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KR900004231B1 - Latent heat agent - Google Patents

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KR900004231B1
KR900004231B1 KR1019870004228A KR870004228A KR900004231B1 KR 900004231 B1 KR900004231 B1 KR 900004231B1 KR 1019870004228 A KR1019870004228 A KR 1019870004228A KR 870004228 A KR870004228 A KR 870004228A KR 900004231 B1 KR900004231 B1 KR 900004231B1
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calcium chloride
latent heat
chloride hexahydrate
diatomaceous earth
heat material
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KR880012727A (en
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김종엽
한성옥
김재설
이종호
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한국동력 자원연구소
박긍식
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    • C09K5/00Heat-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
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Abstract

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Description

잠열재 (潛熱材)Latent heat

제 1 도는 본 발명의 잠열재의 실시예의 일부절취 사시도이다.1 is a partially cutaway perspective view of an embodiment of a latent heat material of the present invention.

* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings

1 : 외부용기 2 : 염화칼슘 6수염과 규조토분말혼합액1: outer container 2: calcium chloride hexahydrate and diatomaceous earth powder mixture

3 : 조핵제용기 4 : 조핵제3: nucleating agent container 4: nucleating agent

5 : 열전도체5: thermal conductor

본 발명은 냉난방 또는 축열시설에 사용되는 잠열재, 보다 상세하게는 염화칼슘(CaCl2)을 이용한 잠열재에 관한 것이다.The present invention relates to a latent heat material used in cooling and heating or heat storage facilities, and more particularly, a latent heat material using calcium chloride (CaCl 2 ).

현재 일반적으로 사용되는 냉난방방식(태양열이용포함)은 작동시간을 임의로 조정하기 어렵고 일정시간 난방기를 작동시켜 실내온도를 적정온도 이상으로 올려 놓은 다음 난방기의 가동을 중지하여 실내온도가 일정온도이하로 내려가면 난방기를 다시 가동시키는 방식, 즉 간헐난방을 하고 있으며, 따라서 주간에는 실내가 과열되기까지 하는 반면 야간에는 과냉각현상이 야가되기도 하는 실정이므로(냉방에 있어서는 냉방기로 실내온도를 낮추었다가 올라가면 다시 냉방기를 가동시킴), 실내온도를 쾌적하게 유지하기 어려울 뿐 아니라 과열 또는 과냉현상에 의해 에너지의 상당한 손실을 초래하고 있는 실정이다.Currently, the heating and cooling method (including solar heat use) is difficult to arbitrarily adjust the operating time, operate the heater for a certain time, raise the room temperature above the proper temperature, and then stop the operation of the heater to lower the temperature below the certain temperature. When the heater is turned on again, that is, intermittent heating, the room is overheated during the day, but the supercooling phenomenon may become nighttime at night (in the case of cooling, if the room temperature is lowered with the air conditioner, then the air conditioner is raised again). It is difficult to maintain the room temperature comfortably, as well as causing a considerable loss of energy due to overheating or subcooling.

이러한 현상의 부분적인 해결책으로서 물이나 자갈 또는 건물의 구조체를 이용하는 현열(sensible heat)방식이 채택되고 있으나 일시적인 과열 및 과냉현상을 완전히 해결할 수 없을 뿐 아니라, 이러한 물이나 자갈등은 단위부피당 열용량이 적어 축열시설에 많은 재료와 공간이 소요되므로 이러한 방법으로는 에너지절약효과에 한계가 있다.As a partial solution of this phenomenon, sensible heat method using water, gravel or building structure is adopted, but it is not able to completely solve the temporary overheating and subcooling phenomenon, and such water or gravel has low heat capacity per unit volume. Since a large amount of materials and space are required for the heat storage facility, this method has a limit in energy saving effect.

이처럼 현열을 이용하는 열에너지저장방식의 단점을 해결하기 위한 방안으로서 물질의 상변화(phase-change)에 따른 잠열(latent heat)을 이용하고자 하는 연구가 세계적으로 주목을 받고 있다.As a way to solve the shortcomings of the thermal energy storage method using sensible heat, a study to use the latent heat according to the phase-change of the material has attracted worldwide attention.

