JPH0692578B2 - Heat storage material - Google Patents
Heat storage materialInfo
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- JPH0692578B2 JPH0692578B2 JP62179355A JP17935587A JPH0692578B2 JP H0692578 B2 JPH0692578 B2 JP H0692578B2 JP 62179355 A JP62179355 A JP 62179355A JP 17935587 A JP17935587 A JP 17935587A JP H0692578 B2 JPH0692578 B2 JP H0692578B2
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- Japan
- Prior art keywords
- heat storage
- storage material
- salt
- weight
- insoluble
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、融解潜熱を利用する蓄熱材に関する。TECHNICAL FIELD The present invention relates to a heat storage material utilizing latent heat of fusion.
多くの水化物は、その融解潜熱として40cal/g以上の値
を有し、潜熱利用蓄熱材として好適な性質を多く備えて
いる。Many hydrates have a value of 40 cal / g or more as their latent heat of fusion, and have many properties suitable as a latent heat storage material.
融点の高い例ではアンモニウムみようばん（融点94℃，
融解熱56cal/g）やBa（OH）２・8H2O（融点78℃，融解
熱70cal/g）あるいはMg（NO3）２・6H2O（融点89℃、融
解熱約40cal/g）などがある。In the case of high melting point, ammonium alum (melting point 94 ℃,
Heat of fusion 56cal / g) and Ba (OH) 2 · 8H 2 O ( melting point 78 ° C., a heat of fusion 70 cal / g) or Mg (NO 3) 2 · 6H 2 O ( melting point 89 ° C., a heat of fusion of about 40 cal / g) and so on.
これらの潜熱利用蓄熱材は、ヒーターなどの手段により
融解させて液相状態にしておき、温度が低下した時、試
料の固化に伴なう固化熱を利用して、暖房、保温などを
行なわせるものである。These latent heat storage materials are melted by means such as a heater to be in a liquid phase state, and when the temperature drops, the heat of solidification accompanying the solidification of the sample is used to perform heating, heat retention, etc. It is a thing.
固化熱を順調に取り出すためには、液相→固相への相変
化を順調に行なわせる必要があり、そのためには、試料
の過冷却を防止しなければならない。その目的のため
に、通常、蓄熱材組成物とは異なる物質である核生成材
を少量、0.01〜数重量％加えることが行なわれる。In order to smoothly extract the heat of solidification, it is necessary to smoothly perform the phase change from the liquid phase to the solid phase, and for that purpose, it is necessary to prevent the sample from being overcooled. For that purpose, usually, a small amount of 0.01 to several% by weight of a nucleating material, which is a substance different from the heat storage material composition, is added.
例えば、アンモニウムみようばんには、セシウムみよう
ばんなどが、有効な核生成材であることが知られてい
る。For example, it is known that cesium miu-ban and the like are effective nucleating agents for ammonium miu-ban.
例えば、CH3COONa3H2Oに対する核生成材である無水CH3C
OONaとNa2HPO4との混合物では、過冷却度として２〜５
℃必要であつた。また、CaCl2・6H2Oに対する核生成材
である各種バリウム塩では過冷却度として５〜10℃必要
であつた。For example, anhydrous CH 3 C which is a nucleating material for CH 3 COONa3H 2 O.
In the case of a mixture of OONa and Na 2 HPO 4 , the degree of supercooling is 2 to 5
C was necessary. Also, various barium salts, which are nucleating materials for CaCl 2 .6H 2 O, required a supercooling degree of 5 to 10 ° C.
上記アンモニウムみようばんの融液は強酸性であり、し
かもその生長速度が小さいため、みうばん結晶の生長速
度が取り出し得る放熱速度を律速していた。Since the melt of ammonium miuban was strongly acidic and its growth rate was small, the growth rate of miubaban crystals limited the heat release rate that could be taken out.
一方、Ba（OH）２・8H2Oの融液は強アルカリ性であり、
漏洩した場合には、無害とはいえない物質である。On the other hand, Ba (OH) 2 · 8H 2 O in the melt is strongly alkaline,
In case of leakage, it is not a harmless substance.
