CN107326415A - A kind of transparent electrical-heating film of Low emissivity and preparation method thereof - Google Patents
A kind of transparent electrical-heating film of Low emissivity and preparation method thereof Download PDFInfo
- Publication number
- CN107326415A CN107326415A CN201710522481.6A CN201710522481A CN107326415A CN 107326415 A CN107326415 A CN 107326415A CN 201710522481 A CN201710522481 A CN 201710522481A CN 107326415 A CN107326415 A CN 107326415A
- Authority
- CN
- China
- Prior art keywords
- film
- cracking
- preparation
- low emissivity
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- 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
- H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
-
- 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
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/013—Heaters using resistive films or coatings
-
- 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
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/017—Manufacturing methods or apparatus for heaters
-
- 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
- H05B2214/00—Aspects relating to resistive heating, induction heating and heating using microwaves, covered by groups H05B3/00, H05B6/00
- H05B2214/02—Heaters specially designed for de-icing or protection against icing
Abstract
The invention discloses transparent electrical-heating film of a kind of Low emissivity and preparation method thereof.The preparation method comprises the following steps：(1) cracking template is prepared on conductive substrates；(2) using galvanoplastic in the deposited metal in the crack of template that is cracked；(3) the cracking template is removed, the composite construction of the conductive substrates and metal grill is obtained, the as described transparent electrical-heating film of Low emissivity.The transparent electrical-heating film of Low emissivity of the present invention has low radiance, while having good translucency in visible wavelength range.Low emissivity electrically conducting transparent of the present invention heating film has superpower electric conductivity, and very high steady temperature and the rate of heat addition quickly can be obtained there is provided the heating voltage of very little as electrical-heating film；The Low emissivity electrically conducting transparent heating film that for example prepared by the specific embodiment of the invention 2, in the case where providing 5V biass, its rate of heat addition can reach 7.7 DEG C/s, and maximum temperature can reach more than 100 DEG C.
Description
Technical field
The present invention relates to transparent electrical-heating film of a kind of Low emissivity and preparation method thereof, belong to energy-conservation, conductive material field.
Background technology
With the progressively implementation of national energy strategy, Low emissivity energy-saving glass is in quick increased in the application of building field
Trend, is primarily characterized in that its higher infrared reflectivity and low convective heat-transfer coefficient can effectively reduce indoor and outdoor heat
Radiation transmission, reduce building energy consumption, reach the purpose of energy-saving and emission-reduction.Transparent heating film can be widely applied to outdoor display
In terms of device, the wind screen defrosting of vehicle or aircraft, indoor window type heating, its operation principle is to flow through electrically conducting transparent in electric current
Joule heat is produced during film and realizes heating effect, most important performance parameter is optical clarity and electrical conductivity.If will be upper
State transparent electrical-heating film and low emissivity glass combines to form a kind of electrically heated glass with low radiation functions, it becomes possible to reduce
The radiation loss of electrical-heating film, improves its efficiency of heating surface, while creating higher business added value for low emissivity glass.Mesh
Before, in the market has had electrical heating concurrently and the coated glass of low radiance mainly passes through physical vapour deposition (PVD) or chemical gaseous phase
Doped oxide film prepared by deposition process, for example：Tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO) and aluminium doping
Zinc oxide (AZO).But, the visible light transmissivity of doped oxide film is more than under conditions of 80%, and surface resistance is typically larger than
10 Ω/, the efficiency of heating surface is relatively low, limits its application in terms of Low emissivity electrically heated glass.
In recent years, metal nano wire grid is because of its high conductivity and the advantage of wide spectral range high transmittance, as transparent
The good candidate material of heating film.At present, the preparation method of metal grill mainly includes scattered single-crystal metal nanometer collimation method and mould
Two kinds of plate method.Wherein, disperse single-crystal metal nanometer collimation method have that preparation technology is simple, easily realize large area and prepare and substrate it is suitable
The advantages of answering property is good.But, the contact resistance because the sectional area of monocrystal nanowire is smaller, between line and line is larger, so point
The electric conductivity that throwaway crystalline substance metal nano collimation method obtains film is poor.By contrast, the metal cross-sectional area that prepared by template is larger,
Contact resistance between line and line is smaller, and light transmission rate is controllable, bigger in the application potential of transparent heating art.Generally come
Say, template can be divided into Lithographic template method, electrospinning template, cracking template etc. again.Wherein, cracking template, which has, prepares work
Skill is simple, and low cost and other advantages are of great interest.It is combined using metal nano grid and low emissivity glass, is to realize
The effective way of Low emissivity electrically heated glass.
