CN105098064A - Load zinc oxide nanotube array film type phase change material and preparation method and application thereof - Google Patents
Load zinc oxide nanotube array film type phase change material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a zinc oxide nanotube array film type phase change material and a preparation method and an application thereof. The phase change material contains a zinc oxide nanotube array film carrier and the phase change material loaded on the zinc oxide nanotube array film carrier. Total weight of the phase change material acts as a benchmark, the content of the phase change material is 5-95 wt%, preferably 70-90 wt%, and the content of the zinc oxide nanotube array film carrier is 5-95 wt%, preferably 10-30 wt%. The zinc oxide nanotube array film is enabled to act as the carrier by the inventor to be applied to the field of packaging phase change material represented by paraffin for the first time. Melting/crystallization temperature of paraffin can be changed by the zinc oxide nanotube array film with a specific shape, heat conduction is facilitated, and the phase change material is particularly suitable for production of small precision electronic devices.
Description
Technical field
The present invention relates to a kind of load zinc oxide nano tube array film-type phase-change material and preparation method thereof, the invention still further relates to and use the application of this phase-change material in the production of electronic device, belong to field of energy source materials.
Background technology
Phase-change material (phasechangematerials, PCMs) is also called latent heat storage material (latentthermalenergystorage, LTES) and has that energy storage density is large, be approximately the advantages such as isothermal in energy storage and exoergic process.
At present, domestic and international various phase-change material heat transfer enhancement technology be mainly included in phase-change material add metallic stuffing, add graphite, graft process, carry out encapsulated and multiple phase change materials etc.Because metal material is perishable, do not mate with a lot of phase-change material, its density is large in addition, causes the weight of whole hold over system to increase, reduces the energy storage density of system.Be all generally that phase-change material is prepared into shaping phase-change material during interpolation graphite, this composite material macroscopically still can keep solid forms when undergoing phase transition, and can not leak, and does not need to encapsulate, but also there is the shortcoming of phase-change material precipitation.Encapsulation degree prepared by intercalation and packaging efficiency lower, therefore environment for use is required relatively harsh.Microcapsules technology is due to its complicated process of preparation, and the selection of phase-change material and wall material has certain directionality, substantially can only study at organic material category at present, and this will cause its heat conduction, heat-resisting, fire-resistant function reduction.And be that the organic phase-change latent heat storage material ubiquity conductive coefficient of representative is low with paraffin, the shortcoming of heat exchange property difference.In sum, most of phase-change material and encapsulation technology thereof all have certain limitation in the scope of application and use field.
Therefore, the encapsulation technology of phase-change material is the hot issue of phase-change material research and the technical bottleneck of practical application.
Summary of the invention
The object of the invention is to overcome in prior art is that the organic phase-change latent heat storage material of representative exists the shortcoming that thermal conductivity is low, heat exchange property is poor with paraffin, a kind of load zinc oxide nano tube array film-type phase-change material and preparation method thereof is provided, and uses this application of load zinc oxide nano tube array film-type phase-change material in the production of electronic device.
The invention provides a kind of load zinc oxide nano tube array film-type phase-change material, wherein, this load zinc oxide nano tube array film-type phase-change material contains zinc oxide nano tube array thin-film carrier and the phase-change material of load on described zinc oxide nano tube array thin-film carrier, and with the total weight of this load zinc oxide nano tube array film-type phase-change material for benchmark, the content of described phase-change material is 5-95 % by weight, be preferably 20-50 % by weight, be more preferably 30-40 % by weight, the content of described zinc oxide nano tube array thin-film carrier is 5-95 % by weight, be preferably 50-80 % by weight, be more preferably 60-70 % by weight.
Present invention also offers a kind of preparation method of above-mentioned load zinc oxide nano tube array film-type phase-change material, the method comprises phase-change material load on zinc oxide nano tube array thin-film carrier.
In addition, present invention also offers the application of a kind of above-mentioned load zinc oxide nano tube array film-type phase-change material in the production of electronic device.
