CN102040878A - Infrared reflexive aggregate and preparation method thereof - Google Patents
Infrared reflexive aggregate and preparation method thereof Download PDFInfo
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- CN102040878A CN102040878A CN2010105135488A CN201010513548A CN102040878A CN 102040878 A CN102040878 A CN 102040878A CN 2010105135488 A CN2010105135488 A CN 2010105135488A CN 201010513548 A CN201010513548 A CN 201010513548A CN 102040878 A CN102040878 A CN 102040878A
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- infrared reflective
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000010445 mica Substances 0.000 claims abstract description 47
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 47
- 239000011787 zinc oxide Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 35
- 238000002203 pretreatment Methods 0.000 claims description 29
- 229960001296 zinc oxide Drugs 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- -1 metal oxide compound Chemical class 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000003672 processing method Methods 0.000 claims description 11
- 238000003980 solgel method Methods 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011247 coating layer Substances 0.000 claims description 9
- 238000007669 thermal treatment Methods 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229940044658 gallium nitrate Drugs 0.000 claims description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 47
- 239000011248 coating agent Substances 0.000 abstract description 46
- 238000005253 cladding Methods 0.000 abstract 2
- 238000009500 colour coating Methods 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 238000002310 reflectometry Methods 0.000 description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 13
- 239000000945 filler Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000000470 constituent Substances 0.000 description 10
- 239000000049 pigment Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000009413 insulation Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052811 halogen oxide Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses an infrared reflexive aggregate. In the infrared reflexive aggregate, pretreated mica is taken as a substrate, and a clading layer with the thickness of between 0.5 and 5 micrometers is coated on the outer surface of the substrate; the thickness of the mica is between 0.5 and 5 micrometers, and the grain diameter is between 0.5 and 120 micrometers; and the cladding layer is doped zinc oxide, and the doped zinc oxide consists of ZnO serving as a main metal oxide and doping metal in a molar ratio of 0.1 to 10 percent. The invention also provides a preparation method of the infrared reflexive aggregate simultaneously, which comprises the following steps of: 1) pretreating the mica; and 2) coating the cladding layer outside the outer surface of the pretreated mica serving as the substrate. In the aggregate, the excellent infrared reflexive performance of the doped zinc oxide serving as a film is reserved, the aggregate is used for preparing a transparent or semitransparent infrared reflexive coating film, and thus, the problem of the infrared reflection of deep color coatings is solved to a certain extent.
Description
Technical field
The present invention relates to a kind of infrared reflective aggregate and preparation method thereof; Relate in particular to the mica sheet is that substrate, doping zinc-oxide are infrared external reflection aggregate of coating layer and preparation method thereof.
Background technology
Sun power is the essential condition of human survival and life, but the intensive radiation has brought inconvenience also for human life.Being radiated the solar energy on the earth surface, approximately is per second 750W/m
2Under irradiation of sunlight, heat constantly accumulates in by the radiating body surface, and its surface temperature is constantly raise.Buildings roof and the rising of exterior wall surface temperature can cause that surrounding environment and indoor temperature are too high, and the comfort level of reduced circumstances increases the power consumption of air conditioner refrigerating.
At present, building energy consumption has accounted for 20～30% of total energy consumption; Wherein, the thermal losses of body of wall and roofing has accounted for 15% of building energy consumption.In area cold in winter and hot in summer, if take to intercept the problem that the mode of insulation may exist be, during the broiling summer, the office building internal calorific power of this area is excessive, adopt the isolation-type insulation may cause pocketed heat to leave, even outside heat is intercepted, pocketed heat also can cause the increase of refrigeration duty.And adopt reflection type thermal insulation coating that body of wall and roofing are carried out the effective means that heat insulation processing is reduction body of wall and roofing energy consumption.
Existing reflection-type coating mainly is to be the whitewash of reflection aggregate with the Rutile type Titanium Dioxide, although can reach reflecting effect preferably at visible light and near-infrared region, still has stronger absorption in the far infrared region of 8～13.5 μ m; Therefore, reflected solar heat, to the reflect radiation heat deficiency of low-temp radiating body although film; So filming by radiant exchange still to absorb the radiant heat of ground low-temp radiating body.
