CN1840603A - Salt eutectic phase-change material and method for making same - Google Patents
Salt eutectic phase-change material and method for making same Download PDFInfo
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- CN1840603A CN1840603A CNA2005100651319A CN200510065131A CN1840603A CN 1840603 A CN1840603 A CN 1840603A CN A2005100651319 A CNA2005100651319 A CN A2005100651319A CN 200510065131 A CN200510065131 A CN 200510065131A CN 1840603 A CN1840603 A CN 1840603A
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The provided eutectic salt phase-change material for both refrigeration and heating includes all in common product of transmission medium, eutectic salt, host crystal, and clay instead of smoked silicon as surfactant, and can overcome defect in prior art and the safety led smoked silicon. This invention has high heat exchange efficiency, high chemical stability, and can serve for long time.
Description
Technical field the present invention relates to a kind of salt eutectic phase-change material with and preparation method thereof, relate in particular to utilization and can form the clay of hydrate as tensio-active agent.
The storage of background technology thermal energy promptly is that high temperature energy or low temperature energy are temporarily stored, to do application after a while.The demand that reaches for the renewable energy resources day by day increases because energy prices constantly rise, and the storage of thermal energy is paid close attention to just day by day.The storage of thermal energy can reduce time and the ratio coupling between energy supply and energy requirement, and therefore, it is playing the part of vital role in energy saving with in preserving.Thermal energy can be stored with different forms:
(1) thermal energy storage of sensible heat-in hot storage system or condensation storage system, all can be relevant with the temperature variation of storage medium with sensible heat form energy stored.
(2) thermal energy storage of chemical reaction-in hot storage system or condensation storage system, with the chemical reaction generate energy heat energy that takes place in the storage medium.
(3) thermal energy storage (thermal energy storage of latent heat) of phase change material (Phase Change Materials)-in hot storage system or condensation storage system, energy mainly sees through phase change material (being situated between between solid-state and the liquid state) as storage medium, and stores (usually in fusion) with the form of latent heat.
Cold storage system freezed hot storage medium in the period of low freezing demand, and hot storage medium is in low-temperature condition, and the low warm storage medium that these store is applied to air-conditioning aspect or other refrigerating process after a while.Modal hot storage medium is water, ice, phase-transition material (as eutectic salts etc.).Wherein, the Chemical Composition of the eutectic salts in the phase change material is the mixture of inorganic salt, water and other element, forms solid phase in a predetermined temperature, does the heat storage.Can not melt, can not produce single solid phase harmoniously is the modal Chemical Problem of this type of phase change material, for example: during their fusings, often produce the lower salt hydrate of hydrate.Since density and Chemical Composition variation, the bottom of equipment often produces the throw out after the decomposition, has reduced the fusion crystalline cycle, phase change material is apt to deteriorate, also causes the phase change material supercool but.
Be the part head it off, in the prior art, nuclei of crystallization material and tensio-active agent often are added in the salt eutectic phase-change material.Tensio-active agent is to be used for preventing that the lower salt hydrate of hydrate in the phase change material from producing, and nuclei of crystallization material can provide the nuclei of crystallization to give phase change material as seed, and the supercool that makes phase change material but chance reduces, and reaches the mutually solid temperature of expection.
Therefore, the salt eutectic phase-change material of prior art often comprises following composition: salt hydrate, nuclei of crystallization material and tensio-active agent.
In the prior art, the smoked silicon (silica fume) of atomizing shape is the most frequently used tensio-active agent, but because its weight is very light, disseminates easily in environment on every side, and intractable in the making processes of phase change material is also brought many potential danger.Also have and use Mierocrystalline cellulose as tensio-active agent, but its effect is relatively poor.
Therefore purpose of the present invention is that a kind of another kind of tensio-active agent that does not have the problems referred to above will be provided.