In the present invention, the present inventor finds through a large amount of scientific researches, zinc oxide is typical polar crystal, sufficient at reactant ion, under weakly acidic pH or weakly acidic nature, first six side's long column shape crystal can be grown to along [0001] crystal orientation, again because the specific surface energy in end face (002) face is much larger than nonpolar side, polar surface can the optimum solvation when thing extraneous factor affects, and makes zinc oxide nano rod finally form the zinc oxide nano mitron of hollow.And zinc oxide nano tube array a kind ofly has the homogeneous loose structure of high specific surface area, character, has good fillable.
Therefore, the present inventor using zinc oxide nano tube array film as carrier, first Application is to the packaging phase change material field taking paraffin as representative, the zinc oxide nano tube array film with the higher specific area aperture of nano-grade size can change the thawing/crystallization temperature of paraffin, promote the conduction of heat, and compared with traditional porous phase transformation encapsulating material, under the synthetic technological condition of maturation, zinc oxide nano tube array has no particular limits and requirement growth substrate, and its growth thickness can control at nanoscale Fa Neinei, and adopt load zinc oxide nano tube array film-type phase-change material provided by the invention to be particularly useful in the production of miniature precision electronic device.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the SEM figure of ZnO nano nano-pipe array thin film;
In Fig. 2, (a) is the SEM picture (low power) of the ZnO nanotube/array film embedding liquid paraffin; B () is for embedding the SEM picture (high power) of the ZnO nanotube/array film of liquid paraffin; C () is for embedding SEM figure (low power) of the ZnO nanotube/array film of solid-state paraffin; And (d) is SEM figure (high power) of the ZnO nanotube/array film embedding solid-state paraffin;
The DSC curve of Fig. 3 to be loading ZnO nano-pipe array thin film type phase-change material prepared by paraffin refined wax and embodiment 1 in theoretical phase transition temperature be paraffin of 25 DEG C;
The DSC curve of Fig. 4 to be loading ZnO nano-pipe array thin film type phase-change material prepared by paraffin refined wax and embodiment 2 in theoretical phase transition temperature be paraffin of 30 DEG C.
Reference numeral
1, paraffin refined wax 2, loading ZnO nano-pipe array thin film type phase-change material
3, paraffin refined wax 4, loading ZnO nano-pipe array thin film type phase-change material
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.
The invention provides a kind of load zinc oxide nano tube array film-type phase-change material, wherein, this load zinc oxide nano tube array film-type phase-change material contains zinc oxide nano tube array thin-film carrier and the phase-change material of load on described zinc oxide nano tube array thin-film carrier, and with the total weight of this load zinc oxide nano tube array film-type phase-change material for benchmark, the content of described phase-change material is 5-95 % by weight, be preferably 20-50 % by weight, be more preferably 30-40 % by weight, the content of described zinc oxide nano tube array thin-film carrier is 5-95 % by weight, be preferably 50-80 % by weight, be more preferably 60-70 % by weight.In this case, gratifying phase-change material can be obtained.
According to the present invention, the thickness of described zinc oxide nano tube array thin-film carrier can be 1:0.2-1 with the ratio of the thickness of the phase-change material of described load on zinc oxide nano tube array thin-film carrier, is preferably 1:0.7-0.9, is more preferably 1:0.7-0.8.
According to the present invention, the thickness of described zinc oxide nano tube array thin-film carrier can be 3-5 micron, is preferably 4-5 micron.
According to the present invention, described zinc oxide nano tube array thin-film carrier is made up of zinc oxide nano mitron, and the cross section of described zinc oxide nano mitron is regular hexagon, the external diameter of described zinc oxide nano mitron is 1-2 micron, be preferably 1-1.5 micron, pipe thickness is 10-200 nanometer, is preferably 10-50 nanometer.
