JPS6318988B2 - - Google Patents
Info
- Publication number
- JPS6318988B2 JPS6318988B2 JP18253381A JP18253381A JPS6318988B2 JP S6318988 B2 JPS6318988 B2 JP S6318988B2 JP 18253381 A JP18253381 A JP 18253381A JP 18253381 A JP18253381 A JP 18253381A JP S6318988 B2 JPS6318988 B2 JP S6318988B2
- Authority
- JP
- Japan
- Prior art keywords
- sodium acetate
- heat storage
- storage material
- sodium
- acetate trihydrate
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
- 239000013078 crystal Substances 0.000 claims description 32
- 230000006911 nucleation Effects 0.000 claims description 31
- 238000010899 nucleation Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 30
- 238000005338 heat storage Methods 0.000 claims description 25
- 239000011232 storage material Substances 0.000 claims description 25
- 235000017281 sodium acetate Nutrition 0.000 claims description 22
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 20
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 229920001169 thermoplastic Polymers 0.000 claims description 16
- 239000004416 thermosoftening plastic Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- XNNKOVGFHZTMCJ-UHFFFAOYSA-M sodium;bromide;dihydrate Chemical compound O.O.[Na+].[Br-] XNNKOVGFHZTMCJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000004203 carnauba wax Substances 0.000 claims description 4
- 235000013869 carnauba wax Nutrition 0.000 claims description 4
- 239000001993 wax Substances 0.000 claims description 4
- LJJVHQAQGPFMHL-UHFFFAOYSA-M O.O.O.[Na+].[O-]C=O Chemical compound O.O.O.[Na+].[O-]C=O LJJVHQAQGPFMHL-UHFFFAOYSA-M 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000004781 supercooling Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 230000002265 prevention Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- ZBTUYCUNQBRXOR-UHFFFAOYSA-L sodium succinate hexahydrate Chemical compound O.O.O.O.O.O.[Na+].[Na+].[O-]C(=O)CCC([O-])=O ZBTUYCUNQBRXOR-UHFFFAOYSA-L 0.000 description 1
- 229940074453 sodium succinate hexahydrate Drugs 0.000 description 1
- PAYGMRRPBHYIMA-UHFFFAOYSA-N sodium;trihydrate Chemical compound O.O.O.[Na] PAYGMRRPBHYIMA-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は蓄熱材に関する。さらに詳しくは、本
発明は結晶核生成材を酢酸ナトリウム・３水塩ま
たはそれを主成物とする混合物に加えてえられる
過冷却の防止せられた蓄熱材に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat storage material. More specifically, the present invention relates to a heat storage material that is prevented from supercooling and is obtained by adding a crystal nucleation material to sodium acetate trihydrate or a mixture containing the same as a main component.
融解潜熱を利用する50〜60℃域の蓄熱材として
はハイポ（Na2S2O3・5H2O、融点48℃、融解熱
約50cal/ｇ）が知られているが、そのものは２水
塩を晶出しやすく相変化安定性に劣ることおよび
過冷却しやすく末だその解決策が見出されていな
いことなどのために最近ではあまり注目されてい
ない。酢酸ナトリウム・３水塩（CH3COONa・
3H2O、融点58℃、融解熱60cal/ｇ）はハイポに
くらべて相変化安定性にすぐれていることから、
ハイポに代る蓄熱材として注目されるようになつ
てきている。しかし酢酸ナトリウム・３水塩はハ
イポと同じく過冷却しやすいという欠点を有して
いるため、融解潜熱を利用する蓄熱材として用い
るには、いかにしてこの過冷却を防止するかが大
きなポイントである。 Hypo (Na 2 S 2 O 3 5H 2 O, melting point 48°C, heat of fusion approximately 50 cal/g) is known as a heat storage material in the 50 to 60°C range that uses latent heat of fusion. Recently, it has not received much attention because it tends to crystallize salts, has poor phase change stability, and is prone to supercooling, and no solutions have been found for this problem. Sodium acetate trihydrate (CH 3 COONa)
3H 2 O, melting point 58℃, heat of fusion 60cal/g) has superior phase change stability compared to hypo.