It is to have adopted the clay that can form hydrate to replace the smoked silicon etc. of prior art as tensio-active agent that summary of the invention the object of the present invention is to provide a kind of salt eutectic phase-change material and its making method, characteristics of the present invention.
The present invention has been owing to adopted smoked silicon etc. that the clay that can form hydrate replaces prior art as tensio-active agent, formation be single solid-phase construction, exist in the prior art thereby solved:
Can not reach jointly harmoniously fusing,
Can not produce single solid phase,
Chemical Composition is easy to generate variation, reaches
Problems such as efficient is low,
Also solved
The safety problem that smoked Silicon surfactant brings.
Therefore, the present invention does not have the misgivings on the safety owing to do not use smoked silicon; Again owing to produce single solid phase, also with regard to do not have of the prior artly can not to reach fusing harmoniously jointly, can not produce single solid phase, Chemical Composition is easy to generate variation, reach problems such as efficient is low.
Technical scheme provided by the invention is summarized as follows:
A kind of salt eutectic phase-change material is characterized in that: choose can form hydrate clay as the tensio-active agent in the described phase change material.This is the contribution place of the present invention to prior art.
Specific embodiments is:
Wherein said salt eutectic phase-change material comprises transmission medium, eutectic salts and nuclei of crystallization material.(transmission medium, eutectic salts and nuclei of crystallization material are salt eutectic phase-change material components well known in the art.)
The example of the clay of wherein said formed hydrate as tensio-active agent is a concavo-convex handful stone clay powder (Attapulgite Clay).
According to the general knowledge of this area, be appreciated that the weight percent of described tensio-active agent in making material should be advisable with 10-15%.
According to the general knowledge of this area, the weight percent that wherein said nuclei of crystallization material is made in the material at phase change material is 1-3%.
According to the general knowledge of this area, wherein said nuclei of crystallization material well known be sodium tetraborate.
According to the general knowledge of this area, wherein said eutectic salts can be the composition of single kind of salt hydrate or multiple salt hydrate.
According to the general knowledge of this area, wherein said eutectic salts is selected from ammonia chloride, sal glauberi, Repone K, sodium-chlor.
A kind of embodiment be wherein said eutectic salts according to following parts by weight ratio, make 6-8 Celsius ℃ low-temperature phase-change material:
As eutectic salts:
Ammonia chloride 40-45%
Sal glauberi 25-30%
Repone K 1-3%
Sodium-chlor 1-3%
Sodium tetraborate 1-3% as nuclei of crystallization material
Concavo-convex handful stone clay powder 10-15% as tensio-active agent
Transmission medium 1-21%
A kind of embodiment be the purity of wherein said ammonia chloride, sal glauberi, Repone K, sodium-chlor, sodium tetraborate reach 97% or more than.
A kind of embodiment is that described clay powder particulate magnitude range is the 200-400 order.
According to the general knowledge of this area, a kind of of wherein said transmission medium is water.
The present invention also provides the making method of above-mentioned salt eutectic phase-change material, and step comprises:
Other of clay powder and salt eutectic phase-change material made the step of material mixing.
A kind of embodiment is that the concrete steps of described making method comprise:
Earlier concavo-convex handful stone clay powder, eutectic salts are mixed, add transmission medium again and increase the temperature of mixture,, uninterruptedly stir the mixture up to forming starchiness with the increasing degree of 5 ℃ of per minutes, add sodium tetraborate afterwards again, again to keep starchy temperature constantly to stir the mixture one hour.After finishing above program, mixture is injected a high temperature resistant and etch-proof container, put into an environment that can be maintained at starchy temperature again eight hours, cool off injected plastic then or metal vessel is standby.
