CN1782018A - Composite fixing phase change material of 79-83 deg.c and its preparing method - Google Patents
Composite fixing phase change material of 79-83 deg.c and its preparing method Download PDFInfo
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- CN1782018A CN1782018A CN 200510116706 CN200510116706A CN1782018A CN 1782018 A CN1782018 A CN 1782018A CN 200510116706 CN200510116706 CN 200510116706 CN 200510116706 A CN200510116706 A CN 200510116706A CN 1782018 A CN1782018 A CN 1782018A
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- 239000012782 phase change material Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title description 6
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 52
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 52
- 239000012188 paraffin wax Substances 0.000 claims abstract description 39
- 230000008859 change Effects 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000004580 weight loss Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000003723 Smelting Methods 0.000 abstract 4
- 239000011358 absorbing material Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 26
- 238000007493 shaping process Methods 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The composite fixed 76-83 deg C phase change material and its preparation belongs to the field of phase change heat accumulating material technology. The present invention has SEBS of smelting point 76-81.6 deg C as the packing and oil absorbing material and paraffin of phase change latent heat 200-220 kJ/kg as main energy storing material, and consists of paraffin in 66-80 wt%, high density polyethylene in 11-15 wt%, SEBS in 4-12 wt% and expanded graphite in 3-7 wt%. The composite phase change material is prepared through smelting paraffin in a reactor, adding and smelting high density polyethylene and SEBS, adding expanded graphite and mixing homogeneously, molding at 200-300 KPa pressure to form plate, cooling and demoulding. The material may be set directly inside boiler to contact water as heat transferring medium, and after soaking in hot water in temperature above the smelting point for 200 hr, it has weight loss less than 2 % and phase change latent heat change less than 10 %.
Description
Technical field
The present invention relates to a kind of paraffin as main heat accumulation agent, high density polyethylene is sealed propping material, hydrogenated styrene-butadiene-styrene triblock copolymer SEBS makes the encapsulation oil absorption material, and expanded graphite EG makes the composite shape-setting phase-change material and the preparation method of heat conductive filler.
Background technology
The energy is the basis of human survival and development.Along with science and technology development, human demand to the energy increases day by day, but not high to rate of energy simultaneously, makes that the supply of the energy is gradually nervous.Be used for the energy storage technology in fields such as industrial afterheat recovery, phase-changing energy-storing electric space heating appliance, energy-saving type air conditioner, not only can reduce energy consumption, but also can make power system reach the effect of " peak load shifting ".So-called " peak load shifting " is meant power load transferred to the same day or go the low power consumption season from peak of power consumption.Advantages such as wherein phase-change accumulation energy has that energy storage density is big, energy storage capacity is big, homo(io)thermism, process are easy to control, can be repeatedly used become tool development potentiality, use maximum and most important heat accumulation mode at present.Wherein, the solid-liquid phase change material has the extensive attention that advantages such as energy storage density is big, energy storage process approximately constant temperature, volume change is little, process is easy to control obtain the various countries scientist.But solid-state-liquid mutual conversion that traditional solid-liquid phase change material can take place in use must be used special container encloses, has increased the thermal resistance between heat-transfer medium and the phase change material, has reduced heat transfer efficiency, and cost has also improved.For addressing these problems, in recent years, some scientific workers adopted some technology, made the solid-liquid phase change material still keep original shape when undergoing phase transition, thereby had had the performance of solid-solid phase transition material.People such as Xiao Min (Energy Conversion; Management, 2002,48 (1): P103) studied the composite phase-change material that paraffin and thermoplastic elastomer SBS and graphite are formed; Adopting double roll mill is that 56-58 ℃ paraffin and SBS banburying is even with fusing point, and the massfraction of paraffin is 0.20-0.80.People such as Qin Penghua (Tsing-Hua University's journal (natural science edition), 2003,43 (6): 833-835) prepared paraffin/height (low) density polyethylene shaping phase-change material, adopting fusing point is that 60-62 ℃ paraffin and high density polyethylene(HDPE) or new LDPE (film grade) blend make, and wherein the massfraction of paraffin is 0.7-0.9.People such as Ye Hong (Solar Energy Materials; Solar Cells, 2000,64 (1): 37-44) with paraffin and high density polyethylene(HDPE) blended melting, make the phase change material with certain intensity of dimensionally stable after the cooling, wherein contain paraffin 70-75%.But up to the present, can be used under the comparatively high temps environment, the qualitative phase change material that packaging effect is good does not also obtain very big progress.
Summary of the invention
The objective of the invention is to, use fusing point at 76-81.6 ℃, latent heat of phase change at the paraffin of 200-220kJ/kg as main heat accumulating, adopt high oil-absorbent material that it is encapsulated to solve the leakage problems of phase change material, prepare a kind of qualitative phase-changing energy storage material that can be used for comparatively high temps such as boiler.Present method adopts has the hydrogenated styrene-butadiene-styrene triblock copolymer (SEBS) of high oil absorbency as packaged material, the bound energy of the network structure of SEBS is quite high, have more advantages of excellent stability, thermotolerance than SBS, and it is fabulous with the consistency of paraffin, together the paraffin encapsulation is lived with dendritic HDPE, thereby stopped oozing out of paraffin.
Composition of the present invention is that the quality percentage composition is 66-80%, fusing point is 76-81.6 ℃, and latent heat of phase change is the paraffin of 200-220kJ/kg, the 11-15% high density polyethylene(HDPE), 4-12% hydrogenated styrene-butadiene-styrene triblock copolymer SEBS, and 3-7% expanded graphite.
The invention is characterized in, adopt the stronger SEBS of oil absorbency, prepare with following step as packaged material:
1) getting mass percentage content is 66-80%, and fusing point is that 76-81.6 ℃ of latent heat of phase change put into the reactor heating and melting up to the paraffin of 200-220kJ/kg, and heating fluid wax temperature is to 100-120 ℃;
2) get in the high density polyethylene(HDPE) adding liquid wax that mass percentage content is 11-15%, be heated to 140-160 ℃, the rotating speed stirring with 100-120r/min fuses into one until paraffin and high density polyethylene(HDPE), becomes thick liquid;
3) get the hydrogenated styrene-butadiene-styrene triblock copolymer that mass percentage content is 4-12%, join in the blend of liquid wax and high density polyethylene(HDPE), be stirred to fusion;
4) adding mass percentage content is the expanded graphite of 3-7%, is stirred to evenly;
5) mixture is taken out put into mould, be pressed into tabularly with the pressure of 200-300kPa, take out the cooling back.
The present invention utilizes the high oil absorbency energy of SEBS, adopts earlier with high density polyethylene(HDPE) the preliminary encapsulation of paraffin to be got up, and the method that paraffin is encapsulated better with the high oil absorbency of SEBS is prepared a kind of transformation temperature at 76-84 ℃ shaping phase-change material again.SEBS and high density polyethylene(HDPE) can form highly cross-linked three-dimensional net structure, and paraffin encapsulation is lived, and make the paraffin also can seepage when heating, and can keep definite shape, can directly put into the heating fluid clear water.Also do not have the paraffin seepage through thermal cycling test repeatedly, rate of weight loss is lower than 2%, and material property is stable.
Description of drawings
The transformation curve of the embodiment 1 that Fig. 1 records for differential thermal calorimetric scanner.
Wherein the Peak value is for to be that the temperature at place, phase transformation peak, Peak Height are heat flow value herein, and Area is an integral area, and Delta H is the latent heat of phase change of this sample, the temperature of Onset value when beginning to undergo phase transition, the temperature when the End value is finished for phase transformation.
Embodiment
Embodiment 1
With the 800g fusing point is 81.6 ℃, latent heat of phase change is that the paraffin of 209.1kJ/kg is put into reactor, in 100-120 ℃ of heat fused, the high density polyethylene(HDPE) of 150g is put into wherein, temperature is risen to 140-160 ℃, rotating speed stirring with 100r/min combines together until paraffin and high density polyethylene(HDPE), become thick liquid, add the SEBS of 100g, stir, add the 50g expanded graphite at last, stir.Blend is taken out the mould of putting into 140*140*10mm, with the pressure compression moulding of 300kPa.After cooling, from mould, take out, promptly make shaping phase-change material.The peak value that the Pyris Diamond differential scanning calorimeter of use U.S. PE company records the solubility curve of material is 82.31 ℃, and latent heat of phase change is 149.2kJ/kg.The shaping phase-change material of intercepting 30*30*10mm size is put into 88 ℃ of hot water and was soaked 200 hours, and material does not have obvious distortion, weighs after the oven dry, and rate of weight loss is lower than 0.5%; The latent heat of phase change variation of measuring material is lower than 10%.
Embodiment 2
With the 800g fusing point is 81.6 ℃, latent heat of phase change is that the paraffin of 212.5kJ/kg is put into reactor, in 100-120 ℃ of heat fused, the high density polyethylene(HDPE) of 100g is put into wherein, temperature is risen to 140-160 ℃, rotating speed stirring with 120r/min combines together until paraffin and high density polyethylene(HDPE), become thick liquid, add the SEBS of 50g, stir, add the 50g expanded graphite at last, stir.Blend is taken out the mould of putting into 140*140*10mm, with the pressure compression moulding of 200kPa.After cooling, from mould, take out, promptly make shaping phase-change material.The peak value that the Pyris Diamond differential scanning calorimeter of use U.S. PE company records the solubility curve of material is 81.62 ℃, and latent heat of phase change is 168.8.The shaping phase-change material of intercepting 30*30*10mm size is put into 88 ℃ of hot water and was soaked 200 hours, and material does not have obvious distortion, weighs after the oven dry, and rate of weight loss is lower than 0.5%, and the latent heat of phase change variation of measuring material is lower than 10%.
Embodiment 3
With the 800g fusing point is 81.6 ℃, latent heat of phase change is that the paraffin of 212.5kJ/kg is put into reactor, in 100-120 ℃ of heat fused, the high density polyethylene(HDPE) of 150g is put into wherein, temperature is risen to 140-160 ℃, rotating speed stirring with 120r/min combines together until paraffin and high density polyethylene(HDPE), become thick liquid, add the SEBS of 50g, stir, add the 50g expanded graphite at last, stir.Blend is taken out the mould of putting into 140*140*10mm, with the pressure compression moulding of 300kPa.After cooling, from mould, take out, promptly make shaping phase-change material.The peak value that the Pyris Diamond differential scanning calorimeter of use U.S. PE company records the solubility curve of material is 83.83 ℃, and latent heat of phase change is 153.0kJ/kg.The shaping phase-change material of intercepting 30*30*10mm size is put into 88 ℃ of hot water and was soaked 200 hours, and material does not have obvious distortion, weighs after the oven dry, and rate of weight loss is lower than 2%, and the latent heat of phase change variation of measuring material is lower than 10%.
Embodiment 4
With the 800g fusing point is 81.6 ℃, latent heat of phase change is that the paraffin of 209.1kJ/kg is put into reactor, in 100-120 ℃ of heat fused, the high density polyethylene(HDPE) of 120g is put into wherein, temperature is risen to 140-160 ℃, rotating speed stirring with 110r/min combines together until paraffin and high density polyethylene(HDPE), become thick liquid, add the SEBS of 60g, stir, add the 40g expanded graphite at last, stir.Blend is taken out the mould of putting into 140*140*10mm, with the pressure compression moulding of 200kPa.After cooling, from mould, take out, promptly make shaping phase-change material.The peak value that the Pyris Diamond differential scanning calorimeter of use U.S. PE company records the solubility curve of material is 81.21 ℃, and latent heat of phase change is 164.4kJ/kg.The shaping phase-change material of intercepting 30*30*10mm size is put into 88 ℃ of hot water and was soaked 200 hours, and material does not have obvious distortion, weighs after the oven dry, and rate of weight loss is lower than 1%, and the latent heat of phase change variation of measuring material is lower than 10%.
Embodiment 5
With the 800g fusing point is 81.6 ℃, latent heat of phase change is that the paraffin of 212.5kJ/kg is put into reactor, in 100-120 ℃ of heat fused, the high density polyethylene(HDPE) of 120g is put into wherein, temperature is risen to 140-160 ℃, rotating speed stirring with 100r/min combines together until paraffin and high density polyethylene(HDPE), become thick liquid, add the SEBS of 80g, stir, add the 50g expanded graphite at last, stir.Blend is taken out the mould of putting into 140*140*10mm, with the pressure compression moulding of 200kPa.After cooling, from mould, take out, promptly make shaping phase-change material.The peak value that the Pyris Diamond differential scanning calorimeter of use U.S. PE company records the solubility curve of material is 82.37 ℃, and latent heat of phase change is 163.7kJ/kg.The shaping phase-change material of intercepting 30*30*10mm size is put into 88 ℃ of hot water and was soaked 200 hours, and material does not have obvious distortion, weighs after the oven dry, and rate of weight loss is lower than 2%, and the latent heat of phase change variation of measuring material is lower than 10%.
Embodiment 6
With the 800g fusing point is 76 ℃, latent heat of phase change is that the paraffin of 216.9kJ/kg is put into reactor, in 100-120 ℃ of heat fused, the high density polyethylene(HDPE) of 180g is put into wherein, temperature is risen to 140-160 ℃, rotating speed stirring with 120r/min combines together until paraffin and high density polyethylene(HDPE), become thick liquid, add the SEBS of 140g, stir, add the 80g expanded graphite at last, stir.Blend is taken out the mould of putting into 140*140*10mm, with the pressure compression moulding of 300kPa.After cooling, from mould, take out, promptly make shaping phase-change material.The peak value that the Pyris Diamond differential scanning calorimeter of use U.S. PE company records the solubility curve of material is 76.72 ℃, and latent heat of phase change is 142.6kJ/kg.The shaping phase-change material of intercepting 30*30*10mm size is put into 88 ℃ of hot water and was soaked 200 hours, and material does not have obvious distortion, weighs after the oven dry, and rate of weight loss is lower than 1%, and the latent heat of phase change variation of measuring material is lower than 10%.
Claims (2)
1, a kind of 76-83 ℃ composite shape-setting phase-change material, it is characterized in that, composition is that the quality percentage composition is 66-80%, fusing point is 76-81.6 ℃, latent heat of phase change is the paraffin of 200-220kJ/kg, the 11-15% high density polyethylene(HDPE), 4-12% hydrogenated styrene-butadiene-styrene triblock copolymer SEBS, and 3-7% expanded graphite.
2, the preparation method of composite shape-setting phase-change material according to claim 1 is characterized in that, comprises following each step:
1) getting mass percentage content is 66-80%, and fusing point is that 76-81.6 ℃ of latent heat of phase change put into the reactor heating and melting up to the paraffin of 200-220kJ/kg, and heating fluid wax temperature is to 100-120 ℃;
2) get in the high density polyethylene(HDPE) adding liquid wax that mass percentage content is 11-15%, be heated to 140-160 ℃, the rotating speed stirring with 100-120r/min fuses into one until paraffin and high density polyethylene(HDPE), becomes thick liquid;
3) get the hydrogenated styrene-butadiene-styrene triblock copolymer that mass percentage content is 4-12%, join in the blend of liquid wax and high density polyethylene(HDPE), be stirred to fusion;
4) adding mass percentage content is the expanded graphite of 3-7%, is stirred to evenly;
5) mixture is taken out put into mould, be pressed into tabularly with the pressure of 200-300kPa, take out the cooling back.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101167065A CN1304519C (en) | 2005-10-28 | 2005-10-28 | Composite fixing phase change material of 79-83 deg.c and its preparing method |
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| CNB2005101167065A CN1304519C (en) | 2005-10-28 | 2005-10-28 | Composite fixing phase change material of 79-83 deg.c and its preparing method |
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| CN1782018A true CN1782018A (en) | 2006-06-07 |
| CN1304519C CN1304519C (en) | 2007-03-14 |
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| CN103075904A (en) * | 2011-10-26 | 2013-05-01 | 上海卫星工程研究所 | Filling method of phase-change material in phase-change heat pipe |
| CN104371666A (en) * | 2014-12-04 | 2015-02-25 | 西南科技大学 | Preparation method of high-thermal-conductivity low-leakage phase-change composite |
| CN106905927A (en) * | 2015-12-23 | 2017-06-30 | 上海邦中高分子材料有限公司 | A kind of composite shape-setting phase-change material and preparation method |
| WO2018103306A1 (en) * | 2016-12-09 | 2018-06-14 | 航天特种材料及工艺技术研究所 | Thermal management module for use in square battery, manufacturing method for module, and applications thereof |
| CN108531140A (en) * | 2018-05-31 | 2018-09-14 | 华中科技大学 | A kind of preparation method of paraffinic base sizing phase change plate |
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| CN103075904A (en) * | 2011-10-26 | 2013-05-01 | 上海卫星工程研究所 | Filling method of phase-change material in phase-change heat pipe |
| CN104371666A (en) * | 2014-12-04 | 2015-02-25 | 西南科技大学 | Preparation method of high-thermal-conductivity low-leakage phase-change composite |
| CN106905927A (en) * | 2015-12-23 | 2017-06-30 | 上海邦中高分子材料有限公司 | A kind of composite shape-setting phase-change material and preparation method |
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| CN108912639A (en) * | 2018-07-09 | 2018-11-30 | 江苏启能新能源材料有限公司 | A kind of heatproof alkali resistant materials for packaging phase change material |
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| CN1304519C (en) | 2007-03-14 |
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