It is attracting attention as a heat storage material that can replace hypo. However, like hypo, sodium acetate trihydrate has the disadvantage of being easily supercooled, so the key point in using it as a heat storage material that utilizes the latent heat of fusion is how to prevent this supercooling. be.
この過冷却を防止する方策として、本発明者ら
は酢酸ナトリウム・３水塩に水分を添加する方法
（特開昭51−126980号公報参照）を提供してきて
いる。この方法でえられる蓄熱材は水分の添加に
よりかなり過冷却が破れやすくなるとはいえ、長
期使用に対する信頼性に欠けるものである。また
本発明者らは酢酸ナトリウム・３水塩にコハク酸
ナトリウム・６水塩（Na2C4H4O4・6H2O）を結
晶核生成材として加える方法（特開昭55−16035
号公報参照）を提供してきているが、この方法で
は30℃以下にまで冷却されないと過冷却防止効果
を発現しえず、用途が制限される。さらに本発明
者らは酢酸ナトリウム・３水塩にその他の塩、た
とえば臭化ナトリウム・２水塩（NaBr・2H2O）
などを添加する方法（特開昭53−14173号公報参
照）を提供してきている。その方法によりえられ
る蓄熱材、たとえば臭化ナトリウム・２水塩を10
重量％を含有する蓄熱材は結晶核生成材を添加し
なくても、1000サイクル以上のヒートサイクル試
験（60℃→40℃→60℃を１サイクルとして１日８
サイクル）において順調に相変化をくり返すが、
蟻酸ナトリウム・３水塩（HCOONa・3H2O）
を16重量％含有する蓄熱材では結晶核生成が生じ
るとはいえ、高度の信頼性を有していない。 As a measure to prevent this supercooling, the present inventors have proposed a method of adding water to sodium acetate trihydrate (see Japanese Patent Laid-Open No. 126980/1983). Although the heat storage material obtained by this method is considerably susceptible to overcooling due to the addition of moisture, it lacks reliability for long-term use. The present inventors also proposed a method of adding sodium succinate hexahydrate (Na 2 C 4 H 4 O 4 6H 2 O) to sodium acetate trihydrate as a crystal nucleation material (Japanese Patent Laid-Open No. 55-16035
However, this method does not have the effect of preventing supercooling unless it is cooled to below 30°C, which limits its use. Furthermore, the present inventors added other salts to sodium acetate trihydrate, such as sodium bromide dihydrate (NaBr.2H 2 O).
A method of adding the like (see Japanese Patent Application Laid-open No. 14173/1983) has been proposed. The heat storage material obtained by this method, such as sodium bromide dihydrate, is
The heat storage material containing 50% by weight can be heat cycle tested for more than 1000 cycles (60℃ → 40℃ → 60℃ is 8 cycles per day) without adding a crystal nucleation material.
Although the phase changes are repeated smoothly during the cycle),
Sodium formate trihydrate (HCOONa・3H 2 O)
Although crystal nucleation occurs in a heat storage material containing 16% by weight, it does not have a high degree of reliability.
これらの方法のほかに物理的な方法によつて結
晶核生成を促し、過冷却を防止する方法も知られ
ている。たとえば、米国特許第4077390号明細書
には蓄熱材中に金属片を加え、それを外部力によ
つて折り曲げることにより結晶核生成を行なう方
法が開示されている。しかし、このような物理的
方法は結晶核生成のための外部操作をそのつど行
なわなければならず、実用的な方法とはいいがた
い。 In addition to these methods, methods are also known in which physical methods are used to promote crystal nucleation and prevent supercooling. For example, US Pat. No. 4,077,390 discloses a method of generating crystal nuclei by adding a metal piece to a heat storage material and bending the metal piece by an external force. However, such physical methods require external operations for crystal nucleation each time, and cannot be said to be a practical method.