そうした観点から、例えば特開昭61-51079号公報に示さ
れているMg（NO3）２・6H2O融液のPHは、略中性に近
く、実用上好ましい物質であり、その過冷却を有効に防
止する物質、即ち核生成材としては、MgO、MgCO3、MgSO
4等のマグネシウム塩やCaO、CaCO3、CaSO4等のカルシウ
ム塩、Sr（OH）２、SrCO3等のストロンチウム塩ではな
く、塩基性酸化鉛などの鉛系化合物を用いる方が、核生
成効果が長期間持続するため好ましいということが述べ
られている。From this perspective, the PH of the Mg (NO 3) 2 · 6H 2 O melt shown in JP-Sho 61-51079, close to substantially neutral, a practically preferable material, the supercooling The substances that effectively prevent the above, that is, nucleating agents include MgO, MgCO 3 , and MgSO 4.
Magnesium salt and CaO 4 such as calcium salts, such as CaCO 3, CaSO 4, rather than the Sr (OH) 2, SrCO 3, etc. strontium salt, is preferable to use a lead-based compounds such as basic lead oxide, the nucleation effects Is preferred because it lasts for a long time.
この発明は、かかる問題点を解決するためになされたも
ので、融液が中性近傍で、過冷却防止効果がより長期間
安定に保持される蓄熱材を得ることを目的とする。The present invention has been made to solve such a problem, and an object thereof is to obtain a heat storage material in which the melt is near neutral and the effect of preventing supercooling is stably maintained for a longer period of time.
この発明の蓄熱材は、Mg（NO3）２・6H2OあるいはMg（N
O3）２・6H2Oを主成分とする組成物に、MgF2、Mg（OH）
２、MgAl2O4、MgFeO4、MgMoO4、MgSiO3、Mg2SiO4、MgTi
O3、MgWO4およびMgZrO3から選ばれた水に不溶性のマグ
ネシウム塩、CaF2、Ca（OH）２、CaAl2O4、CaMoO4、CaS
iO3、Ca2SiO4およびCaWO4から選ばれた水に不溶性のカ
ルシウム塩ならびにBaF2、BaCO3、BaSO4、BaMoO4、BaSi
O3、BaTiO3、BaWO4およびBaZrO3から選ばれた水に不溶
性のバリウム塩の内の少なくとも一種を加えたものであ
る。Heat storage material of the invention, Mg (NO 3) 2 · 6H 2 O or Mg (N
The O 3) compositions based on 2 · 6H 2 O, MgF 2 , Mg (OH)
2 , MgAl 2 O 4 , MgFeO 4 , MgMoO 4 , MgSiO 3 , Mg 2 SiO 4 , MgTi
Water-insoluble magnesium salt selected from O 3 , MgWO 4 and MgZrO 3 , CaF 2 , Ca (OH) 2 , CaAl 2 O 4 , CaMoO 4 , CaS
Water-insoluble calcium salt selected from iO 3 , Ca 2 SiO 4 and CaWO 4, and BaF 2 , BaCO 3 , BaSO 4 , BaMoO 4 , BaSi
At least one of insoluble barium salts is added to water selected from O 3 , BaTiO 3 , BaWO 4, and BaZrO 3 .
この発明において、上記塩を全然加えない場合には、Mg
（NO3）２・6H2Oは通常、融点から70℃付近まで冷却さ
れないと、固化を開始しなかつた。即ち、固化するま
で、過冷却度として89−70≒20℃、約20度が必要であつ
た。In the present invention, when the above salt is not added at all, Mg
(NO 3) 2 · 6H 2 O are usually if not cooled from the melting point to around 70 ° C., it has failed to initiate the solidification. That is, the degree of supercooling needed to be 89-70≅20 ° C., about 20 ° C. until it solidified.
しかし、上記、マグネシウム塩、カルシウム塩、バリウ
ム塩を核生成材として、Mg（NO3）２・6H2Oに少量加え
ると、過冷却は通常87〜88℃で破れて固化が始まり、固
化潜熱を放出するのが確認できた。即ち、これらの核生
成材を用いた場合には固化開始までの過冷却度は僅か数
度であつた。この性能は、上記CH3COONa・3H2O,CaCl2・
6H2Oの水化物に対する二例の核生成材の性能に比して、
そん色のないものである。However, the magnesium salt, calcium salt, barium salt as nucleating material, adding Mg (NO 3) 2 · 6H 2 O in a small amount, the supercooling solidification starts torn at normal 87-88 ° C., solidifying latent heat Was confirmed to be released. That is, when these nucleating materials were used, the degree of supercooling until the start of solidification was only a few degrees. This performance is based on the above CH 3 COONa ・ 3H 2 O, CaCl 2・
Compared to the performance of the two nucleating materials for 6H 2 O hydrate,
It has no color.
この発明に係わるマグネシウム塩としては、MgF2、Mg
（OH）２、MgAl2O4、MgFeO4、MgMoO4、MgSiO3、Mg2Si
O4、MgTiO3、MgWO4およびMgZrO3から選ばれたものを用
い、これらは全て白色粉末であつた。The magnesium salt according to the present invention includes MgF 2 , Mg
(OH) 2 , MgAl 2 O 4 , MgFeO 4 , MgMoO 4 , MgSiO 3 , Mg 2 Si
A material selected from O 4 , MgTiO 3 , MgWO 4 and MgZrO 3 was used, and all were white powders.
この発明に係わるカルシウム塩としては、CaF2、Ca（O
H）２、CaAl2O4、CaMoO4、CaSiO3、Ca2SiO4およびCaWO4
から選ばれたものを用い、これらは全て白色粉末であつ
た。The calcium salt according to the present invention includes CaF 2 , Ca (O
H) 2 , CaAl 2 O 4 , CaMoO 4 , CaSiO 3 , Ca 2 SiO 4 and CaWO 4
The powders were all white powders.
この発明に係わるバリウム塩としては、BaF2、BaCO3、B
aSO4、BaMoO4、BaSiO3、BaTiO3、BaWO4およびBaZrO3か
ら選ばれたものを用いる。Examples of the barium salt according to the present invention include BaF 2 , BaCO 3 , B
A material selected from aSO 4 , BaMoO 4 , BaSiO 3 , BaTiO 3 , BaWO 4 and BaZrO 3 is used.
これらの内、マグネシウム塩は、蓄熱材自体がマグネシ
ウム塩のMg（NO3）２・6H2Oであるため、両者間に化学
反応の生じる余地はなく、核生成材として加えたマグネ
シウム塩は長期にわたつて、安定に存在する。しかしな
がら、多くのカルシウム塩やバリウム塩（BaTiO3とBaZr
O3を除く）は、Mg（NO3）２・6H2Oと化学反応を生じ、
多くのマグネシウム塩を生じる。しかし、反応終了後
も、核生成効果はそれほど変化しない。生成したマグネ
シウム塩が新らたに、核生成効果を生み出すからである
と考えられる。BaTiO3とBaZrO3はMg（NO3）２・6H2Oと
反応せず、長期にわたつて安定に存在する。Of these, magnesium salt, since the heat storage material itself is Mg (NO 3) 2 · 6H 2 O of the magnesium salt, no room of occurrence of a chemical reaction between them, magnesium salts added as nucleation material long Existence stable throughout However, many calcium and barium salts (BaTiO 3 and BaZr
Excluding O 3) results in a Mg (NO 3) 2 · 6H 2 O and chemistry,
This produces many magnesium salts. However, the nucleation effect does not change so much after the reaction. It is considered that this is because the produced magnesium salt newly produces a nucleation effect. BaTiO 3 and BaZrO 3 does not react with Mg (NO 3) 2 · 6H 2 O, long term cotton connexion stably exist.
これらのマグネシウム塩、カルシウム塩およびバリウム
塩がもつMg（NO3）２・6H2Oに対する、有効な核生成能
力の根源的理由については、現時点では明らかではな
い。例えば、マグネシウム塩でみると、MgF2は体心正方
晶、Mg（OH2）は六方晶、MgAl2O4は立方晶であり結晶系
さえ一致しない。おそらく、なんらかの事情に基づき、
これらの核生成材表面で不均質核生成を生じるのであろ
う。Mg（NO3）２・6H2Oの（融解熱／水化熱）比は約0.4
で、CaCl2・6H2Oのそれに近く、融液中には固体結晶構
造に近い構造がある程度温存されていると考えられる。These magnesium salts, Mg (NO 3) with calcium salts and barium salts for 2 · 6H 2 O, for fundamental reasons of effective nucleation ability is not clear at present. For example, looking at magnesium salts, MgF 2 is a body-centered tetragonal system, Mg (OH 2 ) is a hexagonal system, and MgAl 2 O 4 is a cubic system, and even the crystal systems do not match. Perhaps based on some circumstances
Heterogeneous nucleation will occur at the surface of these nucleating materials. Mg (NO 3) 2 · 6H 2 O of (heat of fusion / Mizukanetsu) ratio is about 0.4
Therefore, it is considered that a structure close to that of CaCl 2 .6H 2 O and a structure close to a solid crystal structure is preserved in the melt to some extent.
なお、これらマグネシウム塩、カルシウム塩、バリウム
塩は、粉末状の方が好ましく、その粒度は数十メツシユ
以下が好適である。なお、添加量は0.05〜３重量％間が
最適である。0.05重量％以下では核生成効果の発現がい
くらか不安定であり、３重量％以上の添加は不必要、か
つコスト的に不利を招くだけである。The magnesium salt, calcium salt, and barium salt are preferably in powder form, and the particle size thereof is preferably several tens of meshes or less. The optimum addition amount is between 0.05 and 3% by weight. The expression of the nucleation effect is somewhat unstable at 0.05% by weight or less, and the addition of 3% by weight or more is unnecessary and causes a disadvantage in cost.
実施例１ 工業用Mg（NO3）２・6H2Oに、MgF2粉末を0.05重量％加
え、ガラス試験管中に入れ、ゴム栓で密栓したものを、
温湯中（95〜80℃）で相変化をくり返させたところ、
（１日、８サイクル）、300回以上、順調に相変化をく
り返した。固化開始温度は88±１℃であつた。Example 1 0.05% by weight of MgF 2 powder was added to industrial Mg (NO 3 ) 2 .6H 2 O, the mixture was placed in a glass test tube and sealed with a rubber stopper.
After repeating the phase change in hot water (95-80 ℃),
(1 day, 8 cycles) The phase change was repeated steadily 300 times or more. The solidification start temperature was 88 ± 1 ° C.
実施例２ 工業用Mg（NO3）２・6H2Oに、Mg（OH）２粉末を３重量
％加え、実施例１と同様の試験を行なつたところ、実施
例１と同性能の結果が得られた。Example 2 Industrial Mg (NO 3) 2 · 6H 2 O, Mg (OH) 2 powder added 3 wt%, Example 1 where was row summer to the same tests as in Example 1 and results of the performance was gotten.
実施例３ 実施例１において、MgF2の代りにMgAl2O4粉末を１重量
％加え、実施例１と同様の試験を行なつたところ、実施
例１と略同性能の結果が得られた。固化開始温度は87±
１℃であつた。Example 3 In Example 1, when MgAl 2 O 4 powder was added in an amount of 1% by weight in place of MgF 2 and the same test as in Example 1 was performed, the results of substantially the same performance as in Example 1 were obtained. . Solidification start temperature is 87 ±
It was 1 ° C.
実施例４ 実施例１において、MgF2の代りに、MgSiO3粉末を0.5重
量％加え、実施例１と同様の試験を行なつたところ、実
施例１と同性能の結果が得られた。Example 4 In Example 1, when MgSiO 3 powder was added in an amount of 0.5% by weight in place of MgF 2 and the same test as in Example 1 was performed, the same performance results as in Example 1 were obtained.