In addition, utilize Rutile type Titanium Dioxide can't satisfy the individual demand of user merely to color as the reflection aggregate.Although use light color have the pigment of high index the time, still can obtain higher near-infrared reflection effect, when using dark pigment, tend to run into the problem of near-infrared region absorption.The method that is used to solve dark color at present and is coating infrared reflective problem has two kinds:
(1) utilizes the pigment that better reflecting effect is arranged in the near-infrared region, use color theory and be mixed with various dark pigments.This method can obtain good effect at the application of paints initial stage, but owing to do not consider the tolerance difference of the coating of different colours for environment, thereby in use, film and can depart from the color that originally set.
(2) select the pigment more weak, and will film to be coated on and apply in the substrate that has than the coating of high infrared reflection ability infrared ray absorption.The prerequisite of this method is that dark pigment must be a kind of material more weak to the near-infrared region gamma absorption, the limitation that this has just caused material to select.
In solar heat reflection type coating, to contributive scattering and the reflection that comprises filler to light of the overall reflective of filming, and the reflectivity of general oxide filler own is not high, therefore, what work mainly is the scattering process of filler, and for metal, the reflectivity of its flaky material is very high, and scattering process is just no longer so obvious.
When ZnO is mixed, ZnO has just had the character of metalloid.For metalloid, there is a stagnation point that makes that optical property is undergone mutation, when lambda1-wavelength during greater than this stagnation point, incident light just can't penetrate and form reflection.And this stagnation point is directly proportional with two/first power of carrier concentration, therefore, improves the system carrier concentration, can make this stagnation point generation blue shift.When stagnation point was blue shifted to the near-infrared region, the doping zinc-oxide film had just had the good reflection potential to the ir radiation that comprises near-infrared region and far infrared region radiation.
When doping ZnO exists as film, its infrared external reflection is very effective, but reduction along with yardstick, may will occur unusual, it is exactly metal that a good example is arranged, for visible light, when the yardstick of metallic particles (as silver) is reduced to a certain critical size, reflect visible light effectively just, and become black.So, when metal is used as paint filler, often be made into flakey.
People such as Alain Demourgues increased the phenomenon that reduces with regard to once having described doping zinc-oxide powder infrared reflective with doping in Investigation of Ga Substitution in ZnO Powder andOpto-Electronic Properties one literary composition.CN 1951985A utilizes the conductive nano oxide powder to prepare a kind of transparent heat-insulating film, but its function as thermal isolation film only is the infrared absorbance that relies on the conductive nano oxide powder, infrared rays is converted into thermal energy storage within filming, therefore, film when acting on glass when this, tend to make glass to become antisolar glass, under the sunlight at high noon in summer, its surface temperature may reach more than 100 ℃, even a spot of water droplet also can cause the glass explosion.
And when the form with transparent film exists, the doping zinc-oxide infrared reflectance increases with the increase of doping, Ma Quanbao etc. have done detailed description to this phenomenon in " preparation and the characteristic research of transparent highly-conductive near-infrared reflection ZnO:Ga film " literary composition.Therefore, be used for reflection type thermal insulation coating, then keep its good properties of infrared reflection that is coated with membrane stage and just seem very important for doping zinc-oxide being made filler.
In the application of reality, the preparation method of doping zinc-oxide film has following several, comprise magnetron sputtering, chemical Vapor deposition process (CVD), Pintsch process spraying, sol-gel method etc., but in actually operating, exist many problems in these methods, comprise that equipment cost is too high, the enforcement personnel need pass through Special Training, filming condition harshness etc.
Mix with base-material if conductive zinc oxide is made filler, the application of paint coating process directly is coated on the surface that need carry out heat insulation modification, has not only solved actual operational issue, can also be applied to improve the heat insulation of old building.In addition, for filming itself, the conductive zinc oxide filler can increase the electroconductibility of filming, thereby suppresses the accumulation of static electricity of film coated surface, thereby can suppress because the dust absorption of the film coated surface that electrostatic attraction causes.
