CN102291860B - Method for manufacturing automatic temperature-limiting oxide electric-heating film - Google Patents
Method for manufacturing automatic temperature-limiting oxide electric-heating film Download PDFInfo
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- CN102291860B CN102291860B CN 201110102380 CN201110102380A CN102291860B CN 102291860 B CN102291860 B CN 102291860B CN 201110102380 CN201110102380 CN 201110102380 CN 201110102380 A CN201110102380 A CN 201110102380A CN 102291860 B CN102291860 B CN 102291860B
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Abstract
The invention relates to a method for manufacturing an automatic temperature-limiting oxide electric-heating film, which comprises the following processes of: preparing a film-forming solution, purifying substrates, film forming, manufacturing electrodes and electrifying and aging. The method is characterized in that: according to the formulation of the film-forming solution, tin tetrachloride (100g) is a major ingredient; antimony trichloride (1.8g) is a doping agent; copper dichloride (1.7g) and manganous dichloride (2g) are high-temperature anti-aging agents; barium titanate (5g) is a stabilizing agent with high-pressure resistance; hydrofluoric acid (suitable amount) is a doping dissolvent agent; and absolute ethyl alcohol (100g) is a solvent. The method for manufacturing the automatic temperature-limiting oxide electric-heating film has the advantages that: the formulation is optimized and the best use of everything is made; antimony and fluorine are co-doped, thus the quality of a film layer is enhanced; the copper dichloride and the manganous dichloride are selected as additives, thus the anti-aging performance of the film layer is increased; the barium titanate with characteristics is selected as an additive, so that the stability of resistance under high pressure is protected and the film layer has an automatic temperature-limiting performance, slow attenuation under high temperature, a long service, good conductivity and stability and strong adaptability. The method for manufacturing the automatic temperature-limiting oxide electric-heating film is suitable for manufacturing oxide electric-heating films.
Description
Technical field
The invention belongs to a kind of Ohmic resistance heating film take material or material character as feature, particularly a kind of have from limit warm nature can the manufacture method of oxide electric heating film.
Background technology
The transparent conductive oxide material is the important a member in the semiconductor family, and because it has good photoelectric and energy-saving effect, application prospect is even more important and extensive.Transparent conductive oxide film commonly used mainly comprises: SnO
2, In
2O
3, ZnO, Cd
2InO
4And doping system, their common shortcoming is poor high temperature stability, and decay is fast, and the life-span is short, has limited the scope of application.Chinese patent application number: propose in 200710119631.5 " production methods with self-constant temperature transparent high-temperature electric heating membrane pipe " with the chloride of tin, antimony, copper, nickel and ethanol by weight 8: 1: 1: mix at 1: 10 and to make coating liquid, adopt the spray pyrolysis method masking, can obtain that " positive temperature coefficient has self-constant temperature performance and long service life; good stability, safe and reliable Electric radiant Heating Film." compared with the prior art, this patent has strengthened the consumption of dopant Sb and other additives greatly, want to achieve the goal with the raising positive temperature coefficient.But we know the displacement of employing high-valence cationic, can improve the electric property of intrinsic nesa coating, but are not The more the better.When doping reached a certain critical value, electron concentration was tending towards a saturation value, and as continuing to improve doped level, exogenous impurity reacts with oxygen in film, generates nonconducting second-phase, causes electron mobility sharply to descend.Under the comprehensive function of carrier concentration and mobility, mobility plays a leading role, and resistivity is in rising trend, and conductivity descends thereupon.Therefore, want to guarantee electric heating Film conductivity and stability, must consider resistivity, carrier concentration and the mobility three of rete and the dialectical relationship between alloy class and the quantity, optimize prescription, guarantee from the source.
Summary of the invention
The objective of the invention is according to the existing problem of above-mentioned technology, the screening and optimizing prescription provides a kind of manufacture method from limitting warm oxide electric heating film, guarantees electric heating Film conductivity and stability from the source.