叙上の問題を克服しうる結晶核生成材を含んだ
蓄熱材が本発明者らにより見出されている。すな
わち、無水酢酸ナトリウムとある種のナトリウム
塩、なかんづくNa2HPO4またはNaH2PO4など
をプレス成形してえられる結晶核生成材は酢酸ナ
トリウム・３水塩からなる蓄熱材に加えたばあい
持続する過冷却防止効果を発現する。その効果を
長期にわたつて持続させるために、成形体に有機
溶剤で溶解したプラスチツクを浸み込ませて補強
したり、あるいはプラスチツク粉末を添加してプ
レス成形したのちそのプラスチツク粉末を幾分か
融解させるために100℃程度に加熱したり、また
は室温で硬化するプラスチツク類を少量添加した
りする工夫もなされている。 The present inventors have discovered a heat storage material containing a crystal nucleation material that can overcome the above problems. In other words, when a crystal nucleation material obtained by press-molding anhydrous sodium acetate and certain sodium salts, especially Na 2 HPO 4 or NaH 2 PO 4 , is added to a heat storage material made of sodium acetate trihydrate, Demonstrates a lasting supercooling prevention effect. In order to maintain this effect over a long period of time, the molded product is reinforced by impregnating it with plastic dissolved in an organic solvent, or by adding plastic powder and press-molding it, and then melting some of the plastic powder. In order to do this, efforts have been made to heat it to around 100 degrees Celsius, or to add small amounts of plastics that harden at room temperature.
しかしながら、それらの結晶核生成材の製造法
はプレス工程以外の追加工程を必要とするだけで
なく、その追加工程が煩雑であり、またえられる
結晶核生成材の品質保持が非常に困難である。 However, these methods of producing crystal nucleation materials not only require additional steps other than the pressing step, but these additional steps are complicated, and it is extremely difficult to maintain the quality of the resulting crystal nucleation materials. .
本発明者らは、かかる従来の現状に鑑み鋭意研
究を重ねた結果、プレス成形をホツトプレス成形
に代え、その成形時に熱可塑性有機物質を加える
ことにより、より信頼性の高い結晶核生成材を短
時間のうちに再現性よく製造しうるという事実を
見出し、本発明を完成するにいたつた。 As a result of extensive research in view of the current state of the art, the present inventors have found that by replacing press molding with hot press molding and adding a thermoplastic organic substance during the molding process, a more reliable crystal nucleation material can be produced in a shorter time. The present invention was completed based on the discovery that it can be manufactured within a short period of time and with good reproducibility.
すなわち本発明は、
無水酢酸ナトリウムとそれ以外のナトリウム塩お
よび熱可塑性有機物質からなる混合物をホツトプ
レス成形してえられる結晶核生成材を、酢酸ナト
リウム・３水塩またはそれを主成分とする混合物
に加えてなる蓄熱材に関する。 That is, the present invention provides a crystal nucleation material obtained by hot press molding a mixture of anhydrous sodium acetate, other sodium salts, and a thermoplastic organic substance, into sodium acetate trihydrate or a mixture containing it as a main component. It also relates to a heat storage material.
本発明に用いる無水酢酸ナトリウム以外のナト
リウム塩としては、好ましくはC6H5Na2PO4・
2H2O、NaBr、NaCl、NaNH4HPO4・4H2O、
CH2（COONa）2・H2O、ステアリン酸ナトリウ
ム、オレイン酸ナトリウム、Na3PO4、
Na5P3O10、Na2HPO4、Na2HPO4・2H2O、
NaH2PO4、NaH2PO4・H2O、NaH2PO4・
2H2Oなどがあげられるが、なかんづく
Na2HPO4、Na2HPO4・2H2O、NaH2PO4、
NaH2PO4・H2O、NaH2PO4・2H2Oまたはそれ
らの混合物が好適である。 The sodium salt other than anhydrous sodium acetate used in the present invention is preferably C 6 H 5 Na 2 PO 4 .
2H2O , NaBr, NaCl , NaNH4HPO4・4H2O ,
CH 2 (COONa) 2・H 2 O, sodium stearate, sodium oleate, Na 3 PO 4 ,
Na 5 P 3 O 10 , Na 2 HPO 4 , Na 2 HPO 4・2H 2 O,
NaH 2 PO 4 , NaH 2 PO 4・H 2 O, NaH 2 PO 4・
Examples include 2H 2 O, among others.