잠열을 이용한 측열방식에서는 적은 부피와 중량으로 많은 열을 저장할 수 있어야 하며, 재료의 선택에 있어서, 첫째, 용융온도가 사용온도에 적합하고, 둘째, 과냉각현상이 적으며, 셋째, 용융잠열이 크고, 넷째, 화학적으로 안정되며, 다섯째, 가격이 저렴하고 대량구입이 용이하고, 여섯째, 가연성, 독성, 부식성이 없으며, 일곱째, 상변화에 따른 체적변화가 적고, 여덟째, 열전도가 높을 것등이 고려되어야 한다.In the latent heat measurement method, it is necessary to store a large amount of heat with a small volume and weight. In the material selection, first, the melting temperature is suitable for the use temperature, and second, the subcooling phenomenon is small, and the third, the latent heat of melting is large. Fourth, it is chemically stable, fifth, low price, easy to buy in bulk, sixth, no flammability, no toxic, no corrosiveness, seventh, small volume change due to phase change, eighth, high thermal conductivity, etc. Should be.

이러한 목적에 적합한 잠열을 이용한 에너지저장재료로는 무기수화물, 유기화합물 및 합금등이 있는데, 이중에서 가장 활발히 연구되고 있는 것으로는 무기수화염과 탄화수소류를 들수 있으나 합금 및 탄화수소류는 경제성 및 범용성에 다소의 문제점이 있다.The energy storage materials using latent heat suitable for this purpose include inorganic hydrates, organic compounds, and alloys. Among them, inorganic hydrates and hydrocarbons are the most actively studied, but alloys and hydrocarbons are somewhat economical and versatile. There is a problem.

염화칼슘은 탄산나트륨(NACO3)의 제조시에 부산물로서 나오는데 그 용도가 적어 재설제로 사용되는 것 외에는 폐기물로 처리되고 있어 상대적으로 가격이 싼 장점이 있다.Calcium chloride is produced as a by-product in the manufacture of sodium carbonate (NACO 3 ), and its use is relatively low, since it is used as a snow removal agent because its use is small.

이와같은 염화칼슘의 수화물(CaCl2·2H2O, CaCl2·4H2O, CaCl2·6H2O)중에서 염화칼슘 6수염(CaCl2·6H2O)은 상변화온도가 30℃이고 부피변화가 상대적으로 적으며 용융열이 40ca1/g으로서 20°→30℃의 온도 변화에 따른 현열 및 잠열에 의한 열교환량은 물이 20。-90℃로 변할때의 현열에 의한 열교환량과 같다. 이들 자갈과 비교하면, CaCl2·6H2O 1톤 자갈 35톤과 같은 열량을 저장할 수 있음을 의미한다.In the same salt hydrate (CaCl 2 · 2H 2 O, CaCl 2 · 4H 2 O, CaCl 2 · 6H 2 O) from the salt 6 beard (CaCl 2 · 6H 2 O) is the phase change temperature of 30 ℃ and the volume change Relatively little, the heat of fusion is 40ca1 / g, and the amount of heat exchanged by sensible and latent heat according to the temperature change of 20 ° → 30 ° C is the same as the amount of heat exchanged by sensible heat when water changes to 20 ° -90 ° C. Compared with these gravel, it means that it can store calories such as 35 tons of CaCl 2 · 6H 2 O 1 ton gravel.

이처럼 CaCl2·6H2O가 잠열재로서 우수한 성능을 갖고 있으나 실용화가 어려운 것은 용융온도(30℃)에서 상변화를 일으키지 않으려는 과냉각현상과 용융상태의 염화칼슘의 고화 반응중 α-CaCl2·4H2O가 생성되어서 발생되는 침전현상에 의해 가역반응회수가 30-50회에 지나지 않게 되기 때문이다.As such, CaCl 2 · 6H 2 O has excellent performance as a latent material, but it is difficult to put into practical use in the case of supercooling not to cause phase change at melting temperature (30 ℃) and α-CaCl 2 · 4H during the solidification reaction of calcium chloride in the molten state. This is because the number of reversible reactions is only 30-50 times due to precipitation caused by the formation of 2 O.

