CN109068418A - A kind of SnO2Composite carbon nanometer tube Electric radiant Heating Film and preparation method thereof - Google Patents
A kind of SnO2Composite carbon nanometer tube Electric radiant Heating Film and preparation method thereof Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 107
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 41
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 41
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
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- 239000002904 solvent Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000005507 spraying Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000004134 energy conservation Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 111
- 238000005485 electric heating Methods 0.000 description 21
- 239000000758 substrate Substances 0.000 description 18
- 239000007921 spray Substances 0.000 description 17
- 239000010409 thin film Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
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- 230000035945 sensitivity Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- -1 carbon nanotube compound Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WMHSAFDEIXKKMV-UHFFFAOYSA-N oxoantimony;oxotin Chemical compound [Sn]=O.[Sb]=O WMHSAFDEIXKKMV-UHFFFAOYSA-N 0.000 description 1
- 238000000554 physical therapy Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of SnO2Composite carbon nanometer tube Electric radiant Heating Film and preparation method thereof, the Electric radiant Heating Film are cubic rutile structure, the carbon nanotube and SnO for being 0.0002~0.002:1 including mass ratio2；Preparation method is that pink salt and modifying agent are added in solvent to be configured to mixed solution, modified carbon nanotube is added to stir evenly, Electric radiant Heating Film precursor liquid is made, Electric radiant Heating Film precursor liquid is sprayed on coated basal plate, then the coated basal plate is annealed under the conditions of 470~570 DEG C 10~20min, and SnO is made2Composite carbon nanometer tube Electric radiant Heating Film.Electric radiant Heating Film resistance of the invention is smaller, emissivity is high, the thermal efficiency is excellent, and chemical stability is strong, the heater element that existing heating resistor, the thermal efficiency can be replaced bad, energy conservation and environmental protection；Preparation method is simple simultaneously, and energy conservation and environmental protection being capable of industrialized production.
Description
Technical field
The invention belongs to electric heating field of membrane preparation more particularly to a kind of SnO2Composite carbon nanometer tube Electric radiant Heating Film and its preparation side
Method.
Background technique
Electric radiant Heating Film is divided into high temperature, low temperature electric heating film.High-temperature electric heating membrane is generally used for electronic apparatus, military affairs etc., nowadays scientific and technological
The Electric radiant Heating Film of production；Low temperature electric heating film is the translucent polyester film that can be generated heat after a kind of energization, by conductive special ink,
Metal current-carrying item is processed, hot pressing is made between insulation polyester film.Electric heating heating film principle is product under the action of electric field,
Carbon molecules group in heater generates " Brownian movement ", occurs violent friction and shock between carbon molecules, the thermal energy of generation with
Far infrared radiation and the form of convection current are externally transmitted, and the conversion ratio of electric energy and thermal energy is up to 98% or more, the effect of carbon molecules
It is brought rapidly up system surfaces.
Electric radiant Heating Film mainly includes following four major types at present:
(1) (CN103173003A: a kind of carbon nanotube-water-soluble polymer composite and flexible electric heating is thin for carbon system electric-heating thin film
Film, preparation method and its usage；CN103545053A: the preparation method of transparent conductive film and the CF base with the conductive film
The preparation method of plate).
(2) metal system electric-heating thin film (CN107257589A: a kind of electric-heating thin film material and preparation method thereof；
CN1213946: red infrared radiation electrothermal film and its production method；CN106039567A metal nanometer line transparent conductive film, application
The physiotherapy equipment and its working method of metal nanometer line transparent conductive film).
(3) (CN106920598A: one kind preparing the side of tin oxide conductive film to semiconductor system electric-heating thin film on a silicon substrate
Method；CN106374010A: the preparation method of a kind of nanometer of silver composite tin oxide transparent conductive film).
(4) macromolecular electric-heating thin film (CN205080913U: conductive film, conductive thin film roll, photoelectric sensitivity conductive film,
Photoelectric sensitivity conductive film roll, conductive film base material and device；A kind of CN103804704A: preparation of polyimides composite conductive thin film
Method and conductive film).
Above-mentioned carbon system Electric radiant Heating Film higher cost, it is lower using temperature；Metal system electric heating membrane preparation method is unsuitable for realizing work
Industry metaplasia produces；Semiconductor thermoelectric film sheet resistance is higher, and emissivity is lower；Macromolecular electric-heating thin film is limited by material itself,
High-temperature electric conduction film can not be prepared.
