CN1082803A - A kind of thermostable transparent electric heating film and production method thereof - Google Patents
A kind of thermostable transparent electric heating film and production method thereof Download PDFInfo
- Publication number
- CN1082803A CN1082803A CN 92106609 CN92106609A CN1082803A CN 1082803 A CN1082803 A CN 1082803A CN 92106609 CN92106609 CN 92106609 CN 92106609 A CN92106609 A CN 92106609A CN 1082803 A CN1082803 A CN 1082803A
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- China
- Prior art keywords
- heating film
- electric heating
- transparent electric
- thermostable transparent
- modifying agent
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Abstract
The invention provides a kind of thermostable transparent electric heating film and production method thereof, particularly a kind of tin ash Electric radiant Heating Film and production method thereof of mixing antimony and one or more modifying agents, it is by the chloride that contains antimony, muriatic one or more the spraying filming liquid of the chloride of tin and Cr, Ni, Co, Ce, V, Cd, Mn, Cu, Fe, form through hydrolysis on matrix surface by the spraying plating process spraying plating, has good thermal stability, the advantage of stable conductivity.This Electric radiant Heating Film can be widely used in on the heating appliances as heat medium such as water or air as heater element.
Description
The present invention relates to a kind of tin ash semiconductor transparent electric heating film and production method thereof of mixing antimony, particularly a kind of semiconductor thermostable transparent electric heating film that in mixing the tin ash Electric radiant Heating Film of antimony, adds the oxide of modifying agent Cr, Ni, Co, Mn, Ce, V, Cu, Fe and Cd.
At present, prior art is with SnO
2Be matrix, with Sb
2O
5Be the Electric radiant Heating Film of activating agent, use under hot conditions two kinds of phenomenons usually take place: (1) thermal stability is bad, easily damaged.(2) under long-term (being generally more than 100 hours) hot conditions, impurity Sn
0, Sn
2+, Sb
3+Oxidized gradually, conductivity sharply descends, and Electric radiant Heating Film power reduces significantly, thereby has lost use value.Its reason is the equal tool multivalence of a Sn and Sb attitude, with the SnO of high-temperature hydrolysis process formation
2In the conducting film crystal, except containing Sn
4+And Sb
5+Still contain Sn outward,
0, Sn
2+And Sb
3+, these low price ions are stayed in the crystal with doped forms, have improved the initialization conductivity of Electric radiant Heating Film.When Electric radiant Heating Film during at hot operation, under the atmospheric oxidn effect, the ion combination valency of lower valency is saturated gradually, and the doping of lower valency is reduced, and causes conductivity to descend.For solving this deficiency, 88108194.9 doped-semiconductor electrothermal film a kind of application number was disclosed is on May 31st, 1989, wherein mixed boron to improve the thermal stability of film, because of an amount of boron can reduce the crystal boundary barrier.But boron is slowly volatilization at high temperature, and the chemical composition of film is changed, and thermal stability is damaged and burns.This technology to Electric radiant Heating Film at high temperature conductivity descend gradually and do not take technical measures, caused the rapid decline of power, lost the use value of hot operation.Another kind method is that Electric radiant Heating Film is incubated several hours to tens hours about 900 ℃, carries out oxidation processes, makes Sn
0, Sn
2+, Sb
3+Be oxidized to Sn respectively
4+, Sb
5+, it is saturated to reach valence state, thereby tries to achieve stable conductivity.But owing to can not reach oxidation balance at short notice, thereby this Electric radiant Heating Film after insulation is handled will continue oxidation in continuous high temperature work, cause conductivity than 3～5 orders of magnitude of decline before handling, and power is extremely low.Therefore, this heat-treating methods does not have practical value.
Purpose of the present invention is to overcome the deficiency of above-mentioned prior art, and a kind of thermostable transparent electric heating film and production method thereof that keeps stable conductivity and good thermal stability under high temperature (300～850 ℃) condition of work is provided.
Purpose of the present invention can reach by following measure, mix by the chloride ethanol water of tin and the chloride ethanolic solution of antimony, adding is as the metal chloride aqueous solution of modifying agent or one or more composition spraying filming liquids of ethanolic solution, the matrix of desiring to execute film is heated to 400～780 ℃ (deciding with basic material), by spraying plating process hydrolysis on matrix surface, form the tin ash Electric radiant Heating Film of mixing antimony and mixing a kind of modifying agent metal oxide at least.
Metal chloride in the above-mentioned spraying filming liquid is meant CrCl
36H
2O, NiCl
26H
2O, CoCl
26H
2O, CeCl
4, VCl
5, CdCl
22H
2O, MnCl
24H
2O, CuCl
22H
2O, FeCl
36H
2O preferably adds above-mentioned metal chloride more than 2 kinds in spraying filming liquid.In the Electric radiant Heating Film, SnO
2And Sb
2O
5Percentage composition be respectively 86.0～99.2% and 0.5～13.0%, best percentage composition is respectively 92.0～96.0% and 3.0%～6.0%.Total percentage composition of modifying agent metal oxide is 0.1%～3.0%, and best percentage composition is 0.3～1.2%.Preferably contain modifying agent metal oxide Cr more than 2 kinds in the Electric radiant Heating Film
2O
3, NiO, CoO, CeO
2, V
2O
5, CdO, Mn
2O
3, CuO, Fe
2O
3
The present invention compared with prior art has the following advantages: (1) is because the present invention is in the Electric radiant Heating Film of matrix to the tin ash of mixing antimony, one or more metal oxides have been added, metal ion oxidation potential in these metal oxides is higher than the oxidation potential of Sn and Sb, they impel the Sn and the Sb that are in unsaturated valence state to become saturated valence state, make the chemical state of Electric radiant Heating Film Main Ingredients and Appearance Sn and Sb stable, thereby make this n N-type semiconductor N stable conductivity.(2), thereby the heat-resistant stability and the temperature tolerance of crystal have also been improved because these metal oxide resistances to elevated temperatures are good.
For describing the present invention in detail, provide several embodiment below.
Embodiment 1.
Anhydrous SnCl with 250g
4Or the SnCl of 336.3g
45H
2The SnCl of O or 216.4g
22H
2O mixes with absolute ethyl alcohol and the 100ml deionized water of 250ml, stirs, and is mixed with component (1); SbCl with 100g
3Or the SbCl of 131.1g
5Mix with the absolute ethyl alcohol of 100ml, stir, be mixed with component (2); Respectively with the CrCl of 2g
36H
2O, NiCl
26H
2O, CoCl
26H
4O, CeCl
4, VCl
5, CdCl
22 1/2 H
2O mixes with the deionized water of 5ml, stirs, and is mixed with component (3), (4), (5), (6), (7), (8); Again respectively with the MnCl of 2g
24H
2O, CuCl
22H
2O, FeCl
36H
2O mixes with the absolute ethyl alcohol of 5ml, stirs, and is mixed with component (9), (10), (11).Said components (1), (2) are mixed by a certain percentage, get in a certain amount of component (3)～(11) one or more again, generally getting (3) more than 2 kinds～(11) component mixes mutually with (1), (2) mixed solution, stir, the matrix of desiring to execute film is heated to 400～800 ℃, preferably 450～680 ℃ (determining this temperature by basic material) forms the tin ash Electric radiant Heating Film of mixing antimony and containing the modifying agent metal oxide by spraying plating process hydrolysis on matrix surface.This Electric radiant Heating Film is in the heat that continues thousands of hours, good thermal stability, and stable conductivity, square resistance value can reach 10 Ω/, not only but spraying plating is used for making electric cup, electric chafing dish, electric coffee kettle, electric shower-bath at bottom, the sidewall of containing the liquid object vessel, also can be used for the dry combustion method occasion, being particularly suitable for manufacturing electric heater, roaster, industrial stoving and electric heater unit, is desirable efficient, energy-saving heating element.
Embodiment 2.
Get component (1) 80ml among the embodiment 1, component (2) 3ml, component (5) 0.5ml, component (9) 0.6ml, component (11) 0.45ml mixes and stirs, and quartz glass plate is heated to 620 ℃, with the pressure of spray gun mixed solution and sprayed is plated on the quartz glass plate surface, has promptly formed the tin ash Electric radiant Heating Film of mixing antimony, cobalt, cadmium, manganese, iron with 20KPa.This Electric radiant Heating Film contains SnO
2Mass percent be 94.9%, Sb
2O
54.49%, CoO 0.18%, Mn
2O
30.28%, Fe
2O
30.15%.During the energising of this Electric radiant Heating Film, high temperature resistantly reach 670 ℃, behind 5,000 continuous throughout the twenty-four hour24s, measure stable conductivity.
Embodiment 3.
Get component among the embodiment 1 (1) 75ml, component (2) 3.2ml, component (3) 1ml, component (5) 0.7ml, component (8) 0.4ml mixes and stirs, send lux type glass tube to be heated to 540 ℃ matrix, with spray gun with the pressure of 20KPa with mixed solution equably spraying plating promptly formed the tin ash Electric radiant Heating Film of mixing antimony, chromium, cobalt, cadmium, SnO in this Electric radiant Heating Film to the glass tube surface
2Quality account for 94.05%, Sb
2O
5Account for 5.06%, Cr
2O
3Account for 0.34%, CoO accounts for 0.27%, and CdO accounts for 0.27%.This Electric radiant Heating Film is high temperature resistant 570 ℃, through 3,000 hours work after, stable conductivity.
Embodiment 4.
Get component among the embodiment 1 (1) 78ml.Component (2) 4.3ml, component (6) 0.2ml, component (9) 0.6ml, component (10) 0.45ml, mixing also stirs, with spray gun with the pressure of 20KPa with above-mentioned mixed solution equably spraying plating just formed the tin ash Electric radiant Heating Film of mixing antimony, cerium, manganese, copper to being heated on 500 ℃ the devitrified glass surface.This Electric radiant Heating Film contains SnO
292.8%, Sb
2O
56.46%, CeOCl
20.16%, Mn
2O
30.28%, CuO 0.3%.This Electric radiant Heating Film is high temperature resistant 520 ℃, through 3,000 continuous throughout the twenty-four hour24s, its stable conductivity.
Claims (5)
1, a kind of thermostable transparent electric heating film is characterized in that, to being in the Electric radiant Heating Film of matrix with the tin ash of mixing antimony, adds at least a metal oxide and makes modifying agent.These metal oxides are: Cr
2O
3, NiO, CoO, CeO
2, V
2O
5, CdO, Mn
2O
3, CuO, Fe
2O
3
2, according to the described a kind of thermostable transparent electric heating film of claim 1, it is characterized in that SnO
2And Sb
2O
5The quality percentage composition be 86.0～99.2% and 0.5～13.0%, best percentage composition is respectively 92.0～96.0% and 3.0～6.0%, total percentage composition of one or more modifying agent metal oxides is 0.1～3.0%, best percentage composition is 0.3～1.2%.
3, according to claim 1 or 2 described a kind of thermostable transparent electric heating films, the modifying agent metal oxide of interpolation is preferably more than 2 kinds.
4, a kind of manufacture method of thermostable transparent electric heating film is characterized in that, spraying filming liquid is the chloride ethanolic solution mixing with the chloride ethanol water of tin and antimony, adds one or more compositions of the modifying agent metal chloride aqueous solution or ethanolic solution.
According to the manufacture method of the described a kind of thermostable transparent electric heating film of claim 4, it is characterized in that 5, the modifying agent metal chloride is CrCl
3, 6H
2O, NiCl
26H
2O, CoCl
26H
2O, CeCl
4, VCl
5, CdCl
22 1/2 H
2O, MnCl
24H
2O, CuCl
22H
2O, FeCl
36H
2O.Preferably add more than 2 kinds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92106609A CN1036432C (en) | 1992-07-09 | 1992-07-09 | Thermostable transparent electric heating film and its producing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92106609A CN1036432C (en) | 1992-07-09 | 1992-07-09 | Thermostable transparent electric heating film and its producing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1082803A true CN1082803A (en) | 1994-02-23 |
| CN1036432C CN1036432C (en) | 1997-11-12 |
Family
ID=4942266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92106609A Expired - Fee Related CN1036432C (en) | 1992-07-09 | 1992-07-09 | Thermostable transparent electric heating film and its producing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1036432C (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000018189A1 (en) * | 1998-09-18 | 2000-03-30 | Email Limited | Thin film heating element |
| AU751515B2 (en) * | 1998-09-18 | 2002-08-15 | Grimwood Management Pty Ltd | Thin film heating element |
| CN100426936C (en) * | 2003-12-02 | 2008-10-15 | 北京明盛电通能源新技术有限公司 | High-temp. high-efficiency multifunction inorganic electrothermal film and manufacturing method thereof |
| CN100441056C (en) * | 2005-01-05 | 2008-12-03 | 林正平 | Method for manufacturing semiconductor electric heating membrane |
| CN100466865C (en) * | 2005-03-21 | 2009-03-04 | 冷同桂 | Composite metal electrothermic film sol and preparing process thereof |
| CN104080208A (en) * | 2013-03-26 | 2014-10-01 | 颜彬 | Manufacturing method of electrothermal film |
| CN105898905A (en) * | 2016-05-09 | 2016-08-24 | 苏州思创源博电子科技有限公司 | Process for machining electric heating element |
| CN105916220A (en) * | 2016-05-09 | 2016-08-31 | 苏州思创源博电子科技有限公司 | Composite electric heating film preparation method |
| CN105992408A (en) * | 2015-02-11 | 2016-10-05 | 佛山市顺德区美的电热电器制造有限公司 | Manufacturing method of electrothermal film layer, the electrothermal film layer, electric heating disc and cooking utensil |
| CN106162953A (en) * | 2015-04-17 | 2016-11-23 | 佛山市顺德区美的电热电器制造有限公司 | The preparation method of Electric radiant Heating Film powder, cooking container, preparation method and cooking apparatus |
| CN106793195A (en) * | 2017-02-24 | 2017-05-31 | 江苏森电采暖科技有限公司 | Long-life heating and preparation method thereof |
| CN107172727A (en) * | 2017-05-31 | 2017-09-15 | 广西泰亿诺新能源有限公司 | Nano electroheating film film liquid is formulated and preparation method and the preparation method of electrothermal tube |
| CN112851334A (en) * | 2021-02-04 | 2021-05-28 | 宁波云川环保科技有限公司 | Heating body based on silicon nitride and preparation process thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033225A (en) * | 1988-11-26 | 1989-05-31 | 上海大华化轻工业公司 | Doped-semiconductor electrothermal film |
| CN1060193A (en) * | 1990-09-21 | 1992-04-08 | 中国科学院长春应用化学研究所 | The preparation method of high efficient infrared radiation meterial |
-
1992
- 1992-07-09 CN CN92106609A patent/CN1036432C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000018189A1 (en) * | 1998-09-18 | 2000-03-30 | Email Limited | Thin film heating element |
| AU751515B2 (en) * | 1998-09-18 | 2002-08-15 | Grimwood Management Pty Ltd | Thin film heating element |
| CN100426936C (en) * | 2003-12-02 | 2008-10-15 | 北京明盛电通能源新技术有限公司 | High-temp. high-efficiency multifunction inorganic electrothermal film and manufacturing method thereof |
| CN100441056C (en) * | 2005-01-05 | 2008-12-03 | 林正平 | Method for manufacturing semiconductor electric heating membrane |
| CN100466865C (en) * | 2005-03-21 | 2009-03-04 | 冷同桂 | Composite metal electrothermic film sol and preparing process thereof |
| CN104080208B (en) * | 2013-03-26 | 2015-04-29 | 颜彬 | Manufacturing method of electrothermal film |
| CN104080208A (en) * | 2013-03-26 | 2014-10-01 | 颜彬 | Manufacturing method of electrothermal film |
| CN105992408A (en) * | 2015-02-11 | 2016-10-05 | 佛山市顺德区美的电热电器制造有限公司 | Manufacturing method of electrothermal film layer, the electrothermal film layer, electric heating disc and cooking utensil |
| CN105992408B (en) * | 2015-02-11 | 2020-03-10 | 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 |
| CN106162953A (en) * | 2015-04-17 | 2016-11-23 | 佛山市顺德区美的电热电器制造有限公司 | The preparation method of Electric radiant Heating Film powder, cooking container, preparation method and cooking apparatus |
| CN105898905A (en) * | 2016-05-09 | 2016-08-24 | 苏州思创源博电子科技有限公司 | Process for machining electric heating element |
| CN105916220A (en) * | 2016-05-09 | 2016-08-31 | 苏州思创源博电子科技有限公司 | Composite electric heating film preparation method |
| CN106793195A (en) * | 2017-02-24 | 2017-05-31 | 江苏森电采暖科技有限公司 | Long-life heating and preparation method thereof |
| CN107172727A (en) * | 2017-05-31 | 2017-09-15 | 广西泰亿诺新能源有限公司 | Nano electroheating film film liquid is formulated and preparation method and the preparation method of electrothermal tube |
| CN112851334A (en) * | 2021-02-04 | 2021-05-28 | 宁波云川环保科技有限公司 | Heating body based on silicon nitride and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1036432C (en) | 1997-11-12 |
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