CN103183922B - For the carrier of phase-change accumulation energy and phase-changing energy storage material and their preparation method - Google Patents
For the carrier of phase-change accumulation energy and phase-changing energy storage material and their preparation method Download PDFInfo
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- CN103183922B CN103183922B CN201110444095.2A CN201110444095A CN103183922B CN 103183922 B CN103183922 B CN 103183922B CN 201110444095 A CN201110444095 A CN 201110444095A CN 103183922 B CN103183922 B CN 103183922B
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Abstract
The invention provides a kind of carrier for phase-change accumulation energy and preparation method thereof, and a kind of phase-changing energy storage material and preparation method thereof.Described carrier inside has multiple nano pore, and described carrier be by by containing one or more the raw material be selected from vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin through solidifying to form.The carrier adopting method of the present invention to prepare and phase-changing energy storage material have excellent heat transfer property and carrier not easily breaks.
Description
Technical field
The present invention relates to a kind of carrier for phase-change accumulation energy and preparation method thereof and a kind of phase-changing energy storage material and preparation method thereof.
Background technology
Phase-change accumulation energy is a kind of hidden heat energy storage mode, phase-changing energy storage material utilizes phase change material in the process undergone phase transition, can heat (cold) amount of absorbing environmental, and when needed between environment release heat (cold) amount, thus reach and control the object of ambient temperature.
Phase change material becomes liquid after melting and has unsetting property, and therefore, prior art is generally be encapsulated in microcapsule by phase change material to form microcapsules of storing energy through phase change.At present, the method preparing microcapsule phase-change energy storage material has interfacial polymerization, situ aggregation method and spray-drying process.As the three kinds of methods preparing microcapsule phase-change energy storage material, it has respective limitation.The particle diameter of the microcapsule product that interfacial polymerization obtains affects by temperature, stirring velocity, reaction vessel shape, emulsifier and solubility thereof etc., processing condition are complicated, wayward; Situ aggregation method capsule material used is thermosetting resin, is easily extruded and partial rupture in the course of processing; Spray process is simple, but the improvement result of this physics coating function to shortcomings such as the leakage of phase change material and volumetric expansions is limited.In addition, the heat transfer area of microcapsule phase-change energy storage material is less, heat-transfer effect is not ideal enough; And when this microcapsule phase-change energy storage material is in comparatively in rugged environment, outer wall capsule easily breaks, phase change material easily runs off.
Summary of the invention
The object of the invention is to adopt the phase-changing energy storage material heat-transfer effect that obtains of prior art not good and the crackly defect of outer wall capsule to overcome, and provide a kind of and there is excellent heat transfer property and carrier for phase-change accumulation energy of not easily breaking of outer wall capsule and preparation method thereof, and a kind of phase-changing energy storage material and preparation method thereof.
The invention provides a kind of carrier for phase-change accumulation energy, wherein, described carrier inside has multiple nano pore, and described carrier be by by containing one or more the raw material be selected from vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin through solidifying to form.
Present invention also offers the preparation method of the above-mentioned carrier for phase-change accumulation energy, wherein, the method comprises:
(1) prepare polystyrene-alumina formwork, the polystyrene in described polystyrene-alumina formwork is the spaced nanometer fibrous polystyrene be fixed on alumina formwork;
(2) by polystyrene-alumina formwork obtained for step (1) with containing one or more the contact raw be selected from vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin, the condition of described contact makes described raw material solidify and by coated for nanometer fibrous polystyrene and fixing;
(3) remove alumina formwork and polystyrene, obtain the carrier for phase-change accumulation energy; Wherein, removing the method for polystyrene is to eliminate the matrix material of alumina formwork and eluent solution comes into contact to remove polystyrene, described elutriant be selected from ethyl acetate, tetrahydrofuran (THF) and butylacetate one or more.
In addition, present invention also offers a kind of phase-changing energy storage material, wherein, described phase-changing energy storage material comprises above-mentioned carrier and phase change material; Described phase change material is filled in the nano pore of described carrier inside, and described phase change material is sealed in described carrier.
Present invention also offers the preparation method of above-mentioned phase-changing energy storage material, wherein, the method comprises:
(1) phase change material is filled in multiple nano pores of above-mentioned carrier;
(2) the carrier sealing being filled with phase change material step (1) obtained, makes described phase change material be sealed in described carrier.
Carrier inside for phase-change accumulation energy provided by the invention has multiple nano pore, described nano pore has special small-size effect, phase change material is inserted in described nano pore, can contact area be enlarged markedly, be conducive to the heat transfer property improving described phase-changing energy storage material.What is more important, described carrier be by by containing one or more the raw material be selected from vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin through solidifying to form, therefore, the higher and toughness of the intensity of described carrier better, is not easily broken.In addition, phase change material is encapsulated in microcapsule and forms microcapsules of storing energy through phase change by prior art employing, and the carrier of the phase-changing energy storage material obtained is generally hollow structure, easily deforms, very easily break when being subject to extraneous shock, thus cause the loss of phase change material; And the carrier for phase-changing energy storage material provided by the invention is the continuous carrier that inside has multiple nano pore, be non-hollow structure, have many stressed point of suppon, when being subject to extraneous shock, described carrier not easily breaks, phase change material not easily runs off.