2013, Chinese patent CN103227240A is disclosed prepared the transparent electricity of porous metal film based on cracking template
The method of pole, this method is one layer of cracking template of spin coating on substrate first, then by the method for physical deposition in template table
Face deposited metal, finally goes removing template to obtain metal mesh structure.The metal grill size and shape obtained by this method
Shape is controllable, and metal line surface is smooth, and the phenomenon being mutually lapped is not present between line and line.Under identical transmitance, be cracked template
The electrical conductivity of the metal grill of preparation is apparently higher than single-crystal metal nano wire grid.But, method disclosed in CN103227240A
The methods such as spin coating, the physical deposition of middle use are difficult to realize prepared by large area, constrain the popularization of this method.
The content of the invention
It is an object of the invention to provide a kind of transparent electrical-heating film with low radiation functions and preparation method thereof.This hair
The high infrared reflection rate and high visible light transmissivity of bright utilization metal-oxide film and ultrathin metallic film double-decker are realized low
Radiation and visible transparent function, efficient electrical-heating function is realized using the high transmittance and low resistivity properties of metal grill.
In preparation process, using being cracked, template and galvanoplastic are combined, using metal oxide and super thin metal double-decker as negative electrode,
Electroplating deposition metal grill on ultrathin metallic film, and it is used as anti-reflection layer and coating, one side by the use of second layer metal oxide
The visible light transmissivity of ultra-thin metal layer can be improved, the chemical stability of metal grill on the other hand can be improved.Party's legal system
Standby Low emissivity electrical-heating film has excellent visible light transmissivity and electrical heating effect and good application value and wide
Wealthy market prospects.
The technique that the present invention is combined using cracking template with galvanoplastic, by Low emissivity transparent conductive film and wire netting
Lattice are combined, and obtain Low emissivity electrical-heating film.
The preparation method of the transparent electrical-heating film of Low emissivity provided by the present invention, comprises the following steps：
(1) cracking template is prepared on conductive substrates；
(2) using galvanoplastic in the deposited metal in the crack of template that is cracked；
(3) the cracking template is removed, the composite construction of the conductive substrates and transparent metal grid is obtained, is described
The transparent electrical-heating film of Low emissivity.
In above-mentioned preparation method, in step (1), the conductive substrates are by substrate and the Low emissivity being deposited on its surface
Transparent conductive film is constituted；
The substrate can select conventional for glass, quartz or PET etc..
In above-mentioned preparation method, the Low emissivity transparent conductive film refers to the electrically conducting transparent with low radiance
" low radiance " in film, the present invention refers to thering is stronger albedo to infrared light, has hyperpyrexia to infrared light
The Low emissivity of the preparation of the embodiment of the present invention 1 and 2 of reflectivity, such as electroplating current to be obtained under the conditions of 0.05A can electrical-heating film
Shading coefficient be respectively 0.576 and 0.592.
Heretofore described Low emissivity transparent conductive film is concretely sequentially deposited to the metal oxidation on the substrate
The composite membrane of thing film or metal oxide film and ultrathin metallic film；
The material of the metal oxide film can be wide band gap semiconducter, such as ITO (indium oxide mixes tin), AZO (doped zinc oxides
Aluminium) or FTO (fluorine doped tin oxide), with high visible light transmissivity；
The material of the ultrathin metallic film can be Ag, Al or Pt, with low radiance and high conductivity, can specifically use
It is prepared by sputtering, vacuum vapour deposition or chemical reduction method；
The thickness of the ultrathin metallic film is less than 30 nanometers.
In above-mentioned preparation method, in step (1), the liquid that will be cracked is carried out using knife coating on the surface of the conductive substrates
Coating forms cracking film, then forms the cracking template in dry spontaneous cracking under room temperature (15~25 DEG C)；
The cracking liquid is not dissolved in electrolyte and being capable of spontaneous shape after being dried using cracking nail polish glue, TiO 2 sol etc.
Into the compound of cracking grid.
It is as follows the step of the knife coating in above-mentioned preparation method：
The conductive substrates are fixed on the working panel of doctor knife coater, bar is fixed on to the table of the conductive substrates
Face；The cracking liquid is added dropwise in the front end of the bar, controls the bar to move ahead, and then the cracking liquid is coated on described
The surface of conductive substrates；
The thickness of the cracking film is directly proportional to the specification size and pace of the bar：When the bar specification
With pace it is too small when, obtained film is excessively thin, its be cracked grid it is discontinuous；When the bar specification is excessive, what is obtained is thin
Film is blocked up, masterplate easily occurs and comes off, the problems such as crackle is wide；Bar pace is excessive, easily causes film uneven.It is comprehensive
On, the specification of the bar is preferably 5~15um by the present invention, and pace is preferably 5~35r/min；And the bar
When specification is 5~7um, the pace for controlling the bar is 30~35r/min, and the specification of the bar is 10~15um
When, the pace for controlling the bar is 5~15r/min.
In above-mentioned preparation method, in step (2), the condition of the galvanoplastic is as follows：
Electrolyte is gold plating liquid, silver plating liquid or copper plating bath；
Anode is titanium iridium electrode；
Negative electrode is the conductive substrates that the surface covers the cracking masterplate；
Power supply is DC constant current power supply.
In above-mentioned preparation method, size and the electroplating time of electric current can directly affect the thickness and quality of deposited metal,
So as to influence the electric conductivity of metal grill；
Determined by the specific embodiment of the invention, the bar that the electric current exported in the DC constant current power supply is 0.01~0.1A
1~15min is electroplated under part.
In above-mentioned preparation method, in step (3), the cracking mould is removed using trichloro ethylene or chloroform dissolving
Plate；
Detailed process is preferably：Sample after deposited metal is positioned in the beaker for filling trichloro ethylene solution, ultrasound,
Then alcohol rinse, deionized water rinsing remaining reagent, nitrogen drying.
After step (3), methods described also includes depositing the metal-oxide film to the composite structure surface
Step, the metal-oxide film, which has, reduces metal film and metal grill to the reflex of visible ray, can be lifted to low
The visible light transmissivity of radiation transparent electrical-heating film, while metal film and metal grill can be protected, makes it in electrical heating
It is difficult to be oxidized in journey.
The transparent electrical-heating film of Low emissivity that preparation method of the present invention is obtained falls within protection scope of the present invention.
The transparent electrical-heating film of Low emissivity of the present invention has low radiance, while having in visible wavelength range good
Good translucency.
Low emissivity electrically conducting transparent heating film of the present invention has superpower electric conductivity, and as electrical-heating film, there is provided very little
Heating voltage can obtain very high steady temperature and the rate of heat addition quickly；For example prepared by the specific embodiment of the invention 2
Low emissivity electrically conducting transparent heats film, and in the case where providing 5V biass, its rate of heat addition can reach 7.7 DEG C/s, maximum temperature
It can reach more than 100 DEG C.
The present invention has advantages below：
1st, cracking masterplate method is combined with galvanoplastic and prepares metal grill
Compared to physical deposition method, galvanoplastic operation is simpler, without vacuum condition and equipment, cost it is low, be more easy to realize
It is prepared by large area.Because physical method deposited metal needs to use a large amount of metals, and only few part metals can deposit to mould
In the crack of plate, and electroplate and only occur in the conductive film surface that crack exposes, therefore use galvanoplastic deposited metal can be with
The very effective waste for avoiding noble metal.In addition, electroplate liquid is easily entered among the narrow crack to hundreds of nanometers, it can keep away
The problem of being unfavorable for the deposited metal in narrow crack template caused by the occlusion effect for exempting from physical deposition mode presence, so as to obtain
Narrow metal wire and the metal grill of high transmittance.
2nd, the electrical conductivity of metal wire can be by electroplating time and the size control of electroplating current
Because the width of metal wire is determined by Fracture Width, so extension electroplating time or increase electroplating current, metal wire
Thickness increase, width it is constant, so as to reduce its surface resistance on the premise of metal grill translucency is not reduced.Low areal resistance
Metal grill ensure that the electric heating function of the transparent electrical-heating film of Low emissivity is realized at lower voltages.
3rd, selection high carrier concentration and metal-oxide film/ultrathin metallic film double-decker of high conductivity are as low
Radiation function layer
Ultrathin metallic film is respectively provided with very high carrier concentration with metal-oxide film, so as to have to infrared light very strong
Reflex, indoor and outdoor heat exchange can be weakened, the purpose of energy-saving and emission-reduction is reached.Metal-oxide film/super thin metal
The conductive characteristic of membrane composite film can ensure that galvanoplastic deposited metal is smoothly implemented.
4th, in metal oxide/metal/metal grid laminated film surface covering metal-oxide film
The metal-oxide film of covering, which has, reduces metal film and metal grill to the reflex of visible ray, can be lifted
To the visible light transmissivity of the transparent electrical-heating film of Low emissivity, while can protect metal film and metal grill in atmosphere and electricity
It is not oxidized in heating process.