CN1077729 narrated a kind of to the infrared rays ray have the conducting pigment of high reflection ability, its principal feature be with the stannic oxide of doping halogen and/or titanium oxide as coating layer, be substrate with the flaky material; But its shortcoming is also clearly: the first, and the reserves of occurring in nature Sn are few, and the cost that uses it to prepare conductive layer is very high; The second, its described method wayward (in preparation process, needing to keep stablizing of suspension PH) for preparing pigment, and material preparation cycle long (preparation process need reach 10～14 hours time) with NaOH.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of infrared external reflection aggregate, and the good properties of infrared reflection when this aggregate has kept doping zinc-oxide as film can be used for preparing transparent or semitransparent infrared external reflection and films; Thereby solved dark color to a certain extent is the infrared external reflection difficult problem of coating.
In order to solve the problems of the technologies described above, the invention provides a kind of infrared reflective aggregate, be substrate with mica after the pre-treatment, at the outside surface of substrate the coating layer that thickness is 0.5～5 μ m is set; Micaceous thickness (mean thickness) is that 0.5～5 μ m, particle diameter (median size) are 0.5～120 μ m; Coating layer is a doping zinc-oxide, and this doping zinc-oxide is made up of ZnO and doping metals as the base metal oxide compound, and the mol ratio of doping metals and ZnO is 0.1%～10%.
Improvement as infrared reflective aggregate of the present invention: doped metallic elements is Ga or Al.
The present invention also provides above-mentioned infrared reflective aggregate processing method simultaneously, may further comprise the steps successively:
1), micaceous pre-treatment:
Selecting thickness (mean thickness) for use is that 0.5～5 μ m, particle diameter (median size) are the mica of 0.5～120 μ m; The acid solution I of mica and mass concentration 1%～20% was mixed in 40～90 ℃ water bath with thermostatic control 30～50 minutes, after filtration and washing (after the filtration, be neutral), must wash mica afterwards gained residue washing to gained washings; Described mica with the mass/volume ratio of acid solution I is: every 100g mica/500～2000ml acid solution I;
The acid solution II that adds 500ml～2000ml mass concentration 5%～20% after above-mentioned washing in the mica mixed 30～50 minutes in 40～90 ℃ of waters bath with thermostatic control, through suction filtration, washing (is decompress filter, then be neutral with gained residue washing to gained washings) and dry, must pre-treatment after mica; Mica with the mass/volume ratio of acid solution II is: every 100g mica/500～2000ml acid solution;
2), be substrate with mica after the pre-treatment, at the outside surface of substrate the coating layer that thickness is 0.5～5 μ m is set; Select following any one method for use:
Method A, homogeneous precipitation method:
1., the inorganic salt of zinc, the inorganic salt that contain doping metals, precipitation agent are mixed with respectively concentration is 0.1～1,0.03～1, the aqueous solution of 0.2～1mol/L, then with above-mentioned 3 kinds of aqueous solution successively according to 0.5～10: 0.05～5: 0.5～10 volume ratio is mixed, and dilute with water is 1～2 times again; Get mixed solution;
2., after 1. step adds above-mentioned pre-treatment in the mixed solution of gained mica, be warming up to 70～90 ℃ of hydrolysis reaction 1～5h under continuing to stir; With hydrolysis reaction product suction filtration, washing (2～5 times) and the drying of gained, get powder; The micaceous amount ratio is after mixed solution and the pre-treatment: mica after 100～1000ml mixed solution/5～50g pre-treatment;
3., with step 2. the powder of gained in 200～1000 ℃ of thermal treatment 1～12h, the infrared reflective aggregate;
Method B, sol-gel method:
1., the inorganic salt with zinc, the inorganic salt that contain doping metals, solvent I and thanomin mix, mixing solutions; Mixing solutions is warming up to 40～70 ℃, stirs 1h～10h, obtain homogeneous colloidal solution;
The mol ratio that contains the inorganic salt of the inorganic salt of doping metals and zinc is 0.1%～15%; The inorganic salt of zinc and the mol ratio of thanomin are 1: 0.5～2;
2., deionized water that mica, also dropping (slowly dripping) process solvent II are diluted after the adding pre-treatment in homogeneous colloidal solution; Up to forming gel;
Micaceous amount ratio after homogeneous colloidal solution and the pre-treatment (volume/mass ratio) is 100～1000ml/5～50g; Through the deionized water of solvent II dilution be solvent II with deionized water according to 1～20: 1 volume ratio is mixed and is then got;
3., with step 2. the gel of gained in 40～100 ℃ of down dry 4～12h, and in 200～1000 ℃ of thermal treatment 1～12h, the infrared reflective aggregate.
Improvement as infrared reflective aggregate processing method of the present invention: the inorganic salt that contain doping metals are gallium fluoride, gallium chloride, gallium nitrate, gallium sulfate, aluminum fluoride, aluminum chloride, aluminum nitrate, Tai-Ace S 150 or Neutral ammonium fluoride.
Be described as follows: nitrogen element in the nitric acid and the element sulphur in the sulfuric acid can be removed by thermal treatment in sol-gel method, and can remove by washing or heat treatment process in homogeneous precipitation method; In addition, the ionic radius of the ratio of ionic radii oxygen of chlorine is a lot of greatly, so chlorine can not form effective doping.
As infrared reflective aggregate processing further improvements in methods of the present invention:
Step 2) in the homogeneous precipitation method of method A: precipitation agent is urea or methane amide;
Step 2) in the sol-gel method of method B: solvent I and solvent II are ethylene glycol monomethyl ether or Virahol.
As infrared reflective aggregate processing further improvements in methods of the present invention: in the pre-treatment of step 1) micaceous, acid solution I and acid solution II are: sulphuric acid soln, hydrochloric acid soln, phosphoric acid solution or salpeter solution.
As infrared reflective aggregate processing further improvements in methods of the present invention: step 2) in the sol-gel method of method B, the consumption of solvent I is: the concentration (Zn of inorganic salt in mixing solutions that makes zinc
2+Concentration) be 0.5M～1.0M, M is mol/L.
The objective of the invention is to develop a kind of novel sheet infrared external reflection aggregate and preparation method thereof, thereby can utilize the properties of infrared reflection of doping zinc-oxide film better, the good properties of infrared reflection when keeping doping zinc-oxide as film.Also can solve simultaneously the infrared absorption problem of powder conductive zinc oxide.
Infrared reflective aggregate of the present invention all has reflecting effect preferably in far infrared and near-infrared region.During actual the use, infrared reflective aggregate of the present invention and varnish or polymer emulsion according to solids constituent weight ratio 10: 90～50: 50, are coated on the substrate, can form transparent or semitransparent filming with infrared external reflection ability; If the coating that adds infrared reflective aggregate of the present invention is coated on the original outer wall coating of old building as finish paint, just can play the effect that improves old building exterior wall heat-proof quality, when described coating reaches certain thickness, original infrared external reflection ability of filming will not influence the whole infrared external reflection ability of system.
The invention has the beneficial effects as follows and prepared a kind of novel infrared reflective aggregate that can be used for reflection type thermal insulation coating, adjusting by sizes of substrate and coating thickness, when being used for transparent base-material and being coated on substrate surface, can reach 70%～90% infrared external reflection effect.In addition, doped zinc oxide coated conductivity, also make this aggregate is used to film after, film coated surface is not easy to take place accumulation of static electricity, thereby has improved the contamination resistance of filming.
In sum, the present invention aims to provide a kind of coating aggregate and preparation method thereof that utilizes the excellent properties of infrared reflection of doping zinc-oxide film, utilize homogeneous coprecipitation method or sol-gel method that the doping zinc-oxide film is coated on the mica substrate surface, thereby the properties of infrared reflection of the excellence that has been had when having kept doping zinc-oxide as film, itself and varnish or polymer emulsion are mixed and made into transparent or semitransparent filming, being coated on dark is on filming, can solve the infrared external reflection difficult problem that dark system films, having widened dark color is the scope of selecting for use of coating pigment.
Embodiment
Embodiment 1, a kind of infrared reflective aggregate processing method, carry out following steps successively:
One, micaceous pre-treatment
1), selecting mean thickness for use is that 0.6 μ m, median size are the mica of 45 μ m; Take by weighing the above-mentioned mica of 50g and add in the there-necked flask, in there-necked flask, add the hydrochloric acid soln (mass concentration 5%) of 1000ml again; There-necked flask being placed water-bath (80 ℃ of constant temperature), mixed 40 minutes, after the filtration, with the filter residue deionized water wash, is neutral until washings; Must wash the back mica;
2), the phosphoric acid solution of mica and 1000ml (mass concentration 5%) is put into another there-necked flask after above-mentioned washing, this there-necked flask is placed water-bath (65 ℃ of constant temperature), stirred 40 minutes, decompress filter, with the filter residue deionized water wash, to washings is neutral, is dried to constant weight in 60 ℃ thereafter; Mica after the pre-treatment.
Two, homogeneous precipitation method prepares doping zinc-oxide coating mica filler:
1), with Zn (NO
3)
26H
2O, AlCl
36H
2O, CO (NH
2)
2Be mixed with concentration respectively and be 0.1,0.05, the aqueous solution of 0.2mol/L, above-mentioned 3 kinds of aqueous solution are mixed according to 10: 1: 5 volume ratio successively, thereafter again with one times of deionized water dilution (promptly adding 1 volume deionized water doubly); Get mixed solution;
2), the mixed solution of 500ml is poured in the there-necked flask, and in there-necked flask, add mica after the pre-treatment of 5g; Be warming up to 75 ℃ of hydrolysis reaction 1.5h under continuing to stir.With the hydrolysis reaction product decompress filter of gained, washing three times, until there is not precipitation (that is, utilizing silver nitrate solution to check in the washings whether C1 is arranged) with silver nitrate solution check washings; Be dried to constant weight under 80 ℃; Get powder;
3), with step 2) powder of gained is in 500 ℃ of following thermal treatment 1h, the infrared reflective aggregate.
After measured: the thickness of the doping zinc-oxide coating layer of this infrared reflective aggregate is 1 μ m.The mol ratio of doped metallic elements Al and ZnO is 0.042.
Test 1-1, the infrared reflective aggregate of embodiment 1 gained and the solids constituent of acrylic ester emulsion are mixed according to the weight ratio of 20: 80 (that is, this 80 correspondence is the solids component of acrylic ester emulsion); Being coated with and making thickness is filming of 200 μ m.Measure the reflectivity of coating according to GB/T2680-1994, the result is: in the near-infrared region and the reflectivity of far infrared region can reach 70%, visible light transmittance rate can reach 60%.
Testing 1-2, being used for dark color is coating:
With the iron oxide black be filler and acrylic ester emulsion solids constituent according to 20: 80 (promptly, this 80 correspondence be the solids component of acrylic ester emulsion) weight ratio mix, and be coated with and make the black coating film that thickness is 200 μ m, measure reflectivity according to GB/T2680-1994, its result is: its reflectivity only is 4% in the near-infrared region; Thereafter will test 1-1 gained coating and be coated on the above-mentioned black coating film, drying and forming-film under room temperature, second layer coating thickness are 300 μ m, measure reflectivity according to GB/T2680-1994, and the result is: its reflectivity can reach 50% in the near-infrared region.
At this moment, because experiment 1-1 gained coating is transparent, so finding of naked eye still is a black.
Embodiment 2, a kind of infrared reflective aggregate processing method, carry out following steps successively:
One, micaceous pre-treatment:
With embodiment 1.
Two, homogeneous precipitation method prepares doping zinc-oxide coating mica infrared external reflection aggregate:
1), with ZnSO
4, Al
2(SO
4)
3, methane amide is mixed with respectively that concentration is 0.2,0.035, the aqueous solution of 0.25mol/L, above-mentioned 3 kinds of aqueous solution are mixed according to 10: 0.75: 1.25 volume ratio, thereafter again with one times of deionized water dilution; Get mixed solution;
2), the mixed solution of 250ml is poured in the there-necked flask, and in there-necked flask, add mica after the pre-treatment of 5g; Be warming up to 80 ℃ of hydrolysis reaction 2.5h under continuing to stir.With the hydrolysis reaction product decompress filter of gained, washing three times, drying; Get powder;
3), with step 2) powder of gained is in 600 ℃ of following thermal treatment 4h, the infrared reflective aggregate.
On inspection, the doping zinc-oxide coating thickness of this infrared reflective aggregate is 1 μ m.The mol ratio of doped metallic elements Al and ZnO is 0.015.
Experiment 2-1, the infrared reflective aggregate of embodiment 2 gained is mixed according to 20: 80 weight ratio with the solids constituent of acrylic ester emulsion; Being coated with and making thickness is filming of 200 μ m.Measure the reflectivity of coating according to GB/T2680-1994, the result is: above-mentioned filming detected, and the result is: in the near-infrared region and the reflectivity of far infrared region can reach 60%, visible light transmittance rate can reach 70%.
Testing 2-2, being used for dark color is coating:
With the barba hispanica is that filler mixes according to 20: 80 weight ratio with the solids constituent of acrylic ester emulsion, being coated on and making thickness on the white substrate is that the blueness of 200 μ m is filmed, measure reflectivity according to GB/T2680-1994, its result is: its reflectivity only is 25% in the near-infrared region.Thereafter will test 2-1 gained coating and be coated on above-mentioned blueness films, drying and forming-film under room temperature, second layer coating thickness are 300 μ m, measure reflectivity according to GB/T2680-1994, and the result is: its reflectivity can reach 50% in the near-infrared region.
At this moment, because experiment 2-1 gained coating is transparent, so finding of naked eye still is blue.
Embodiment 3, a kind of infrared reflective aggregate processing method, carry out following steps successively:
One, micaceous pre-treatment:
With embodiment 1.
Two, the Prepared by Sol Gel Method doping zinc-oxide coats mica infrared external reflection aggregate
1), gets 0.2molZn (CH
3COO)
22H
2O and 0.004molAlCl
36H
2O places there-necked flask.Get the ethylene glycol monomethyl ether of 256.37g and the thanomin of 12.22g (MEA) and add in the there-necked flask, mix, contain 0.75M Zn thereby be mixed with
2+The ionic mixing solutions.1h is stirred in warming while stirring to 60 ℃, obtains homogeneous AZO colloidal solution.
2), get above-mentioned 250ml homogeneous AZO colloidal solution, add mica after the 12g pre-treatment, and slowly drip deionized water through the ethylene glycol monomethyl ether dilution (ethylene glycol monomethyl ether is mixed according to 19: 1 volume ratio with deionized water and get); Up to forming gel;
3), with step 2) gel of gained is in 60 ℃ of dry 5h down, and in retort furnace 500 ℃ of thermal treatment 1h, the infrared reflective aggregate.
Through surveying, the doping zinc-oxide coating thickness of this infrared external reflection aggregate is 1 μ m.The mol ratio of doped metallic elements Al and ZnO is 0.018.
Experiment 3-1, the infrared reflective aggregate of embodiment 3 gained is mixed according to 20: 80 weight ratio with the solids constituent of acrylic ester emulsion; Being coated with and making thickness is filming of 200 μ m.Measure the reflectivity of coating according to GB/T2680-1994, the result is: in the near-infrared region and the reflectivity of far infrared region can reach 75%, visible light transmittance rate can reach 50%.
Testing 3-2, being used for dark color is coating:
With the iron oxide black is that filler mixes according to 20: 80 weight ratio with the solids constituent of acrylic ester emulsion, and makes the black coating film that thickness is 200 μ m, measures reflectivity according to GB/T2680-1994, and its result is: its reflectivity only is 4% in the near-infrared region.Thereafter will test 3-1 gained coating and be coated on the above-mentioned black coating film, drying and forming-film under room temperature, second layer coating thickness are 300 μ m, measure reflectivity according to GB/T2680-1994, and the result is: its reflectivity can reach 40% in the near-infrared region.
At this moment, because experiment 3-1 gained coating is transparent, so finding of naked eye still is a black.
Embodiment 4, a kind of infrared reflective aggregate processing method, carry out following steps successively:
One, micaceous pre-treatment:
With embodiment 1.
Two, the Prepared by Sol Gel Method doping zinc-oxide coats mica infrared external reflection aggregate
1), gets 0.2mol Zn (CH
3COO)
22H
2O and 0.03molAl
2(SO
4)
3, place there-necked flask.Get the ethylene glycol monomethyl ether of 262.03g and the thanomin of 9.76g (MEA) and add in the there-necked flask, mix, contain 0.6MZn thereby be mixed with
2+The ionic mixing solutions.5h is stirred in warming while stirring to 50 ℃, can obtain homogeneous AZO colloidal solution.
2), get above-mentioned 250ml homogeneous AZO colloidal solution, add mica after the 9g pre-treatment, and slowly drip deionized water after isopropanol (Virahol is mixed according to 14: 1 volume ratio with deionized water and get); Up to forming gel;
3), with step 2) gel of gained is in 60 ℃ of dry 5h down, and in retort furnace 600 ℃ of thermal treatment 2h, infrared sexual reflex aggregate.
Through surveying, the doping zinc-oxide coating thickness of this infrared external reflection aggregate is 1 μ m.The mol ratio of doped metallic elements Al and ZnO is 0.026.
Experiment 4-1, the infrared reflective aggregate of embodiment 4 gained is mixed according to 20: 80 weight ratio with the solids constituent of acrylic ester emulsion; Being coated with and making thickness is filming of 200 μ m.Measure the reflectivity of coating according to GB/T2680-1994, the result is: in the near-infrared region and the reflectivity of far infrared region can reach 80%, visible light transmittance rate can reach 60%.
Testing 4-2, being used for dark color is coating:
With the barba hispanica is that filler mixes according to 20: 80 weight ratio with the solids constituent of acrylic ester emulsion, being coated on and making thickness on the white substrate is that the blueness of 200 μ m is filmed, measure reflectivity according to GB/T2680-1994, its result is: its reflectivity only is 25% in the near-infrared region; Thereafter will test 4-1 gained coating and be coated on above-mentioned blueness films, drying and forming-film under room temperature, second layer coating thickness are 300 μ m, measure reflectivity according to GB/T2680-1994, and the result is: its reflectivity can reach 60% in the near-infrared region.
At this moment, because experiment 4-1 gained coating is transparent, so finding of naked eye still is blue.
Comparative Examples 1-1:
Select for use median size be the rutile titania powder of 1 μ m as the reflection aggregate, and make at 30: 70 with weight ratio with the solids constituent of acrylic ester emulsion and to film.Visible light of filming and near-infrared region reflectivity can reach 70～90%, have covered substrate fully but film, therefore can't be as transparent red external reflectance application of paints.Although, in that to be suitable for particle diameter littler (during＜200nm) titanium oxide powder, can reach transparent purpose, but because the restriction of particle diameter and best scattering wavelength relationship, the rutile titania powder of small particle size is used to film then can't the usable reflection near-infrared radiation, and its near-infrared region reflectivity only is 30%.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (7)
1. infrared reflective aggregate, it is characterized in that: with mica after the pre-treatment is substrate, at the outside surface of substrate the coating layer that thickness is 0.5～5 μ m is set; Described micaceous thickness is that 0.5～5 μ m, particle diameter are 0.5～120 μ m; Described coating layer is a doping zinc-oxide, and described doping zinc-oxide is made up of ZnO and doping metals as the base metal oxide compound, and the mol ratio of described doping metals and ZnO is 0.1%～10%.
2. infrared reflective aggregate according to claim 1 is characterized in that: described doped metallic elements is Ga or Al.
3. infrared reflective aggregate processing method as claimed in claim 1 or 2 is characterized in that may further comprise the steps successively:
1), micaceous pre-treatment:
Selecting thickness for use is that 0.5～5 μ m, particle diameter are the mica of 0.5～120 μ m; The acid solution I of described mica and mass concentration 1%～20% was mixed in 40～90 ℃ water bath with thermostatic control 30～50 minutes, after filtration and the washing, must wash the back mica; Described mica with the mass/volume ratio of acid solution I is: every 100g mica/500～2000ml acid solution I;
The acid solution II that adds 500～2000ml mass concentration 5%～20% after above-mentioned washing in the mica mixed 30～50 minutes in 40～90 ℃ of waters bath with thermostatic control, through suction filtration, washing and drying, mica after the pre-treatment; Described mica with the mass/volume ratio of acid solution II is: every 100g mica/500～2000ml acid solution;
2), be substrate with mica after the pre-treatment, at the outside surface of substrate the coating layer that thickness is 0.5～5 μ m is set; Select following any one method for use:
Method A, homogeneous precipitation method:
1., the inorganic salt of zinc, the inorganic salt that contain doping metals, precipitation agent are mixed with respectively concentration is 0.1～1,0.03～1, the aqueous solution of 0.2～1mol/L, then with above-mentioned 3 kinds of aqueous solution successively according to 0.5～10: 0.05～5: 0.5～10 volume ratio is mixed, 1～2 times of redilution; Get mixed solution;
2., after 1. step adds described pre-treatment in the mixed solution of gained mica, continue to stir down and be warming up to 70～90 ℃ of hydrolysis reaction 1～5h, with hydrolysis reaction product suction filtration, washing and the drying of gained, must powder; The micaceous amount ratio is after described mixed solution and the pre-treatment: mica after 100～1000ml mixed solution/5～50g pre-treatment;
3., with step 2. the powder of gained in 200～1000 ℃ of thermal treatment 1～12h, the infrared reflective aggregate;
Method B, sol-gel method:
1., the inorganic salt with zinc, the inorganic salt that contain doping metals, solvent I and thanomin mix, mixing solutions; Described mixing solutions is warming up to 40～70 ℃, stirs 1h～10h, obtain homogeneous colloidal solution; The mol ratio that contains the inorganic salt of the inorganic salt of doping metals and described zinc is 0.1%～15%; The inorganic salt of described zinc and the mol ratio of thanomin are 1: 0.5～2;
2., the deionized water that mica, also dropping process solvent II are diluted after the adding pre-treatment in described homogeneous colloidal solution; Up to forming gel;
The micaceous amount ratio is 100～1000ml/5～50g after described homogeneous colloidal solution and the pre-treatment; Described deionized water through solvent II dilution be solvent II with deionized water according to 1～20: 1 volume ratio is mixed and is got;
3., with step 2. the gel of gained in 40～100 ℃ of down dry 4～12h, and in 200～1000 ℃ of thermal treatment 1～12h, the infrared reflective aggregate.
4. infrared reflective aggregate processing method according to claim 3 is characterized in that: the inorganic salt that contain doping metals are gallium fluoride, gallium chloride, gallium nitrate, gallium sulfate, aluminum fluoride, aluminum chloride, aluminum nitrate, Tai-Ace S 150 or Neutral ammonium fluoride.
5. infrared reflective aggregate processing method according to claim 4 is characterized in that:
Described step 2) in the homogeneous precipitation method of method A: described precipitation agent is urea or methane amide;
Described step 2) in the sol-gel method of method B: described solvent I and solvent II are ethylene glycol monomethyl ether or Virahol.
6. infrared reflective aggregate processing method according to claim 5 is characterized in that: in the pre-treatment of described step 1) micaceous, described acid solution I and acid solution II are: sulphuric acid soln, hydrochloric acid soln, phosphoric acid solution or salpeter solution.
7. infrared reflective aggregate processing method according to claim 6 is characterized in that: described step 2) in the sol-gel method of method B, the consumption of described solvent I is: making the concentration of inorganic salt in mixing solutions of zinc is 0.5M～1.0M.
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| CN102651432A (en) * | 2012-05-17 | 2012-08-29 | 上海大学 | Method for preparing thin film type LED |
| CN103540171A (en) * | 2013-10-11 | 2014-01-29 | 南京理工大学 | Preparation method of single-coating cobalt titanate green/mica pearlescent composite pigment |
| CN103788717A (en) * | 2014-01-18 | 2014-05-14 | 南京理工大学 | Composite oxide coated mica pearled composite pigment and preparation method thereof |
| CN103788718A (en) * | 2014-01-18 | 2014-05-14 | 南京理工大学 | Coated mica pearlescent compound paint doped with composite oxide and preparation thereof |
| CN103788719A (en) * | 2014-01-18 | 2014-05-14 | 南京理工大学 | Preparation method of single-coating cobalt chromite green coating mica pearlescent compound pigment |
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| CN110347012A (en) * | 2019-06-26 | 2019-10-18 | 深圳市华星光电技术有限公司 | A kind of mask plate and preparation method thereof |
| CN110564183A (en) * | 2019-08-22 | 2019-12-13 | 魏军刚 | graphene-coated mica material and preparation method and application thereof |
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