実施例５ 実施例１において、MgF2の代りにCaF2粉末を２重量％加
え、実施例１と同様の試験を行なつたところ、実施例１
とほぼ同性能の結果が得られた。Example 5 The same test as in Example 1 was conducted by adding 2% by weight of CaF 2 powder in place of MgF 2 in Example 1, and
The result of almost the same performance was obtained.
実施例６ 実施例１において、MgF2の代りにCaWO4を0.5重量％加
え、実施例１と同様の試験を行ない、実施例１とほぼ同
性能の結果を得た。Example 6 In Example 1, 0.5% by weight of CaWO 4 was added instead of MgF 2 , the same test as in Example 1 was performed, and the result of almost the same performance as in Example 1 was obtained.
実施例７ 実施例１において、MgF2の代りに、BaF2粉末を0.5重量
％加え、実施例１と同様の試験を行ない、実施例１と同
性能の結果を得た。固化開始温度は88±１℃であつた。Example 7 In Example 1, 0.5% by weight of BaF 2 powder was added instead of MgF 2 , the same test as in Example 1 was performed, and the same performance result as in Example 1 was obtained. The solidification start temperature was 88 ± 1 ° C.
実施例８ 実施例１においてMgF2の代りにBaTiO3粉末あるいはBaZr
O3粉末を0.5重量％加え、実施例１と同様の試験を行な
い、実施例１とほぼ同性能の結果を得た。固化開始温度
は87±１℃であつた。Example 8 BaTiO 3 powder or BaZr was used instead of MgF 2 in Example 1.
O 3 powder was added in an amount of 0.5% by weight, the same test as in Example 1 was performed, and the result of substantially the same performance as in Example 1 was obtained. The solidification start temperature was 87 ± 1 ° C.
実施例９ Ca（NO3）２・4H2Oを2.5重量％,Mg（NO3）２・6H2Oに添
加した混合物は、融点86℃融解熱34cal/gである。この
混合物にBaZrO3を0.1重量％加え実施例１と同様の70〜1
00℃間のヒートサイクル試験において、200回以上、順
調に相変化をくり返した。Example 9 Ca (NO 3) 2 · 4H 2 O 2.5 wt%, Mg (NO 3) mixture was added to 2 · 6H 2 O is a melting point of 86 ° C. The heat of fusion 34cal / g. To this mixture was added 0.1% by weight of BaZrO 3 and the same 70 to 1 as in Example 1.
In the heat cycle test between 00 ° C, the phase change was repeated 200 times or more smoothly.
実施例10 MgCl2・6H2Oを7.6重量％,Mg（NO3）２・6H2Oに添加した
混合物は、融点78℃、融解熱32cal/gである。この混合
物にBaZrO3を0.1重量％加え実施例１と同様の70〜100℃
間のヒートサイクル試験において200回以上、順調に相
変化をくり返した。Example 10 A mixture obtained by adding MgCl 2 .6H 2 O to 7.6% by weight of Mg (NO 3 ) 2 .6H 2 O has a melting point of 78 ° C. and a heat of fusion of 32 cal / g. To this mixture was added 0.1% by weight of BaZrO 3 , and the same as in Example 1 was conducted at 70 to 100 ° C.
During the heat cycle test, the phase change was repeated steadily more than 200 times.
以上説明したとおり、この発明はMg（NO3）２・6H2Oあ
るいはMg（NO3）２・6H2Oを主成分とする組成物に、MgF
2、Mg（OH）２、MgAl2O4、MgFeO4、MgMoO4、MgSiO3、Mg
2SiO4、MgTiO3、MgWO4およびMgZrO3から選ばれた水に不
溶性のマグネシウム塩、CaF2、Ca（OH）２、CaAl2O4、C
aMoO4、CaSiO3、Ca2SiO4およびCaWO4から選ばれた水に
不溶性のカルシウム塩ならびにBaF2、BaCO3、BaSO4、Ba
MoO4、BaSiO3、BaTiO3、BaWO4およびBaZrO3から選ばれ
た水に不溶性のバリウム塩の少なくとも一種を加えたも
のを用いることにより、融液が中性近傍で、過冷却防止
効果がより長時間安定に保持される蓄熱材を得ることが
できる。Or as described in the present invention is Mg (NO 3) 2 · 6H 2 O or Mg (NO 3) compositions based on 2 · 6H 2 O, MgF
2 , Mg (OH) 2 , MgAl 2 O 4 , MgFeO 4 , MgMoO 4 , MgSiO 3 , Mg
2 Water-insoluble magnesium salt selected from SiO 4 , MgTiO 3 , MgWO 4 and MgZrO 3 , CaF 2 , Ca (OH) 2 , CaAl 2 O 4 , C
Water-insoluble calcium salt selected from aMoO 4 , CaSiO 3 , Ca 2 SiO 4 and CaWO 4, and BaF 2 , BaCO 3 , BaSO 4 , Ba
By using a mixture of water selected from MoO 4 , BaSiO 3 , BaTiO 3 , BaWO 4 and BaZrO 3 with at least one insoluble barium salt, the melt is in the vicinity of neutrality and the supercooling prevention effect is further improved. It is possible to obtain a heat storage material that is stably maintained for a long time.
Claims (2)
6H2Oを主成分とする組成物に、MgF2、Mg（OH）２、MgAl
2O4、MgFeO4、MgMoO4、MgSiO3、Mg2SiO4、MgTiO3、MgWO
4およびMgZrO3から選ばれた水に不溶性のマグネシウム
塩、CaF2、Ca（OH）２、CaAl2O4、CaMoO4、CaSiO3、Ca2
SiO4およびCaWO4から選ばれた水に不溶性のカルシウム
塩ならびにBaF2、BaCO3、BaSO4、BaMoO4、BaSiO3、BaTi
O3、BaWO4およびBaZrO3から選ばれた水に不溶性のバリ
ウム塩の内の少なくとも一種を加えた蓄熱材。1. A Mg (NO 3) 2 · 6H 2 O or Mg (NO 3) 2 ·
The composition containing 6H 2 O as the main component, MgF 2 , Mg (OH) 2 , MgAl
2 O 4 , MgFeO 4 , MgMoO 4 , MgSiO 3 , Mg 2 SiO 4 , MgTiO 3 , MgWO
4 and MgZrO 3 water-insoluble magnesium salt, CaF 2 , Ca (OH) 2 , CaAl 2 O 4 , CaMoO 4 , CaSiO 3 , Ca 2
Water-insoluble calcium salt selected from SiO 4 and CaWO 4 and BaF 2 , BaCO 3 , BaSO 4 , BaMoO 4 , BaSiO 3 , BaTi
A heat storage material obtained by adding at least one of insoluble barium salts selected from O 3 , BaWO 4 and BaZrO 3 .
ウム塩の内の少なくとも一種が0.05〜３重量％である特
許請求の範囲第１項記載の蓄熱材。2. The heat storage material according to claim 1, wherein at least one of magnesium salt, calcium salt and barium salt is contained in an amount of 0.05 to 3% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62179355A JPH0692578B2 (en) | 1987-07-16 | 1987-07-16 | Heat storage material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62179355A JPH0692578B2 (en) | 1987-07-16 | 1987-07-16 | Heat storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6422983A JPS6422983A (en) | 1989-01-25 |
| JPH0692578B2 true JPH0692578B2 (en) | 1994-11-16 |
Family
ID=16064395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62179355A Expired - Fee Related JPH0692578B2 (en) | 1987-07-16 | 1987-07-16 | Heat storage material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692578B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609098B (en) * | 2018-12-12 | 2021-01-22 | 上海交通大学 | Composite phase-change heat storage material and preparation thereof |
| CN113913161B (en) * | 2021-11-18 | 2024-02-23 | 上海电气集团股份有限公司 | Phase change material and preparation method thereof, temperature control box and temperature control system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6151079A (en) * | 1984-08-21 | 1986-03-13 | Central Glass Co Ltd | Thermal energy storage material |
-
1987
- 1987-07-16 JP JP62179355A patent/JPH0692578B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6422983A (en) | 1989-01-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |