WO1994012587A1 - Materiau accumulateur de chaleur, et procede et appareil de mise en ×uvre de ce materiau - Google Patents

Materiau accumulateur de chaleur, et procede et appareil de mise en ×uvre de ce materiau Download PDF

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Publication number
WO1994012587A1
WO1994012587A1 PCT/CA1992/000521 CA9200521W WO9412587A1 WO 1994012587 A1 WO1994012587 A1 WO 1994012587A1 CA 9200521 W CA9200521 W CA 9200521W WO 9412587 A1 WO9412587 A1 WO 9412587A1
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WO
WIPO (PCT)
Prior art keywords
heat
cacl
temperature
srcl
accumulating material
Prior art date
Application number
PCT/CA1992/000521
Other languages
English (en)
Inventor
Emanuil A. Levitsky
Mikhail M. Tokarev
Albert V. Fedotov
Original Assignee
Harot Technology Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harot Technology Inc. filed Critical Harot Technology Inc.
Priority to AU29394/92A priority Critical patent/AU2939492A/en
Priority to PCT/CA1992/000521 priority patent/WO1994012587A1/fr
Publication of WO1994012587A1 publication Critical patent/WO1994012587A1/fr

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Classifications

    • 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

Definitions

  • the present invention relates to compositions of heat-accumulating material, and to methods of and equipment for the use thereof. More particularly, the invention relates to such compositions, methods and equipment intended for controlling temperature and moisture exchange between the surface of the human body and the environment. In the preferred form, the invention optimizes heat and moisture exchange while maintaining comfortable conditions for the body in uncomfortable environmental conditions and during hard work.
  • Anatomical and physiological features of the human body require the optimization of heat conditions thereof, especially of the feet.
  • extreme climate conditions low temperature and high moisture content
  • overcooling of the feet resulting in a decrease of a person's fitness to work and an increase of cases of catarrhal diseases.
  • a main problem complicating the optimization of heat conditions for the feet is moisture evolution which runs to 1 gram per hour during rest and up to 2 grams per hour during hard work.
  • the enclosed nature of foot-wear makes for a high equilibrium moisture content (usually more than 60% relative humidity).
  • moisture condensation occurs, and the thermal conductivity of the sole and other parts of a shoe or boot considerably increases, and, therefore, loss of heat from the foot also increases.
  • Solving both problems of optimization simultaneously is necessary: the optimization of heat exchange and of moisture exchange.
  • a crystalline hydrate of calcium chloride CaCl 2 .6H 2 0, preferably in the form of microparticles (particle-size less than 100 nm) may be used as a heat accumulating system.
  • Such microparticles may be synthesized in micropores of suitable size in macroparticles of a thermally inert ceramic matrix, e.g., of silica gel (in granules or powder) for the stabilization of the microparticles and the effective use thereof.
  • a reversible process of crystalline hydrate CaCl 2 .6H 2 0 decomposition (dehydration) and formation (hydration) may be used for the storage of low potential heat energy and for the release thereof.
  • the rate and the extent of the reaction will be determined by temperature as well as by ambient humidity. For example, when dry air or nitrogen is blown over the salt granules, the salt decomposition temperature decreases to 0- 30°C. In some cases, the decomposition occurs at a temperature of -10°C (for example in an absolutely dry nitrogen stream) .
  • the charging of the above chemical heat accumulator usually requires temperatures not lower than 100°C or a sharp decrease of air humidity (relative humidity less than 1%).
  • the main purpose of the present invention is to provide heat-accumulating material for self-heating parts of clothing and foot-wear.
  • Said material should be capable of being charged in different conditions available in private life, e.g., near heating devices (ovens, hot-water, radiators, heating registers, etc. ) in a certain period of time.
  • the conditions for the charging of the material should be mild, such as, for example, a temperature not exceeding 60 ⁇ C, and a relative humidity of 10 - 20%. Under such mild conditions prolonged regular use of synthetic and natural materials for the shoe insole or other clothing items is possible.
  • the main problem to be solved is increasing the temperature sensitivity of heat accumulators of the above type.
  • the preferred material according to the present invention accumulates heat in a humid environment (relative humidity up to 20%) at a temperature up to about 60 ⁇ C and is in conformity with the above requirements.
  • the inventors have surprisingly found that introduction of 5 to 50% by weight of the salt SrCl 2 .6H 2 0, based on the total weight of the mixture, into microcrystals of CaCl 2 .6H 2 0 considerably increases the temperature sensitivity of these crystals, and the temperature needed for the charging (dehydration) of the heat-accumulating material decreases to 60°C.
  • compositions containing CaCl 2 and 1 to 2% SrCl 2 are described in U.S. Patent No. 4,613,444 (January 31, 1982). However, according to the inventors' experiments, SrCl 2 .6H 2 0 in small amounts (less than 5% by weight) do not influence the temperature sensitivity of CaCl 2 .6H 2 0 microcrystals.