CaCl2·6H2O를 난방용 잠열재로 사용할 경우, 6수화물의 조성을 가진 염화칼슘용액이 가열되어 있는 상태에서 냉각되기 시작할때 열역학적으로 먼저 안정한 염화칼슘 4수염이 생성되며, 이 염화칼슘 4수염은 온도가 계속 내려감에 따라 생성된 염화칼슘 6수염 및 과량의 물에 의한 묽은 염화칼슘용액과 공존하게 된다. 이때 다시 가열을 시작하게 되면 먼저 염화칼슘 6수염이 열을 흡수하여 용융되고 온도가 더 상승하여 염화칼슘 4수염이 용융되어 완전히 균일한 용액으로 된 후, 다시 고화반응이 일어나는 것이 타당하나, 실제로는 염화칼슘 4수염은 안정한 화합물로서 온도가 상승하여도 용융되지 않고 용액중에 침전으로 남아있게 된다. 이 상태의 용액을 다시 냉각시킬 경우 또 다른 염화칼슘 4수염이 생성되고, 다시 가열하여도 용융되지 않으므로 잠열재의 가열-냉각이 반복되면서 염화칼슘 4수염의 양이 누적되고, 따라서 열저장량이 감소하게 된다.When CaCl 2 · 6H 2 O is used as a latent heating material, a thermodynamically stable calcium chloride tetrahydrate is formed first when the calcium chloride solution of the hexahydrate composition starts to cool while it is heated. As it is lowered, it coexists with dilute calcium chloride solution produced by calcium chloride hexahydrate and excess water. At this time, when heating is started again, it is appropriate that calcium chloride hexahydrate absorbs heat and melts, and the temperature rises further, so that the calcium chloride tetrachloride is melted into a completely uniform solution, and then solidification reaction takes place again. Beard is a stable compound that does not melt at elevated temperatures and remains precipitated in solution. When the solution in this state is cooled again, another calcium chloride tetrachloride is formed, and since it does not melt even when heated again, the amount of calcium chloride tetrahydrate accumulates as heat-cooling of the latent heat material is repeated, thus reducing the amount of heat storage.

또한, 염화칼슘 6수염이 용융된 상태에서 온도가 30℃이하로 내려가게 되면, 이론적으로는 고체상태의 염화칼슘 6수염으로 상전이를 시작하여야 하는데, 실제로 액상의 염화칼슘은 준안정상태이므로 온도가 내려가도 상변화를 하지 않고 액체상태로 유지되는, 이른바 과냉각 현상이 발생하게 된다.In addition, when the temperature drops below 30 ° C in the state of melting the calcium chloride hexahydrate, theoretically, the phase transition should be started to the solid calcium chloride hexahydrate. The so-called supercooling phenomenon, which remains in the liquid state without change, occurs.

이러한 침전현상 및 과냉각현상으로 인하여 염화칼슘을 파이프 온돌용 자갈등의 대체품으로서 일정한 용기에 넣어 축열재로 사용한다고 할때, 난방가열에 의한 액화, 난방중지에 의한 고화현상의 1일동안의 가역반응을 1회로 본다면 30-50일이 지난후에는 잠열재로서의 역할이 중지된다고 볼 수 있다.Due to this precipitation phenomenon and supercooling phenomenon, when calcium chloride is used as a heat storage material in a constant container as a substitute for gravel for pipe ondol, the reversible reaction during one day of liquefaction by heating and solidification by stopping heating If you look at it once, it can be said that the role of latent heat will cease after 30-50 days.

CaCl2·6H2O를 잠열저장재로서 실용화하기 위해서는 이러한 과냉각 및 침전현상을 방지해야 하는데, 이 분야에서의 연구가 가장 진전된 불란서에서는 규조토의 미세분말을 염화칼슘에 혼입하는 방법이 실용화되고 있다. 이렇게 규조토분말을 혼입하는 기술도 엄격히 비밀로 되어있으나, 판상형 규조토 1%, 침상형 규조토10%, 원통형 규조토 2% 등 규조토 미세분말을 12-15%의 비율로 염화칼슘에 혼입하는 것으로 알려져 있다.In order to use CaCl 2 · 6H 2 O as a latent heat storage material, such supercooling and precipitation phenomenon should be prevented. In France, the most advanced research in this field, a method of incorporating diatomaceous earth fine powder into calcium chloride has been put to practical use. The technology for incorporating diatomaceous earth powder is also strictly kept secret, but it is known that diatomaceous earth fine powder, such as plate-like diatomaceous earth 1%, needle-like diatomaceous earth 10%, and cylindrical diatomaceous earth 2%, is mixed with calcium chloride at a ratio of 12-15%.

위와 같은 방법에서는 규조토 분말의 표면이 미세하나마 요철을 이루고 있으므로 염화칼슘의 과냉을 막고 침전을 막아주는 역할을 하나, 규조토의 무수히 많은 공극으로 인하여 열전도도가 낮고 규조토가 차지하는 부피가 커지므로 축열효과가 감소되는 결점이 있다.In the above method, the surface of the diatomaceous earth powder is minute but irregular, thus preventing the supercooling of calcium chloride and preventing precipitation, but due to the numerous pores of the diatomaceous earth, the thermal conductivity is low and the volume occupied by the diatomaceous earth reduces the heat storage effect. There is a drawback.

본 발명자들은 규조토 미세분말이 혼입된 염화칼슘의 위와같은 결점을 해결하기 위하여 오랫동안 연구를 계속한 결과 과냉각방지 및 침전방지를 위해 물리적인 방법과 화학적인 방법을 병용함이 효과적이라는 것을 알게 되어 본 발명을 완성하게 되었다.The present inventors have long researched to solve the above drawbacks of calcium chloride in which diatomaceous earth fine powder is incorporated, and found that it is effective to use a physical method and a chemical method together to prevent supercooling and precipitation. It was completed.

본 발명의 잠열재는 구형 또는 육면체등의 용기에 염화칼슘 6수염, 염화스트론튬 6수염 및 미량의 규조토 분말을 넣고, 용기의 외부로 그 일부가 노출될 수 있도록 열전도체를 삽입하고 밀봉하여 완성된 것이다.The latent heat material of the present invention is completed by inserting calcium chloride hexahydrate, strontium chloride hexahydrate, and a small amount of diatomaceous earth powder into a container such as a spherical or hexahedron and inserting and sealing a heat conductor to expose a part of the diatomaceous earth to the outside of the container.

본 발명자들은 염화칼슘의 안정화를 깨뜨리는 규조토분말의 사용에 있어서 이미 언급한 여러가지 문제점을 가지고 있기 때문에 그 역할을 대신할 수 있는 방법을 연구하던중 염화칼슘에 열전도체를 삽입하여 잠열재 내부의 온도가 고정되지 않고 외부의 온도에 따라 변화하도록 함으로써 염화칼슘의 냉각시에 염화칼슘 6수염의 과냉을 5℃정도 줄이고 열전달모우드를 조정하여 염화칼슘 4수염의 안정화를 깨뜨리고 침전현상을방지할 수 있다는 것을 밝혀냈다.Since the present inventors have various problems mentioned above in the use of diatomaceous earth powder to break the stabilization of calcium chloride, the temperature inside the latent heat material is not fixed by inserting a thermal conductor into the calcium chloride while studying a method to replace the role. By changing the temperature according to the external temperature, it was found that the cooling of the calcium chloride hexahydrate can be reduced by about 5 ° C. during cooling of the calcium chloride, and the heat transfer mode can be adjusted to break the stabilization of the calcium chloride tetrachloride and prevent precipitation.

또한 염화칼슘 6수염의 과냉각 현상에 있어서, 일반적으로 액체가 과냉각되는 경향은 액체속에 새로운 상(相)의 생성이 용이하지 않기 때문에 액체의 결정화가 이루어지려면 결정화가 일어날 수 있는 어떤중심, 즉 핵이 필요하기 때문으로서 본 발명의 실시예에서는 염화스트론튬 6수염을 결정핵으로 사용하였는데, 이것은 염화스트톤튬 6수염과 염화칼슘 6수염이 결정구조에 있어서 육방정계로 동일하며, 격자상수(결정단위 cell의 크기)가 거의 같아서 결정핵으로 작용하기에 유효하다는 것을 밝혀낸 것이다.In addition, in the supercooling phenomenon of calcium chloride hexahydrate, the tendency of the liquid to be supercooled generally does not facilitate the formation of a new phase in the liquid, so that the crystallization of the liquid requires some center of crystallization, that is, a nucleus. Therefore, in the embodiment of the present invention, strontium chloride hexahydrate was used as the crystal nucleus, which means that strontium chloride hexahydrate and calcium chloride hexahydrate are the same hexagonal in crystal structure and lattice constant (size of crystal unit cell) Was found to be nearly the same, so it is effective to act as a nucleus.

이상 설명한 바와 같은 본 발명의 실시예를 설명하면 아래와 같다. 염화칼슘 6수염의 조성을 가진 염화칼슘용액과, 체적비 2%의 규조토분말의 혼합물(2)을 육면체의 외부용기(1)에 채우고, 체적비 0.5%의 염화스트론튬 6수염(4)를 조핵체용기(3)에 넣고, 한쪽 끝이 염화스트론튬 6수염이 담긴 내부용기(3)에 삽입된 막대형상의 열전도체(5)를 외부와 접촉할 수 있는 돌출부(5')를 갖도록 하여 밀봉재(6)로 밀봉하여 본 발명의 잠열재를 만들었다.An embodiment of the present invention as described above is described below. A mixture of a calcium chloride solution having a composition of calcium chloride hexahydrate and a diatomaceous earth powder having a volume ratio of 2% (2) is filled into an outer container (1) of a hexahedron, and a strontium chloride hexahydrate (4) having a volume ratio of 0.5% is a nucleus container (3). The rod-shaped thermal conductor 5 inserted into the inner container 3 containing strontium chloride hexahydrate with a protrusion 5 'for contacting the outside and sealed with a sealing material 6 at one end thereof. The latent heat material of the present invention was made.

본 발명의 실시예외에도, 염화스트톤튬 6수염의 경우 더 많이 사용하여도 무방하지만 결제성을 고려할 때 염화칼슘에 대해서 체적비 0.1-2%를 사용하는 것이 적합하고, 조핵제로서 염화스트론튬 6수염 이외에도 염화칼슘 6수염과 결정구조 및 격자상수가 유사한 다른 물질, 즉 CaOH2(칼슘하이드록사이드), Sr(NO3)2·6H2O등의 물질을 대신 사용할 수 있음이 밝혀졌는데, 실제 사용에 있어서는 그 함량과 가격이 고려되어야 할 것이다.In addition to the embodiment of the present invention, in the case of strontium chloride hexahydrate, it is possible to use more, but considering the settlement, it is suitable to use a volume ratio of 0.1-2% for calcium chloride, and calcium chloride in addition to strontium chloride hexahydrate as a nucleating agent. It has been found that other materials with similar crystalline structure and lattice constant as hepatitis, such as CaOH 2 (calcium hydroxide) and Sr (NO 3 ) 2 · 6H 2 O, can be used instead. Content and price should be considered.

또한 염화칼슘의 과냉 및 침전방지를 위해 삽입하는 열전도체는 구리 및 기타 전도성 물질은 모두 가능하며, 형태에 있어서 막대형상외에도 가지를 많이 갖는 형상이 적합하다.In addition, the thermal conductor inserted to prevent the supercooling and precipitation of calcium chloride can be copper and other conductive materials, and the shape having many branches in addition to the rod shape is suitable.

한편 조핵제를 사용하고 열전도체를 끼워 넣어도 염화칼슘의 안정화를 방지하는데 있어서 규조토 분말의 사용이 상당한 도움이 된다는 것이 실험결과 밝혀졌으며, 그 사용량은 염화칼슘에 대해 0.05-10%정도로 충분하다.Experimental results have shown that the use of diatomaceous earth powder can significantly help to prevent stabilization of calcium chloride even if nucleating agents are used and thermal conductors are inserted, and the amount used is about 0.05-10% of calcium chloride.

또한 염화스트론튬 6수염의 용융온도는 62℃이므로 염화칼슘 6수염보다 높아서 가열시에 용해되지 않으며, 가열, 냉각과정이 반복되는 잠열재내에서 계속적으로 사용할 수 있다.In addition, the melting temperature of strontium chloride hexahydrate is 62 ° C, which is higher than that of calcium chloride hexahydrate, so that it does not dissolve during heating, and can be used continuously in a latent heat material in which the heating and cooling processes are repeated.

본 발명에 의한 잠열재는 염화칼슘의 침전현상 및 과냉현상의 단점을 효율적으로 보완하였기 때문에 그 주성분인 염화칼슘 6수염의 액화 및 고화의 과정이 반복되면서 나타나는 열의 흡수 및 방출효과가 우수하여, 난방기를 가동시켰을 경우의 과열현상과 난방기의 가동을 중지하였을 경우의 과냉현상을 발생하지 않고, 실내를 항상 쾌적한 온도로 유지할 수 있도록 해주며, 흡열작용을 이용하여 냉방용으로도 사용할 수 있다.Since the latent heat material according to the present invention effectively compensates for the disadvantages of precipitation and subcooling of calcium chloride, the heat absorption and release effect of the liquefaction and solidification of calcium chloride hexahydrate, which is a main component thereof, is excellent, and the heater is operated. It does not generate overheating in case of heating and overcooling in case of stopping the operation of heater, and keeps the room at a comfortable temperature at all times. It can also be used for cooling by using endothermic action.

이에따라 상당한 에너지절감효과를 가져오고, 또한 원료의 단가가 저렴한 장점과 본 발명의 잠열재를 사용하는 냉난방시설의 구조 및 특성을 고려하여 용도에 맞는 형태, 즉 구형, 육면체형 혹은 원통형등으로 변형이 가능하므로 폭넓은 범위로 사용할 수 있으며, 무게나 부피가 적으므로 작업이 매우 용이한 장점이 있다.Accordingly, in consideration of the advantages of low energy cost and low cost of raw materials and the structure and characteristics of the heating and cooling facility using the latent heat material of the present invention, the shape, that is, spherical, hexahedral or cylindrical, is modified. It can be used in a wide range because it is possible, and there is an advantage that the work is very easy because the weight or volume is small.

Claims (7)

염화칼슘 6수염과, 미량의 규조토분말의 혼합물이 담긴 용기에 미량의 조핵제가 담긴 용기를 넣고, 한쪽 끝이 조핵제와 접촉된 열전도체가 용기외부로 노출되게 삽입, 밀봉하여서 조핵제, 규조토 분말 그리고 열전도체가 염화칼슘 6수염의 과냉방지 및 염화칼슘 4수염의 침전 및 안정화를 방지하는 것을 특징으로 하는 잠열재.A container containing a small amount of nucleating agent is placed in a container containing a mixture of calcium chloride hexahydrate and a small amount of diatomaceous earth powder. A latent heat material, characterized in that the sieve prevents subcooling of calcium chloride hexahydrate and precipitation and stabilization of calcium chloride hexahydrate. 제 1 항에 있어서, 조핵제는 염화스트론튬 6수염인 것을 특징으로 하는 잠열재.The latent heat material according to claim 1, wherein the nucleating agent is strontium chloride hexahydrate. 제 1 항에 있어서, 조핵제가 염화칼슘 6수염과 결정구조 및 격자상수가 비슷한 Ca(OH)2, Sr(NO3)2·6H2O등의 하나인 것을 특징으로 하는 잠열재.2. The latent heat material according to claim 1, wherein the nucleating agent is one of Ca (OH) 2 , Sr (NO 3 ) 2 .6H 2 O, etc. having a crystal structure and lattice constant similar to that of calcium chloride hexahydrate. 제 1 항에 있어서, 열전도체는 구리인 것을 특징으로 하는 잠열재.The latent heat material according to claim 1, wherein the heat conductor is copper. 제 1 항, 제 4 항중 어느 한항에 있어서, 열전도체가 하나이상의 가지가 형성되어 있거나 없는 막대형상인 것을 특징으로 하는 잠열재.The latent heat material according to any one of claims 1 to 4, wherein the heat conductor is rod-shaped with or without one or more branches. 제 1 항에 있어서, 규조토분말이 염화칼슘 6수염에 대하여 0.05-10%의 체적비를 갖는 것을 특징으로하는 잠열재.The latent heat material according to claim 1, wherein the diatomaceous earth powder has a volume ratio of 0.05-10% with respect to the calcium chloride hexahydrate. 제 1 항, 제 2 항, 제 3 항중 어느 한항에 있어서, 조핵제가 염화칼슘 6수염에 대하여 0.1-2%의 체적비를 갖는 것을 특징으로 하는 잠열재.4. The latent heat material according to any one of claims 1, 2 and 3, wherein the nucleating agent has a volume ratio of 0.1-2% with respect to the calcium chloride hexahydrate.
KR1019870004228A 1987-04-30 1987-04-30 Latent heat agent Expired KR900004231B1 (en)

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