Brief description of the drawings
Fig. 1 is the flow chart of preparation method of the present invention.
Fig. 2 is the optical microscope image of cracking masterplate prepared by the embodiment of the present invention 1.
Fig. 3 is that the scanning electron for making ITO/Cu grids obtained by conductive substrates with ito thin film prepared by the embodiment of the present invention 1 shows
Micro mirror image.
Fig. 4 makees conductive substrates and in metal grill Surface coating AZO for prepared by the embodiment of the present invention 2 with AZO/Ag films
The scanning electron microscope image of obtained sample.
Fig. 5 is the transmission spectrum of the sample that different electroplating currents are obtained in the embodiment of the present invention 1.
Fig. 6 is the transmission and reflectance spectrum for preparing sample in the embodiment of the present invention 1 under the conditions of 0.05A.
Fig. 7 be the embodiment of the present invention 2 in AZO/Ag films make conductive substrates and metal grill surface covering AZO obtained by
The transmission and reflectance spectrum of sample (electroplating current is 0.05A).
Fig. 8 is AZO/Ag/Au grids/temperature of the AZO laminated films under different heating voltage prepared by the embodiment of the present invention 2
Degree changes over time curve.
Fig. 9 is the electric heated defrosting procedure chart of AZO/Ag/Au grids/AZO laminated films prepared by the embodiment of the present invention 2
Picture.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent used etc., unless otherwise specified, are commercially obtained in following embodiments.
Embodiment 1, the Low emissivity electrical-heating film based on ito thin film and Cu grid composite constructions
First, the selection of Low emissivity conductive functional layers
In the present embodiment, selection surface resistance for 7 Ω/ PET/ITO conductive films as substrate, the substrate is to infrared light
With very strong albedo.
2nd, knife coating prepares cracking net template
In the present embodiment, the cracking nail polish glue that selection is not reacted with electrolyte is as cracking masterplate raw material, and be cracked masterplate
Specific preparation process it is as follows：
(1) conductive substrates are cut into suitable size, be fixed on doctor knife coater working panel；
(2) bar of 7 μm of specifications is selected, bar is fixed in leveling groove, lifting handle is put down, it is ensured that bar and conduction
Substrate is fitted completely；
(3) pace of bar is set to 35r/min, forward travel distance is set to 15cm；
(4) cracking nail polish glue is equably dropped in into bar front end, bar is at the uniform velocity advanced, cracking nail polish glue is spread evenly across
Conductive substrates surface；
(5) cracking masterplate is positioned under room temperature (20 DEG C) and dries 10min, spontaneous cracking forms cracking grid masterplate, does
The thickness of cracking template is 2 μm or so after dry, and the width in crack is at 1 μm or so.
The optical microscope image of the cracking template prepared is as shown in fig. 2, it can be seen that the crackle connection of cracking grid
Property is good, and surface topography is homogeneous.
3rd, using electroplating technology in masterplate crack deposited metal Cu
Condition in the present embodiment from galvanoplastic is as follows：
Electrolyte is copper plating bath；Anode is titanium iridium electrode；Negative electrode is the ito thin film that the surface covers cracking masterplate；Electricity
Source is DC constant current power supply, regulation input current be respectively 0.01A, 0.03A, 0.04A, 0.05A, 0.06A, 0.07A, 0.08A,
0.09A, 0.1A, electroplating time are 5min.
Because reduction reaction only occurs in conductive region, so metal is only deposited in crack, the region blocked by template
Do not have metal deposit, it is to avoid the waste of metal.
4th, cracking template is removed
The sample of deposited metal is taken out, is positioned in the beaker for filling trichloro ethylene, beaker is put into supersonic cleaning machine,
With 60W power ultrasonic 2min, then alcohol is used successively, deionized water rinsing is clean, nitrogen drying.
The SEM of the transparent electric heating film of Low emissivity (ITO/Cu grids laminated film) manufactured in the present embodiment
Image is as shown in Figure 3, it can be seen that metal grill width has good connectivity at 1 μm or so.
The transparent electric heating film performance measurement result of Low emissivity manufactured in the present embodiment is as follows：
Metal thickness and its surface resistance such as table 1 in metal grill in the transparent electric heating film of Low emissivity manufactured in the present embodiment
Shown in, the transmission spectrum of the transparent electric heating film of Low emissivity is as shown in figure 5, the transmission of the sample prepared under the conditions of 0.05A and anti-
Penetrate spectrum as shown in Figure 6.
Sample its metal thickness that the present invention is obtained it can be seen from said determination result between 0.18~1.4 μm,
Corresponding surface resistance is 1.93~0.17 Ω/, and its transmitance is not influenceed by metal thickness substantially, is held in 61% left
Right (Fig. 5) (includes substrate), while having high heat reflectivity (Fig. 6) to infrared light.
The shading coefficient for the sample for calculating electroplating current simultaneously to obtain under the conditions of 0.05A (blocks for weighing film
The ability of solar energy, shading coefficient is smaller to represent that film sunshade ability is stronger；The shading coefficient of simple glass is 0.9 or so)
For 0.586.
Table 1-1 ITO and different electroplating current gained ITO/Cu laminated films metal thickness h, Rs, T%
Because Cu grids are in the case of input load, Cu atoms can be made under electrical potential difference effect to a direction skew
Into copper mesh thread breakage.The characteristic causes copper mesh can not bear too big load during electrical heating, and heating-up temperature can only
Reach 60 DEG C or so.In one layer of Al of copper mesh Surface coating2O3Diaphragm, can effectively improve this problem.
Embodiment 2, the Low emissivity electrical-heating film based on AZO/Ag/Au grids/AZO composite constructions
First, the preparation of low radiation functions layer
In the present embodiment, selection AZO/Ag Low emissivities conductive film is used as Low emissivity layer.Its specific preparation method is as follows：
(1) by aluminum oxide (Al2O3) and zinc oxide (ZnO) mixed-powder (mol ratio Al2O3：ZnO=2：98) fully grind
Mill, is pressed into after target and sinters 4h under the conditions of 950 DEG C of high temperature, obtain target.Growth chamber is vacuumized using molecular pump and is less than
10-6Torr, is passed through argon gas afterwards so that pressure is 5 × 10 in growth chamber-3Torr.Quartz substrate (1mm is thick) is placed on pallet
On, temperature is maintained at room temperature, and is rotated with 15rpm speed；When growing sample using magnetically controlled sputter method, Power Control exists
80W.Growth rate is 2.35nm/min, by controlling growth time so that AZO thickness is 40nm.
(2) it is used as target with argent.Growth chamber is vacuumized less than 10 using molecular pump-6Torr, is passed through argon afterwards
Gas so that pressure is 7.5 × 10 in growth chamber-3Torr.The sample for having grown aluminium-doped zinc oxide is placed on pallet,
Temperature is maintained at room temperature, and is rotated with 20rpm speed；When growing sample using magnetically controlled sputter method, Power Control is in 35W.
Growth rate is 0.08nm/s, is 200s so that silver film thickness is 16nm by controlling growth time.Obtain AZO/Ag ultra-thin
Transparent conductive film.Its surface resistance is 5 Ω/ or so.
2nd, knife coating prepares cracking net template
In the present embodiment, selection cracking nail polish glue is as cracking masterplate raw material, and specific preparation process is as follows：
(1) AZO/Ag laminated films are fixed on doctor knife coater working panel；
(2) bar of 7 μm of specifications is selected, bar is fixed in leveling groove, lifting handle is put down, it is ensured that bar and AZO/
Ag laminated films are fitted completely；
(3) pace of bar is set to 35r/min, forward travel distance is set to 15cm；
(4) cracking nail polish glue is equably dropped in into bar front end, bar is at the uniform velocity advanced, cracking nail polish glue is spread evenly across
AZO/Ag laminated films surface；
(5) cracking masterplate is positioned over air drying 10min, spontaneous cracking forms cracking grid masterplate, tortoise after drying
The thickness of masterplate is split at 2 μm or so.
The optical microscope image of the cracking template of above-mentioned preparation does not have substantial differences with Fig. 2.
3rd, using electroplating technology in masterplate crack deposited metal Au
Condition in the present embodiment from galvanoplastic is as follows：
Electrolyte is gold plating liquid；Anode is titanium iridium electrode；Negative electrode is that the AZO/Ag of surface covering cracking masterplate is combined
Film；Power supply is DC constant current power supply, and regulation input current is 0.05A, and electroplating time is 5min.
4th, cracking template is removed
The sample of deposited metal is taken out, is positioned in the beaker for filling trichloro ethylene, beaker is put into supersonic cleaning machine,
With 60W power ultrasonic 2min, then alcohol is used successively, deionized water rinsing is clean, nitrogen drying.Obtain AZO/Ag/Au grids
Laminated film.
5th, metal grill Surface coating AZO
With aluminum oxide (Al2O3) and the target of zinc oxide (ZnO) mixed-powder compacting sintering be used as target.Will be raw with molecular pump
Long chamber is vacuumized less than 10-6Torr, is passed through argon gas afterwards so that pressure is 5 × 10 in growth chamber-3Torr.By AZO/
Ag/Au grid laminated films are placed on pallet, and temperature is maintained at room temperature, and is rotated with 15rpm speed；Using magnetron sputtering side
When method grows sample, Power Control is in 80W.Growth rate is 2.35nm/min, by controlling growth time to cause the top of growth
Layer AZO thickness is 40nm.Obtain the Low emissivity electrically conducting transparent heating film of AZO/Ag/Au grids/AZO composite constructions.
The electron microscopic of the transparent electric heating film of Low emissivity (AZO/Ag/Au grids/AZO laminated films) manufactured in the present embodiment
Mirror image is as shown in Figure 4, it can be seen that the surface topography of AZO/Ag/Au grids/AZO laminated films is combined with ITO/Cu grids
Film is similar, metal grill even thickness, is respectively provided with good connectivity.
The transparent electric heating film of Low emissivity (AZO/Ag/Au grids/AZO laminated films) performance measurement knot manufactured in the present embodiment
Fruit is as follows：
The surface resistance of conductive Low emissivity transparent heating film manufactured in the present embodiment is 0.12 Ω/ or so, through and reflection
Spectrum is as shown in Figure 7, it is known that the mean transmissivity in its visible wavelength range is 74% (including substrate) left and right, higher than ITO/
The 60% of Cu grid laminated films；Can be calculated its shading coefficient is 0.572, less than the 0.586 of ITO/Cu grid laminated films,
Illustrate that AZO/Ag/Au grids/AZO laminated films have more preferable low radiance, this is primarily due to compared with ito thin film,
AZO/Ag laminated films are stronger to the reflex of infrared light.
AZO/Ag/Au grids manufactured in the present embodiment/temperature variation curve of the AZO laminated films under different heating voltage
As shown in Figure 8, it can be seen that in the case where providing 5V Dc biases, its rate of heat addition can reach 7.7 DEG C/s, maximum temperature
More than 100 DEG C are can reach, and can keep stable.The heat endurance of AZO/Ag/Au grids/AZO laminated films is attributed to covering
The protective effect played in the AZO films of top layer.
The electric heated defrosting effect presentation process of AZO/Ag/Au grids/AZO composite film glass manufactured in the present embodiment is shone
Piece is as shown in Figure 9.Wherein, before figure (a) is application voltage, AZO/Ag/Au grids/AZO composite film glass is placed in equipped with liquid
Above the culture dish of nitrogen in the near future, rapid knot has expired frost on glass, causes it to become opaque；After scheming (b) for voltage unlatching, by
In glass substrate temperature rise, the frost on surface starts to melt；It is the photograph after the glass surface frost removal completely within 1min to scheme (c)
Piece.
Claims (10)
1. a kind of preparation method of the transparent electrical-heating film of Low emissivity, comprises the following steps：
(1) cracking template is prepared on conductive substrates；
(2) using galvanoplastic in the deposited metal in the crack of template that is cracked；
(3) the cracking template is removed, the composite construction of the conductive substrates and metal grill is obtained, as described Low emissivity is saturating
Bright electrical-heating film.
2. preparation method according to claim 1, it is characterised in that：In step (1), the conductive substrates are by substrate and sink
Product is in the Low emissivity transparent conductive film composition on its surface.
3. preparation method according to claim 2, it is characterised in that：The Low emissivity transparent conductive film is to be sequentially depositing
Metal-oxide film or the thin composite membrane with ultrathin metallic film of metal oxide；
The material of the metal oxide film is wide band gap semiconducter；
The material of the ultrathin metallic film is Ag, Al or Pt；
The thickness of the ultrathin metallic film is less than 30nm.
4. preparation method according to claim 3, it is characterised in that：After step (3), methods described is also included to described
The step of composite structure surface deposits the metal-oxide film.
5. the preparation method according to any one of claim 1-4, it is characterised in that：In step (1), cracking liquid is used
Knife coating is coated to form cracking film on the surface of the conductive substrates, then forms institute in the spontaneous cracking of air drying
State cracking template.
6. preparation method according to claim 4, it is characterised in that：The step of knife coating, is as follows：
The conductive substrates are fixed on the working panel of doctor knife coater, bar is fixed on to the surface of the conductive substrates；
The cracking liquid is added dropwise in the front end of the bar, controls the bar to move ahead, and then the cracking liquid is coated on into the conduction
The surface of substrate.
7. the preparation method according to any one of claim 1-6, it is characterised in that：In step (2), the galvanoplastic
Condition is as follows：
Electrolyte is gold plating liquid, silver plating liquid or copper plating bath；
Anode is titanium iridium electrode；
Negative electrode is the conductive substrates that surface covers the cracking masterplate；
Power supply is DC constant current power supply.
8. preparation method according to claim 7, it is characterised in that：The electric current exported in the DC constant current power supply is 0.01
1~15min is electroplated under conditions of~0.1A.
9. the transparent electrical-heating film of Low emissivity prepared by method any one of claim 1-8.
10. the transparent electrical-heating film of Low emissivity described in claim 9 is in preparation or as in low radiation film or electrical-heating film
Application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710522481.6A CN107326415B (en) | 2017-06-30 | 2017-06-30 | A kind of transparent electrical-heating film of Low emissivity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710522481.6A CN107326415B (en) | 2017-06-30 | 2017-06-30 | A kind of transparent electrical-heating film of Low emissivity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107326415A true CN107326415A (en) | 2017-11-07 |
| CN107326415B CN107326415B (en) | 2019-02-19 |
Family
ID=60199415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710522481.6A Active CN107326415B (en) | 2017-06-30 | 2017-06-30 | A kind of transparent electrical-heating film of Low emissivity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107326415B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109862631A (en) * | 2019-04-04 | 2019-06-07 | 浙江大学 | A kind of preparation method of NEW TYPE OF COMPOSITE plate Electric radiant Heating Film |
| CN110273170A (en) * | 2019-06-13 | 2019-09-24 | 东北师范大学 | A kind of metal nanometer line network and preparation method thereof of graphene or metal oxide cladding |
| CN110600165A (en) * | 2019-08-24 | 2019-12-20 | 泉州柔丝蓝新材料科技有限公司 | Flexible transparent conductive film and preparation process thereof |
| CN115195226A (en) * | 2022-05-30 | 2022-10-18 | 浙江大学温州研究院 | Transparent electric heating composite film and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1111980A (en) * | 1997-06-27 | 1999-01-19 | Asahi Glass Co Ltd | Transparent conductive glass substrate and its production |
| CN102173133A (en) * | 2011-02-28 | 2011-09-07 | 福耀玻璃工业集团股份有限公司 | Compound functional sandwich glass containing metal nano-structured conductive layer |
| CN102795793A (en) * | 2012-09-11 | 2012-11-28 | 福耀玻璃工业集团股份有限公司 | Electrically-heatable low-emissivity coated laminated glass |
| CN103227240A (en) * | 2013-04-10 | 2013-07-31 | 华南师范大学 | Method for preparing porous metal film transparent conducting electrode based on cracking template method |
| CN104822249A (en) * | 2015-05-21 | 2015-08-05 | 哈尔滨工业大学 | Electromagnetic shielding optical window making method |
| CN105350043A (en) * | 2015-11-13 | 2016-02-24 | 华南师范大学 | Method for preparing high-performance metallic network transparent conducting electrode through metal plating method |
| CN106328260A (en) * | 2016-08-24 | 2017-01-11 | 华南师范大学 | Full-liquid phase preparation method of metal mesh transparent conductive electrode |
-
2017
- 2017-06-30 CN CN201710522481.6A patent/CN107326415B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1111980A (en) * | 1997-06-27 | 1999-01-19 | Asahi Glass Co Ltd | Transparent conductive glass substrate and its production |
| CN102173133A (en) * | 2011-02-28 | 2011-09-07 | 福耀玻璃工业集团股份有限公司 | Compound functional sandwich glass containing metal nano-structured conductive layer |
| CN102795793A (en) * | 2012-09-11 | 2012-11-28 | 福耀玻璃工业集团股份有限公司 | Electrically-heatable low-emissivity coated laminated glass |
| CN103227240A (en) * | 2013-04-10 | 2013-07-31 | 华南师范大学 | Method for preparing porous metal film transparent conducting electrode based on cracking template method |
| CN104822249A (en) * | 2015-05-21 | 2015-08-05 | 哈尔滨工业大学 | Electromagnetic shielding optical window making method |
| CN105350043A (en) * | 2015-11-13 | 2016-02-24 | 华南师范大学 | Method for preparing high-performance metallic network transparent conducting electrode through metal plating method |
