performed for 3 or more microcapsules, and the average value of the oxide film thickness of each microcapsule is calculated.
  • the average value of the entire oxide film of these three or more microcapsules is calculated, and this value is adopted as the average thickness.
  • the type of oxide film can be specified by AES (Auger electron spectroscopy) analysis.
  • the microcapsules for latent heat storage material according to the present invention have such an extremely thin shell on the order of nanometers, and on the other hand, have the property of having few surface defects.
  • Such a microcapsule for a latent heat storage material can be a microcapsule for a latent heat storage material having an excellent latent heat amount and durability.
  • the melting point of the latent heat storage material microcapsules according to the present invention is 300 to 550 ° C.
  • the appropriate temperature of the exhaust gas purification catalyst of an automobile is about 400 ° C. Therefore, the melting point of the microcapsules is preferably 350 to 450 ° C. for the purpose of keeping the exhaust temperature of the automobile near the temperature.
  • the melting point of the microcapsules refers to the melting start temperature when differential scanning calorimetry (DSC) is performed.
  • the latent heat amount of the latent heat storage material microcapsules according to the present invention is 0.3 to 1.2 GJm -3 , and in a preferred embodiment, the latent heat amount is 0.5 to 1.2 GJm -3 . In a more preferred embodiment, the latent heat amount is 0.6 to 1.0 GJm -3 .
  • the latent heat amount of the microcapsules refers to the heat flow change accompanying the solid-liquid phase change when the differential scanning calorimetry (DSC) is performed.
  • the core volume expansion coefficient at the time of melting of the microcapsules for latent heat storage material according to the present invention is 5 to 9%, preferably 6 to 9%, and more preferably 7 to 9%. Since the volume expansion coefficient when the metal core constituting the microcapsule changes from a solid phase to a liquid phase is small, the oxide film constituting the shell is less likely to be damaged during repeated use. Therefore, it is expected that the durability will be improved.
  • the volume expansion coefficient at the time of melting of the microcapsules for heat storage latent heat material means the prediction result of software (Factsage), not the measured value.
  • the latent heat storage material microcapsules according to the present invention are provided in the form of a powder containing a plurality of latent heat storage material microcapsules.
  • the powder has an average particle size of 20-80 ⁇ m.
  • the average particle size of the powder is preferably 20 to 50 ⁇ m, more preferably 20 to 38 ⁇ m, from the viewpoint of forming a shell with few surface defects.
  • the average particle size described in the present specification is determined by a laser diffraction type particle size distribution meter (eg, HORIBA LA-920). ) Is the value when measured. More specifically, the volume distribution of the particle group is measured by a laser diffraction type particle size distribution meter, and the value of the cumulative 50% by volume diameter (D50) is regarded as the average particle size.
  • a laser diffraction type particle size distribution meter eg, HORIBA LA-920.
  • a heat storage device including a powder containing microcapsules for a latent heat storage material.
  • the melting point can be easily adjusted in the range of about 300 to 550 ° C., which can be realized by changing the Zn content.
  • the latent heat amount is large in the latent heat storage material microcapsules according to the embodiment of the present invention. Therefore, the latent heat storage material microcapsule can be suitably used for, for example, a latent heat storage device, and the latent heat storage device is preferably installed in the exhaust system of an automobile for the purpose of adjusting the exhaust temperature. You may.
  • a heat storage device including a powder containing microcapsules for a latent heat storage material can be installed on the outer periphery of an exhaust passage of an automobile. Further, the heat storage device can store not only the exhaust heat of the automobile but also various unused heat generated in the above-mentioned temperature range.
  • Zn—Al binary alloy particles are prepared as raw materials.
  • the content ratio of Al and Zn in the Zn—Al binary alloy particles can be appropriately adjusted according to the required characteristics.
  • Zn—Al binary alloy particles are provided in powder form.
  • the raw material powder has an average particle size of 20-80 ⁇ m. From the viewpoint of forming a shell with few surface defects, the average particle size of the powder is preferably 20 to 38 ⁇ m.