Of the present invention from limitting the manufacture method of warm oxide electric heating film to comprise: preparation film forming liquid, purify base material, film forming on the base material is made electrode, and energising is aging, and its concrete technology is:
(1) take butter of tin as major ingredient, trichloride antimony is dopant, and dichloride copper and manganous chloride are the high temperature age resister, and barium titanate is high pressure resistance stabilizer, and hydrofluoric acid is the doping cosolvent in right amount, and absolute ethyl alcohol is solvent preparation film forming liquid,
Film forming formula of liquid components by weight is as follows:
Butter of tin (S
nCl
45H
2O)---100g .... major ingredient
Trichloride antimony (SbCl
3)----1.8g .... dopant
Dichloride copper (CuCl
22H
2O)---1.7g .... age resister
Manganous chloride (MnCl
24H
2O)---2.0g .... age resister
Barium titanate (B
aTiO
3)---5.0g .... high pressure resistance stabilizer
Hydrofluoric acid (HF)---an amount of ... the doping cosolvent
Absolute ethyl alcohol (CH
3CH
2OH)---100g .... solvent
Compound method:
The first step takes by weighing barium titanate (B by prescription
aTiO
3), be dissolved in the hydrofluoric acid (HF), become barium titanate solution, build, for subsequent use,
Second step takes by weighing other each component-butter of tin (S by prescription
nCl
45H
2O), trichloride antimony (SbCl
3), dichloride copper (CuCl
22H
2O), manganous chloride (MnCl
24H
2O), be dissolved in absolute ethyl alcohol (CH
3CH
2OH) in, stir the lower barium titanate solution that slowly adds the first step, stir, set to 0 in-8 ℃ the refrigerator standby film forming and use.
(2) purify base material
Glass, ceramic-like hard heatproof insulating substrate, be erected in the supersonic wave cleaning machine, rinse well with running water, wipe steam, place 120-150 ℃ of lower baking oven to dry, build, for subsequent use.To micarex, heatproof insulating substrate that the mineral wool stationery is soft, with absorbent cotton dusting off greasy dirt.(being stained with in case of necessity a wipes of alcohol)
(3) film forming
The heatproof insulating substrate that purge drying is good is loaded onto to clamping apparatus, send in the generation stove of 600-650 ℃, with through purification, removing the compressed air (pressure is 0.2-0.4MPa) of profit impurity, the atomization of film forming liquid is sprayed into to the generation stove, each component generation series of chemical of airborne oxygen and steam and film forming liquid under high temperature, the oxide conducting crystal grain that generates embeds in the substrate surface lattice, the accumulation film forming, make the substrate surface of originally insulation form all good functional films of one deck stability, electric conductivity
In like manner:
The copper Mn oxide that generates is a kind of semi-conducting material that has good stability, and synergistic effect can be prevented aging decay under the Electric radiant Heating Film high temperature.
(4) make electrode
At the appropriate location of Electric radiant Heating Film brushing silver slurry, after 150-200 ℃ of oven dry, send into 600-650 ℃ of reduction furnace reductase 12 0-30 minute as required, it is qualified sending a telegraph the silvery white that the utmost point is even compact.
(5) energising is aging
With the mechanical connection method at electrode place extracting power supply cord, with aging 3-10 minute of the voltage energising that is higher than 1.25 times of operating voltages, make Ordering lattice, become the high and unsettled SnO of resistivity and hang down again very stable SnO2 phase into resistivity, improve the conductivity and stability of rete.
The present invention compared with prior art, its advantage is:
1, optimize prescription, make the best use of everything
The transparent conductive oxide film is semi-conducting material, the size of its resistivity, the height of carrier concentration and the speed of carrier mobility be the important parameter that reflects that directly rete conductivity is fine or not with stability, and three and alloy class, quantitative relation are not quite similar very closely.Identical is at the beginning all with the increase of doping towards favourable future development, after doping reaches certain value, then go over to the opposite side, different is three's critical value size is different.Consider the dialectical relationship between three and alloy class, the quantity, our screening and optimizing film forming liquid prescription has not only been saved raw material, makes and makes the best use of everything, and has also effectively improved film forming speed and stability.
2, antimony (Sb) fluorine (F) is mixed altogether, improves film quality
In order to improve the conductivity of rete, usually adopt doping high-valence cationic displacement Sn
4+Ion, or the at a low price anion displacement O that mixes
2-Ion.We adopt the mode of mixing altogether,
Use Sb
5+With F-difference displacement Sn
4+And O
2-
The conductivity of rete and stability all are significantly increased as a result.
3, screening dichloride copper (CuCl
22H
2O) and manganous chloride (MnCl
24H
2O) make additive, improve the rete ageing resistance
The cupric oxide and the manganese oxide that generate with water or oxygen reaction under dichloride copper and the manganous chloride high temperature, further solid solution is the copper Mn oxide mangaic acid copper of ternary:
Mangaic acid copper is well semi-conducting material of stability, and the SnO that mixes
2Film forms Polycrystal Composites, helps to improve the whole ageing resistance of rete.
4, select individual barium titanate to make additive, the stability under the protection resistance high pressure
Barium titanate is a kind of important ferroelectric, and (dielectric constant is very large, and the material that changes with external electric field) has stable electric hysteresis character.Select it to make additive, can strengthen rete form stored electric energy with polarization in certain temperature range, rather than consume electric energy with the form of electric current, avoid electric current to cause the permanent change of microstructure and resistance under the rete high pressure, put forward high-resistance voltage ability to bear, guarantee the high-voltage stability of film resistance.
Embodiment
Of the present invention from limitting the manufacture method of warm oxide electric heating film to comprise: preparation film forming liquid, purify base material, film forming on the base material is made electrode, and energising is aging, and its concrete technology is:
(1) preparation film forming liquid
The formulation weight ratio is:
Butter of tin (S
nCL
45H
2O)---100g .... major ingredient
Trichloride antimony (SbCl3)---1.8g .... dopant
Dichloride copper (CuCl
22H
2O)---1.7g .... age resister
Manganous chloride (MnCl
24H
2O)---2.0g .... age resister
Barium titanate (B
aTiO
3)---5.0g .... high pressure resistance stabilizer
Hydrofluoric acid (HF)---an amount of ... the doping cosolvent
Absolute ethyl alcohol (CH
3CH
2OH)---100g .... solvent
Preparation steps:
The first step takes by weighing barium titanate (B by prescription
aTiO
3), be dissolved in the hydrofluoric acid (HF), build, for subsequent use.
Second step takes by weighing other each components by prescription, is dissolved in the absolute ethyl alcohol, stirs slowly to add barium titanate solution down, stirs, and sets to 0 in-8 ℃ the refrigerator for subsequent use.
(2) purify base material
Glass, ceramic-like hard heatproof insulating substrate, be erected in the supersonic wave cleaning machine, rinse well with running water, wipe steam, place 120-150 ℃ of lower baking oven to dry, build, for subsequent use.To micarex, heatproof insulating substrate that the mineral wool stationery is soft, get final product with absorbent cotton dusting off greasy dirt.(being stained with in case of necessity a wipes of alcohol)
(3) film forming
The heatproof insulating substrate that purge drying is good is loaded onto clamping apparatus, send in 600-650 ℃ the generation stove, with the compressed air (pressure is 0.2-0.4MPa) of removing profit impurity through purification, the atomizing of film forming liquid is sprayed into the generation stove, each component generation series of chemical of airborne oxygen and steam and film forming liquid under the high temperature, the oxide conducting crystal grain that generates embeds in the substrate surface lattice, the accumulation film forming, make the substrate surface of originally insulation form one deck stability, conductivity is good functional film all.
(4) make electrode
At the appropriate location of Electric radiant Heating Film brushing silver slurry, after 150-200 ℃ of oven dry, send into 600-650 ℃ of reduction furnace reductase 12 0-30 minute as required, it is qualified sending a telegraph the silvery white that the utmost point is even compact.
(5) energising is aging
In electrode place mechanical connection method, extracting power supply cord with aging 3-10 minute of the voltage energising that is higher than 1.25 times of operating voltages, makes Ordering lattice, becomes the high and unsettled SnO of resistivity and hangs down again very stable SnO into resistivity
2Phase improves the conductivity of rete with stable.
Claims (3)
1. a manufacture method of certainly limitting warm oxide electric heating film comprises preparation film forming liquid, purifies film forming on base material, the base material, makes electrode, switches on and wear out, and it is characterized in that:
Described film forming liquid forms weight ratio:
S
nCL
45H
2O---100g....... major ingredient
SbCl
3---the 1.8g....... dopant
CuCl
22H
2O---1.7g....... age resister
MnCl
24H
2O---2.0g....... age resister
B
aTiO
3---5.0g....... high pressure resistance stabilizer
HF---an amount of ... the doping cosolvent
CH
3CH
2OH---100g....... solvent
Compound method is:
The first step: take by weighing barium titanate by prescription, be dissolved in the hydrofluoric acid, build, for subsequent use,
Second step; Take by weighing other each components by prescription, be dissolved in the absolute ethyl alcohol, stir and slowly to add barium titanate solution down, stir, set to 0 in-8 ℃ the refrigerator standby film forming and use.
2. as claimed in claim 1 from limitting the manufacture method of warm oxide electric heating film, it is characterized in that: described purification base material, hard heatproof insulating substrate, be erected in the supersonic wave cleaning machine and rinse well with running water, wipe steam, in 120-150 ℃ of lower oven dry, build, for subsequent use, to soft heatproof insulating substrate, with absorbent cotton dusting off greasy dirt.
3. as claimed in claim 1 from the manufacture method of limitting warm oxide electric heating film, it is characterized in that: film forming on the described base material, that the good heatproof insulating substrate of purge drying is loaded onto clamping apparatus, send in 600-650 ℃ the generation stove, with the compressed air of removing profit impurity through purification, the atomizing of film forming liquid is sprayed in the generation stove, each component generation series of chemical of airborne oxygen and steam and film forming liquid under the high temperature, the oxide conducting crystal grain that generates embeds in the substrate surface lattice, the accumulation film forming, form one deck stability on the insulating substrate surface, the functional film that conductivity is good, make electrode at the appropriate location of film brushing silver slurry, lead-in wire, energising is aging, makes electric heating element.
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|---|---|---|---|
| CN 201110102380 CN102291860B (en) | 2011-04-25 | 2011-04-25 | Method for manufacturing automatic temperature-limiting oxide electric-heating film |
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|---|---|---|---|
| CN 201110102380 CN102291860B (en) | 2011-04-25 | 2011-04-25 | Method for manufacturing automatic temperature-limiting oxide electric-heating film |
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| CN102291860B true CN102291860B (en) | 2013-02-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3245921A4 (en) * | 2015-02-11 | 2018-06-20 | Foshan Shunde Midea Electrical Heating Appliances Manufacturing Co. Ltd. | Electrothermal film layer manufacturing method, electrothermal film layer, electrically-heating plate, and cooking utensil |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103757612B (en) * | 2013-05-30 | 2016-04-20 | 杨葆华 | The manufacture method of Environmental protection multifunction electric conduction film |
| CN104091882A (en) * | 2014-07-03 | 2014-10-08 | 陈国栋 | Double-layer high-radiation electrothermal film structure and manufacturing method |
| CN105992409B (en) * | 2015-02-11 | 2020-03-20 | 佛山市顺德区美的电热电器制造有限公司 | Manufacturing method of electric heating film layer, electric heating disc and cooking utensil |
| CN106358325A (en) * | 2016-08-30 | 2017-01-25 | 丁玉琴 | Method for preparing high temperature and strong adhesion type electric heating film |
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| EP0252489A2 (en) * | 1986-07-11 | 1988-01-13 | Nukem GmbH | Transparent conductive film system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6329410A (en) * | 1986-07-11 | 1988-02-08 | ヌ−ケン・ゲ−エムベ−ハ− | Transparent conducting layer system |
| JPH02259366A (en) * | 1989-03-29 | 1990-10-22 | Nippon Alum Mfg Co Ltd | Far infrared ray radiating titanium material |
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2011
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| EP0252489A2 (en) * | 1986-07-11 | 1988-01-13 | Nukem GmbH | Transparent conductive film system |
| CN1032673C (en) * | 1992-12-11 | 1996-08-28 | 戴金利 | Semiconductor electric-heating thin film and manufacture thereof |
| EP0654956A1 (en) * | 1993-11-24 | 1995-05-24 | U'LAMP ENTERPRISES Co., Ltd. | A method of manufacturing an electric heating film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3245921A4 (en) * | 2015-02-11 | 2018-06-20 | Foshan Shunde Midea Electrical Heating Appliances Manufacturing Co. Ltd. | Electrothermal film layer manufacturing method, electrothermal film layer, electrically-heating plate, and cooking utensil |
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| CN102291860A (en) | 2011-12-21 |
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