  • the microcrystals CaCl 2 .6H 2 0 have an amorphization temperature of 18°C. When 5% by weight SrCl 2 .6H 2 0 is added, based on the total weight of the mixture, the temperature thereof changes minimally (up to 20 ⁇ C).
  • the amorphization temperature is 25°C.
  • Both salts used in the heat accumulator namely CaCl 2 and SrCl 2
  • the preferred form of device of the present invention i.e. a device for the use of the heat-accumulating material, comprises a "foot heater" insole consisting of two layers of elastic material placed one on top of another and connected in any suitable manner, and providing a cavity therebetween, to receive the heat-accumulating material.
  • the upper layer is preferably made of hydrophilic woven or non- woven material, e.g. felt material, of natural fibre or threads.
  • 20-40 g of the heat-accumulating material in powder - like or micro- granulated form is placed in the cavity between the two layers.
  • the lower layer is preferably made of a hydrophobic synthetic material. The hydrophobic layer serves hermetically to seal the part of the body being heated against moisture and to keep the evolved moisture in the hydrophilic layer.
  • the "foot heater” insole has a dual effect. Firstly condensed moisture is absorbed, and, secondly, the foot is heated as the heat accumulator is discharged. The following reaction occurs: water is chemically connected with CaCl 2 , and about 0.5 kcal of heat per 1 g of moisture absorbed is evolved.
  • the heat-accumulating material employed in the quantity mentioned above (20-40 g) ensures comfortable conditions for the foot (absence of liquid moisture, and a temperature of 20-25°C) during a long cycle of continuous use (12-15 hours) even in the most unfavourable weather conditions.
  • the sample is characterized by a calorimetric spectrum having an endoeffect at a temperature of 25°C, associated with crystal amorphization.
  • Example 2 The procedure of Example 1 is repeated, except that the weight ratio CaCl 2 :SrCl 2 is 95 to 5.
  • the sample is characterized by a calorimetric spectrum with endoeffect at a temperature of 20 ⁇ C, with crystal amorphization.
  • Example 2 The procedure of Example 1 is repeated, except that the associated weight ratio CaCl 2 :SrCl 2 is 50 to 50.
  • the sample is characterized by a calorimetric spectrum with endoeffect at a temperature of 25 ⁇ C, associated with crystal amorphization.
  • Example 1 The procedure of Example 1 is repeated, except that a CaCl 2 solution is used for the impregnation.
  • Thermal treatment conditions temperature 60 ⁇ l ⁇ C, air relative humidity 10-20%, sample weight 3g.
  • the dehydration of the heat-accumulating material of the invention proceeds much more intensively than that of CaCl 2 .6H 2 0 (particle size ⁇ 100 nm) .
  • the sample in Example 1 is dehydrated in 2 hours after the beginning of the experiment, while the sample in Example 4 is dehydrated only in 8 hours.
  • the weight loss of the second sample after 8 hours of the experiment was almost twice as much as that of the first one.
  • the dehydration process is similar in quality, but the promotion with 10% SrCl 2 .6H 2 0 considerably increased the dehydration process and made it possible for it to proceed at temperature which is not excessively high ( 60 ° C ) .
  • the promotion of the heat-accumulating material based on caCl 2 .6H 2 0 microcrystals with small quantities (10% of weight) of SrCl 2 .6H 2 0 enables considerable increase of temperature sensitivity of the CaCl 2 .6H 2 0 microcrystals and enables the charging to proceed under mild conditions, without requiring high-temperature heating sources or almost complete air dehumidification.
  • Examples 6 and 7 illustrate conditions or the discharging of the heat-accumulating material charged according to Example 5.
  • a 3g sample of the heat-accumulating material produced under the conditions of Example 1 is placed in air at a relative humidity of 60%, at a temperature of 10°c.
  • the hydration by means of moisture saturation (gain in moisture weight 0.6 g) proceed in the course of 2 hours. Heat release is about 0.5 kcal (0.8 kcal/g of moisture) .
  • the sample temperature (in adiabatic conditions, i.e., without heat losses) after the hydration is 25°C.
  • Example 6 The procedure of Example 6 was repeated, except that liquid water was introduced at a temperature of 10°C. In this case, the heat release was 0.3 kcal/g of water or 0.2 kcal/g of sample weight. Final temperature was also 25°C, however the hydration occurred instantly. The final temperature stabilization during the discharging of the heat- accumulator at the level of 25 ⁇ C was determined by phase change in the heat-accumulating material (transition from the crystal state to the amorphous state). As a result, risk of overheating of the foot is eliminated, and the foot heater insole temperature will be set at the level of 24-25"c which corresponds to the optimal temperature of the human foot.
  • 35 g of the heat-accumulating material is uniformly placed between two layers of cotton cloth sewn together lengthwise and across with a thread seam, the distance between the parallel seams being 15 mm.
  • the form of the cloth layers resembled that of a man's foot.
  • the use of the "foot heater” insole includes two operations:
  • the discharging of a heat-accumulator occurs inside a boot during contact of a foot with a "foot heater” insole.
  • the accumulator capacity ensures complete moisture absorption during 4-6 hours, the average increase of temperature being 10 ⁇ C (from 10-15 ⁇ C to 20-25 ⁇ C).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