Therefore, now need that a kind of resistance is smaller, emissivity is high, the thermal efficiency is excellent and at low cost, energy-saving and environment-friendly electric heating
Film.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide that a kind of resistance is smaller, emissivity is high, the thermal efficiency is excellent, and at
This low, energy-saving and environment-friendly Electric radiant Heating Film；
The second object of the present invention is to provide the preparation method of the Electric radiant Heating Film.
Technical solution: SnO of the invention2Composite carbon nanometer tube Electric radiant Heating Film, for cubic rutile structure, including mass ratio
For the carbon nanotube and SnO of 0.0002~0.002:12。
The present invention is by by carbon nanotube and SnO2Combine the Electric radiant Heating Film of preparation, the structure between being compounded in film of carbon nanotube
A nanometer bridge is built, to improve the conductivity of film, enhances SnO2The conductive capability of film reduces the heat transfer resistance of Electric radiant Heating Film,
To improve the thermal efficiency of Electric radiant Heating Film.Preferably, the diameter of carbon nanotube can be 10~50nm, and the carbon nanotube of the size is easy to
Dispersion, is conducive to and SnO2Realize effectively compound, raising electric conductivity.If diameter is less than 10nm, then carbon nanotube is difficult to disperse；
If diameter is greater than 50nm, then difficult and SnO2It carries out compound.
The present invention prepares SnO2The method of composite carbon nanometer tube Electric radiant Heating Film, includes the following steps:
(1) carbon nano-tube modification: prepare acid solution, be added carbon nanotube mix, under the conditions of 70~90 DEG C react 0.5~
1.5h, centrifugation, drying, is made modified carbon nanotube；
(2) it prepares Electric radiant Heating Film precursor liquid: pink salt and modifying agent being added in solvent and are configured to mixed solution, be added and be modified
Carbon nanotube afterwards stirs evenly, and Electric radiant Heating Film precursor liquid is made；Wherein, in the Electric radiant Heating Film precursor liquid tin element concentration be 0.2~
The molar ratio of 0.8mol/L, modifying agent and tin element is 0.005~2:1；
(3) prepare Electric radiant Heating Film: Electric radiant Heating Film precursor liquid sprayed on coated basal plate, then by the coated basal plate 470~
Anneal 10~20min under the conditions of 570 DEG C, and SnO is made2Composite carbon nanometer tube Electric radiant Heating Film.
The present invention is adulterated by using modifying agent, is increased in Electric radiant Heating Film and is provided electron species, and carrier concentration is increased, into
And reduce the square resistance of tin oxide base thin film.
Furtherly, in step (1), acid solution is the concentrated nitric acid and concentrated sulfuric acid mixed solution of 1~3:1 of volume ratio.Using
The concentrated acid strong oxidizing property modified carbon nano-tube of the compounding is easy to operate, good to carbon nano-tube modification effect, and can realize to strong acid
Recycle, reduce production cost.Mass concentration of the carbon nanotube in acid solution preferably can be 10~20g/L.
It further says, in step (2), modifying agent preferably may include antimony chloride, yttrium nitrate, lanthanum nitrate or cerous nitrate.It is molten
Agent preferably can be mixed solution, ethyl alcohol, ethylene glycol monomethyl ether or the dimethylformamide of ethyl alcohol and dimethylformamide.It is added and is modified
Carbon nanotube afterwards stirs evenly after being first 5~10min of ultrasonic disperse, stirs 5~10min, 0.5~1h of re-ultrasonic dispersion, and stirring 1~
2h.It is stirred for can speed up the decomposition rate of modified carbon nanotube in a solvent using such ultrasound repeatedly, reduces and reunite
Phenomenon.
Furtherly, in step (3), first by basal plate preheating to 450~550 DEG C before spraying.The flow of spraying be 3~
5ml/ times, spraying is spaced 1~2min every time.It is good using such spray pattern effect, it can be realized and film thickness is regulated and controled, film
Electric heating property is stablized, and easy to operate, at low cost, it is easy to accomplish industrialized production.
