CN100364923C - Temperature induced emissivity reversibly variable material - Google Patents
Temperature induced emissivity reversibly variable material Download PDFInfo
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- CN100364923C CN100364923C CNB2003101085615A CN200310108561A CN100364923C CN 100364923 C CN100364923 C CN 100364923C CN B2003101085615 A CNB2003101085615 A CN B2003101085615A CN 200310108561 A CN200310108561 A CN 200310108561A CN 100364923 C CN100364923 C CN 100364923C
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Abstract
The present invention is temperature induced emissivity reversibly variable material used for air-conditioning type construction material. The material is formed by burning La2O3, SrCO3, Mn3O4, Na2O, K2O and CaO according to certain quality proportioning at 850 to 1100 DEG C for 5 to 15 hours and at 1150 to 1250 DEG C for 10 to 20 hours. The material can perform a low emissivity property under the condition of low temperature; as a result, the heat dissipation of the surface of objects is reduced; after temperature rises, the material performs a high emissivity property; as a result, the heat dissipation of the surfaces of the objects is increased. Two different properties perform reversible and reparative variation following the temperature; the present invention is suitable for creating heat comfortable environment for constructions; the present invention can be used as coating material of the outer walls of the constructions, the finishing material of cement base, etc. The present invention can also be used for vehicles, ships, large storage tanks, large steel structures, daily articles, military camouflage, space navigation thermal control coating, etc., and the present invention has a large economical benefit and a large social benefit.
Description
Technical field
The invention belongs to the Materials Science and Engineering technical field, be specifically related to a kind of warm emissivity induced reversible change material that is used for air-conditioning-type building material, can be used for building external paint, cement-base plastering material etc., also can be used for aspects such as shipping vehicle, large-scale storage tank, large-scale steel structure, articles for daily use, camouflage, aerospace thermal control coating.
Technical background
The cool in summer and warm in winter of house is the human dream of pursuing since ancient times, because this is the importance of human " having enough to eat and wear " basic living necessities.But real world often occurs cold in winter and hot in summer, and this is because the sun in the summer in winter bigger variation takes place to the ground input angle on the one hand, is that on the other hand the solar absorptance of material of construction and thermal emissivity can not change with seasonal variation.Therefore people can only come the constructing architecture thermally comfortable environment with heating and refrigeration, and the cost of spending is the fossil energy of mass consumption earth preciousness, and contaminate environment, the Global Greenhouse Effect of aggravating.According to statistics, the American Architecture energy consumption has accounted for 38% of the whole America total energy consumption, China only heating energy consumption also accounted for about 10% of national total energy consumption.Along with the generally use of air-conditioning, the building energy consumption growth trend is swift and violent, and the energy and environment protection situation are more pressing.Be save energy, people have taked multiple mode that buildings is incubated insulation, as adopting light porous material, adiabatic coating etc., though these methods have certain energy-saving effect, can't fundamentally solve architectural energy consumption and environmental protection problem.In view of the architectural environment characteristics, people also adopt some other method to improve building thermal environments, as offering vent window at the top, house, adopt solar reflection coating and light color cooling coating, adopting selective solar spectrum absorbing coating etc., though above-mentioned the whole bag of tricks has certain thermoregulation effect, utilize sun power but all fail all fully to dispose in two seasons of summer in winter, thus concerning requiring buildings cool in summer and warm in winter equal very big limitation of existence.
As everybody knows, the total solar radiation on per second arrival ground can be up to 60,000,000,000,000 kilowatts, be equivalent to more than 50,000 times of present global gross generation, and sun power is a kind of permanent, clean harmless energy, is undoubtedly a kind of effective way that solves architectural energy consumption so make full use of sun power.In this regard, people have studied material such as Te Langbai (Trombe) wall, solar cell, TIM (Transparent Insulation Materials) material, thermal-arrest roof, adjustable sun wall and device and fully dispose and utilize sun power.Wherein the TIM material of Germany scientist development adds the aluminium foil heavy curtain then and combines for to apply solar energy absorbing paint on wall face.Roll the aluminium foil curtain winter, relies on the photo-thermal conversion of solar energy absorbing paint to make indoor intensification; Put down the aluminium foil curtain summer, relies on aluminium foil surface that the height reflection and the high emission effect of self of sunlight are made room temperature lowering; The folding and unfolding of curtain relies on automatic gear control to finish.This TIM material can almost completely break away to the dependence of the earth fossil energy people and life cosily.More than these results show that people can be used to the constructing architecture thermally comfortable environment by the reasonable disposal to sun power, thereby thoroughly solve architectural energy consumption and environmental protection problem.But this mode applies being very limited on a large scale because the equipment therefor complex structure costs an arm and a leg on buildings.