Matériau accumulateur de chaleur comportant des cristaux de CaCl2 et de SrCl2 renfermant de 5 à 50 % en poids environ de SrCl2, en fonction du poids du mélange. On peut déshydrater ce matériau à 60 °C environ et dans un milieu à humidité relative comprise entre 10 et 20 %. De préférence, on provoque la co-cristallisation du mélange afin de former des cristaux de dimensions inférieures à 100 nm environ, dans les pores d'une matrice poreuse thermiquement inerte telle que le gel de silice.
PCT/CA1992/000521 1992-12-01 1992-12-01 Materiau accumulateur de chaleur, et procede et appareil de mise en ×uvre de ce materiau WO1994012587A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU29394/92A AU2939492A (en) 1992-12-01 1992-12-01 Heat accumulating material, method of and equipment for the use thereof
PCT/CA1992/000521 WO1994012587A1 (fr) 1992-12-01 1992-12-01 Materiau accumulateur de chaleur, et procede et appareil de mise en ×uvre de ce materiau

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CA1992/000521 WO1994012587A1 (fr) 1992-12-01 1992-12-01 Materiau accumulateur de chaleur, et procede et appareil de mise en ×uvre de ce materiau

Publications (1)

Publication Number Publication Date
WO1994012587A1 true WO1994012587A1 (fr) 1994-06-09