Na 2 HPO 4 , Na 2 HPO 4・2H 2 O, NaH 2 PO 4 ,
NaH 2 PO 4 .H 2 O, NaH 2 PO 4 .2H 2 O or mixtures thereof are preferred.
熱可塑性有機物質としてはポリエチレン、ポリ
プロピレン、ポリスチレン、ポリ塩化ビニル、
ABS樹脂、アクリル樹脂などのプラスチツク類、
松脂、カルナウバワツクスなどの天然ワツクス
類、さらには合成ワツクス類なども本発明に使用
しうる。これらの熱可塑性有機物質は少なくとも
粒径１mm以下の粉末状として用いられる。粒径が
１mmよりも大きなものを使用するとプレス成形し
てえられる結晶核生成材中に充分なカサ密度で混
合することができなくなるので好ましくない。 Thermoplastic organic substances include polyethylene, polypropylene, polystyrene, polyvinyl chloride,
Plastics such as ABS resin and acrylic resin,
Natural waxes such as pine resin and carnauba wax, as well as synthetic waxes, can also be used in the present invention. These thermoplastic organic substances are used in powder form with a particle size of at least 1 mm or less. It is not preferable to use particles with a particle size larger than 1 mm because they cannot be mixed with a sufficient bulk density into the crystal nucleation material obtained by press molding.
無水酢酸ナトリウム、それ以外のナトリウム塩
および熱可塑性有機物質は充分に混合、粉砕した
のち、ホツトプレス成形して所望の結晶核生成材
とすることができる。 Anhydrous sodium acetate, other sodium salts, and thermoplastic organic substances can be sufficiently mixed and pulverized, and then hot press molded to obtain a desired crystal nucleation material.
ホツトプレス成形は室温（約30℃）以上で、か
つ用いる熱可塑性有機物質の融点以下の温度範囲
で行なうのが好ましい。温度の選択は用いる熱可
塑性有機物質の種類や、結晶核生成材の最終カサ
密度などを基準にして行なわれ、融点に近い温度
であるほどえられる結晶核生成材を高密度にする
ことができる。 Hot press molding is preferably carried out at a temperature above room temperature (approximately 30° C.) and below the melting point of the thermoplastic organic material used. The temperature is selected based on the type of thermoplastic organic substance used and the final bulk density of the crystal nucleation material, and the closer the temperature is to the melting point, the higher the density of the crystal nucleation material obtained. .
またホツトプレス成形の圧力も同様に熱可塑性
物質や、結晶核生成材の最終カサ密度などを基準
にして適宜選択され、高い温度でプレス成形する
ものほどプレス圧力は低くてもよく、逆に低い温
度でプレス成形しなければならないものほど高い
圧力が必要である。通常、プレス圧力は数百Kg/
cm2ないし数トン／cm2の範囲で行なわれる。 Similarly, the pressure for hot press molding is appropriately selected based on the thermoplastic material and the final bulk density of the crystal nucleation material. The higher the pressure required, the higher the pressure required. Usually the press pressure is several hundred kg/
It is carried out in the range of cm 2 to several tons/cm 2 .
本発明における核生成材を酢酸ナトリウム・３
水塩からなる蓄熱材に加えたばあいに過冷却防止
効果を発現する理由については末だ充分な理論的
根拠をえておらず、現時点では理論的に説明する
ことができない。しかし、Na2HPO4などのナト
リウム塩および無水酢酸ナトリウムにポリエチレ
ンなどの熱可塑性有機物質を加えてプレス成形し
た結晶核生成材は、熱可塑性有機物質を加えずに
プレス成形してえられる従来の結晶核生成材にく
らべてすぐれた過冷却防止効果を発現する。すな
わち、Na2TPO4などのナトリウム塩とポリエチ
レンなどの熱可塑性有機物質の両者は共存すると
相互に妨害し合うのではなくて、かえつて逆に協
同し合つてその過冷却防止効果の発現を促進し合
うかのように働く。またポリエチレンなどの熱可
塑性有機物質は結合剤としての役割もあわせ有し
ており、その含有割合を増加させるほど蓄熱材中
でも溶解や崩壊のしにくいより強固な結晶核生成
材をつくることができる。ホツトプレス成形する
ことにより、結晶核生成材の密度が向上せられる
だけでなく、その機械的強度も向上し、かつその
過冷却防止能力が従来のものよりも高信頼性、長
寿命とすることができる。 The nucleation material in the present invention is sodium acetate 3
There is still no sufficient theoretical basis for why the supercooling prevention effect occurs when added to a heat storage material made of aqueous salt, and it cannot be explained theoretically at this point. However, the crystal nucleation material obtained by press-molding sodium salts such as Na 2 HPO 4 and anhydrous sodium acetate by adding thermoplastic organic substances such as polyethylene is different from conventional crystal nucleation materials obtained by press-molding without adding thermoplastic organic substances. Demonstrates superior supercooling prevention effect compared to crystal nucleation materials. In other words, when sodium salts such as Na 2 TPO 4 and thermoplastic organic substances such as polyethylene coexist, they do not interfere with each other, but rather work together to promote their supercooling prevention effect. We work as if we were meant to be together. Thermoplastic organic substances such as polyethylene also have the role of a binder, and as their content increases, a stronger crystal nucleation material that is less likely to dissolve or disintegrate even in a heat storage material can be created. Hot press molding not only improves the density of the crystal nucleation material, but also improves its mechanical strength, and its ability to prevent supercooling makes it more reliable and has a longer lifespan than conventional materials. can.
たとえばNa2HPO420％（重量％、以下同様）、
ポリエチレン20％および無水酢酸ナトリウム60％
からなる混合物を１トン／cm2の圧力下において室
温でプレス成形してえられる結晶核生成材は密度
が低いため、溶融状態にある酢酸ナトリウム・３
水塩中では浮くが、同圧力下において80℃でホツ
トプレス成形してえられる結晶核生成材は密度が
高いため、溶融状態にある酢酸ナトリウム・３水
塩中では底に沈み結晶核生成材としてよりすぐれ
た効果を発現できる。 For example, Na 2 HPO 4 20% (weight %, same below),
20% polyethylene and 60% anhydrous sodium acetate
The crystal nucleating material obtained by press-molding a mixture consisting of 1 ton/cm 2 at room temperature under a pressure of 1 ton/cm 2 has a low density.
Although it floats in aqueous salt, the crystal nucleation material obtained by hot press molding at 80℃ under the same pressure has a high density, so it sinks to the bottom in molten sodium acetate trihydrate and becomes a crystal nucleation material. It can produce better effects.
本発明における結晶核生成材は、酢酸ナトリウ
ム・３水塩のみからなる蓄熱材だけでなく、たと
えば酢酸ナトリウム・３水塩に蟻酸ナトリウム・
３水塩を５〜20％加えた蓄熱材、酢酸ナトリウ
ム・３水塩に臭化ナトリウム・２水塩を５〜15％
加えた蓄熱材などの酢酸ナトリウム・３水塩に
種々の第２成分を加えた蓄熱材に対して使用で
き、同等のまたはそれ以上の過冷却防止効果を長
期にわたつて発現する。 The crystal nucleation material in the present invention is not only a heat storage material consisting only of sodium acetate trihydrate, but also a heat storage material consisting of sodium acetate trihydrate and sodium formate.
Heat storage material with 5-20% trihydrate added, 5-15% sodium bromide/dihydrate added to sodium acetate/trihydrate
It can be used for heat storage materials made by adding various second components to sodium acetate trihydrate, etc., and exhibits the same or better supercooling prevention effect over a long period of time.
以上に述べたように、無水酢酸ナトリウムにそ
れ以外のナトリウム塩および熱可塑性有機物質粉
末を混合したのちホツトプレス成形してえられる
結晶核生成材はつぎのような長所を有している。 As mentioned above, the crystal nucleation material obtained by hot-pressing the mixture of anhydrous sodium acetate, other sodium salts, and thermoplastic organic material powder has the following advantages.
(イ) 強固であり、長期信頼性がある。(b) It is strong and has long-term reliability.
(ロ) 品質管理が容易であり、再現性が高い。(b) Quality control is easy and reproducibility is high.
(ハ) 製造のための作業工程が少ない。(c) There are fewer work processes for manufacturing.
(ニ) カサ密度が高い。(d) High bulk density.
つぎに実施例をあげて本発明の蓄熱材をより詳
細に説明するが、本発明はそれらの実施例のみに
限定されるものではない。 Next, the heat storage material of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例 １
Na2HPO420％、ポリエチレン粉末（平均粒径
100μ）20％および無水酢酸ナトリウム60％をよ
く混合、粉砕したのち、この混合物の約１ｇを80
℃、1000Kg/cm2でホツトプレス成形し、直径15mm、
厚さ３mmの円板形の結晶核生成材をえた。Example 1 Na 2 HPO 4 20%, polyethylene powder (average particle size
100μ) 20% and anhydrous sodium acetate 60% and pulverized, approximately 1g of this mixture was mixed with 80%
℃, hot press molded at 1000Kg/ cm2 , diameter 15mm,
A disk-shaped crystal nucleation material with a thickness of 3 mm was obtained.
つぎに酢酸ナトリウム・３水塩１Kgを加えた金
属アルミ製容器内にこの円板を１枚入れて密封し
た。このものを70℃→45℃→70℃を１サイクルと
したヒートサイクル試験（１日８サイクル、以下
同様）に供したところ、約53℃で過冷却が破れ、
順調に相変化を400回以上くり返した。 Next, one of the disks was placed in a metal aluminum container to which 1 kg of sodium acetate trihydrate was added, and the container was sealed. When this product was subjected to a heat cycle test (8 cycles per day, the same applies hereinafter) in which one cycle was 70°C → 45°C → 70°C, supercooling broke at about 53°C.
The phase change was successfully repeated over 400 times.
実施例 ２
NaH2PO425％、松脂粉末（100メツシユ）15
％および無水酢酸ナトリウム60％をよく混合、粉
砕したのち、この混合物の約１ｇを60℃、200Kg/
cm2の圧力でホツトプレス成形して、直径15mm、厚
さ３mmの円板形の結晶核生成材をえた。Example 2 NaH 2 PO 4 25%, rosin powder (100 mesh) 15
After thoroughly mixing and pulverizing % and 60% anhydrous sodium acetate, approximately 1 g of this mixture was heated to 200 kg/kg at 60°C.
A disk-shaped crystal nucleation material with a diameter of 15 mm and a thickness of 3 mm was obtained by hot press molding at a pressure of cm 2 .
つぎに酢酸ナトリウム・３水塩90％および臭化
ナトリウム・２水塩10％からなる混合物1.5Kgを
加えた直径50mm、長さ800mmの円筒形黒色ポリエ
チレン容器に、この円板２枚を入れて密封した。
このものを60℃→40℃→60℃を１サイクルとした
ヒートサイクル試験に供したところ、約50℃で過
冷却が破れ、順調に相変化を1000回以上くり返し
た。 Next, these two disks were placed in a cylindrical black polyethylene container with a diameter of 50 mm and a length of 800 mm to which 1.5 kg of a mixture consisting of 90% sodium acetate trihydrate and 10% sodium bromide dihydrate was added. Sealed.
When this product was subjected to a heat cycle test in which one cycle was 60°C → 40°C → 60°C, supercooling broke at about 50°C, and the phase change was smoothly repeated over 1000 times.
実施例 ３
Na2HPO4・2H2Oの15％、カルナウバワツク
ス粉末20％および無水酢酸ナトリウム65％をよく
混合し、粉砕したのち、この混合物の約１ｇを60
℃、600Kg/cm2でホツトプレス成形し、直径15mm、
厚さ３mmの円板形の結晶核生成材をえた。Example 3 After thoroughly mixing and pulverizing 15% Na 2 HPO 4 2H 2 O, 20% carnauba wax powder and 65% anhydrous sodium acetate, about 1 g of this mixture was
℃, hot press molded at 600Kg/ cm2 , diameter 15mm,
A disk-shaped crystal nucleation material with a thickness of 3 mm was obtained.
つぎに酢酸ナトリウム・３水塩84％および蟻酸
ナトリウム・３水塩16％からなる混合物２Kgを加
えたポリエチレン容器に、この円板を２枚入れて
密封した。このものを60℃→40℃→60℃を１サイ
クルとしたヒートサイクル試験に供したところ、
約47℃で過冷却が破れ、順調に相変化を500回以
上くり返した。 Next, two of the disks were placed in a polyethylene container containing 2 kg of a mixture consisting of 84% sodium acetate trihydrate and 16% sodium formate trihydrate, and the container was sealed. When this product was subjected to a heat cycle test with one cycle of 60℃→40℃→60℃,
Supercooling broke at about 47°C, and the phase change smoothly repeated over 500 times.
実施例 ４
NaH2PO4および松脂粉末に代えて、
NaH2PO4・H2Oおよびポリプロピレン粉末（50
メツシユ）を用い、ホツトプレス成形の条件を70
℃、400Kg/cm2としたほかは実施例２と同様にして
実験を行なつた。その結果、約50℃で過冷却が破
れ、順調に相変化を1000回以上くり返した。Example 4 Instead of NaH 2 PO 4 and rosin powder,
NaH 2 PO 4 H 2 O and polypropylene powder (50
(mesh) and hot press molding conditions to 70
The experiment was conducted in the same manner as in Example 2 except that the temperature was 400 Kg/cm 2 . As a result, supercooling broke down at about 50°C, and the phase change smoothly repeated over 1000 times.
実施例 ５
Na2HPO4・2H2Oおよびカルナウバワツクス
粉末に代えて、NaH2PO4およびポリ塩化ビニル
粉末（30メツシユ）を用いたほかは実施例３と同
様にして実験を行なつた。その結果、約47℃で過
冷却が破れ、順調に相変化を1000回以上くり返し
た。Example 5 An experiment was conducted in the same manner as in Example 3, except that NaH 2 PO 4 and polyvinyl chloride powder (30 mesh) were used instead of Na 2 HPO 4 2H 2 O and carnauba wax powder. Ta. As a result, supercooling was broken at approximately 47°C, and the phase change smoothly repeated over 1000 times.
実施例 ６
Na2HPO4およびポリエチレン粉末に代えて、
NaH2PO4・2H2Oおよびポリスチレン粉末（30
メツシユ）を用いたほかは実施例１と同様にして
実験を行なつた。その結果、約50℃で過冷却が破
れ、順調に相変化を1000回以上くり返した。Example 6 Instead of Na 2 HPO 4 and polyethylene powder,
NaH 2 PO 4 2H 2 O and polystyrene powder (30
The experiment was carried out in the same manner as in Example 1, except that Mesh was used. As a result, supercooling broke down at about 50°C, and the phase change smoothly repeated over 1000 times.
実施例 ７
ポリエチレン粉末に代えてポリメチルメタクリ
レート粉末を用いたほかは実施例１と同様にして
実験を行なつた。その結果、約50℃で過冷却が破
れ、順調に相変化を1000回以上くり返した。Example 7 An experiment was conducted in the same manner as in Example 1 except that polymethyl methacrylate powder was used instead of polyethylene powder. As a result, supercooling broke down at about 50°C, and the phase change smoothly repeated over 1000 times.
Claims (1)
塩および熱可塑性有機物質からなる混合物をホツ
トプレス成形してえられる結晶核生成材を、酢酸
ナトリウム・３水塩またはそれを主成物とする混
合物に加えてなる蓄熱材。 ２ 前記ナトリウム塩がNa2HPO4、
Na2HPO4・2H2O、NaH2PO4、NaH2PO4・
H2OまたはNaH2PO4・2H2Oである特許請求の
範囲第１項記載の蓄熱材。 ３ 前記熱可塑性有機物質がポリエチレン、ポリ
プロピレン、ポリスチレン、ポリ塩化ビニル、
ABS樹脂、アクリル樹脂などのプラスチツク類、
松脂、カルナウバワツクスなどの天然ワツクス類
または合成ワツクス類である特許請求の範囲第１
項または第２項記載の蓄熱材。 ４ 前記熱可塑性有機物質が平均粒子径１mm以下
の粉末である特許請求の範囲第３項記載の蓄熱
材。 ５ ホツトプレス成形が室温よりも高くかつ熱可
塑性有機物質の融点よりも低い温度で、数百〜数
千Kg/cm2の圧力下に行なわれる特許請求の範囲第
１項、第２項、第３項または第４項記載の蓄熱
材。 ６ 酢酸ナトリウム・３水塩を主成物とする混合
物が酢酸ナトリウム・３水塩80〜95重量％および
蟻酸ナトリウム・３水塩20〜５重量％の混合物ま
たは酢酸ナトリウム・３水塩85〜95重量％および
臭化ナトリウム・２水塩15〜５重量％の混合物で
ある特許請求の範囲第１項、第２項、第３項、第
４項または第５項記載の蓄熱材。[Scope of Claims] 1. A crystal nucleation material obtained by hot press molding a mixture of anhydrous sodium acetate, other sodium salts, and a thermoplastic organic substance, containing sodium acetate trihydrate or sodium acetate trihydrate as the main component. A heat storage material added to the mixture. 2 the sodium salt is Na 2 HPO 4 ,
Na 2 HPO 4・2H 2 O, NaH 2 PO 4 , NaH 2 PO 4・
The heat storage material according to claim 1, which is H2O or NaH2PO4.2H2O . 3 The thermoplastic organic substance is polyethylene, polypropylene, polystyrene, polyvinyl chloride,
Plastics such as ABS resin and acrylic resin,
Claim 1, which is a natural wax such as pine resin or carnauba wax, or a synthetic wax
The heat storage material according to item 1 or 2. 4. The heat storage material according to claim 3, wherein the thermoplastic organic substance is a powder with an average particle size of 1 mm or less. 5. Claims 1, 2, and 3 in which the hot press molding is carried out at a temperature higher than room temperature and lower than the melting point of the thermoplastic organic substance and under a pressure of several hundred to several thousand kg/ cm2 . The heat storage material according to item 1 or 4. 6 A mixture containing sodium acetate trihydrate as the main component is a mixture of 80 to 95% by weight of sodium acetate trihydrate and 20 to 5% by weight of sodium formate trihydrate or 85 to 95% of sodium acetate trihydrate % of sodium bromide dihydrate and 15 to 5% by weight of sodium bromide dihydrate.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18253381A JPS5883083A (en) | 1981-11-12 | 1981-11-12 | Thermal energy storage material |
| NL8200269A NL191418C (en) | 1981-03-09 | 1982-01-26 | Material for storing heat; method of preparing this material. |
| US06/343,767 US4400287A (en) | 1981-03-09 | 1982-01-28 | Heat storage material |
| DE19823208254 DE3208254A1 (en) | 1981-03-09 | 1982-03-08 | HEAT STORAGE MATERIAL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18253381A JPS5883083A (en) | 1981-11-12 | 1981-11-12 | Thermal energy storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5883083A JPS5883083A (en) | 1983-05-18 |
| JPS6318988B2 true JPS6318988B2 (en) | 1988-04-20 |
Family
ID=16119964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18253381A Granted JPS5883083A (en) | 1981-03-09 | 1981-11-12 | Thermal energy storage material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5883083A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6153386A (en) * | 1984-08-21 | 1986-03-17 | Hitachi Chem Co Ltd | Heat-storing material |
| JP3774530B2 (en) * | 1997-02-28 | 2006-05-17 | 住化プラステック株式会社 | Manufacturing method of heat storage material |
-
1981
- 1981-11-12 JP JP18253381A patent/JPS5883083A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5883083A (en) | 1983-05-18 |
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