The utility model has the advantages that compared with prior art, remarkable advantage of the invention are as follows: the SnO2Composite carbon nanometer tube electrothermal film electric
Resistance is smaller, emissivity is high, the thermal efficiency is excellent, and chemical stability is strong, existing heating resistor, the thermal efficiency can be replaced bad
Heater element, energy conservation and environmental protection；By the doping of modifying agent, increase in Electric radiant Heating Film and electron species be provided, increases carrier concentration,
Nanometer bridge is constructed in combination with being compounded between film for carbon nanotube, to improve the conductivity of film, enhances SnO2Film
Conductive capability reduces the heat transfer resistance of Electric radiant Heating Film, improves the thermal efficiency of Electric radiant Heating Film；In addition, the preparation method of the Electric radiant Heating Film
Simply, energy conservation and environmental protection, being capable of industrialized production.
Detailed description of the invention
Fig. 1 is the XRD diagram of modified carbon nanotube；
Fig. 2 is SnO2The SEM of composite carbon nanometer tube Electric radiant Heating Film schemes；
Fig. 3 is SnO2Base Electric radiant Heating Film and SnO2The XRD comparison diagram of composite carbon nanometer tube Electric radiant Heating Film；
Fig. 4 is SnO2Base Electric radiant Heating Film SEM figure.
Specific embodiment
Technical solution of the present invention is described in further detail with reference to the accompanying drawings and examples.
The raw material that the present invention uses is commercially available to be obtained.Wherein, the size of carbon nanotube is 10~50nm, pure
Degree is greater than 96%.
Embodiment 1
The present invention prepares SnO2The method of composite carbon nanometer tube Electric radiant Heating Film includes the following steps:
(1) modified carbon nano-tube: taking 1g carbon nanotube, be added to 50ml by volume ratio 3:1 concentrated nitric acid and concentrated sulfuric acid group
At mixed liquor in, be put into insulating box after mixing, under the conditions of 80 DEG C constant temperature handle 1h, be then continuously added deionization
Water is centrifuged to pH=7, and modified carbon nanotube is made in drying in 60 DEG C of insulating boxs；
(2) it prepares Electric radiant Heating Film precursor liquid: weighing the SnCl of 21.0136g4·5H2The SbCl of O and 0.253g3It is dissolved in 100ml
In ethyl alcohol, it is configured to mixed solution, SnCl in the mixed solution4Concentration be 0.6mol/L；Weigh the modified carbon of 0.0021g
Nanotube is added in mixed solution, stirs 10min after first ultrasonic disperse 5min on magnetic stirring apparatus, then ultrasound 1h is placed on magnetic
1h is stirred on power blender, Electric radiant Heating Film precursor liquid is made, wherein carbon nanotube and SnCl4·5H2The mass ratio of O is 0.0001:
1, correspondingly, carbon nanotube and SnO2Mass ratio be 0.0002:1.
(3) it prepares Electric radiant Heating Film: glass substrate being heated, its temperature is made to rise to 500 DEG C, by the presoma of above-mentioned preparation
Solution takes 50ml to pour into spray gun, and the spraying flow for adjusting spray coating liquor is 5ml, and lance head is at a distance from quartz glass substrate
10cm, spray pressure 2kg, spray nozzle aperture are 1mm, and spraying interval time every time is that after 1.5min is sprayed, will plate
Ilm substrate is annealed 20min under the conditions of 520 DEG C, takes out coated basal plate, and room temperature is cooling, can be prepared by electric-heating thin film.The embodiment
Specific reaction process it is as follows:
Sn(OEt)4→SnO2+2H2O↑
Electric radiant Heating Film prepared by the embodiment carries out performance detection, and the result of acquisition is as shown in table 1 below.
The performance table of the Electric radiant Heating Film of 1 embodiment 1 of table preparation
| Square resistance/(Ω/) | Emissivity | Heating efficiency/% | Logical 220V voltage stabilization heating temperature/DEG C |
| 105 | 0.9 | 92 | 320 |
By table 1 it is found that the Electric radiant Heating Film prepared by the present invention thermal efficiency with higher, good chemical stability etc. are excellent
Point, for square resistance less than 140 Ω/, emissivity reaches 0.9, and electric conversion efficiency > 90% can substitute traditional heating electric
Resistance and the bad heater element of the thermal efficiency.
Using scanning electron microscope to modified carbon nanotube and SnO2Composite carbon nanometer tube Electric radiant Heating Film carries out structural characterization, obtains
The result obtained is as depicted in figs. 1 and 2.As shown in Figure 1, the carbon nanotube highest peak by modification is more sharp, comes relatively
Other two peaks are said with regard to unobvious, sharp characteristic peak peak appears in (002) crystal face, and the weaker peak of peak intensity appears in
(100) crystal face, (110) crystal face.As shown in Figure 2, SnO2There is slightly protrusion on the surface of composite carbon nanometer tube Electric radiant Heating Film, illustrates that carbon is received
Mitron is successfully combined to SnO2The surface of base film, the embodiment can successfully prepare SnO2Composite carbon nanometer tube Electric radiant Heating Film.
Embodiment 2
4 groups of parallel tests are designed, basic step is same as Example 1, the difference is that the additional amount of carbon nanotube,
And SnCl4·5H2The mass ratio of O is respectively 0.00025:1,0.0005:1,0.00075:1 and 0.001:1.
Electric radiant Heating Film prepared by the embodiment carries out performance detection, and the result of acquisition is as shown in table 2 below.
The performance table of the Electric radiant Heating Film of 2 embodiment 2 of table preparation
By table 2 it is found that the Electric radiant Heating Film prepared by the present invention thermal efficiency with higher, good chemical stability etc. are excellent
Point, for square resistance less than 140 Ω/, emissivity reaches 0.9, and electric conversion efficiency > 90% can substitute traditional heating electric
Resistance and the bad heater element of the thermal efficiency.
Comparative example 1
Basic step is same as Example 1, the difference is that being added without modifying agent.Specific step is as follows:
(1) modified carbon nano-tube: taking 1g carbon nanotube, be added to 50ml by volume ratio 3:1 concentrated nitric acid and concentrated sulfuric acid group
At mixed liquor in, be put into insulating box after mixing, under the conditions of 80 DEG C constant temperature handle 1h, be then continuously added deionization
Water is centrifuged to pH=7, and modified carbon nanotube is made in drying in 60 DEG C of insulating boxs；
(2) it prepares Electric radiant Heating Film precursor liquid: weighing the SnCl of 21.0136g4·5H2O is dissolved in 100ml ethyl alcohol, is configured to mix
Close solution, SnCl in the mixed solution4Concentration be 0.6mol/L；It weighs the modified carbon nanotube of 0.0021g and mixing is added
In solution, 1min is stirred after first ultrasonic disperse 5min on magnetic stirring apparatus, then ultrasound 10min is placed on magnetic stirring apparatus and stirs
4h is mixed, Electric radiant Heating Film precursor liquid is made, wherein carbon nanotube and SnCl4·5H2The mass ratio of O is 0.0001:1；
(3) it prepares Electric radiant Heating Film: glass substrate being heated, its temperature is made to rise to 500 DEG C, by the presoma of above-mentioned preparation
Solution takes 50ml to pour into spray gun, and the spraying flow for adjusting spray coating liquor is 5ml, and lance head is at a distance from quartz glass substrate
10cm, spray pressure 2kg, spray nozzle aperture are 1mm, and spraying interval time every time is that after 1.5min is sprayed, will plate
Ilm substrate is annealed 20min under the conditions of 520 DEG C, takes out coated basal plate, and room temperature is cooling, can be prepared by Electric radiant Heating Film precursor liquid.
Electric radiant Heating Film prepared by the comparative example carries out performance detection, and the result of acquisition is as shown in table 3 below.
The performance table of comparisons of Electric radiant Heating Film prepared by 3 comparative example 1 of table and embodiment 1
By table 3 it is found that the electric-heating thin film square resistance for not adding modifying agent is larger, heating efficiency is low, and heating temperature is low.
This is because the doping of modifying agent can be in SnO2Middle formation shallow donor's energy level increases carrier concentration in conduction band, is transformed into
Conductor.
Comparative example 2
Basic step is same as Example 1, the difference is that not composite carbon nanometer tube.Specific step is as follows:
(1) it prepares Electric radiant Heating Film precursor liquid: weighing the SnCl of 21.0136g4·5H2The SbCl of O and 0.253g3It is dissolved in 100ml
In ethyl alcohol, it is configured to mixed solution, SnCl in the mixed solution4Concentration be 0.6mol/L；
(2) it prepares Electric radiant Heating Film: glass substrate being heated, its temperature is made to rise to 500 DEG C, by the presoma of above-mentioned preparation
Solution takes 50ml to pour into spray gun, and the spraying flow for adjusting spray coating liquor is 5ml, and lance head is at a distance from quartz glass substrate
10cm, spray pressure 2kg, spray nozzle aperture are 1mm, and spraying interval time every time is that after 1.5min is sprayed, will plate
Ilm substrate is annealed 20min under the conditions of 520 DEG C, takes out coated basal plate, and room temperature is cooling, can be prepared by Electric radiant Heating Film precursor liquid.
Electric radiant Heating Film prepared by the comparative example carries out performance detection, and the result of acquisition is as shown in table 4 below.
The performance table of comparisons of 4 comparative example 2 of table and the Electric radiant Heating Film of embodiment preparation
By table 4 it is found that the emissivity of addition carbon nanotube rear film is higher and square resistance is smaller.This is because carbon is received
Mitron constructs nanometer bridge in the film, so that carrier mobility rate increases, electric conductivity is more preferable, the hair of film under same voltage
Hot temperature is higher.
Electric radiant Heating Film prepared by Electric radiant Heating Film, embodiment 1 and embodiment 2 prepared by the comparative example 2 carries out XRD performance detection,
The result of acquisition is as shown in Figure 3.By the figure it is found that being compared with standard PDF card, the doping of Sb, carbon nanotube it is compound, mix
Antimony tin dioxide thin film is consistent with the XRD spectrum of the antimony-doped stannic oxide film of composite carbon nanometer tube with standard diagram, by
The prototype structure of the inside that is compound and having not been changed film of the doping and carbon nanotube of Sb known to this, is still tetragonal crystal system golden red
Stone structure, three more sharp its crystal faces of peak are (110), (101), (211), in addition with the increase of carbon nanotube compound quantity
The acuity at peak does not have too big variation, shows that the compound of carbon nanotube does not have much affect to phase transition.By comparative example 2
The Electric radiant Heating Film of preparation is scanned Electronic Speculum characterization, the result of acquisition as shown in figure 4, pass through the figure it is found that thin film surface planeness,
There is no apparent crack.
Embodiment 3
Design group parallel test, basic step is same as Example 1, the difference is that tin element in Electric radiant Heating Film precursor liquid
Concentration, respectively 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.8mol/L and 1mol/L.
Electric radiant Heating Film prepared by the embodiment 3 carries out performance detection, and the result of acquisition is described in table 5 below.
The performance table of the Electric radiant Heating Film of 5 embodiment 3 of table preparation
Through table 5 it is found that when the concentration of tin element in Electric radiant Heating Film precursor liquid is 0.2~0.8mol/L, the electric heating of preparation
The advantages that film thermal efficiency with higher, good chemical stability, square resistance reaches 0.9 less than 140 Ω/, emissivity,
Electric conversion efficiency > 90% when being lower than 0.2mol/L, then sprays the sample of same solution, the solute of precipitation if concentration is lower
Less, uneven film thickness is even；If concentration is higher, when being higher than 0.8mol/L, then the sample of same solution is sprayed, is analysed in substrate
Solute out is more, and solute increases to a certain amount of, and there are temperature difference, crystal is shunk the solute of substrate and film layer deposition
Stress is generated, it is cracked.
Embodiment 4
Design group parallel test, basic step is same as Example 1, the difference is that modifying agent in Electric radiant Heating Film precursor liquid
With the molar ratio of tin element, respectively 0.003:1,0.005:1,0.1:1,2:1 and 2.5:1.
Electric radiant Heating Film prepared by the embodiment 4 carries out performance detection, and the result of acquisition is described in table 6 below.
The performance table of the Electric radiant Heating Film of 6 embodiment 4 of table preparation
Through table 6 it is found that when the molar ratio of modifying agent and tin element is 0.005~2:1, the Electric radiant Heating Film of preparation have compared with
The advantages that high thermal efficiency, good chemical stability, square resistance is less than 140 Ω/, and emissivity reaches 0.9, electric heating conversion
Efficiency > 90%, if mole smaller, when being less than 0.005:1, then square resistance is larger；If mole bigger, it is greater than 2:1
When, then square resistance is also larger.This is because modifying agent is in SnO2In solid solution capacity it is limited, volume is too small, is formed by current-carrying
Sub- concentration is larger compared with small cube resistance, if being more than solid solution capacity, the foreign ion that extra modifying agent will become in structure cell hinders to carry
Sub- migration rate is flowed, so that square resistance becomes larger.
Embodiment 5
Design group parallel test, basic step is same as Example 1, the difference is that carbon nanotube is in acid solution
Mass concentration, respectively 8g/L, 10g/L, 15g/L, 20g/L and 25g/L.
Electric radiant Heating Film prepared by the embodiment 5 carries out performance detection, and the result of acquisition is described in table 7 below.
The performance table of the Electric radiant Heating Film of 7 embodiment 5 of table preparation
Through table 7 it is found that when mass concentration of the carbon nanotube in acid solution is 10~20g/L, the Electric radiant Heating Film of preparation
The advantages that thermal efficiency with higher, good chemical stability, square resistance is less than 140 Ω/, and emissivity reaches 0.9, electricity
Thermal conversion efficiency > 90%, if mass concentration is lower, when being less than 10g/L, then carbon nanotube cannot be oxidized modification completely；If
If mass concentration is higher, when being greater than 20g/L, then carbon nanotube connects more groups, is easy to reunite, and make carbon nanotube defect
Increase, square resistance becomes larger.
Embodiment 6
The present invention prepares SnO2The method of composite carbon nanometer tube Electric radiant Heating Film includes the following steps:
(1) modified carbon nano-tube: taking 1g carbon nanotube, be added to 50ml by volume ratio 1:1 concentrated nitric acid and concentrated sulfuric acid group
At mixed liquor in, be put into insulating box after mixing, under the conditions of 70 DEG C constant temperature handle 1.5h, be then continuously added from
Sub- water is centrifuged to pH=7, and modified carbon nanotube is made in drying in 60 DEG C of insulating boxs；
(2) it prepares Electric radiant Heating Film precursor liquid: weighing the SnCl of 21.0136g4·5H2The SbCl of O and 0.253g3It is dissolved in 100ml
In ethylene glycol monomethyl ether, it is configured to mixed solution, SnCl in the mixed solution4Concentration be 0.6mol/L；It is modified to weigh 0.0021g
Carbon nanotube afterwards is added in mixed solution, and 5min, re-ultrasonic dispersion are stirred on magnetic stirring apparatus after first ultrasonic disperse 10min
0.5h, which is placed on magnetic stirring apparatus, stirs 2h, Electric radiant Heating Film precursor liquid is made, wherein carbon nanotube and SnCl4·5H2The quality of O
Than for 0.0001:1；
(3) it prepares Electric radiant Heating Film: glass substrate being heated, its temperature is made to rise to 450 DEG C, by the presoma of above-mentioned preparation
Solution takes 50ml to pour into spray gun, and the spraying flow for adjusting spray coating liquor is 3ml/ times, and lance head is at a distance from quartz glass substrate
For 10cm, spray pressure 2kg, spray nozzle aperture is 1mm, and spraying interval time every time is that after 1min is sprayed, will plate
Ilm substrate is annealed 20min under the conditions of 470 DEG C, takes out coated basal plate, and room temperature is cooling, can be prepared by electric-heating thin film.
Embodiment 7
The present invention prepares SnO2The method of composite carbon nanometer tube Electric radiant Heating Film includes the following steps:
(1) modified carbon nano-tube: taking 1g carbon nanotube, be added to 50ml by volume ratio 1:1 concentrated nitric acid and concentrated sulfuric acid group
At mixed liquor in, be put into insulating box after mixing, under the conditions of 90 DEG C constant temperature handle 0.5h, be then continuously added from
Sub- water is centrifuged to pH=7, and modified carbon nanotube is made in drying in 60 DEG C of insulating boxs；
(2) it prepares Electric radiant Heating Film precursor liquid: weighing the SnCl of 21.0136g4·5H2The SbCl of O and 0.253g3It is dissolved in 100ml
In dimethylformamide, it is configured to mixed solution, SnCl in the mixed solution4Concentration be 0.6mol/L；0.0021g is weighed to change
Property after carbon nanotube be added in mixed solution, stir 5min after first ultrasonic disperse 10min on magnetic stirring apparatus, then ultrasound point
Scattered 0.5h, which is placed on magnetic stirring apparatus, stirs 2h, Electric radiant Heating Film precursor liquid is made, wherein carbon nanotube and SnCl4·5H2The matter of O
Amount is than being 0.0001:1；
(3) it prepares Electric radiant Heating Film: glass substrate being heated, its temperature is made to rise to 550 DEG C, by the presoma of above-mentioned preparation
Solution takes 50ml to pour into spray gun, and the spraying flow for adjusting spray coating liquor is 5ml/ times, and lance head is at a distance from quartz glass substrate
For 10cm, spray pressure 2kg, spray nozzle aperture is 1mm, and spraying interval time every time is that after 2min is sprayed, will plate
Ilm substrate is annealed 10min under the conditions of 570 DEG C, takes out coated basal plate, and room temperature is cooling, can be prepared by electric-heating thin film.
In above-described embodiment, modifying agent also can be replaced yttrium nitrate, lanthanum nitrate or cerous nitrate；Solvent can also be ethyl alcohol and two
The mixed solution of methylformamide, the volume ratio of the two are 1:1.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of SnO2Composite carbon nanometer tube Electric radiant Heating Film, it is characterised in that: the Electric radiant Heating Film is cubic rutile structure, including quality
Than the carbon nanotube and SnO for 0.0002~0.002:12。
2. SnO according to claim 12Composite carbon nanometer tube Electric radiant Heating Film, it is characterised in that: the diameter of the carbon nanotube
For 10~50nm.
3. a kind of prepare SnO described in claim 12The method of composite carbon nanometer tube Electric radiant Heating Film, it is characterised in that including walking as follows
It is rapid:
(1) carbon nano-tube modification: prepare acid solution, be added carbon nanotube mix, under the conditions of 70~90 DEG C react 0.5~
1.5h, centrifugation, drying, is made modified carbon nanotube；
(2) it prepares Electric radiant Heating Film precursor liquid: pink salt and modifying agent being added in solvent and are configured to mixed solution, is added in mass ratio
Modified carbon nanotube stirs evenly, and Electric radiant Heating Film precursor liquid is made；Wherein, the concentration of tin element is 0.2 in the Electric radiant Heating Film precursor liquid
The molar ratio of~0.8mol/L, modifying agent and tin element is 0.005~2:1；
(3) it prepares Electric radiant Heating Film: Electric radiant Heating Film precursor liquid being sprayed on coated basal plate, then by the coated basal plate at 470~570 DEG C
Under the conditions of anneal 10~20min, be made SnO2Composite carbon nanometer tube Electric radiant Heating Film.
4. preparation SnO according to claim 32The method of composite carbon nanometer tube Electric radiant Heating Film, it is characterised in that: step (1)
In, the acid solution is the concentrated nitric acid and concentrated sulfuric acid mixed solution of 1~3:1 of volume ratio.
5. preparation SnO according to claim 32The method of composite carbon nanometer tube Electric radiant Heating Film, it is characterised in that: step (1)
In, mass concentration of the carbon nanotube in acid solution is 10~20g/L.
6. preparation SnO according to claim 32The method of composite carbon nanometer tube Electric radiant Heating Film, it is characterised in that: step (2)
In, the modifying agent includes antimony chloride, yttrium nitrate, lanthanum nitrate or cerous nitrate.
7. preparation SnO according to claim 32The method of composite carbon nanometer tube Electric radiant Heating Film, it is characterised in that: step (2)
In, the solvent is mixed solution, ethyl alcohol, ethylene glycol monomethyl ether or the dimethylformamide of ethyl alcohol and dimethylformamide.
8. preparation SnO according to claim 32The method of composite carbon nanometer tube Electric radiant Heating Film, it is characterised in that: step (2)
In, it is 5~10min of stirring after first 5~10min of ultrasonic disperse, re-ultrasonic dispersion that the modified carbon nanotube of addition, which stirs evenly,
0.5~1h stirs 1~2h.
9. preparation SnO according to claim 32The method of composite carbon nanometer tube Electric radiant Heating Film, it is characterised in that: step (3)
In, first by basal plate preheating to 450~550 DEG C before the spraying.
10. preparation SnO according to claim 32The method of composite carbon nanometer tube Electric radiant Heating Film, it is characterised in that: step (3)
In, the flow of the spraying is 3~5ml/ times, every time 1~2min of spraying interval.
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Cited By (2)
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