Each side effect of the present invention is as follows:
Safety: the present invention does not have the misgivings on the safety owing to do not use smoked silicon;
Single solid-phase construction: because single phase change material has distinctive latent heat characteristic itself, in being applied to hot storage system or condensation storage system, can see through be situated between single solid phase phase change material between solid-state and the liquid state of energy slowly is released or absorbs, temperature is highly stable during phase transformation, so very strong practicality is arranged.Owing to the stability of the clay that is applied to hydrate of the present invention is also very high, be evenly distributed in the whole salt eutectic phase-change material, securely the moisture content of hydrate promptly, the variation that makes single solid-phase construction can not produce concentration because of the variation of moisture content makes a variation, and therefore can be repeatedly used.
Therefore owing to produce single solid phase, also with regard to do not have of the prior artly can not to reach fusing harmoniously jointly, can not produce single solid phase, Chemical Composition is easy to generate variation, reach problems such as efficient is low.Therefore the present invention also has wide, the reusable advantage such as chemometamorphism that can produce for many years and not of safe, practical property is strong, job stability is high, chemical stability is high, the heat exchange of the phase change material of made is more general phase change material efficient height, working temperature.
Economical: as in addition, on economic level, in the present invention, to reach more safely simply, also can reduce the operating cost of making owing to handle clay powder.Transmission medium can adopt water reducing cost,
The molten point of the solid-liquid of low-temperature phase-change material conversion improves industrial applicibility: owing to wherein can be 6-8 ℃, can be applicable in the industrial refrigeration system, particularly being applied to some energy charge is the place that changes along with the time, when for example energy expenditure charge in the daytime is high than the night, can utilize low-temperature phase-change material to freeze more cheap night in charge with the person, and in the daytime cold the discharging of being stored, reduce in the daytime competition to energy requirement.
Of many uses: as in the application of reality refrigeration, heating, can use as hot energy storage in refrigeration in the civilian central air conditioner system and heating, so the present invention to be of many uses.
Description of drawings Fig. 1 has shown the forming process of water-soluble process stage eutectic salts Heshui thing of making processes of the embodiment 1 of phase change material of the present invention.From D as seen, formation be single solid phase, precipitation not.
The implication of mark 11-14 and 21-23 is as follows:
11: positive ion
12: negative ion
13: positive ion
14: negative ion
21: tensio-active agent
22: nuclei of crystallization material
23: transmission medium
Embodiment as mentioned above, the present invention is unexpected to find to use the clay that can form hydrate to replace the normal smoked silicon that uses of prior art as tensio-active agent, can solve exist in the prior art such as: can not reach jointly harmoniously that fusing maybe can not produce single solid phase, Chemical Composition is easy to generate variation, and reach problems such as efficient is low, also solve the safety problem that smoked Silicon surfactant is brought simultaneously.Effect of the present invention is because what form is a kind of single solid phase, therefore derive safety, heat exchanger effectiveness height, practical, working temperature is wide, chemical stability is high, the reusable advantage such as chemometamorphism that can produce for many years and not.
And key of the present invention is to adopt the clay can form hydrate as tensio-active agent, can form the example of clay of hydrate such as concavo-convex handful stone clay powder (that is: Attapulgite Clay) etc.
Under bound by theory not, concavo-convex handful stone clay powder why can successfully form in the following embodiments single solid phase (see Table 1 single latent heat numerical value---what expression formed is " single " solid phase, be different from the non-single solid phase that a plurality of latent heat numerical value occur), precipitation is not because it has the character that can form hydrate.As long as other clay powder can form hydrate, also can form single solid-phase construction and reach goal of the invention.
Below, will be as an example with concavo-convex handful stone clay powder, demonstration: the clay powder that can form hydrate can form single solid-phase construction and reach goal of the invention.But not should be appreciated that scope of the present invention only is subject to the various specific embodiments of embodiment.
At first, the forming process of eutectic salts hydrate is as follows in the water-soluble process stage in the making processes of phase change material:
Figure A has shown and has comprised positive ion 11 and 13 and during two kinds of eutectic salts compound of negative ion 12 and 14, the eutectic salts compound is still with initial steady state and exists, add transmission medium 23, tensio-active agent 21 and nuclei of crystallization material 22 again and increase the temperature of mixture with the increasing degree of per minute five degree, uninterruptedly stir the mixture, when forming starchiness, the positive ion 11 of eutectic salts compound and 13 with negative ion 12 and 14 can separate gradually (B that sees Fig. 1).When constantly stirring the mixture again; tensio-active agent 21 can become protective membrane with the surface of negative ion 12 and 14 at positive ion 11 and 13; and prevent that positive ion 11 and 13 from going further with negative ion 12 and 14 and be in the same place; generation can not reach harmoniously fusing or problem that can not single solid phase jointly; put into an environment that can be maintained at starchy temperature again eight hours; new eutectic salts compound slowly produces under the help of nuclei of crystallization material 22, has formed single crystal solid phase.
Embodiment 1: the process of making low temperature+8 ℃ phase change material
The starting material proportion of present embodiment is as follows:
The eutectic salt:
Ammonia chloride 40-45%
Sal glauberi 25-30%
Repone K 1-3%
Sodium-chlor 1-3%
And
Sodium tetraborate 1-3%
Concavo-convex handful stone clay powder 10-15%
Transmission medium (that is: water) 1-21%
Earlier concavo-convex handful stone clay powder, ammonia chloride, sal glauberi, Repone K and sodium-chlor are mixed, add transmission medium again and increase the temperature of mixture with the increasing degree of per minute five degree, cause 70 degree Celsius up to reaching, become starchiness, uninterruptedly stir the mixture, add sodium tetraborate afterwards again, be maintained at 70 degree Celsius again and constantly stirred the mixture in one hour.After finishing above program, mixture is injected a high temperature resistant and etch-proof container, put into the environment eight hours that can be maintained at 70 degree Celsius again, cool off injected plastic then or metal vessel is standby.Wherein do not precipitate, therefore formed is single crystal solid phase.Molten some during the scanning calorimetric is 8 ℃, and potential heat value is 142kJ/kg.
Embodiment 2: the process of making+32 ℃ of phase change materials
The starting material proportion of present embodiment is as follows:
The eutectic salt:
Sal glauberi 70-75%
And
Sodium tetraborate 1-3%
Concavo-convex handful stone clay powder 10-15%
Transmission medium (water) 7-19%
Earlier concavo-convex handful stone clay powder, sal glauberi are mixed, add transmission medium again and increase the temperature of mixture with the increasing degree of per minute five degree, cause 85 degree Celsius up to reaching, become starchiness, uninterruptedly stir the mixture, add sodium tetraborate afterwards again, take the photograph 85 degree and constantly stirred the mixture in one hour to be maintained at again.After finishing above program, mixture is injected a high temperature resistant and etch-proof container, put into one again and can be maintained at Celsius 85 environment of spending eight hours, cool off injected plastic then or metal vessel is standby.Wherein do not precipitate, therefore formed is single crystal solid phase.Molten some during the scanning calorimetric is 32 ℃, and potential heat value is 190kJ/kg.
Embodiment 3: the process of making+28 ℃ of phase change materials
The starting material proportion of present embodiment is as follows:
The eutectic salt:
Calcium chloride hexahydrate 65-70%
And
Sodium tetraborate 1-3%
Concavo-convex handful stone clay powder 10-15%
Transmission medium (water) 22-24%
Earlier concavo-convex handful stone clay powder, calcium chloride hexahydrate are mixed, add transmission medium again and increase the temperature of mixture with the increasing degree of per minute five degree, cause 65 degree Celsius up to reaching, become starchiness, uninterruptedly stir the mixture, add sodium tetraborate afterwards again, constantly stirred the mixture in one hour to be maintained at 65 degree Celsius again.After finishing above program, mixture is injected a high temperature resistant and etch-proof container, put into one again and can be maintained at Celsius 65 environment of spending eight hours, cool off injected plastic then or metal vessel is standby.Wherein do not precipitate, therefore formed is single crystal solid phase.Molten some during the scanning calorimetric is 28 ℃, and potential heat value is 202kJ/kg.
Embodiment 4: the process of making+58 ℃ of phase change materials
The starting material proportion of present embodiment is as follows:
The eutectic salt:
Magnesium chloride hexahydrate 35-40%
Magnesium nitrate hexahydrate 35-40%
And
Sodium tetraborate 1-3%
Concavo-convex handful stone clay powder 10-15%
Transmission medium (also being water) 2-19%
Earlier concavo-convex handful stone clay powder, magnesium chloride hexahydrate, magnesium nitrate hexahydrate are mixed, add transmission medium again and increase the temperature of mixture with the increasing degree of per minute five degree, cause 90 degree Celsius up to reaching, become starchiness, uninterruptedly stir the mixture, add sodium tetraborate afterwards again, constantly stirred the mixture in one hour to be maintained at 90 degree Celsius again.After finishing above program, mixture is injected a high temperature resistant and etch-proof container, put into one again and can be maintained at Celsius 90 environment of spending eight hours, cool off injected plastic then or metal vessel is standby.Wherein do not precipitate, therefore formed is single crystal solid phase.Molten some during the scanning calorimetric is 58 ℃, and potential heat value is 210kJ/kg.
Table 1
| Embodiment | Transformation temperature (℃) | Density (kg/m 3) | Latent heat (kJ/kg) | Latent heat (MJ/m 3) |
| 1 | 8 | 1503 | 142 | 213 |
| 2 | 32 | 1490 | 190 | 283 |
| 3 | 28 | 1290 | 202 | 261 |
| 4 | 58 | 1340 | 210 | 281 |
The latent heat numerical value that above-mentioned table 1 is obtained when showing the scanning calorimetric of phase change material among each embodiment.When utilizing the scanning calorimeter, when low temperature promotes the temperature of phase change material at leisure with 5 ℃ of per minutes, when reaching when causing the phase deformation states, phase change material can begin slowly to absorb heat energy, become liquid phase until all solid phases, single solid phase is owing to only carry out once phase transformation, so also only occur a latent heat numerical value during scanning calorimetric.Therefore what demonstrate that the product of each embodiment produces is single solid-phase construction.
Claims (14)
1. salt eutectic phase-change material is characterized in that: choose can form hydrate clay as the tensio-active agent in the described phase change material.
2. according to the material of claim 1, wherein said salt eutectic phase-change material comprises transmission medium, eutectic salts and nuclei of crystallization material.
3. according to the material of claim 1, the clay of wherein said formed hydrate as tensio-active agent is concavo-convex handful stone clay powder.
4. according to the described material of one of claim 1-3, the weight percent of wherein said tensio-active agent in making material is 10-15%.
5. material according to claim 2, the weight percent that wherein said nuclei of crystallization material is made in the material at phase change material is 1-3%.
6. material according to claim 2, wherein said nuclei of crystallization material is a sodium tetraborate.
7. material according to claim 2, wherein said eutectic salts are the single kind of salt hydrate or the composition of multiple salt hydrate.
8. according to claim 2 or 7 described materials, wherein said eutectic salts is selected from ammonia chloride, sal glauberi, Repone K and sodium-chlor.
9. material according to claim 8, wherein said eutectic salts are made 6-8 Celsius ℃ low-temperature phase-change material according to following parts by weight ratio:
As eutectic salts:
Ammonia chloride 40-45%
Sal glauberi 25-30%
Repone K 1-3%
Sodium-chlor 1-3%
Sodium tetraborate 1-3% as nuclei of crystallization material
Concavo-convex handful stone clay powder 10-15% as tensio-active agent
Transmission medium 1-21%.
10. according to Claim 8 or 9 described materials, the purity of wherein said ammonia chloride, sal glauberi, Repone K, sodium-chlor, sodium tetraborate reach 97% or more than.