| CN106328260A (en) * | 2016-08-24 | 2017-01-11 | 华南师范大学 | Full-liquid phase preparation method of metal mesh transparent conductive electrode |
Non-Patent Citations (4)
| Title |
|---|
| P.LI 等: "Flexible transparent heaters based on silver nanotrough meshes", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| PENG LI 等: "Highly stable copper wire/alumina/polyimide composite films for stretchable and transparent heaters", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
| 朱荻 等: "《微机电***与微细加工技术》", 31 May 2008, 哈尔滨工程大学出版社 * |
| 钱苗根 等: "《现代表面工程》", 30 September 2012, 上海交通大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109862631A (en) * | 2019-04-04 | 2019-06-07 | 浙江大学 | A kind of preparation method of NEW TYPE OF COMPOSITE plate Electric radiant Heating Film |
| CN110273170A (en) * | 2019-06-13 | 2019-09-24 | 东北师范大学 | A kind of metal nanometer line network and preparation method thereof of graphene or metal oxide cladding |
| CN110600165A (en) * | 2019-08-24 | 2019-12-20 | 泉州柔丝蓝新材料科技有限公司 | Flexible transparent conductive film and preparation process thereof |
| CN110600165B (en) * | 2019-08-24 | 2023-12-08 | 厦门派恩杰科技有限公司 | Flexible transparent conductive film and preparation process thereof |
| CN115195226A (en) * | 2022-05-30 | 2022-10-18 | 浙江大学温州研究院 | Transparent electric heating composite film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107326415B (en) | 2019-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107326415B (en) | A kind of transparent electrical-heating film of Low emissivity and preparation method thereof | |
| CN105350043B (en) | A kind of method that metal plating method prepares metalolic network transparent conductive electrode | |
| CN104681645A (en) | Method for preparing composite transparent conductive electrode based on metal grid and metal nano-wire | |
| Fallahazad et al. | Combination of surface texturing and nanostructure coating for reduction of light reflection in ZnO/Si heterojunction thin film solar cell | |
| EP2717320B1 (en) | Preparation method for surface-textured conductive glass and its application for solar cells | |
| CN103227240A (en) | Method for preparing porous metal film transparent conducting electrode based on cracking template method | |
| Hirahara et al. | Preparation of Al-doped ZnO thin films as transparent conductive substrate in dye-sensitized solar cell | |
| WO2017054265A1 (en) | Low-resistance transparent conductive thin film and preparation method therefor | |
| CN104616726B (en) | One kind is without indium transparency electrode and preparation method thereof | |
| Yan et al. | Investigation of the thickness effect on material and surface texturing properties of sputtered ZnO: Al films for thin-film Si solar cell applications | |
| CN110040976A (en) | A kind of tungsten oxide electrochomeric films material and preparation method thereof | |
| CN102747334A (en) | Zinc-oxide-based transparent conductive film and preparation method thereof | |
| Liu et al. | Indium tin oxide with titanium doping for transparent conductive film application on CIGS solar cells | |
| Ito et al. | Electrochromic properties of iridium oxide thin films prepared by reactive sputtering in O2 or H2O atmosphere | |
| Liang et al. | Structural and optoelectronic properties of transparent conductive c-axis-oriented ZnO based multilayer thin films with Ru interlayer | |
| Meng et al. | Preparation and characterization of dye-sensitized TiO2 nanorod solar cells | |
| CN106784151B (en) | Preparation method of flexible copper indium gallium selenide thin-film solar cell | |
| CN110102457A (en) | A method of preparing nickel oxide nano-crystal electrochomeric films at low temperature | |
| JP2019056181A (en) | Conductive transparent aluminum-doped zinc oxide sputtering film | |
| Niu et al. | Spreadability of Ag layer on oxides and high performance of AZO/Ag/AZO sandwiched transparent conductive film | |
| Chu et al. | Study of Cu-based Al-doped ZnO multilayer thin films with different annealing conditions | |
| CN102220562B (en) | Preparation method of zinc oxide transparent conductive film with sueded structure | |
| Wang et al. | Effect of rapid thermal annealing time on ZnO: F thin films deposited by radio frequency magnetron sputtering for solar cell applications | |
| CN103779430A (en) | Conductive antireflection film of crystalline silicon solar cell and crystalline silicon solar cell | |
| Onodera et al. | Smart windows, switchable between transparent, mirror, and black states, fabricated using rough and smooth indium tin oxide films deposited by spray chemical vapor deposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |