CN103805142A - Silicon nitride-modified phase-change and energy-storage microcapsule and preparation method thereof - Google Patents
Silicon nitride-modified phase-change and energy-storage microcapsule and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon nitride-modified phase-change and energy-storage microcapsule, comprising a shell material and a cladded core material, wherein the shell material comprises the following raw materials in parts by weight: 50-100 parts of high-molecular polymers and 1-20 parts of silicon nitride powder which is evenly dispersed into the high-molecular polymers; the core material comprises 50-100 parts of organic phase-change and energy-storage materials and 1-20 parts of silicon nitride powder which is evenly dispersed into the organic phase-change and energy-storage materials. The invention also provides a preparation method of the phase-change energy-storage microcapsule. The thermal conductivity of the phase-change and energy-storage material is improved, overheat and overcold degrees in the phase-change process are inhibited, and meanwhile, the thermal endurance and the abrasive resistance, the thermal shock resistance, the fatigue resistance and the like also are improved. The silicon nitride-modified phase-change and energy-storage microcapsule is relatively simple in preparation technology, available in raw materials, strong in controllability, and applicable to the industrial large-scale production, an existing industrial processing technology can be fully utilized, and the performance of the phase-change and energy-storage microcapsule is improved.
Description
Technical field
The present invention relates to microcapsules of storing energy through phase change and preparation method thereof, specifically a kind of silicon nitride modification microcapsules of storing energy through phase change and preparation method thereof.
Background technology
The today day by day highlighting in the energy, environmental problem, there is the phase-changing energy storage material (PCMs) of high energy storage density, long service life cycle more and more by people are paid close attention to.The research of microcapsules of storing energy through phase change (MicroPCMs) has overcome PCMs existing series of problems in application, as: liquid fluidity is high, easily leaks, poor with the consistency of body material, strength of microcapsules is low, poor thermal conductivity etc. when phase transformation.The application of MicroPCMs has covered the every field such as aerospace, energy saving building, temperature-regulating fiber, battery management, waste heat of plant recovery, closely bound up with people's life.Although the Research of Microencapsulation of phase-changing energy storage material starts from 20 century 70s, but still there are many major issues to be solved that have, as improve thermal conductivity, accelerate phase change material crystallization velocity, reduce its excessively cold, overheated (reducing the temperature difference in phase transition process); The intensity of adjusting cyst material and heat-shock resistance, antifatigue aging; Explore efficient, less energy-consumption, industry preparation method etc. cheaply.
In bibliographical information, investigators' thermal conductivities that adopt interpolation Graphene and carbon nanotube to improve phase-changing energy storage material more, but due to carbon nanotube high cost, be difficult to suitability for industrialized production, and color is single not attractive in appearance, is very restricted in actual applications.Silicon nitride is a kind of ceramic powder of excellent performance, and thermal conductivity is 16.7W/ (mK), and linear expansivity is 2.75 × 10
-6/ ℃ (20 ~ 1000 ℃), have good wear resistance, anti-oxidant, heat-shock resistance, all have a wide range of applications in a lot of fields, and silicon nitride are applied to the heat conductivity that strengthens microcapsules of storing energy through phase change, there is not yet report both at home and abroad.
Use the particle modified matrix material of silicon nitride nano, can change on the one hand the stressed condition of matrix material, homodisperse nanoparticle has more Active sites and forms larger contact interface with matrix; In the time being subject to external force, the two is difficult for departing from, and a lot of micro-distorted areas, interface can absorb large energy, both can transmit external force, cause again matrix yielding, reaches and strengthens toughness reinforcing object.On the other hand, nano-silicon nitride particle effect can affect crystallization behavior and the crystalline structure of polymkeric substance, affects material property; There is investigator to utilize Avrami equation and Mohs method to prove that nano-silicon nitride particle has good nucleogenesis to macromolecular material, has obvious booster action to crystallisation process, and has proved by experiment this argument.But, because nano-silicon nitride has high surface free energy, easily form and reunite, in the time setting it as filler and add in the middle of polymeric matrix, because the structural difference of inorganic rigid particle and organic phase is larger, consistency is poor, causes nano-silicon nitride particle to be difficult to be dispersed in the middle of polymeric matrix with nanoscale, but easily form the macrobead of assembling, become the central defect of matrix material.This not only cannot realize above-mentioned useful performance, can damage on the contrary the performance of polymkeric substance itself.For silicon nitride can be evenly dispersed in polymkeric substance, must solve the problem of polymkeric substance and silicon nitride consistency.
Summary of the invention
In view of the problem of existing microcapsules of storing energy through phase change existence, the invention provides a kind of silicon nitride modification microcapsules of storing energy through phase change and preparation method thereof, by methods such as ultrasonic dispersion, graft modifications, silicon nitride powder is dispersed in the shell material and core of microcapsules of storing energy through phase change, to improve mechanical property, heat resistance and the heat conductivility of microcapsules of storing energy through phase change.
A kind of silicon nitride modification microcapsules of storing energy through phase change, is made up of shell material and coated core thereof, and in parts by weight, described shell material comprises 50 ~ 100 parts of high molecular polymers and is dispersed in 1 ~ 20 part of silicon nitride powder in described high molecular polymer; Described core comprises 50 ~ 100 parts of organic phase change energy storage materials, and is dispersed in 1 ~ 20 part of silicon nitride powder in these organic phase change energy storage materials.Described microcapsules of storing energy through phase change is spherical in shape.
Wherein, described silicon nitride powder is grafting silicon nitride powder, and particle diameter is 0.005 ~ 10 μ m.This grafting silicon nitride powder is that silicon nitride powder is dried and obtains in silane coupling agent alcoholic solution after ultrasonic dispersion, grafting are processed.
Described high molecular polymer is a kind of in polymethyl acrylate, polymethylmethacrylate, polystyrene, resol, melmac, urea-formaldehyde resin, carbamide resin or two kinds.
Described organic phase change energy storage material is normal paraffin, the fatty alcohol of C8-18 or the lipid acid of C8-18 and the ester thereof of phase change paraffin, C14-C30.
Described organic phase change energy storage material can be lightweight paraffin, 25# phase change paraffin, 30# phase change paraffin, 35# paraffin, 58# paraffin, n-Hexadecane, octadecane, eicosane or n-butyl stearate etc.
The preparation method of silicon nitride modification microcapsules of storing energy through phase change of the present invention, comprises the following steps:
1), 1 ~ 40 part of silane coupling agent adds in 50 ~ 100 parts of liquid alcohol and is mixed with alcoholic solution, then adds 2 ~ 40 parts of silicon nitride powders, supersound process 10 ~ 60min, then keeps soaking state 10 ~ 72h, drier in room temperature or baking oven, obtains modification silicon nitride powder;
2), 50 ~ 100 parts of organic phase change energy storage materials are warming up to thawing, the modification silicon nitride powder, 1 ~ 10 part of emulsifying agent that keep temperature simultaneously and add 1 ~ 20 part of described step 1) to obtain, stir 10 ~ 30min with 500 ~ 1000rpm rotating speed, and then supersound process 10 ~ 120min, emulsion formed;
3), by step 2) emulsion that makes joins in the water of 500 ~ 1000 parts, then adds 1 ~ 20 part of emulsifying agent, stirs 5 ~ 30min with high-speed shearing emulsion machine or clarifixator under 5000 ~ 10000rpm rotating speed;
4), the modification silicon nitride powder that 1 ~ 20 part of described step 1) is obtained, 1 ~ 20 part of linking agent, 0.1 ~ 5 part of initiator join in 50 ~ 100 parts of polymer raw materials, stirs 5 ~ 30min with high-speed shearing emulsion machine or clarifixator under 5000 ~ 10000rpm rotating speed;
5), the product of step 3) and step 4) is mixed, under 500 ~ 3000rpm rotating speed, 25 ~ 100 ℃ of conditions, polymerization 2 ~ 24h;
6), reacted step 5) product is filtered, washing, dried, obtain silicon nitride modification microcapsules of storing energy through phase change.
In aforesaid method, described silane coupling agent is vinyltrimethoxy silane, γ-chloropropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane or gamma-methyl allyl acyloxypropyl trimethoxysilane.
Described polymer raw material is a kind of in methyl acrylate, methyl methacrylate, vinylbenzene, phenol, formaldehyde, trimeric cyanamide, urea or two kinds.
Described emulsifying agent is one or both in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, styrene-maleic anhydride copolymer, Pentyl alcohol, Span-80 and Tween-80.
Described linking agent is polypropylene glycol-2000,1,4 butanediol diacrylate, Vinylstyrene, Viscoat 295, tetramethylol methane tetraacrylate, N-hydroxymethyl acrylic acid amides, toxilic acid or senecioate-hydroxypropyl acrylate.
Described initiator is ammonium persulphate, Diisopropyl azodicarboxylate, benzoyl peroxide, hydrogen peroxide-iron protochloride, sodium-chlor, ammonium chloride or iron trichloride.
Silicon nitride powder granularity of the present invention, between 0.005 ~ 10 μ m, has good wear resistance, and anti-oxidant, heat-shock resistance has improved thermal conductivity, high thermal resistance, wear resistance, heat-shock resistance, fatigue resistance of microcapsules of storing energy through phase change etc.Adopt in the present invention the method for supersound process, silicon nitride powder can be dispersed in phase-changing energy storage material and high molecular polymer uniformly, and by the adjusting of grafting processing, tensio-active agent, make silicon nitride can keep good interface performance, in the stable cross-linked network that is present in microcapsules of storing energy through phase change, improve phase-changing energy storage material thermal conductivity, suppress overheated, condensate depression in its phase transition process, also the heat resistance that has improved phase-changing energy storage material, is effectively improved the intensity of microcapsules of storing energy through phase change, thermal conductivity each side character simultaneously.
Compared with existing microcapsules of storing energy through phase change, the present invention has improved phase-changing energy storage material thermal conductivity, suppresses overheated in its phase transition process, condensate depression, has also improved the performances such as heat-resistant, wear-resistant, heat-shock resistance, fatigue resistance simultaneously.In these microcapsule, adopt graft modification silicon nitride powder, it by original silicon nitride powder in silane coupling agent alcoholic solution, obtain after processing by ultrasonic dispersion surface grafting, this has effectively solved it and has been combined problem with the interface of phase-changing energy storage material and high molecular polymer, has formed an effective heat conducting passage in microcapsules of storing energy through phase change inside.And silicon nitride stable performance, nontoxic, preparation is simple, can environment not produced and be polluted, environmental protection.
Preparation technology of the present invention is relatively simple, raw material is easy to get, controllability is strong, can make full use of existing industrial processes technology, has improved the performance of microcapsules of storing energy through phase change, is applicable to commercial scale production.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 1 microcapsules of storing energy through phase change;
Fig. 2 is the local SEM figure amplifying of Fig. 1;
Fig. 3 is the infrared spectrum of microcapsules of storing energy through phase change of the present invention;
Fig. 4 is the TG figure of silicon nitride modification microcapsules of storing energy through phase change of the present invention and unmodified microcapsules of storing energy through phase change;
Fig. 5 is the thermal conductivity test pattern of phase-changing energy storage material of the present invention and silicon nitride
Fig. 6 is the DSC figure of microcapsules of storing energy through phase change of the present invention.
Embodiment
Realization, functional characteristics and the advantage of the object of the invention, in connection with embodiment, are described further.Should be appreciated that embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Below in conjunction with specific embodiment, the present invention is described in detail.
1), take 3g gamma-methyl allyl acyloxypropyl trimethoxysilane (KH570) and add in 10g ethanol and be mixed with alcoholic solution, then add 1.5g silicon nitride powder, supersound process 15min, then soaks 48h, in 50 ℃ of baking ovens, dries, and obtains grafting silicon nitride powder.2), 12g Octadecane is warming up to thawing, the grafting silicon nitride powder, the 1g styrene-maleic anhydride copolymer that keep temperature simultaneously and add 0.5g step 1) to obtain, stir 15min with 600rpm rotating speed, and then supersound process 15min, forms emulsion.3), by step 2) emulsion that makes joins in 200g deionized water, then adds 1g sodium lauryl sulphate, 2g vinylbenzene Ma-come acid anhydride copolymer, stirs 10min with high-speed shearing emulsion machine under 6000rpm rotating speed.4), grafting silicon nitride powder, 3g tetramethylol methane tetraacrylate, 0.3g azo-bis-isobutyl cyanide that 1g step 1) is obtained join in 10g methyl methacrylate, stirs 10min with high-speed shearing emulsion machine under 6000rpm rotating speed.5), the product of step 3) and step 4) is mixed, at 1000rpm rotating speed, 80 ℃, polymerization 8h.6), reacted step 5) product is filtered, washing, dried, obtain silicon nitride modification microcapsules of storing energy through phase change.
1), take 3g γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560) and add in 30g methyl alcohol and be mixed with alcoholic solution, then add 2g silicon nitride powder, supersound process 10min, then soak 10h, in 50 ℃ of baking ovens, dry, obtain grafting silicon nitride powder.2), 50g n-butyl stearate is warming up to thawing, the grafting silicon nitride powder, the 1g styrene-maleic anhydride copolymer that keep temperature simultaneously and add 1g step 1) to obtain, stir 10min with 600rpm rotating speed, and then supersound process 15min, forms emulsion.3), by step 2) emulsion that makes joins in the deionized water of 500g, adds 1g sodium lauryl sulphate, 2g styrene-maleic anhydride copolymer, stirs 5min with high-speed shearing emulsion machine under 5000rpm rotating speed.4), grafting silicon nitride powder, 1g tetramethylol methane tetraacrylate, 0.1g azo-bis-isobutyl cyanide that 1g step 1) is obtained join in 50g methyl methacrylate, stirs 10min with high-shear homogenizer under 6000rpm rotating speed.5), the product of step 3) and step 4) is mixed, at 500rpm rotating speed, 60 ℃, polymerization 4h.6), reacted step 5) product is filtered, washing, dried, obtain silicon nitride modification microcapsules of storing energy through phase change.
Embodiment 3
1), take 30g gamma-methyl allyl acyloxypropyl trimethoxysilane (KH570) and add in 100g ethanol and be mixed with alcoholic solution, then add 15g silicon nitride powder, supersound process 40min, then soaks 60h, natural drying at room temperature obtains grafting silicon nitride powder.2), 70g n-butyl stearate is warming up to thawing, the grafting silicon nitride powder, the 1g styrene-maleic anhydride copolymer that keep temperature simultaneously and add 5g step 1) to obtain, stir 20min with 800rpm rotating speed, and then supersound process 50min, forms emulsion.3), by step 2) emulsion that makes joins in the deionized water of 800g, adds 2g sodium lauryl sulphate, styrene-maleic anhydride copolymer 10g stirs 20min with high-speed shearing emulsion machine under 10000rpm rotating speed.4), grafting silicon nitride powder, 10g Vinylstyrene, 4g azo-bis-isobutyl cyanide that 10g step 1) is obtained join in 50g methyl methacrylate, stirs 20min with high-speed shearing emulsion machine under 8000rpm rotating speed.5), the product of step 3) and step 4) is mixed, at 3000rpm rotating speed, 100 ℃, polymerization 20h.6), reacted step 5) product is filtered, washing, dried, obtain silicon nitride modification microcapsules of storing energy through phase change.
1), take 5g gamma-methyl allyl acyloxypropyl trimethoxysilane (KH570) and add in 20g ethanol and be mixed with alcoholic solution, then add 11g silicon nitride powder, supersound process 50min, then soaks 70h, natural drying at room temperature obtains grafting silicon nitride powder.2), 80g n-butyl stearate is warming up to thawing, the grafting silicon nitride powder, the 10g styrene-maleic anhydride copolymer that keep temperature simultaneously and add 10g step 1) to obtain, stir 25min with 900rpm rotating speed, and then supersound process 15min, forms emulsion.3), step is 2) emulsion that makes, join in the deionized water of 1000g, add 8gSpan-80,12gTween-80, under 9000rpm rotating speed, stir 25min with clarifixator.4), grafting silicon nitride powder, 15g Vinylstyrene, 5g azo-bis-isobutyl cyanide that 1g step 1) is obtained join in 60g vinylbenzene, stirs 30min with clarifixator under 9000rpm rotating speed.5), the product of step 3) and step 4) is mixed, at 2500rpm rotating speed, 50 ℃, polymerization 15h.6), reacted step 5) product is filtered, washing, dried, obtain silicon nitride modification microcapsules of storing energy through phase change.
Embodiment 5
1), take 30g gamma-methyl allyl acyloxypropyl trimethoxysilane (KH570) and add in 100g ethanol and be mixed with alcoholic solution, then add 40g silicon nitride powder, supersound process 15min, then soaks 70h, natural drying at room temperature obtains grafting silicon nitride powder.2), 80g n-butyl stearate is warming up to thawing, the grafting silicon nitride powder, the 10g styrene-maleic anhydride copolymer that keep temperature simultaneously and add 20g step 1) to obtain, stir 30min with 1000rpm rotating speed, and then supersound process 100min, emulsion formed.3), by step 2) emulsion that makes, join in the deionized water of 500g, add 5g sodium lauryl sulphate, 10g styrene-maleic anhydride copolymer stirs 15min with high-speed shearing emulsion machine under 8000rpm rotating speed.4), grafting silicon nitride powder, 17g polypropylene glycol-2000,3g tetramethylol methane tetraacrylate, 5g azo-bis-isobutyl cyanide that 20g step 1) is obtained join in 90g methyl acrylate, stirs 25min with high-speed shearing emulsion machine under 8000rpm rotating speed.5), the product of step 3) and step 4) is mixed, at 3000rpm rotating speed, 70 ℃, polymerization 15h.6), reacted step 5) product is filtered, washing, dried, obtain silicon nitride modification microcapsules of storing energy through phase change.
Referring to the SEM figure of Fig. 1,1 silicon nitride modification microcapsules of storing energy through phase change embodiment illustrated in fig. 2, can find out that by figure microcapsules of storing energy through phase change is all regular spherical, diameter is 10 ~ 50 μ m, the projection that surface uniform disperses is silicon nitride.
The result that uses Infrared spectroscopy to analyze silicon nitride modification microcapsules of storing energy through phase change, with reference to figure 3 infrared spectrums, is present in these microcapsule by Fig. 3 susceptible of proof silicon nitride.
Silicon nitride modification microcapsules of storing energy through phase change shown in Figure 4 and do not add the TG curve of the phase-change microcapsule of silicon nitride modification, the curve that in Fig. 4, top curve is silicon nitride modification, curve is unmodified curve on the lower.Can find out that microcapsules of storing energy through phase change heat resisting temperature through silicon nitride modification is apparently higher than unmodified microcapsules of storing energy through phase change.Silicon nitride particles in the microcapsules of storing energy through phase change of silicon nitride modification has not only improved the rigidity of microcapsules of storing energy through phase change, has played enhancement, and because itself has high thermal resistance, has also improved the overall heat resistance of microcapsules of storing energy through phase change.
Fig. 5 is the thermal conductivity graphic representation of silicon nitride modification phase change material, and along with the increase of silicon nitride content, thermal conductivity improves gradually as seen from Figure 5.
Fig. 6 is the DSC graphic representation of silicon nitride modification microcapsules of storing energy through phase change, is found out by Fig. 6, and exothermic peak broadening has also occurred swarming, and hot-fluid tends towards stability, and Process of absorption or liberation of heat peak is mutually close, and excessively cold, superheating phenomenon is eased.The intensity, the thermal conductivity etc. that have improved microcapsules of storing energy through phase change through silicon nitride modification, have very large advantage in actual applications.
By specific embodiment, the present invention has been done to detailed explanation above, these concrete descriptions can not think that the present invention only only limits to the content of these embodiment.Those skilled in the art conceive according to the present invention, these descriptions any improvement of making in conjunction with general knowledge known in this field, be equal to replacement scheme, all should be included in the protection domain of the claims in the present invention.
Claims (10)
1. a silicon nitride modification microcapsules of storing energy through phase change, formed by shell material and coated core thereof, in parts by weight, it is characterized in that, described shell material comprises 50 ~ 100 parts of high molecular polymers and is dispersed in 1 ~ 20 part of silicon nitride powder in described high molecular polymer; Described core comprises 50 ~ 100 parts of organic phase change energy storage materials and is dispersed in 1 ~ 20 part of silicon nitride powder in described organic phase change energy storage material.
2. phase-change energy storage capsule according to claim 1, is characterized in that, described silicon nitride powder is grafting silicon nitride powder, and particle diameter is 0.005 ~ 10 μ m; This grafting silicon nitride powder is that silicon nitride powder is dried and obtains in silane coupling agent alcoholic solution after ultrasonic dispersion, grafting are processed.
3. microcapsules of storing energy through phase change according to claim 1 and 2, it is characterized in that, described high molecular polymer is a kind of in polymethyl acrylate, polymethylmethacrylate, polystyrene, resol, melmac, urea-formaldehyde resin, carbamide resin or two kinds.
4. microcapsules of storing energy through phase change according to claim 1 and 2, is characterized in that, described organic phase change energy storage material is phase change paraffin, the normal paraffin of C14-C30, the fatty alcohol of C8-18 or the lipid acid of C8-18 and ester thereof.
5. microcapsules of storing energy through phase change according to claim 1 and 2, it is characterized in that, described organic phase change energy storage material is lightweight paraffin, 25# phase change paraffin, 30# phase change paraffin, 35# paraffin, 58# paraffin, n-Hexadecane, octadecane, eicosane or n-butyl stearate.
6. as the preparation method of claim 1-5 silicon nitride modification microcapsules of storing energy through phase change as described in any one, it is characterized in that, comprise the following steps:
1), 1 ~ 40 part of silane coupling agent is added in 50 ~ 100 parts of alcohol and is mixed with alcoholic solution, then add 2 ~ 40 parts of silicon nitride powders, supersound process 10 ~ 60min, then keeps soaking state 10 ~ 72h, drier in room temperature or baking oven, obtains grafting silicon nitride powder;
2), 50 ~ 100 parts of organic phase change energy storage materials are warming up to thawing, the grafting silicon nitride powder, 1 ~ 10 part of emulsifying agent that keep temperature simultaneously and add 1 ~ 20 part of described step 1) to obtain, stir 10 ~ 30min with 500 ~ 1000rpm rotating speed, and then supersound process 10 ~ 120min, emulsion formed;
3), by step 2) emulsion that makes joins in the water of 500 ~ 1000 parts, then adds 1 ~ 20 part of emulsifying agent, stirs 5 ~ 30min with high-speed shearing emulsion machine or clarifixator under 5000 ~ 10000rpm rotating speed;
4), the grafting silicon nitride powder that 1 ~ 20 part of described step 1) is obtained, 1 ~ 20 part of linking agent, 0.1 ~ 5 part of initiator join in 50 ~ 100 parts of polymer raw materials, stirs 5 ~ 30min with high-speed shearing emulsion machine or clarifixator under 5000 ~ 10000rpm rotating speed;
5), the product of step 3) and step 4) is mixed, under 500 ~ 3000rpm rotating speed, 25 ~ 100 ℃ of conditions, polymerization 2 ~ 24h;
6), reacted step 5) product is filtered, washing, dried, obtain silicon nitride modification microcapsules of storing energy through phase change.
7. preparation method according to claim 6, it is characterized in that, described silane coupling agent is vinyltrimethoxy silane, γ-chloropropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane or gamma-methyl allyl acyloxypropyl trimethoxysilane.
8. preparation method according to claim 6, is characterized in that, described polymer raw material is a kind of in methyl acrylate, methyl methacrylate, vinylbenzene, phenol, formaldehyde, trimeric cyanamide, urea or two kinds.
9. preparation method according to claim 6, it is characterized in that, described linking agent is polypropylene glycol-2000,1,4 butanediol diacrylate, Vinylstyrene, Viscoat 295, tetramethylol methane tetraacrylate, N-hydroxymethyl acrylic acid amides, toxilic acid or senecioate-hydroxypropyl acrylate.
10. preparation method according to claim 6, is characterized in that, described emulsifying agent is one or both in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, styrene-maleic anhydride copolymer, Pentyl alcohol, Span-80 and Tween-80; Described initiator is ammonium persulphate, Diisopropyl azodicarboxylate, benzoyl peroxide, hydrogen peroxide-iron protochloride, sodium-chlor, ammonium chloride or iron trichloride.
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