11. material according to claim 1, wherein the particulate magnitude range of clay powder is the 200-400 order.
12. according to claim 1 or 9 described materials, wherein said transmission medium is a water.
13. the making method of each described salt eutectic phase-change material among the claim 1-12, step comprises:
Other of each described salt eutectic phase-change material among clay powder and the claim 1-12 made the step of material mixing.
14. the described making method of claim 13, step comprises:
Earlier concavo-convex handful stone clay powder, eutectic salts are mixed, add transmission medium again and increase the temperature of mixture,, uninterruptedly stir the mixture up to forming starchiness with the increasing degree of 5 ℃ of per minutes, add sodium tetraborate afterwards again, again to keep starchy temperature constantly to stir the mixture one hour.After finishing above program, mixture is injected a high temperature resistant and etch-proof container, put into an environment that can be maintained at starchy temperature again eight hours, cool off injected plastic then or metal vessel is standby.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994053A (en) * | 2011-09-08 | 2013-03-27 | 中国石油化工股份有限公司 | Composite coolant and preparation method thereof, and demulsification method of high-wax crude oil produced fluid |
| CN103756645A (en) * | 2014-01-24 | 2014-04-30 | 熊建平 | Cold-chain transportation phase change material and preparation method thereof |
| CN104531084A (en) * | 2014-12-09 | 2015-04-22 | 河南派尔生物技术有限公司 | Constant temperature liquid |
| CN105885801A (en) * | 2014-09-23 | 2016-08-24 | 李敬武 | Novel cool storage agent, preparation method of novel cool storage agent and medical cold compress product containing novel cool storage agent |
| CN108603098A (en) * | 2016-02-12 | 2018-09-28 | 日本冷链有限公司 | Cold-storage material, cold insulation storage apparatus and cold insulation transportation resources |
| CN113136175A (en) * | 2020-01-24 | 2021-07-20 | 纯钧新材料(深圳)有限公司 | Preparation method of inorganic phase change material as coolant |
| TWI750607B (en) * | 2019-07-08 | 2021-12-21 | 大陸商深圳市前海萬綠源環保科技有限公司 | Method of using eutectic salt phase change material and clay preparation device |
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2005
- 2005-03-31 CN CNA2005100651319A patent/CN1840603A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102994053A (en) * | 2011-09-08 | 2013-03-27 | 中国石油化工股份有限公司 | Composite coolant and preparation method thereof, and demulsification method of high-wax crude oil produced fluid |
| CN102994053B (en) * | 2011-09-08 | 2015-04-29 | 中国石油化工股份有限公司 | Composite coolant and preparation method thereof, and demulsification method of high-wax crude oil produced fluid |
| CN103756645A (en) * | 2014-01-24 | 2014-04-30 | 熊建平 | Cold-chain transportation phase change material and preparation method thereof |
| CN103756645B (en) * | 2014-01-24 | 2016-04-27 | 熊建平 | Cold-chain transportation phase change material and preparation method thereof |
| CN105885801A (en) * | 2014-09-23 | 2016-08-24 | 李敬武 | Novel cool storage agent, preparation method of novel cool storage agent and medical cold compress product containing novel cool storage agent |
| CN104531084A (en) * | 2014-12-09 | 2015-04-22 | 河南派尔生物技术有限公司 | Constant temperature liquid |
| CN108603098A (en) * | 2016-02-12 | 2018-09-28 | 日本冷链有限公司 | Cold-storage material, cold insulation storage apparatus and cold insulation transportation resources |
| TWI750607B (en) * | 2019-07-08 | 2021-12-21 | 大陸商深圳市前海萬綠源環保科技有限公司 | Method of using eutectic salt phase change material and clay preparation device |
| CN113136175A (en) * | 2020-01-24 | 2021-07-20 | 纯钧新材料(深圳)有限公司 | Preparation method of inorganic phase change material as coolant |
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