  • the raw material Zn—Al binary alloy particles are subjected to boehmite treatment to form a film.
  • boehmite treatment a precursor of an oxide film constituting the shell can be formed.
  • the raw material Zn—Al alloy particles are placed in high-temperature water to form a film on the alloy surface. The higher the purity of the water, the better. Specifically, distilled water, pure water, deionized water and the like can be used.
  • the Zn—Al alloy particles can be boehmite-treated under the conditions of a water temperature of 80 to 100 ° C. and 3 to 12 hours.
  • the boehmite treatment is preferably carried out with stirring. After the boehmite treatment, the liquid temperature may be lowered to room temperature by allowing to cool. Then, the particles after the boehmite treatment are collected, suction-filtered, and dried. The reason for drying the particles after the boehmite treatment is to remove excess water on the particle surface.
  • the Boehmite-treated Zn—Al binary alloy particles are oxidized. More specifically, the high temperature treatment is carried out in an oxygen-containing atmosphere.
  • the oxidation treatment can be carried out, for example, by raising the temperature to a holding temperature under the condition of a temperature rising rate of 10 ° C./min or more, and holding the temperature under the conditions of the holding temperature and an oxygen-containing atmosphere.
  • the oxygen-containing atmosphere may be an atmosphere containing oxygen, for example, an oxygen atmosphere in which oxygen having a purity of 99.5% is supplied at a flow rate of 200 mL / min, or an air atmosphere.
  • the holding temperature of the oxidation treatment is preferably 700 ° C. to 910 ° C., more preferably 750 ° C. to 850 ° C., and even more preferably 780 ° C. to 830 ° C. This promotes the formation of a reoxidized film. Therefore, even if a crack (crack develops and becomes a surface defect) occurs in the shell, the surface defect of the shell can be reduced by forming a reoxidized film.
  • the rate of temperature rise when the temperature is raised to the holding temperature also significantly affects the characteristics of the microcapsules for the latent heat storage material.
  • the difference between the melting point of Al—Zn and the oxidation temperature of Al is relatively large. Therefore, by increasing the heating rate, the reoxidized film is formed in the shell at an early stage. This makes it possible to reduce surface defects.
  • the rate of temperature rise to the holding temperature is preferably 10 ° C./min or more, more preferably 30 ° C./min or more, and even more preferably 50 ° C./min or more.
  • the upper limit of the heating rate is not particularly limited, but the heating rate up to the holding temperature can be 200 ° C./min or less, 100 ° C./min or less, and 80 ° C./min or less. You can also.
  • the temperature lowering rate is not particularly limited and may be any rate.
  • the temperature lowering rate may be ⁇ 40 ° C./min to ⁇ 60 ° C./min.
  • the time for maintaining at the holding temperature can be, for example, 30 minutes to 5 hours, preferably 1 hour to 5 hours.
  • the longer the holding temperature is maintained the thicker the oxide film of the shell tends to be.
  • the double oxide film is likely to be damaged. Therefore, when the oxidation treatment is performed at 850 ° C. or higher, the time is preferably 2 hours or less, and when the oxidation treatment is performed at 900 ° C. or higher, the time is preferably 1.5 hours or less.
  • Examples 1 to 2 and 4 and Comparative Examples 1 to 2> (1. Preparation of powder containing microcapsules for heat storage latent heat material) Powders containing microcapsules for heat storage latent heat materials of Examples 1 to 2 and 4 and Comparative Examples 1 and 2 were prepared by the following procedure.
  • a Zn—Al binary alloy (Zn-30% by mass Al) powder having a Zn mass ratio of 70% and an Al mass ratio of 30% was prepared by a rotary disk atomizing method.
  • the average particle size of the powder was measured using a laser diffraction type particle size distribution meter (manufactured by HORIBA, model LA-920) and found to be 20 to 38 ⁇ m.
  • an oxide film containing Zn and O and an oxide film containing Al and O adjacent to the inside of the oxide film were detected. It was.
  • an oxide film (AlOOH film) containing Al and O was detected in the shell on the surface layer of the particles according to Comparative Example 2.
  • the AlOOH film is a film formed in a solid phase state in which the core is not volume-expanded. Therefore, at the moment when the temperature was raised and the core portion was melted, the film of the particles according to Comparative Example 2 was torn. Further, Al and Zn were detected in the metal core of the particles according to any of the examples, but O was not detected.
  • Example 1 As compared with Example 2 in which the temperature rising rate was 10 ° C./min and the holding temperature was 800 ° C., the cracks were reoxidized in the particles of Example 1 in which the heating rate was 50 ° C./min and the holding temperature was 800 ° C. It was better closed by the coating, and almost no particles with residual cracks could be confirmed. It is considered that the reason why the particles of Example 1 had few cracks was that the rate of temperature rise was high and that the reoxidation reaction proceeded rapidly.
  • the mass ratio of ZnAl 2 O 4 was 4% or less in the particles according to Examples 1 to 2 and 4.
  • ZnAl 2 O 4 was not detected because the sample was not subjected to the oxidation treatment.
  • the melting point of the microcapsules for the heat storage latent heat material was determined by differential scanning calorimetry (DSC) (manufactured by METTLER TORDO, model DSC823e). The results are shown in Table 2.
  • DSC differential scanning calorimetry
  • the melting point of the microcapsules for the heat storage latent heat material was about 379 ° C. It is considered that this is because the alloy inside was exposed and strongly oxidized due to the breakage of the oxide film, and the composition of the inner core fluctuated greatly.
  • the latent heat amount of the microcapsules for the heat storage latent heat material was determined by differential scanning calorimetry (DSC) (manufactured by METTLER TOLEDO, model DSC823e). The results are shown in Table 2.
  • Example 3> (1. Preparation of powder containing microcapsules for heat storage latent heat material) Other than using a Zn—Al binary alloy (Zn-40% by mass Al) powder (average particle size: 20 to 38 ⁇ m) having a Zn mass ratio of 60% and an Al mass ratio of 40% as the raw material powder. , The raw material powder was subjected to boehmite treatment and oxidation treatment under the same conditions as in Example 1.
  • Example 5> (1. Preparation of powder containing microcapsules for heat storage latent heat material) Other than using a Zn—Al binary alloy (Zn-10 mass% Al) powder (average particle size: 20 to 38 ⁇ m) having a Zn mass ratio of 90% and an Al mass ratio of 10% as the raw material powder. , The raw material powder was subjected to boehmite treatment and oxidation treatment under the same conditions as in Example 1.

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PCT/JP2020/031517 2019-08-23 2020-08-20 潜熱蓄熱材用マイクロカプセル及びその製造方法、並びに、潜熱蓄熱材用マイクロカプセルを含む粉末、及び当該粉末を含む蓄熱装置 Ceased WO2021039599A1 (ja)

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Application Number Priority Date Filing Date Title
EP20856336.1A EP4019605B1 (en) 2019-08-23 2020-08-20 Microcapsule for latent heat storage materials, method for producing same, powder containing microcapsules for latent heat storage materials, and heat storage device comprising said powder
JP2021542820A JP7471663B2 (ja) 2019-08-23 2020-08-20 潜熱蓄熱材用マイクロカプセル及びその製造方法、並びに、潜熱蓄熱材用マイクロカプセルを含む粉末、及び当該粉末を含む蓄熱装置
US17/636,349 US12617991B2 (en) 2019-08-23 2020-08-20 Microcapsule for latent heat storage materials, method for producing same, powder containing microcapsules for latent heat storage materials, and heat storage device comprising said powder

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JP2019-153237 2019-08-23
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WO2025203526A1 (ja) * 2024-03-28 2025-10-02 日産自動車株式会社 蓄熱材及びその製造方法

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