It is that template has the carrier of multiple nano pore with preparation that the present invention make use of the polystyrene-alumina formwork with nanofibre-like structure dexterously, and preparation method is easy.The nano pore of the carrier adopting method of the present invention to prepare is evenly distributed, and the performance of the phase-changing energy storage material obtained is more excellent.In addition, the carrier adopting method of the present invention to prepare be by by containing one or more the raw material be selected from vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin through solidifying to form, be inert material, therefore, in the nano pore of described carrier also can filling agent be corrosive can phase change material, that is, increase the selectivity of described phase change material, the scope of application is wider.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to the present invention, the described carrier inside for phase-change accumulation energy has multiple nano pore, and described carrier be by by containing one or more the raw material be selected from vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin through solidifying to form.
Wherein, although the bore dia of the present invention to described nano pore is not particularly limited, as long as control just can have excellent heat transfer property at nano level (being less than or equal to 200nm), but those skilled in the art it is understood that, when described nano pore bore dia more hour, heat transfer area is larger, heat-transfer effect better, but also can increase the difficulty preparing described phase-changing energy storage material simultaneously, therefore, combined factors is from every side considered, under preferable case, the bore dia of described nano pore is 110-130nm.In like manner, under preferable case, when the cumulative volume of described nano pore accounts for the 50-95% of carrier bulk, the heat transfer property of the phase-changing energy storage material obtained is more excellent.
The volume of described carrier and shape can be come reasonably to select by the needs used, and are not particularly limited, but for the ease of manufacturing, under preferable case, described carrier is preferably tabular; And the thickness of described plate-shaped support can be selected and change in wider scope, such as, can be 3-5mm.In addition, multiple nano pores of described carrier inside can be interconnected or partly be communicated with and also can not be communicated with.
According to the present invention, the kind of described acrylate and methacrylic ester is conventionally known to one of skill in the art, such as, described acrylate can be selected from methyl acrylate, ethyl propenoate and butyl acrylate one or more; Described methacrylic ester can be selected from methyl methacrylate, β-dimethyl-aminoethylmethacrylate and butyl methacrylate one or more.Described unsaturated polyester refers to the chain macromolecule compound with ester bond and unsaturated double-bond.Described unsaturated polyester is normally by unsaturated dibasic acid and/or unsaturated acid anhydride and dibasic alcohol polycondensation.Described unsaturated dibasic acid and unsaturated acid anhydride such as can be selected from MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE and tetrahydronaphthalic anhydride one or more; Described dibasic alcohol such as can be selected from ethylene glycol, propylene glycol, glycol ether and dipropylene glycol one or more.The condition of described polycondensation is conventionally known to one of skill in the art, will repeat no longer one by one at this.Described epoxy resin such as can be selected from cycloaliphatic epoxy resin, bisphenol A type epoxy resin, organic-silicon-modified bisphenol A type epoxy resin, saturated glycidyl ester type epoxy resin, heterocyclic type and mixed type epoxy resin one or more.Described vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin are all by being commercially available.
Those skilled in the art it is easily understood that, when in described raw material containing one or more in vinylformic acid, acrylate, methacrylic acid, methacrylic ester and unsaturated polyester time, in order to make described raw material be solidified, also containing initiator in described raw material.Kind and the consumption of described initiator are known to the skilled person, and such as, with the total mass of described vinylformic acid, acrylate, methacrylic acid, methacrylic ester and unsaturated polyester for benchmark, the content of described initiator can be 0.1-1 % by weight.Described initiator such as can be selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dicumyl peroxide and dibenzoyl peroxide one or more.
According to the present invention, under preferable case, the described carrier for phase-change accumulation energy is by being solidify to form by the raw material containing epoxy resin.When containing epoxy resin in described raw material, under preferable case, also containing solidifying agent and promotor in described raw material.The kind of described solidifying agent and promotor and materials are conventionally known to one of skill in the art, and such as, with the weight of described epoxy resin for benchmark, the content of described solidifying agent can be 1-2 % by weight, and the content of described promotor can be 1-2 % by weight.Described solidifying agent can for the existing various solidifying agent that can make epoxy resin cure, such as, described solidifying agent can be selected from polyamide resin, isophorone diamine, methylethyl ketone peroxide and cyclohexanone peroxide one or more; Wherein, described polyamide resin can for the polyamide resin purchased from the trade mark of Guangzhou Xing Huan trade Co., Ltd being 115 or 650.The present inventor finds, when the mixture that described solidifying agent is polyamide resin and isophorone diamine, and the weight ratio of described polyamide resin and described isophorone diamine is when being 2-3: 1, the solidification effect of the described raw material containing epoxy resin is very good, and the carrier obtained has better mechanical stability.Described promotor such as can be selected from Dyhard RU 100, adipic dihydrazide and Whitfield's ointment one or more.Described solidifying agent and promotor all can be commercially available.
According to the present invention, the preparation method of the described carrier for phase-change accumulation energy comprises:
(1) prepare polystyrene-alumina formwork, the polystyrene in described polystyrene-alumina formwork is the spaced nanometer fibrous polystyrene be fixed on alumina formwork;
(2) by polystyrene-alumina formwork obtained for step (1) with containing one or more the contact raw be selected from vinylformic acid, vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin, the condition of described contact makes described raw material solidify and by coated for nanometer fibrous polystyrene and fixing;
(3) remove alumina formwork and polystyrene, obtain the carrier for phase-change accumulation energy; Wherein, removing the method for polystyrene is to eliminate the matrix material of alumina formwork and eluent solution comes into contact to remove polystyrene, described elutriant be selected from ethyl acetate, tetrahydrofuran (THF) and butylacetate one or more.