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU667289B2 (en) * 1990-06-15 1996-03-21 Aktsionernoe Obschestvo Zakrytogo Tipa "Ekoterm" Heat accumulating material and its use
CN102827579A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为36℃的无机相变材料(pcm-36)
CN102827573A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为30℃的无机相变材料(pcm-30)
CN102827574A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为31℃的无机相变材料(pcm-31)
CN102827578A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为35℃的无机相变材料(pcm-35)
CN102827576A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为33℃的无机相变材料(pcm-33)
CN102827575A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为32℃的无机相变材料(pcm-32)
CN102827580A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为37℃的无机相变材料(pcm-37)
CN102827582A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为39℃的无机相变材料(pcm-39)
CN102827581A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为38℃的无机相变材料(pcm-38)
CN102838968A (zh) * 2011-06-20 2012-12-26 北京中瑞森新能源科技有限公司 一种相变温度为40℃的无机相变材料(pcm-40)
CN103374336A (zh) * 2012-04-27 2013-10-30 北京中瑞森新能源科技有限公司 一种相变温度为26℃的无机相变材料(pcm-26)
CN103484073A (zh) * 2012-06-15 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为27℃的无机相变材料
CN103484072A (zh) * 2012-06-15 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为24℃的无机相变材料
CN103484071A (zh) * 2012-06-15 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为22℃的无机相变材料
CN103484065A (zh) * 2012-06-14 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为5℃的无机相变材料

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011357A1 (fr) * 1978-09-29 1980-05-28 National Research Development Corporation Utilisation d'un mélange d'hydrates pour emmagasiner la chaleur à une température constante et accumulateur de chaleur contenant ce mélange
EP0063348A1 (fr) * 1981-04-15 1982-10-27 The Dow Chemical Company Compositions susceptibles de changer réversiblement leurs phases à base de hexahydrate de chlorure de calcium et d'autres chlorures
EP0091701A1 (fr) * 1982-02-23 1983-10-19 SOLVAY & Cie (Société Anonyme) Mélange pour la préparation de compositions pour l'absorption et l'accumulation de calories

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011357A1 (fr) * 1978-09-29 1980-05-28 National Research Development Corporation Utilisation d'un mélange d'hydrates pour emmagasiner la chaleur à une température constante et accumulateur de chaleur contenant ce mélange
EP0063348A1 (fr) * 1981-04-15 1982-10-27 The Dow Chemical Company Compositions susceptibles de changer réversiblement leurs phases à base de hexahydrate de chlorure de calcium et d'autres chlorures
EP0091701A1 (fr) * 1982-02-23 1983-10-19 SOLVAY & Cie (Société Anonyme) Mélange pour la préparation de compositions pour l'absorption et l'accumulation de calories

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 88, 1978, Columbus, Ohio, US; abstract no. 138621b, V. N.DANILIN ET AL. 'heat-storage composition based on calcium chloride crystal hydrate' page 122 ; *
PATENT ABSTRACTS OF JAPAN vol. 7, no. 68 (M-201)(1213) 19 March 1983 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU667289B2 (en) * 1990-06-15 1996-03-21 Aktsionernoe Obschestvo Zakrytogo Tipa "Ekoterm" Heat accumulating material and its use
CN102827582A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为39℃的无机相变材料(pcm-39)
CN102827581A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为38℃的无机相变材料(pcm-38)
CN102827574A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为31℃的无机相变材料(pcm-31)
CN102827578A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为35℃的无机相变材料(pcm-35)
CN102827576A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为33℃的无机相变材料(pcm-33)
CN102827575A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为32℃的无机相变材料(pcm-32)
CN102827573A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为30℃的无机相变材料(pcm-30)
CN102827579A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为36℃的无机相变材料(pcm-36)
CN102827580A (zh) * 2011-06-17 2012-12-19 北京中瑞森新能源科技有限公司 一种相变温度为37℃的无机相变材料(pcm-37)
CN102838968A (zh) * 2011-06-20 2012-12-26 北京中瑞森新能源科技有限公司 一种相变温度为40℃的无机相变材料(pcm-40)
CN103374336A (zh) * 2012-04-27 2013-10-30 北京中瑞森新能源科技有限公司 一种相变温度为26℃的无机相变材料(pcm-26)
CN103484065A (zh) * 2012-06-14 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为5℃的无机相变材料
CN103484073A (zh) * 2012-06-15 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为27℃的无机相变材料
CN103484072A (zh) * 2012-06-15 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为24℃的无机相变材料
CN103484071A (zh) * 2012-06-15 2014-01-01 中瑞森(天津)新能源科技有限公司 一种相变温度为22℃的无机相变材料

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