According to the present invention, described phase-change material is not particularly limited, and described phase-change material can be one or more in mineral-type phase-change material, organic phase-change material and complex class phase-change material; Wherein, described mineral-type phase-change material can be one or more in crystalline hydrate salt, molten salts, metal and alloy type thereof; Described organic phase-change material can be one or more in paraffin, acetic acid and other organic substances; Preferably, described phase-change material is organic phase-change material, and more preferably, described organic phase change material is paraffin.
According to the present invention, particularly, the preparation of described zinc oxide nano tube array thin-film carrier can comprise the steps:
(1) colloid synthesis: by zinc acetate (Zn (CH
3cOO)
22H
2o) monoethanolamine (NH is dissolved into
2oCH
2cH
2and ethylene glycol monoemethyl ether (CH OH)
3oCH
2cH
2oH) form mixed solution in, and this mixed solution is carried out magnetic agitation and obtain uniform and stable zinc acetate (Zn (CH
3cOO)
22H
2o) colloidal solution;
Wherein, the concentration of described zinc acetate colloidal solution can be 0.05mol/L-0.75mol/L, is preferably 0.09mol/L-0.2mol/L, is more preferably 0.1mol/L; In addition, zinc acetate (Zn (CH
3cOO)
22H
2and monoethanolamine (NH O)
2oCH
2cH
2oH) concentration can be identical, preferably, and zinc acetate (Zn (CH
3cOO)
22H
2and monoethanolamine (NH O)
2oCH
2cH
2oH) concentration can be 0.005M, 0.01M and 0.05M independently of one another;
Wherein, the condition of this mixed solution being carried out magnetic agitation can be: mixed solution is stirred 10-60min at 40-80 DEG C of lower magnetic force, preferably, stirs 30min at 60 DEG C of lower magnetic forces; In addition, in the present invention, the equipment carrying out magnetic agitation is not particularly limited, the various magnetic stirring apparatus that can be well known to those skilled in the art;
(2) whirl coating technique: the zinc acetate colloidal solution obtained through step (1) is dripped to substrate substrate carried out whirl coating process and obtain with zinc acetate glued membrane;
Wherein, described substrate is not particularly limited, and can be one or more in glass, ITO, pottery and metal, be preferably glass, and in the present invention, preferably, substrate to be immersed in acetone or alcohol with cleaning in ultrasonic 10min, then to dry with deionized water rinsing;
Wherein, the substrate with zinc acetate colloidal solution with the whirl coating speed whirl coating of 1000r/min-5000r/min on desk-top sol evenning machine, preferably, can be placed on desk-top sol evenning machine with the whirl coating speed whirl coating 30s of 3000r/min by described whirl coating process; In addition, in described whirl coating process, whirl coating number of times can be 1-3 time, is preferably 2 times; In substrate, the uniform zinc acetate glued membrane of one deck is prepared after whirl coating process;
(3) carry out annealing in process produce zinc oxide crystal seed film by being placed in Muffle furnace with the substrate of zinc acetate glued membrane through step (2); Wherein, substrate with zinc acetate glued membrane being placed in Muffle furnace the annealing temperature of carrying out annealing is 200-500 DEG C, annealing time is 10-30min, preferably, by the substrate with zinc acetate glued membrane in Muffle furnace with the 10min that anneals under 300 DEG C of conditions, one deck zinc oxide crystal seed film can be generated in substrate; In addition, the atmosphere in Muffle furnace is not particularly limited, and can be air or vacuum atmosphere, in the present invention, is preferably vacuum atmosphere;
(4) by zinc nitrate (Zn (NO
3)
2) and hexamethylene tetraammonia ((CH
2)
6n
4) be mixed to get mixed solution;
Wherein, (CH
2)
6n
4concentration can be 0.15M, 0.2M and 0.25M, and Zn (NO
3)
2) and (CH
2)
6n
4can mix by equal-volume;
(5) substrate with zinc oxide crystal seed film produced through step (3) is immersed in the mixed solution of step (4) carries out hydrothermal synthesis reaction.
Wherein, by the substrate with zinc oxide crystal seed film preferably with 45° angle and conducting surface down oblique cutting enter Zn (NO
3)
2with (CH
2)
6n
4mixed solution in, then seal, and put into thermostatic drying chamber isothermal reaction (hydro-thermal reaction) 24-60 hour of 90-95 DEG C, preferably, isothermal reaction 48 hours in the thermostatic drying chamber of 95 DEG C, takes out, clean and dry with deionized water rinsing.
Present invention also offers a kind of preparation method of above-mentioned load zinc oxide nano tube array film-type phase-change material, the method comprises phase-change material load on zinc oxide nano tube array thin-film carrier.
According to the present invention, the process of described load comprises in the phase-change material described zinc oxide nano tube array thin-film carrier being immersed in liquid state.
According to the present invention, the method is first flooded before being also included in and being immersed in liquid phase-change material by described zinc oxide nano tube array thin-film carrier in organic solution.
According to the present invention, described organic solution is not particularly limited, the organic solution that can be well known to those skilled in the art, and preferably, described organic solution is one or more in ethanol, acetone, and more preferably, described organic solution is ethanol.In addition, the time that described zinc oxide nano tube array thin-film carrier is immersed in organic solution is not particularly limited, rule of thumb can determine for those skilled in the art, preferably, be 10-150 minute by the time that described zinc oxide nano tube array thin-film carrier is immersed in organic solution, be preferably 40-80 minute, be more preferably 60 minutes.
According to the present invention, the time that described zinc oxide nano tube array thin-film carrier floods in the phase-change material of liquid state is 3-10 minute, is preferably 3-8 minute, is more preferably 3-5 minute.
According to the present invention, in the method preparing load zinc oxide nano tube array film-type phase-change material, with the total weight of this load zinc oxide nano tube array film-type phase-change material for benchmark, described phase-change material, and with the total weight of this load zinc oxide nano tube array film-type phase-change material for benchmark, the consumption of described phase-change material is 5-95 % by weight, be preferably 20-50 % by weight, be more preferably 30-40 % by weight, the consumption of described zinc oxide nano tube array thin-film carrier is 5-95 % by weight, be preferably 50-80 % by weight, be more preferably 60-70 % by weight.The present inventor finds, in this case, can obtain gratifying phase-change material.
According to the present invention, the thickness of described zinc oxide nano tube array thin-film carrier can be 1:0.2-1 with the ratio of the thickness of the phase-change material of described load on zinc oxide nano tube array thin-film carrier, is preferably 1:0.7-0.9, is more preferably 1:0.7-0.8.
According to the present invention, the thickness of described zinc oxide nano tube array thin-film carrier can be 3-5 micron, is preferably 4-5 micron.
According to the present invention, described zinc oxide nano tube array thin-film carrier is made up of zinc oxide nano mitron, and the cross section of described zinc oxide nano mitron is regular hexagon, the external diameter of described zinc oxide nano mitron is 1-2 micron, be preferably 1-1.5 micron, pipe thickness is 10-200 nanometer, is preferably 10-50 nanometer.
The present inventor finds the shape of zinc oxide nano mitron, external diameter and pipe thickness to control within above-mentioned scope, follow-up, the phase-change material envelope taking paraffin as representative is turned in described zinc oxide nano tube array thin-film carrier, can by changing the thawing/crystallization temperature of paraffin, thus promote the conduction of heat, gratifying phase-change material can be obtained.
According to the present invention, described phase-change material is not particularly limited, and described phase-change material can be one or more in mineral-type phase-change material, organic phase-change material and complex class phase-change material; Wherein, described mineral-type phase-change material can be one or more in crystalline hydrate salt, molten salts, metal and alloy type thereof; Described organic phase-change material can be one or more in paraffin, acetic acid and other organic substances; Preferably, described phase-change material is organic phase-change material, and more preferably, described organic phase change material is paraffin.
According to the present invention, particularly, the preparation of described zinc oxide nano tube array thin-film carrier is consistent with above-mentioned, does not repeat them here.
Present invention also offers the application of phase-change material in the production of electronic device adopting phase-change material of the present invention and adopt method of the present invention to prepare, especially the application in the production of miniature precision electronic device, still more preferably, the application in Small-Sized Precision Thermostat.
Below in conjunction with embodiment, the present invention is described in detail.
In the following Examples and Comparative Examples, zinc acetate (Zn (CH
3cOO)
22H
2o) purchased from Beijing chemical reagents corporation; Monoethanolamine (NH
2oCH
2cH
2oH) purchased from Beijing chemical reagents corporation; Ethylene glycol monoemethyl ether (CH
3oCH
2cH
2oH) purchased from Beijing chemical reagents corporation; Zinc nitrate (Zn (NO
3)
2) purchased from Beijing chemical reagents corporation; Hexamethylene tetraammonia ((CH
2)
6n
4) purchased from Beijing chemical reagents corporation; Paraffin is purchased from Beijing chemical reagents corporation.
In the following Examples and Comparative Examples:
X-ray diffraction analysis (XRD) is that D/Max2500PC type X-ray diffraction analysis instrument carries out in the model purchased from Rigaku company, and test condition be copper target (
), graphite monochromator, operating voltage is 40kV, and electric current is 100mA, light exit slit 1 °, and anti-dispersion slit is 2 °, and receive slit 0.3mm, sweeping speed is 4 ° of min
-1;
ESEM characterizes (SEM) and observes sample topography at the Supra-55 type field emission scanning electron microscope that the model of Hitachi company is S4800 type and Zeiss company, and operating voltage is 10kV; And use the chemical composition of the AXS type X-ray energy spectrometer analytic sample of BRUKER company simultaneously;
Differential thermal test (DSC) carries out on 131Evo, Setaram calorimeter, and programming rate is 5 DEG C/min, argon gas atmosphere;
Pore structure parameter carries out test analysis on U.S. Kang Ta company Atsorb-1 type instrument.
Embodiment 1
By Zn (CH
3cOO)
22H
2o is dissolved into NH
2oCH
2cH
2oH and CH
3oCH
2cH
2mixed solution is formed in OH, wherein, Zn (CH
3cOO)
22H
2o and NH
2oCH
2cH
2the concentration of OH is identical, is 0.05M separately, and mixed solution can be obtained uniform and stable Zn (CH after 60 DEG C of condition lower magnetic forces stir 30min
3cOO)
2colloidal solution;
Substrate of glass is put in ultrasonic 10min in acetone to clean substrate of glass, then dries with deionized water rinsing;
Zn (CH is drawn with glue head dropper
3cOO)
2dripped to after colloidal solution in substrate of glass, will with Zn (CH
3cOO)
2the substrate of glass of colloidal solution is placed in after the whirl coating speed whirl coating 30s of 3000r/min on desk-top sol evenning machine, and whirl coating forms the uniform Zn (CH of one deck on surface 2 times
3cOO)
2glued membrane;
Will with Zn (CH
3cOO)
2the substrate of glass of glued membrane is placed in Muffle furnace, and in vacuum atmosphere, anneal 10min under 300 DEG C of conditions, can generate layer of ZnO crystal seed film on the glass substrate;
Respective concentration is respectively the Zn (NO of 0.15M
3)
2solution and (CH
2)
6n
4zn (NO has been mixed to get with equal-volume
3)
2(CH
2)
6n
4mixed solution;
By the substrate of glass conducting surface with zinc oxide crystal seed film down, Zn (NO is entered with 45° angle oblique cutting
3)
2(CH
2)
6n
4mixed solution in, and put into the thermostatic drying chamber of 95 DEG C, isothermal reaction, after 48 hours, is taken out, and deionized water rinsing is clean and dry.
There is the substrate of glass of ZnO nanotube/array film to cut into 0.5 × 0.5cm as carrier using long, weigh with scale and record example weight now, then put into ethanolic solution to soak 2 hours, transfer in liquid paraffin and soak 5min, after taking out sample, with filter paper by clean for paraffin unnecessary for sample surfaces absorption, weigh the sample soaked after liquid paraffin, namely, load zinc oxide nano mitron film-type phase-change material, of poor quality according to front and back, calculate: with the total weight of this load zinc oxide nano mitron film-type phase-change material for benchmark, the content of the paraffin of this load zinc oxide nano mitron film-type phase-change material load is 30 % by weight, the content of described zinc oxide nano tube array thin-film carrier is 70 % by weight, wherein, the theoretical phase transition temperature of paraffin is 25 DEG C.
Wherein, the thickness of described zinc oxide nano tube array thin-film carrier can be 1:0.8 with the ratio of the thickness of the phase-change material of described load on zinc oxide nano tube array thin-film carrier.
Wherein, the thickness of described zinc oxide nano tube array thin-film carrier is 5 microns; Described zinc oxide nano tube array thin-film carrier is made up of zinc oxide nano mitron, and the cross section of described zinc oxide nano mitron is regular hexagon, and the external diameter of described zinc oxide nano mitron is 1 micron, and pipe thickness is 20 nanometers.
Fig. 1 is the ZnO nanotube/array film obtained.
In addition, this load zinc oxide nano tube array film-type phase-change material can be applied in the production of miniature precision electronic device (electronic device).
Embodiment 2
Prepare load zinc oxide nano tube array film-type phase-change material according to the method identical with embodiment 1, difference is, at ZnO nanotube/array film preparatory phase, and Zn (NO
3)
2solution and (CH
2)
6n
4concentration is 0.25M separately; In the encapsulation paraffin stage, long have the substrate of glass of ZnO nanotube/array film to soak 10min in liquid paraffin, and the theoretical phase transition temperature of paraffin is 30 DEG C.
Wherein, the thickness of described zinc oxide nano tube array thin-film carrier is 5 microns; Described zinc oxide nano tube array thin-film carrier is made up of zinc oxide nano mitron, and the cross section of described zinc oxide nano mitron is regular hexagon, and the external diameter of described zinc oxide nano mitron is 1.5 microns, and pipe thickness is 50 nanometers;
Result is with the total weight of this load zinc oxide nano mitron film-type phase-change material for benchmark, and the paraffin amount of this load zinc oxide nano mitron film-type phase-change material load is 40 % by weight, and the content of described zinc oxide nano tube array thin-film carrier is 60 % by weight;
The thickness of described zinc oxide nano tube array thin-film carrier is 1:0.7 with the ratio of the thickness of the phase-change material of described load on zinc oxide nano tube array thin-film carrier.
In addition, this load zinc oxide nano tube array film-type phase-change material can be applied in the production of miniature precision electronic device (electronic device).
Comparative example 1
Prepare load zinc oxide nano tube array film-type phase-change material according to the method identical with embodiment 1, difference is, colloid concentration is on the low side is 0.01M, 12 hours hydro-thermal reaction time.
Wherein, the thickness of described zinc oxide nano tube array thin-film carrier is 5 microns, and wherein hollow parts length is 1 micron; The cross section of described zinc oxide nano mitron is regular hexagon, and the external diameter of described zinc oxide nano mitron is 500 nanometers, and pipe thickness is 20 nanometers;
Result is with the total weight of this load zinc oxide nano mitron film-type phase-change material for benchmark, and the paraffin amount of this load zinc oxide nano mitron film-type phase-change material load is 4 % by weight, and the content of described zinc oxide nano tube array thin-film carrier is 96 % by weight;
The thickness of described zinc oxide nano tube array thin-film carrier is 1:0.05 with the ratio of the thickness of the phase-change material of described load on zinc oxide nano tube array thin-film carrier.
Comparative example 2
Prepare load zinc oxide nano tube array film-type phase-change material according to the method identical with embodiment 1, difference is, in the encapsulation paraffin stage, long have the substrate of glass of ZnO nanotube/array film to soak 2min in liquid paraffin.
Result is with the total weight of this load zinc oxide nano mitron film-type phase-change material for benchmark, and the paraffin amount of this load zinc oxide nano mitron film-type phase-change material load is 60 % by weight, and the content of described zinc oxide nano tube array thin-film carrier is 40 % by weight;
The thickness of described zinc oxide nano tube array thin-film carrier is 1:1.5 with the ratio of the thickness of the phase-change material of described load on zinc oxide nano tube array thin-film carrier.
Application experiment embodiment 1
Loading ZnO nano-pipe array thin film type phase-change material embodiment 1 prepared carries out differential thermal test on 131Evo, Setaram calorimeter, and programming rate is 5 DEG C/min, argon gas atmosphere.
Fig. 3 is the loading ZnO nano-pipe array thin film type phase-change material of preparation and paraffin refined wax is the DSC curve of the paraffin of 25 DEG C in theoretical phase transition temperature; As shown in Figure 3, reference numerals " 2 " black curve representative be the DSC curve of loading ZnO nano-pipe array thin film type phase-change material.The black curve representative of reference numerals " 1 " be the DSC curve of paraffin refined wax.As seen from the figure, the heat absorption initial temperature point of zinc-oxide film load phase-change material is 24.592 DEG C, endothermic peak temperature is 27.43 degree, lower than heat absorption initial temperature 25.4 DEG C and the endothermic peak temperature 28.4 DEG C of paraffin refined wax, shows that the paraffin of zinc oxide nano tube array load can absorb heat sooner; The Exotherm Onset Temperature point of zinc-oxide film load phase-change material is 30.071 DEG C, exothermic peak temperature is 28.432 DEG C, higher than Exotherm Onset Temperature 26.3 DEG C and the exothermic peak temperature 24.4 DEG C of paraffin refined wax, show that the paraffin of zinc oxide nano tube array load can faster heat release.
Therefore, this load zinc oxide nano tube array film-type phase-change material can be applied in the production of miniature precision electronic device (electronic device).
Application experiment embodiment 2
Loading ZnO nano-pipe array thin film type phase-change material embodiment 2 prepared carries out differential thermal test on 131Evo, Setaram calorimeter, and programming rate is 5 DEG C/min, argon gas atmosphere.
As the DSC curve of Fig. 4 to be the loading ZnO nano-pipe array thin film type phase-change material of preparation and paraffin refined wax in theoretical phase transition temperature be paraffin of 30 DEG C.The black curve representative of reference numerals " 4 " be the DSC curve of loading ZnO nano-pipe array thin film type phase-change material.The black curve representative of reference numerals " 3 " be the DSC curve of paraffin refined wax.As seen from the figure, the heat absorption initial temperature point of zinc-oxide film load phase-change material is 33.794 DEG C, endothermic peak temperature is 36.392 degree, lower than heat absorption initial temperature 34.8 DEG C and the endothermic peak temperature 37.3 DEG C of paraffin refined wax, shows that the paraffin of zinc oxide nano tube array load can absorb heat sooner; The Exotherm Onset Temperature point of zinc-oxide film load phase-change material is 38.814 DEG C, exothermic peak temperature is 36.392 DEG C, higher than Exotherm Onset Temperature 35.2 DEG C and the exothermic peak temperature 33.1 DEG C of paraffin refined wax, the exothermic crystallization temperature of loading ZnO nano-pipe array thin film type phase-change material is higher than paraffin refined wax about 4 DEG C, shows that the paraffin of zinc oxide nano tube array load can faster heat release.
Therefore, this load zinc oxide nano tube array film-type phase-change material can be applied in the production of miniature precision electronic device (electronic device).
Can be found out by embodiment 1-2 and comparative example 1-2: the present inventor using zinc oxide nano tube array film as carrier and apply it to paraffin be representative packaging phase change material in, load zinc oxide nano tube array film-type phase-change material can be prepared.And can find out that zinc oxide nano tube array film that utilization has a given shape (cross section, external diameter and pipe thickness) can change the thawing/crystallization temperature of paraffin by application experiment embodiment 1 and application experiment embodiment 2, promote the conduction of heat, this load zinc oxide nano tube array film-type phase-change material can be applied in the production of miniature precision electronic device.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned execution mode, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
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 compound mode.
In addition, also can carry out combination in any between various different execution mode 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.
Claims (13)
1. a load zinc oxide nano tube array film-type phase-change material, it is characterized in that, this load zinc oxide nano tube array film-type phase-change material contains zinc oxide nano tube array thin-film carrier and the phase-change material of load on described zinc oxide nano tube array thin-film carrier, and with the total weight of this load zinc oxide nano tube array film-type phase-change material for benchmark, the content of described phase-change material is 5-95 % by weight, be preferably 20-50 % by weight, the content of described zinc oxide nano tube array thin-film carrier is 5-95 % by weight, is preferably 50-80 % by weight.
2. phase-change material according to claim 1, wherein, the thickness of described zinc oxide nano tube array thin-film carrier is 1:0.2-1 with the ratio of the thickness of the phase-change material of described load on zinc oxide nano tube array thin-film carrier, is preferably 1:0.7-0.9.
3. phase-change material according to claim 1 and 2, wherein, the thickness of described zinc oxide nano tube array thin-film carrier is 3-5 micron, is preferably 4-5 micron.
4. according to the phase-change material in claim 1-3 described in any one, wherein, described zinc oxide nano tube array thin-film carrier is made up of zinc oxide nano mitron, and the cross section of described zinc oxide nano mitron is regular hexagon, the external diameter of described zinc oxide nano mitron is 1-2 micron, be preferably 1-1.5 micron, pipe thickness is 10-200 nanometer, is preferably 10-50 nanometer.
5. phase-change material according to claim 1 and 2, wherein, described phase-change material is organic phase-change material.
6. phase-change material according to claim 5, wherein, described organic phase-change material is paraffin.
7. according to the phase-change material in claim 1-4 described in any one, wherein, the preparation of described zinc oxide nano tube array thin-film carrier comprises the steps:
(1) zinc acetate is dissolved in monoethanolamine and ethylene glycol monoemethyl ether forms mixed solution, and this mixed solution is carried out magnetic agitation obtain zinc acetate colloidal solution;
(2) the zinc acetate colloidal solution obtained through step (1) is dripped to substrate substrate carried out whirl coating process and obtain with zinc acetate glued membrane;
(3) carry out annealing in process produce zinc oxide crystal seed film by being placed in Muffle furnace with the substrate of zinc acetate glued membrane through step (2);
(4) zinc nitrate and hexamethylene tetraammonia are mixed to get mixed solution;
(5) substrate with zinc oxide crystal seed film produced through step (3) is immersed in the mixed solution of step (4) carries out hydrothermal synthesis reaction.
8. phase-change material according to claim 7, wherein, in step (1), the concentration of described zinc acetate colloidal solution is 0.05mol/L-0.75mol/L;
In step (2), in described whirl coating process, whirl coating number of times is 1-3 time;
In step (3), the temperature of described annealing in process is 200-500 DEG C, and the time of annealing in process is 10-30 minute.
9. the preparation method of the load zinc oxide nano tube array film-type phase-change material in claim 1-8 described in any one, the method comprises phase-change material load on zinc oxide nano tube array thin-film carrier.
10. method according to claim 9, wherein, the process of described load comprises: be immersed in by described zinc oxide nano tube array thin-film carrier in liquid phase-change material.
11. methods according to claim 10, wherein, the method is first flooded before being also included in and being immersed in liquid phase-change material by described zinc oxide nano tube array thin-film carrier in organic solution.
12. methods according to claim 10 or 11, wherein, the time that described zinc oxide nano tube array thin-film carrier floods in the phase-change material of liquid state is 3-10 minute, is preferably 3-8 minute; The time that described zinc oxide nano tube array thin-film carrier floods in organic solution is 10-150 minute, is preferably 40-80 minute.
The application of load zinc oxide nano tube array film-type phase-change material in the production of electronic device in 13. claim 1-8 described in any one.
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