The present invention is not particularly limited the diameter of described spaced nanometer fibrous polystyrene, length and density, but in order to make the carrier obtained, there is more excellent heat transfer property, under preferable case, the diameter of described spaced nanometer fibrous polystyrene is 100-120nm, length is 120-130 μm, and described density is 0.9 × 10
11-1.1 × 10
11root/cm
2; Described density refer to every square centimeter contained by the quantity of nanofiber.
According to the present invention, described polystyrene-alumina formwork can adopt various method to prepare, as long as the polystyrene in described polystyrene-alumina formwork can be made to exist with fibrous form, and nanometer fibrous polystyrene is fixed on alumina formwork, such as, the preparation method of described polystyrene-alumina formwork can comprise:
A metal aluminum sheet is carried out anodic oxidation by (), obtain alumina formwork;
B () is under nonoxidizing atmosphere, under the existence of initiator, the alumina formwork that vinylbenzene and step (a) obtain is contacted, the condition of described contact makes vinylbenzene be polymerized, and generate the nanometer fibrous polystyrene be fixed on described alumina formwork, obtain described polystyrene-alumina formwork.
Wherein, in step (a), metal aluminum sheet being carried out anodised condition can be the anodised condition of existing various routine, as long as described metal aluminum sheet can be oxidized, metal aluminum sheet Surface Creation is made to have the aluminum oxide of vesicular structure, thus be convenient to described vinylbenzene and grow to form nanometer fibrous polystyrene in described vesicular structure, and then obtain polystyrene-alumina formwork, such as, described anodised condition can comprise usually: anode is metallic aluminium, negative electrode is inert material, voltage is 30-50V, electrolytic solution is acidic solution.Described inert material can be existingly variously can be used as the inert material of negative electrode, such as, described inert material can be selected from graphite, metal platinum and metal titanium one or more.Kind and the concentration of described acidic solution are known to the skilled person, such as, the acid in described acidic solution can be selected from oxalic acid, sulfuric acid, hydrochloric acid and phosphoric acid one or more; The concentration of described acidic solution can be 0.2-0.6mol/L usually.The alumina formwork with uneven surface that described vinylbenzene obtains after can only being attached to metallic aluminium oxidation is polymerized, and can not be attached to and do not carry out anodised smooth metallic aluminum surface and be polymerized, therefore, those skilled in the art should it is easily understood that, for the ease of removing described alumina formwork in subsequent step, when metal aluminum sheet is carried out anodic oxidation, at least one surface of described metal aluminum sheet can be covered with inert coating material, the metal aluminum sheet surface being coated with inert coating material is made anodic oxidation not to occur, namely, described vinylbenzene can not be attached to and not carry out anodised region and be polymerized.The inert coating material of the various routines that described inert coating material can be known to the skilled person, such as, can be selected from graphite, metal platinum and metal titanium one or more.
According to the present invention, in order to make the surface tissue of the alumina formwork obtained more regular, under preferable case, described metal aluminum sheet is carried out anodised method and is generally two-step anodization, namely, above-mentioned anodic oxidation is an anodic oxidation, the irregular pellumina that the mixture alumina formwork that an above-mentioned anodic oxidation obtains being placed in chromic acid and phosphoric acid is formed to remove alumina formwork surface; Then, under above-mentioned anodised condition, carry out two-step anodization, obtain the alumina formwork of high-sequential.The concentration of described chromic acid can be 1-2 % by weight usually, and the concentration of described phosphoric acid can be 3-8 % by weight usually; The part by weight of described chromic acid and phosphoric acid is as can be 1-6: 1.
According to the present invention, keep clean to make metal aluminum sheet surface and reduce the internal stress of described metal aluminum sheet, under preferable case, also comprising before carrying out anodic oxidation and described metal aluminum sheet is carried out pre-treatment.Described pre-treatment can be conventional pretreatment process, generally includes described metal aluminum sheet organic solvent washing and anneals.The selection of described organic solvent and the method for annealing are known to the skilled person, and will repeat no longer one by one at this.
According to the present invention, in step (b), described non-oxidizing atmosphere comprises in an inert atmosphere or under vacuum, described inert atmosphere refer to not with any one gas or the gaseous mixture of reactant and product generation chemical reaction, as one or more in nitrogen and periodic table of elements zero group gas, be preferably nitrogen.Keep the method for inert atmosphere or vacuum condition for pass into rare gas element in system, or can be extracted out by the gas in system.The present invention is not particularly limited the weight of described initiator and consumption, as long as described vinylbenzene can be caused to be polymerized, such as, described initiator can be selected from one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, isopropyl benzene hydroperoxide, peroxide diisopropylbenzene(DIPB) and di-cyclohexylperoxy dicarbonate.With described cinnamic total mass for benchmark, the consumption of described initiator can be 0.01-0.1 % by weight usually, is preferably 0.01-0.08 % by weight.Described light trigger all can be commercially available.In step (b), the condition temperature generally including contact and the time contacted of described contact, as long as the condition of described contact can make Styrene solidification be reacted into polystyrene.The temperature of described contact can be selected in wide temperature range, and under normal circumstances, in order to be beneficial to the carrying out of curing reaction further, under preferable case, the temperature of described contact is 60-65 DEG C.The prolongation of described duration of contact is conducive to the raising of styrene conversion rate and molecular weight, but the overlong time of contact is not obvious to the increase rate of described transformation efficiency and molecular weight, and therefore, under preferable case, the time of described contact is 800-900 minute.
What those skilled in the art should understand that is, in step (2), containing one or more the raw material be selected from vinylformic acid, vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin before curing for after liquid, solidification for solid-state, therefore, the shape of the carrier obtained can be controlled by the shape of polystyrene-alumina formwork.For the ease of more accurately controlling the shape of gained carrier and thickness and making solidification effect better, in contact process, use the size of mould can be greater than the size of carrier, to be solidified complete after, by the redundance excision of carrier obtained.
According to the present invention, in step (2), as long as the condition of described contact can make containing one or more the raw material solidification be selected from vinylformic acid, vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin and by coated for nanometer fibrous polystyrene and fixing, such as, the temperature that the condition of described contact generally includes contact can be 100-120 DEG C, and the time of contact can be 30-35 minute.Under preferable case, described carrier be by by the raw material containing epoxy resin through solidifying to form, and also containing solidifying agent and promotor in described raw material, the kind of described solidifying agent and materials reasonably can be selected according in the description of carrier mentioned above, will repeat no more at this.
According to the present invention, in step (3), the method removing alumina formwork can be existing various method, as long as vinylbenzene can be exposed, such as, the method for described removal alumina formwork can be selected from one or more in polishing, polishing and etching.
Above-mentioned carrier provided by the invention normally uses as preparing phase-changing energy storage material, therefore, in order to phase change material can be injected more easily in described carrier, described carrier is non-close carrier (leaving hole) normally, after injection phase change material, described carrier is carried out sealing of hole.Wherein, on described non-close carrier, the size in hole can suitably be selected according to actual needs, and the method for described sealing of hole can be the method for sealing of various routine known in those skilled in the art, as long as described phase change material can be sealed in described carrier.
According to the present invention, described phase-changing energy storage material comprises above-mentioned carrier and phase change material; Described phase change material is filled in the nano pore of described carrier inside, and described phase change material is sealed in described carrier.
According to the present invention, the kind of described phase change material is known to the skilled person, such as, described phase change material can be selected from paraffin, higher aliphatic hydrocarbon, high fatty alcohol, higher fatty acid and high-grade aliphatic ester one or more.It is the straight chain of 6-26 or side chain, saturated or unsaturated aliphatic hydrocarbon that described higher aliphatic hydrocarbon refers to carbonatoms; Described high fatty alcohol refer to carbonatoms be the straight chain of 6-16 or the monohydroxy-alcohol of side chain; Described higher fatty acid refer to carbonatoms be the straight chain of 6-26 or the monocarboxylic acid of side chain; Described high-grade aliphatic ester refer to carbonatoms be the straight chain of 6-18 or the fatty acid ester of side chain.Described phase change material is all by being commercially available.The loading level of the present invention to described phase change material is not particularly limited, and as a rule, the loading level of described phase change material can be the 50-95% of the nano pore cumulative volume of described carrier inside.
According to the present invention, the preparation method of described phase-changing energy storage material comprises:
(1) phase change material is filled in the nano pore of above-mentioned carrier inside;
(2) the carrier sealing being filled with phase change material step (1) obtained, makes described phase change material be sealed in described carrier.
According to the present invention, the kind of described phase change material and loading level reasonably can be selected according to the kind of phase change material described in above-mentioned phase-changing energy storage material and loading level, will repeat no longer one by one at this.
According to the present invention, in step (2), the carrier sealing being filled with phase change material step (1) obtained, makes the described phase change material method be sealed in described carrier can be existing various method, such as, can be with sealing material, the opening of described carrier is sealed.The kind of the present invention to described sealing material is not particularly limited, as long as can described phase change material be sealed in described carrier, but in order to make the phase-changing energy storage material obtained, there is less surface stress, more excellent thermostability and mechanical stability, under preferable case, described sealing material is identical with the material of the described carrier of composition.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will be described the present invention by embodiment.
Embodiment 1
This embodiment is for illustration of the preparation of carrier provided by the invention and phase-changing energy storage material.
(1) inside has the preparation of the carrier of multiple nano pore:
(a) by aluminium flake (long 25cm × wide 10cm × thick 1mm, lower with) successively with washing with acetone to remove grease, at 500 DEG C of annealing 3h to remove the internal stress of aluminium flake and ultrasonic cleaning 15min in acetone, obtain the aluminium flake that cleaning is bright; Aluminium flake after process being put into concentration is that the oxalic acid solution of 0.5mol/L carries out first time anodic oxidation, and wherein, voltage is 40V; After an anodic oxidation, the mixed solution (weight ratio of chromic acid and phosphoric acid is 1: 1) gained aluminium flake being placed in the chromic acid of 1.18 % by weight and the phosphoric acid of 6 % by weight soaks 3h, to remove the irregular oxide film that surface of aluminum plate is formed.Then, the aluminium sheet obtained is carried out two-step anodization under above-mentioned anodic oxidation condition, obtain the alumina formwork that surface has the hole of high-sequential, be called for short AAO template.
B AAO template organic reagent that step (1) obtains by () cleans and is placed in groove with cover, under room temperature (25 DEG C), after air in vacuum pump extraction groove, inject the vinylbenzene of dry deoxygenation (containing Diisopropyl azodicarboxylate initiator, and with described cinnamic gross weight for benchmark, the content of described Diisopropyl azodicarboxylate initiator is 0.01 % by weight) to cover described AAO template, at 65 DEG C, isothermal reaction 900 minutes in a water bath, generate the nanometer fibrous polystyrene be fixed in AAO template, thus obtain polystyrene-alumina formwork.The diameter of described nanometer fibrous polystyrene is 100-120nm, and length is 120-130 μm, and nanofiber density is 0.9 × 10
11root/cm
2.
(c) by 0.69g Whitfield's ointment, 0.46g polyamide resin (purchased from Guangzhou Xing Huan trade Co., Ltd, the trade mark is 115), 0.77g isophorone diamine solution (concentration is 30%) and 69g bisphenol A type epoxy resin (blue star novel material Wuxi resin, E-44) be uniformly mixed, obtain solidifying raw material.Polystyrene-alumina formwork step (b) obtained is placed in mould (long 25cm × wide 10cm × thick 3mm, lower same) in, and described solidification raw material is placed in mould and covers on described polystyrene-alumina formwork to make described composite structure and solidification contact raw, then mould is put into vacuum drying oven vacuum removal bubble, leave standstill 15h, put into baking oven (temperature is 100 DEG C) solidification 35 minutes, raw material is solidified and by coated for nanometer fibrous polystyrene and fixing, obtain plaques (long 25cm × wide 10cm × thick 3mm, lower same).
The metal form of the lower surface of d plaques that step (c) obtains by () carries out polished finish, to expose polystyrene, sample after polishing is put into ethyl acetate solution to soak 15 minutes and drying, obtain the carrier containing nano pore, the bore dia of described nano pore is 110-130nm, and the cumulative volume of described nano pore accounts for 50% of the block volume containing nano pore.
(2) by multiple nano pores of carrier obtained for phase change material paraffin implantation step (1), wherein, the loading level of described phase change material is 95% of the nano pore cumulative volume of described carrier inside.
(3) sealing material is coated in the opening part being filled with the carrier of phase change material obtained by step (2), solidifies at 100 DEG C in temperature and make described phase change material be sealed in described carrier to make carrier seal in 35 minutes; Wherein, described sealing material is that 0.69g Whitfield's ointment, 0.46g polyamide resin are (purchased from Guangzhou Xing Huan trade Co., Ltd, the trade mark is 115), 0.77g isophorone diamine solution (concentration is 30 % by weight) and 69g bisphenol A type epoxy resin (blue star novel material Wuxi resin, E-44) obtain after being uniformly mixed solidifying raw material.
Embodiment 2
This embodiment is for illustration of the preparation of carrier provided by the invention and phase-changing energy storage material.
(1) inside has the preparation of the carrier of multiple nano pore:
(a) by aluminium flake (25cm × 10cm × 1mm) successively with washing with acetone to remove grease, at 500 DEG C of annealing 3h to remove the internal stress of aluminium flake and ultrasonic cleaning 15min in acetone, obtain the aluminium flake that cleaning is bright; Aluminium flake after process being put into concentration is that the oxalic acid solution of 0.3mol/L carries out first time anodic oxidation, and wherein, voltage is 30V; After an anodic oxidation, the mixed solution (weight ratio of chromic acid and phosphoric acid is 1: 1) gained aluminium flake being placed in the chromic acid of 1.18 % by weight and the phosphoric acid of 6 % by weight soaks 3h, to remove the irregular oxide film that surface of aluminum plate is formed.Then, the aluminium sheet obtained is carried out two-step anodization under above-mentioned anodic oxidation condition, obtain the alumina formwork that surface has the hole of high-sequential, be called for short AAO template.
B AAO template organic reagent that step (1) obtains by () cleans and is placed in groove with cover, under room temperature (25 DEG C), after air in vacuum pump extraction groove, inject the vinylbenzene of dry deoxygenation (containing 2,2'-Azobis(2,4-dimethylvaleronitrile) initiator, and with described cinnamic gross weight for benchmark, the content of described 2,2'-Azobis(2,4-dimethylvaleronitrile) initiator is 0.08 % by weight) to cover described AAO template, at 60 DEG C, isothermal reaction 800 minutes in a water bath, generate the nanometer fibrous polystyrene be fixed in AAO template, thus obtain polystyrene-alumina formwork.The diameter of described nanometer fibrous polystyrene is 100-120nm, and length is 120-130 μm, and nanofiber density is about 1.1 × 10
11root/cm
2.
C 1.38g Dyhard RU 100 (is reached Science and Technology Ltd. purchased from Huizhou flourishing age by (), the trade mark is 8215), 1.04g polyamide resin is (purchased from Guangzhou Xing Huan trade Co., Ltd, the trade mark is 115), 1.15g isophorone diamine solution (concentration is 30 % by weight) and 69g bisphenol A type epoxy resin (blue star novel material Wuxi resin, E-44) be uniformly mixed, obtain solidifying raw material.Polystyrene-alumina formwork step (b) obtained is placed in mould (25cm × 10cm × 3mm), and described solidification raw material is placed in mould and covers on described polystyrene-alumina formwork to make described composite structure and solidification contact raw, then mould is put into vacuum drying oven vacuum removal bubble, leave standstill 15h, put into baking oven (temperature is 120 DEG C) solidification 30 minutes, raw material is solidified and by coated for nanometer fibrous polystyrene and fixing, obtains plaques (25cm × 10cm × 3mm).
The metal form of the lower surface of d plaques that step (c) obtains by () carries out polished finish, to expose polystyrene, sample after polishing is put into ethyl acetate solution to soak 20 minutes and drying, obtain the carrier containing nano pore, the bore dia of described nano pore is 110-130nm, and the cumulative volume of described nano pore accounts for 95% of the block volume containing nano pore.
(2) by multiple nano pores of carrier obtained for phase change material stearic acid implantation step (1), wherein, the loading level of described phase change material is 50% of the nano pore cumulative volume of described carrier inside;
(3) sealing material is coated in the opening part being filled with the carrier of phase change material obtained by step (2), solidifies at 120 DEG C in temperature and make described phase change material be sealed in described carrier to make carrier seal in 30 minutes; Wherein, described sealing material is that 1.38g Dyhard RU 100 (reaches Science and Technology Ltd. purchased from Huizhou flourishing age, the trade mark is 8215), 1.04g polyamide resin is (purchased from Guangzhou Xing Huan trade Co., Ltd, the trade mark is 115), 1.15g isophorone diamine solution (concentration is 30 % by weight) and 69g bisphenol A type epoxy resin (blue star novel material Wuxi resin, E-44) obtain after being uniformly mixed solidifying raw material.
Embodiment 3
This embodiment is for illustration of the preparation of carrier provided by the invention and phase-changing energy storage material.
(1) inside has the preparation of the carrier of multiple nano pore:
(a) by aluminium flake (25cm × 10cm × 1mm) successively with washing with acetone to remove grease, at 500 DEG C of annealing 3h to remove the internal stress of aluminium flake and ultrasonic cleaning 15min in acetone, obtain the aluminium flake that cleaning is bright; Aluminium flake after process being put into concentration is that the oxalic acid solution of 0.5mol/L carries out first time anodic oxidation, and wherein, voltage is 40V; After an anodic oxidation, the mixed solution (weight ratio of chromic acid and phosphoric acid is 1: 1) gained aluminium flake being placed in the chromic acid of 1.18 % by weight and the phosphoric acid of 6 % by weight soaks 3h, to remove the irregular oxide film that surface of aluminum plate is formed.Then, the aluminium sheet obtained is carried out two-step anodization under above-mentioned anodic oxidation condition, obtain the alumina formwork that surface has the hole of high-sequential, be called for short AAO template.
B AAO template organic reagent that step (1) obtains by () cleans and is placed in groove with cover, under room temperature (25 DEG C), after air in vacuum pump extraction groove, inject the vinylbenzene of dry deoxygenation (containing dibenzoyl peroxide initiator, and with described cinnamic gross weight for benchmark, the content of described dibenzoyl peroxide initiator is 0.05 % by weight) to cover described AAO template, at 62 DEG C, isothermal reaction 850 minutes in a water bath, generate the nanometer fibrous polystyrene be fixed in AAO template, thus obtain polystyrene-alumina formwork.The diameter of described nanometer fibrous polystyrene is 100-110nm, and length is 120-130 μm, and nanofiber density is about 1 × 10
11root/cm
2.
(c) by 1.04g adipic dihydrazide, 0.74g polyamide resin (purchased from Guangzhou Xing Huan trade Co., Ltd, the trade mark is 115), 0.99g isophorone diamine solution (concentration is 30 % by weight) and 69g epoxy resin is uniformly mixed, obtain solidifying raw material.Polystyrene-alumina formwork step (b) obtained is placed in mould (25cm × 10cm × 3mm), and described solidification raw material is placed in mould and covers on described polystyrene-alumina formwork to make described composite structure and solidification contact raw, then mould is put into vacuum drying oven vacuum removal bubble, leave standstill 15h, put into baking oven (temperature is 110 DEG C) solidification 32 minutes, raw material is solidified and by coated for nanometer fibrous polystyrene and fixing, obtains plaques (25cm × 10cm × 3mm).
The metal form of the lower surface of d plaques that step (c) obtains by () carries out polished finish, to expose polystyrene, sample after polishing is put into ethyl acetate solution to soak 15 minutes and drying, obtain the carrier containing nano pore, the bore dia of described nano pore is 100-120nm, and the cumulative volume of described nano pore accounts for 70% of the block volume containing nano pore.
(2) by multiple nano pores of carrier obtained for phase change material palmitinic acid implantation step (1), wherein, the loading level of described phase change material is 75% of the nano pore cumulative volume of described carrier inside;
(3) sealing material is coated in the opening part being filled with the carrier of phase change material obtained by step (2), solidifies at 110 DEG C in temperature and make described phase change material be sealed in described carrier to make carrier seal in 32 minutes; Wherein, described sealing material is 1.04g adipic dihydrazide, 0.74g polyamide resin (purchased from Guangzhou Xing Huan trade Co., Ltd, the trade mark is 115), 0.99g isophorone diamine solution (concentration is 30%) and 69g epoxy resin obtain after being uniformly mixed solidifying raw material.
Embodiment 4
This embodiment is for illustration of the preparation of carrier provided by the invention and phase-changing energy storage material.
Phase-changing energy storage material is prepared according to the method for embodiment 1, unlike, described solidification raw material is replaced by the mixture of 69g vinylformic acid and 1.23g Diisopropyl azodicarboxylate.
Embodiment 5
This embodiment is for illustration of the preparation of carrier provided by the invention and phase-changing energy storage material.
Phase-changing energy storage material is prepared according to the method for embodiment 1, unlike, described solidification raw material is replaced by the mixture of 69g unsaturated polyester (purchased from Nanchang Ming Rui Raw Materials Company of Chemical Industry, the trade mark is 191) and 1.23g Diisopropyl azodicarboxylate.
Embodiment 6
This embodiment is for illustration of the preparation of carrier provided by the invention and phase-changing energy storage material.
Carrier and phase-changing energy storage material is prepared according to the method for embodiment 1, unlike, have in the step (b) of the carrier of multiple nano pore in preparation inside, it is 55 DEG C by control temperature, reaction times is 750 minutes, make the diameter of the nanometer fibrous polystyrene obtained be 55-75nm, length is 100-110 μm, and nanofiber density is about 0.8 × 10
11root/cm
2; Thus making the bore dia of the nano pore of the described carrier obtained be 60-80nm, the cumulative volume of described nano pore accounts for 40% of the block volume containing nano pore.
Embodiment 7
This embodiment is for illustration of the preparation of carrier provided by the invention and phase-changing energy storage material.
Phase-changing energy storage material is prepared according to the method for embodiment 1, unlike, described polyamide resin and isophorone diamine all replace with quadrol.
Comparative example 1
This comparative example is for illustration of the preparation of reference carrier and phase-changing energy storage material.
At 45 DEG C, by 15g phase-changing energy storage material n-heptadecane, 15g vinylbenzene, 0.1g emulsifying agent Sodium dodecylbenzene sulfonate, 0.25g initiator Diisopropyl azodicarboxylate and 100g deionized water and stirring mixing 30min, and in groove type ultrasonic instrument ultrasonic 2min, formed emulsion; By the emulsion obtained 70 DEG C, rotating speed is polymerized 8h under being the mechanical stirring of 300rpm, obtains the solution containing polymerisate.The solution containing polymerisate obtained is naturally cooled to room temperature, and slowly add saturated NaCl solution to containing polymerisate solution in there is obvious flocks (breakdown of emulsion), filtration is precipitated thing, and cleans throw out deionized water, obtains phase-change microcapsule material.
Test case 1-7
Test case 1-7 is for illustration of the test of the performance of carrier provided by the invention and phase-changing energy storage material.
(1) test of energy-storage property:
DSC (German Netzsch company DSC-204) differential scanning calorimeter is adopted to carry out the measurement of phase-change accumulation energy value (wherein to the phase-changing energy storage material that embodiment 1-7 prepares respectively; test condition is N2 gas shielded, and temperature rise rate is 1 DEG C/min).Acquired results is as shown in table 1 below.
(2) test of heat transfer property:
Respectively the heat transfer property of the phase-changing energy storage material that embodiment 1-7 prepares is tested according to method disclosed in GB-T10294-2008.Acquired results is as shown in table 1.
(3) test of thermostability:
The phase-changing energy storage material prepared by embodiment 1-7 is respectively incubated 1h under transformation temperature, and circulating 2000 times lower than carrying out heating-cooling in transformation temperature 50 DEG C and the temperature range higher than transformation temperature 50 DEG C, observe phase-changing energy storage material whether expand and the carrier surface of phase-changing energy storage material with or without cracking.Acquired results is as shown in table 1.
Contrast test example 1
Contrast test example 1 is for illustration of the test of the carrier of reference and the performance of phase-changing energy storage material.
The carrier prepared comparative example 1 according to the method for test case 1-7 and phase-changing energy storage material carry out the test of performance.Acquired results is as shown in table 1.
Table 1
From the results shown in Table 1, the method for embodiment of the present invention 1-7 is adopted to prepare the energy storage rate of phase-changing energy storage material, thermal conductivity and thermostability all higher than comparative example 1.Can be found out by the contrast of embodiment 1 and embodiment 6, when the bore dia of the nano pore of described carrier and pore volume are in preferable range of the present invention, described phase-changing energy storage material has more excellent energy storage and thermal conduction; Can be found out by the contrast of embodiment 1 with embodiment 7, adopt the preferred solidifying agent of the present invention, the thermostability of gained phase-changing energy storage material and mechanical stability are more excellent.
Claims (18)
1. the carrier for phase-change accumulation energy, it is characterized in that, described carrier inside has multiple nano pore, and described carrier be by by containing one or more the raw material be selected from vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin through solidifying to form; The bore dia of described nano pore is 110-130nm, and the cumulative volume of described nano pore accounts for the 50-95% of carrier bulk.
2. carrier according to claim 1, wherein, described carrier is tabular, and the thickness of described plate-shaped support is 3-5mm.
3. carrier according to claim 1 and 2, wherein, described carrier be by by the mixture containing epoxy resin, solidifying agent and promotor through solidifying to form; With the weight of described epoxy resin for benchmark, the content of described solidifying agent is 1-2 % by weight, and the content of described promotor is 1-2 % by weight.
4. the carrier according to right 3, wherein, described solidifying agent be selected from polyamide resin, isophorone diamine, methylethyl ketone peroxide and cyclohexanone peroxide one or more; Described promotor be selected from Dyhard RU 100, adipic acid dihydrazide and Whitfield's ointment one or more.
5. carrier according to claim 4, wherein, described solidifying agent is the mixture of polyamide resin and isophorone diamine, and the weight ratio of described polyamide resin and isophorone diamine is 2-3:1.
6. described in claim 1 for the preparation method of the carrier of phase-change accumulation energy, it is characterized in that, the method comprises:
(1) prepare polystyrene-alumina formwork, the polystyrene in described polystyrene-alumina formwork is the spaced nanometer fibrous polystyrene be fixed on alumina formwork;
(2) by polystyrene-alumina formwork obtained for step (1) with containing one or more the contact raw be selected from vinylformic acid, acrylate, methacrylic acid, methacrylic ester, unsaturated polyester and epoxy resin, the condition of described contact makes described raw material solidify and by coated for nanometer fibrous polystyrene and fixing;
(3) remove alumina formwork and polystyrene, obtain the carrier for phase-change accumulation energy; Wherein, removing the method for polystyrene is to eliminate the matrix material of alumina formwork and eluent solution comes into contact to remove polystyrene, described elutriant be selected from ethyl acetate, tetrahydrofuran (THF) and butylacetate one or more.
7. preparation method according to claim 6, wherein, in step (1), the diameter of described spaced nanometer fibrous polystyrene is 100-120nm, and length is 120-130 μm, and density is 0.9 × 10
11-1.1 × 10
11root/cm
2.
8. the preparation method according to claim 6 or 7, wherein, in step (2), the temperature that the condition of described contact comprises contact is 100-120 DEG C, and the time of contact is 30-35 minute.
9. preparation method according to claim 6, wherein, in step (2), described raw material is the mixture containing epoxy resin, solidifying agent and promotor; With the weight of described epoxy resin for benchmark, the consumption of described solidifying agent is 1-2 % by weight, and the consumption of described promotor is 1-2 % by weight; Described solidifying agent be selected from polyamide resin, isophorone diamine, methylethyl ketone peroxide and cyclohexanone peroxide one or more; Described promotor be selected from Dyhard RU 100, adipic acid dihydrazide and Whitfield's ointment one or more.
10. preparation method according to claim 9, wherein, described solidifying agent is the mixture of polyamide resin and isophorone diamine, and the weight ratio of described polyamide resin and described isophorone diamine is 2-3:1.
11. preparation methods according to claim 6, wherein, in step (3), remove that the method for alumina formwork is selected from polishing, polishing and etching one or more.
12. preparation methods according to claim 6, wherein, in step (1), the method preparing polystyrene-alumina formwork comprises:
A metal aluminum sheet is carried out anodic oxidation by (), obtain alumina formwork;
B () is under non-oxidizing atmosphere, under the existence of initiator, the alumina formwork that vinylbenzene and step (a) obtain is contacted, the condition of described contact makes vinylbenzene be polymerized, and generate the nanometer fibrous polystyrene be fixed on described alumina formwork, obtain described polystyrene-alumina formwork.
13. preparation methods according to claim 12, wherein, in step (a), it is 30-50V that described anodised condition comprises voltage, and electrolytic solution is acidic solution; Acid in described acidic solution be selected from oxalic acid, sulfuric acid, hydrochloric acid and phosphoric acid one or more; In step (b), the temperature that the condition of described contact comprises contact is 60-65 DEG C, and the time of contact is 800-900 minute.
14. 1 kinds of phase-changing energy storage materials, is characterized in that, described phase-changing energy storage material comprises the carrier in claim 1-5 described in any one, and phase change material; Described phase change material is filled in the nano pore of described carrier inside, and described phase change material is sealed in described carrier.
15. phase-changing energy storage materials according to claim 14, wherein, described phase change material be selected from paraffin, higher aliphatic hydrocarbon, high fatty alcohol, higher fatty acid and high-grade aliphatic ester one or more; The loading level of described phase change material is the 50-95% of the nano pore cumulative volume of described carrier inside.
Described in 16. claims 14, the preparation method of phase-changing energy storage material, is characterized in that, the method comprises:
(1) phase change material is filled in the nano pore of the carrier inside in claim 1-5 described in any one;
(2) the carrier sealing being filled with phase change material step (1) obtained, makes described phase change material be sealed in described carrier.
17. preparation methods according to claim 16, wherein, in step (1), described phase change material be selected from paraffin, higher aliphatic hydrocarbon, high fatty alcohol, higher fatty acid and high-grade aliphatic ester one or more; The loading level of described phase change material is the 50-95% of the nano pore cumulative volume of described carrier; In step (2), the carrier sealing being filled with phase change material step (1) obtained, makes the described phase change material method be sealed in described carrier comprise and is sealed by the opening of described carrier with sealing material.
18. preparation methods according to claim 17, wherein, in step (2), described sealing material is identical with the material forming described carrier.
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| CN106893561A (en) * | 2015-12-17 | 2017-06-27 | 比亚迪股份有限公司 | Phase change composite material and electronic equipment |
| WO2019220662A1 (en) * | 2018-05-15 | 2019-11-21 | 日立化成株式会社 | Curable composition, curable composition set, heat storage material, and article |
| CN112778979B (en) * | 2021-01-07 | 2021-10-26 | 华中科技大学 | High-thermal-conductivity polymer-shaped composite phase-change material and preparation method thereof |
| CN113372671B (en) * | 2021-06-23 | 2022-03-25 | 杭州鲁尔新材料科技有限公司 | Phase-change heat storage film and preparation method thereof |
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