Studies show that, the constructing architecture thermally comfortable environment need a kind of can a large amount of reflected solar radiations and to launch self heat in a large number (be low absorptivity in summer, the low absorptivity-emissivity ratio state of high emissivity), to absorb solar radiation in a large number and seldom launch self heat (be high-absorbility and should convert to winter, the high absorptivity-emissivity ratio state of low-launch-rate) material, regrettably there is not such material can support utilization in the global range at present, so just a severe challenge has been proposed to the Materials science investigator, need development research to go out and be low absorptivity-emissivity ratio state summer, be high absorptivity-emissivity ratio state winter, and in Building Heat comfort temperature (being about 18 ℃) but material of construction that can spontaneous inverse conversion, i.e. air-conditioning-type building material.
The research of air-conditioning-type building material can make problems such as the power consumption of constructing architecture thermally comfortable environment and consequent environmental pollution be solved, can save the fossil energy of earth preciousness in a large number, if in the total about 1,300,000,000 tons of standard coals of the amount of expending of the annual commercial energy resource of China, by building energy consumption level 13%, be expected to save about 1.7 hundred million tons of standard coals every year.
Summary of the invention
The object of the present invention is to provide a kind of warm emissivity induced reversible change material that can be used for air-conditioning-type building material.
Because the emittance performance of general material does not all vary with temperature substantially in the normal temperature scope, carried out outside the native land and adopted the electrochromism method that the emittance of material is modulated research, cooperated as employings c-LixWO3 such as S.F.Cogan and a-WO3 and made the rete that energising front and back emittance changes between 0.33-0.8; Employing s-WO3 such as J.S.Hale and NiO cooperate made the rete that emittance changes before and after the energising between 0.057-0.595; Employings such as A.L.Larsson deposit to a-WO3 or c-WO3 and made the rete that emittance changes before and after the energising on ITO (Indium Tin Oxide) the coated glass surface between 0.2-0.5.This material all needs to make the emittance of material present variation by the variation that wherein electronics or ion produce under the current potential effect, so it can only be applicable to occasions such as window glass, space vehicle, is difficult to adopt at building surface.In view of the material of the emissivity induced reversible change character of buildings needs temperature, the present patent application person has carried out a large amount of exploratory developments.Find the perovskite type material in Ferrite Material after deliberation, about its Curie temperature Tc, be accompanied by by ferrimagnetism and change the paramagnetism process into that considerable change will take place its emittance.Adopt La
2O
3, SrCO
3, Mn
3O
4, Na
2O, K
2Material preparation such as O, CaO has gone out the emissivity induced reversible change material of a kind of temperature.It forms proportioning following (mass ratio):
La
2O
3 5-25％
SrCO
3 0-20％
Mn
3O
4 50-75％
Na
2O，K
2O 0-15％
CaO 0-15％
Total amount satisfies 100%
Its more excellent proportioning following (mass ratio):
La
2O
3 8-20％
SrCO
3 8-15％
Mn
3O
4 55-70％
Na
2O，K
2O 0-10％
CaO 0-10％
Total amount satisfies 100%
In the said components, the active chemical of every kind of material is not less than 95%
The warm emissivity induced reversible change preparation methods that the present invention proposes is as follows: by each composition material of said ratio weighing, (adopting shredder etc.) grinds the composition body, and its fineness is not more than 5% in 0.080mm square hole sieve screen over-size.Pressed by powder after will grinding then is in blocks, fires in 850-1100 ℃ of air 5-15 hour.After taking out cooling, pulverize, regrinding, compressing tablet, again in 1150-1250 ℃ of air in firing 10-20 hour, furnace cooling has promptly made the material of the present invention of solid block to room temperature.
The using method of the emissivity induced reversible change material of the present invention's temperature:
1. the emissivity induced reversible change material of prepared temperature can be ground to form the powder material, be incorporated in common buildings exterior coating or the reversible temperature induced color changing coating of normal temperature in 10-30% ratio (mass ratio), mix, can make original coating possess the emittance temperature and cause the possibility of reversal voltinism.
2. can use the emissivity induced reversible change material of prepared block temperature, after cutting, polishing, stick on other body surfaces, make original surface have the emittance temperature and cause the possibility of reversal voltinism.
The emissivity induced reversible change material of the present invention's temperature has following effect:
A kind of material of the present invention pulverized make coating sample, the adjustable emittance M120 type infrared thermometer that adopts U.S. MICRON company to produce, tested its emittance with variation of temperature by the emittance measuring method of introductions such as Mi Zhengyu, the result is as shown in table 1.
The emittance of the emissivity induced reversible change material of table 1 temperature varies with temperature experimental result
| Temperature, K | 363 | 353 | 350 | 340 | 325 | 305 | 296 | 274 | 263 | |
| Emittance | Material 1 | 0.92 | 0.91 | 0.91 | 0.86 | 0.79 | 0.73 | 0.70 | 0.66 | 0.65 |
| Material 2 | 0.82 | 0.82 | 0.82 | 0.81 | 0.81 | 0.80 | 0.64 | 0.47 | 0.46 | |
By table 1 as seen, the emittance of the emissivity induced reversible change material 1 of this temperature considerable change occurs with temperature, is changed to 0.66-0.86 below the 340K by the 0.90-0.92 more than 340 K, and rangeability is about 0.26, transition temperature is about 340K, and cooling back emittance will be recovered.This experimental result illustrates that this material has the emissivity induced reversible conversion performance of temperature, though its transition temperature is also apparent too high, it is big inadequately that the emittance rangeability also shows, and meets the required direction of using on air-conditioning type building coating.Be also shown in by table 1, the emittance of the emissivity induced reversible change material 2 of this temperature also considerable change occurs with temperature, is changed to 0.46-0.64 below the 296K by the 0.80-0.82 more than the 296K, and rangeability is about 0.36, transition temperature is about 296K, and cooling back emittance also can be recovered.As seen its emittance invert point is more satisfactory.
Material of the present invention presents the low-launch-rate performance at low temperatures, and the thermal transpiration of body surface is reduced; And after temperature raises, then present the high emissivity performance, and the thermal transpiration of body surface is increased, two kinds of different performances can present reversible variation repeatedly with temperature, have the fossil energy of saving, reduce less environmental contamination.Therefore, this material can be used for air-conditioning-type building material, the environment of constructing architecture thermal comfort.In addition, also can be used for aspects such as shipping vehicle, large-scale storage tank, large-scale steel structure, articles for daily use, camouflage, aerospace thermal control coating, have huge economic benefit and social benefit.
Show that after deliberation material of the present invention has perovskite type structure, structure as shown in Figure 1.In this perovskite type structure, undersized mn ion is formed cubic(al)grating, and oxonium ion is positioned at the seamed edge center, large-sized metal ion, as lanthanum, strontium, calcium, barium etc., be positioned at the center of cubic(al)grating, and mn ion wherein has two kinds of valence states that can transform mutually:
Mn3++O2-_Mn4+
Mn4++O2-_Mn3+
When different valence state will appear in mn ion in different temperature fields, this is the major cause that this material has above-mentioned performance.Experiment showed, that this material is not attracted by magnet when invert point is above,, shows that this material has occurred by ferrimagnetism to paramagnetic transformation when invert point is following when temperature then can be attracted by magnet.
Description of drawings
Fig. 1 is the structural diagrams of the emissivity induced reversible change material of the present invention's temperature.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1
The emissivity induced reversible change material mixture ratio of temperature is:
La
2O
3 15％
CaO 10％
Mn
3O
4 70％
Na
2O，K
2O 5％
Total amount satisfies 100%
By each composition material of said ratio weighing, adopt shredder to grind, its fineness is not more than 5% in 0.080mm square hole sieve screen over-size.Pressed by powder after will grinding then is in blocks, fires 14 hours in 950 ℃ of air.After taking out cooling, through pulverizing, regrinding, compressing tablet, again in 1200 ℃ of air in firing 20 hours, furnace cooling has promptly made material of the present invention to room temperature.The emittance of the emissivity induced reversible change material of this temperature is changed to 0.66-0.86 below the 340K by the 0.90-0.92 more than the 340K, and rangeability is about 0.26, and transition temperature is about 340K, and cooling back emittance will be recovered.
Embodiment 2
The emissivity induced reversible change material mixture ratio of temperature is:
La
2O
3 5％
SrCO
3 5％
Mn
3O
4 75％
Na
2O，K
2O 15％
Total amount satisfies 100%
By each composition material of said ratio weighing, adopt shredder to grind, its fineness is not more than 3% in 0.080mm square hole sieve screen over-size.Pressed by powder after will grinding then is in blocks, fires 15 hours in 850 ℃ of air.After taking out cooling, through pulverizing, regrinding, compressing tablet, again in 1150 ℃ of air in firing 20 hours, furnace cooling has promptly made material of the present invention to room temperature.The emittance of the emissivity induced reversible change material of this temperature is changed to 0.58-0.59 below the 320K by the 0.85-0.86 more than the 320K, and rangeability is about 0.27, and transition temperature is about 320K, and cooling back emittance will be recovered.
Embodiment 3
The emissivity induced reversible change material mixture ratio of temperature is:
La
2O
3 25％
SrCO
3 10％
Mn
3O
4 50％
CaO 15％
Total amount satisfies 100%
By each composition material of said ratio weighing, adopt shredder to grind, its fineness is not more than 2% in 0.080mm square hole sieve screen over-size.Pressed by powder after will grinding then is in blocks, fires 5 hours in 1100 ℃ of air.After taking out cooling, through pulverizing, regrinding, compressing tablet, again in 1250 ℃ of air in firing 10 hours, furnace cooling has promptly made material of the present invention to room temperature.The emittance of the emissivity induced reversible change material of this temperature is changed to 0.46-0.64 below the 296K by the 0.80-0.82 more than the 296K, and rangeability is about 0.36, and transition temperature is about 296K, and cooling back emittance also can be recovered.
Embodiment 4
The emissivity induced reversible change material mixture ratio of temperature is:
La
2O
3 10％
SrCO
3 20％
Mn
3O
4 55％
Na
2O，K
2O 10％
CaO 5％
Total amount satisfies 100%
By each composition material of said ratio weighing, adopt shredder to grind, its fineness is not more than 2% in 0.080mm square hole sieve screen over-size.Pressed by powder after will grinding then is in blocks, fires 10 hours in 1100 ℃ of air.After taking out cooling, through pulverizing, regrinding, compressing tablet, again in 1200 ℃ of air in firing 15 hours, furnace cooling has promptly made material of the present invention to room temperature.The emittance of the emissivity induced reversible change material of this temperature is changed to 0.56-0.57 below the 305K by the 0.84-0.86 more than the 305K, and rangeability is about 0.30, and transition temperature is about 305K, and cooling back emittance also can be recovered.
Claims (3)
1. the emissivity induced reversible change material of temperature is characterized in that adopting La
2O
3, SrCO
3, Mn
3O
4, Na
2O, K
2O, CaO fire and form, and each composition material mass percent is: La
2O
3Be 5-25%, SrCO
3Be 0-20%, Mn
3O
4Be 50-75%, Na
2O and K
2The O sum is that 0-15%, CaO are 0-15%; This material has perovskite type structure; Its preparation method is: in above-mentioned each constituent materials ratio weighing, grind to form powder, its fineness is not more than 5% in 0.080mm square hole sieve screen over-size; Compacting was fired in 850-1100 ℃ of air 5-15 hour in flakes then; Cooling is pulverized, regrinding, and compressing tablet was fired 10-20 hour in 1150-1250 ℃ of air again.
2. the emissivity induced reversible change material of temperature according to claim 1 is characterized in that described each composition material mass percent is: La
2O
3Be 8-20%, SrCO
3Be 8-15%, Mn
3O
4Be 55-70%, Na
2O and K
2The O sum is that 0-10%, CaO are 0-10%.
3. the emissivity induced reversible change preparation methods of temperature is characterized in that taking by weighing each constituent materials: La by following mass percent
2O
3Be 5-25%, SrCO
3Be 0-20%, Mn
3O
4Be 50-75%, Na
2O and K
2The O sum is that 0-15%, CaO are 0-15%; Grind to form powder, its fineness is not more than 5% in 0.080mm square hole sieve screen over-size; Compacting was fired in 850-1100 ℃ of air 5-15 hour in flakes then; Cooling is pulverized, regrinding, and compressing tablet was fired 10-20 hour in 1150-1250 ℃ of air again; This material has perovskite type structure.
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| CNB2003101085615A CN100364923C (en) | 2003-11-13 | 2003-11-13 | Temperature induced emissivity reversibly variable material |
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|---|---|---|---|
| CNB2003101085615A CN100364923C (en) | 2003-11-13 | 2003-11-13 | Temperature induced emissivity reversibly variable material |
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| CN1544390A CN1544390A (en) | 2004-11-10 |
| CN100364923C true CN100364923C (en) | 2008-01-30 |
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|---|---|---|---|
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775271B (en) * | 2009-12-29 | 2012-06-06 | 同济大学 | Material with substantial reversible change emissivity induced by temperature under normal temperature |
| CN101768382B (en) * | 2009-12-29 | 2011-05-25 | 同济大学 | High-performance air-conditioning type building coating |
| CN102879247B (en) * | 2012-10-09 | 2014-10-08 | 神华集团有限责任公司 | Method for manufacturing to-be-measured film for infrared analysis and method for measuring Fc, Ec and Et |
| CN104819785B (en) * | 2015-04-24 | 2017-03-22 | 歌尔股份有限公司 | Camera module set-based temperature measurement method |
| CN108715711B (en) * | 2018-04-23 | 2021-05-04 | 中国人民解放军国防科技大学 | Thermochromic emissivity-changing coating and preparation method and application thereof |
| CN108424684B (en) * | 2018-04-23 | 2021-07-09 | 中国人民解放军国防科技大学 | Thermochromic emissivity-variable printing ink and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1170749A (en) * | 1996-07-12 | 1998-01-21 | 南京大学 | Perovskite-like compound as high-temperature magnetic refrigerating working medium |
| US5795670A (en) * | 1995-12-28 | 1998-08-18 | Ngk Insulators, Ltd. | Porous sintered lanthanum manganite bodies and method of manufacturing the same |
| CN1409416A (en) * | 2001-09-20 | 2003-04-09 | 北京有色金属研究总院 | Perovskite rare earth manganese oxide giant magnetic resistance material, preparing process and its use |
-
2003
- 2003-11-13 CN CNB2003101085615A patent/CN100364923C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5795670A (en) * | 1995-12-28 | 1998-08-18 | Ngk Insulators, Ltd. | Porous sintered lanthanum manganite bodies and method of manufacturing the same |
| CN1170749A (en) * | 1996-07-12 | 1998-01-21 | 南京大学 | Perovskite-like compound as high-temperature magnetic refrigerating working medium |
| CN1409416A (en) * | 2001-09-20 | 2003-04-09 | 北京有色金属研究总院 | Perovskite rare earth manganese oxide giant magnetic resistance material, preparing process and its use |
Non-Patent Citations (2)
| Title |
|---|
| La0.2Ca0.8MnO3催化剂活性相的结构和形成机理. 王秋菠等.催化学报，第19卷第2期. 1998 * |
| 磁制冷工质材料的研究进展. 陈鹏等.物理学进展，第19卷第4期. 1999 * |
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