CN102876287B - Self assembly laminated infrared film material and preparation method of self assembly laminated infrared film material - Google Patents
Self assembly laminated infrared film material and preparation method of self assembly laminated infrared film material Download PDFInfo
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Abstract
The invention aims at providing a self assembly laminated infrared film material and a preparation method of the self assembly laminated infrared film material. The material is formed by using infrared absorption material LDHs (layered double hydroxides) nanometer sheets and single-layer oxidized graphene as basic elements through alternate layer-by-layer self assembly, the layer structure with the LDHs nanometer sheet/single-layer oxidized graphene sequence laminated layer is adopted, the layer number is 2 to 40, the material film thickness is 2 to 200nm, the wave band is 8 to 14mum at 25 DEG C, and the infrared emissivity of the material is 0.300 to 0.600. Layer plate metal ions of the LDHs nanometer sheets consist of metal ions M1 and metal ions M2, wherein the mol ratio of the metal ions M1 to the metal ions M2 is 2:1, the metal ions M1 are one kind of ions or the combination of many kinds of ions from Mg<2+>, Co<2+>, Mn<2+> and Zn<2+>, and the metal ions M2 are one kind of ions or the combination of two kinds of ions from Fe<3+> and Co<3+>.
Description
Technical field
The present invention relates to a kind of self-assembly lamination infrared film material and preparation method thereof, belong to the category of preparing of composite film material, be applicable to prepare infrared low-emissivity mould material.
Background technology
The development experience of infrared low-emissivity material from one-component to matrix material, the development from powder coating to mould material.Draw close to nano-sized membrane along with film industrial expansion makes infrared low-emissivity material, nanometer film, as a kind of novel infrared low-emissivity material, can obtain lower infrared emittance by the parameter such as composition, carrier density that regulates film.Chinese patent CN201210060305.2 discloses a kind of fluorinated polyimide infrared low-emissivity thin-film material, although it has lower infrared emittance at 8 ~ 14 μ m, but not easy-regulating of the thickness of its film, and owing to being the film of polymer formation, the surfaceness of material is larger, and internal structure is relatively unordered and light transmission is poor.
Layered double-hydroxide (LDHs) is a kind of layered inorganic functional materials of superior performance, its main body composition is generally made up of the oxyhydroxide of two kinds of metals, its laminate structure is to replace by positively charged oxyhydroxide main body laminate and interlayer anion the three-dimensional structure that packing arrangement forms, the interlamellar spacing of LDHs changes with laminate metal ion is different with interlayer anion kind, LDHs is applied in plastic sheeting for farm use as infrared absorbing material, its excellent infrared absorption effect is mainly by kind and the ratio of LDHs body layer plate metal ion, due to main body laminate electric density and distribution.LDHs is peeled off peeling off in solvent, and the positively charged LDHs nanometer sheet obtaining has laminate metal ion and forms adjustable sex change, laminate electric density and the features such as adjustable sex change that distribute, and is the desirable primitive of constructing static assembling film.Graphene is as the another nano level functional material of Fu Le carbon family, to be got by graphene oxide reduction, except excellent electric property, its mechanical property and Single Walled Carbon Nanotube are suitable, its quality is light, and thermal conductivity is good and surface-area is large, and the carrier density that it is large and carrier mobility are conducive to the reduction of its infrared emittance, abundant oxygen-containing functional group is contained on the surface of graphene oxide, is dispersed in water and just forms the aqueous solution of single-layer grapheme oxide of surface with negative charge.Therefore, the LDHs nanometer sheet of sheet structure and mono-layer graphite oxide alkene are carried out to self-assembly layer by layer by electrostatic interaction and can form novel laminated infrared film material, there is the layer structure of LDHs nanometer sheet/mono-layer graphite oxide alkene order lamination, this has just given the optical property of its uniqueness, and composition and the thickness of this mould material are controlled, internal structure in order, film surfaceness is little and light transmission good.The invention provides a kind of self-assembly lamination infrared film material, this material is a kind of rising infrared stealth novel material, and its research and application have potential economic benefit and social benefit, to military and civilianly have a good application prospect.
Summary of the invention
Technical problem: the object of this invention is to provide a kind of self-assembly lamination infrared film material and preparation method thereof.The Nomenclature Composition and Structure of Complexes of this material is controlled, and internal structure is orderly and surfaceness is little, and the thickness of film, at nano level, has good light transmission, can be used for infrared low-emissivity material.
Technical scheme: a kind of self-assembly lamination infrared film material of the present invention, it is characterized in that this material is to form by self-assembly layer by layer alternately take layered double-hydroxide LDHs nanometer sheet and mono-layer graphite oxide alkene as primitive, there is the layer structure of LDHs nanometer sheet/mono-layer graphite oxide alkene order lamination, the number of plies is 2 ~ 40, material thickness is 2 ~ 200nm, 8 ~ 14 mu m wavebands at 25 ℃, the infrared emittance of this material is 0.300 ~ 0.600.The laminate metal ion of LDHs nanometer sheet is by M
1metal ion and M
2metal ion composition, wherein M
1metal ion and M
2the mol ratio of metal ion is 2:1, M
1metal ion is Mg
2+, Co
2+, Mn
2+, Zn
2+in one or more combination, M
2metal ion is Fe
3+, Co
3+in a kind of or both combination.
The preparation method of above-mentioned self-assembly lamination infrared film material is:
A) press carboxylic acid and M
2the mol ratio of metal is 5 ~ 10:1, by the carboxylic acid aqueous solution of 0.2 ~ 1.0mol/L and M
2metal successively joins in reactor, after normal-temperature reaction 4 ~ 10h, at N
2under atmosphere, in above-mentioned reaction solution, press every gram of M
2metal adds the H of 0.5 ~ 5.0mL 30wt%
2o
2aqueous solution chlorination reaction 0.5 ~ 1h, by M
1metal and M
2the mol ratio of metal is 2:1, then adds M
1metal normal temperature reaction 4 ~ 10h, adjusts pH to 9.5 ~ 10.5 with 8mol/L inorganic base aqueous solution after reaction, and hydrothermal crystallizing 48 ~ 72h at 70 ~ 90 ℃ is cooling, filters, and deionized water wash 4 ~ 6 times, by M
2the mol ratio of metal and deionized water is 1:1000 ~ 5000, disperses with deionized water, obtains the suspension liquid of the LDHs of carboxylate radical intercalation, leaves standstill 24 ~ 48h at 20 ~ 30 ℃, obtains the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of substrate, substrate is silicon wafer or quartz plate, in alkyd mixed solution, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1, substrate is immersed 0.5 ~ 1h in alkyd mixed solution by room temperature, after taking out, use deionized water wash 10 ~ 15 times, add the 10mL98wt% vitriol oil by every square centimeter of substrate, then substrate is immersed to 0.5 ~ 1h in the vitriol oil, after taking-up, spend ion-cleaning 10 ~ 15 times, at N
2air drying 2 ~ 10min under atmosphere, obtains modification substrate.
C) add by every square centimeter of modification substrate the LDHs nanometer sheet aqueous solution making in 40 ~ 100mL step a), modification substrate room temperature is soaked to 5 ~ 15min, take out, use deionized water wash 5 ~ 10 times, at N
2air drying 2 ~ 8min under atmosphere, obtains LDHs assembling substrate.
D) add 40 ~ 100mL, 0.5 ~ 1mg/mL aqueous solution of single-layer grapheme oxide by every square centimeter of LDHs assembling substrate, the LDHs assembling substrate room temperature making in step c) is soaked to 5 ~ 15min, take out, use deionized water wash 5 ~ 10 times, at N
2air drying 2 ~ 8min under atmosphere, obtain self-assembled film material, this self-assembled film material, by the method for step c) and step d), is replaced to self-assembly layer by layer take LDHs nanometer sheet and mono-layer graphite oxide alkene as primitive carries out 2 ~ 40 times, obtain self-assembly lamination infrared film material.
The carboxylic acid of the preparation process of above-mentioned self-assembly lamination infrared film material described in a) be formic acid, acetic acid, propionic acid, oxalic acid, DL-LACTIC ACID, Pfansteihl, phenylformic acid, Whitfield's ointment, L ?(+) ?tartrate, D ?() ?tartrate, DL ?one in tartrate, described mineral alkali is NaOH or KOH.
Beneficial effect: the invention provides a kind of self-assembly lamination infrared film material and preparation method thereof, the Nomenclature Composition and Structure of Complexes of this material is adjustable, and internal structure is orderly and surfaceness is little.
Feature of the present invention is:
(1) LDHs of the carboxylate radical intercalation that prepared by single stage method, can effectively get rid of NO in traditional LDHs preparation method
3 -, Cl
-deng the interference of inorganic anion.
(2) substitute the tradition such as methane amide with water and peel off solvent, there is the advantages such as inexpensive, safety and environmental protection, and it is good to peel off the LDHs nanometer sheet aqueous stability of formation.
(3) make full use of the performances such as the large and carrier mobility of excellent electricity, mechanics, heat conduction, carrier density that mono-layer graphite oxide alkene has is large, itself and LDHs nanometer sheet are replaced to self-assembly layer by layer, and the infrared nanometer mould material of the rhythmo structure obtaining has the features such as light transmission is good, infrared emittance is low.
Embodiment
Embodiment 1:
A) be 8:1 by the mol ratio of DL-LACTIC ACID and Fe powder, the DL-LACTIC ACID aqueous solution of 0.5mol/L and Fe flour gold genus successively joined in reactor, after normal-temperature reaction 10h, at N
2under atmosphere, to the H that adds 1.2mL 30wt% in above-mentioned reaction solution by every gram of Fe powder
2o
2aqueous solution chlorination reaction 0.6h, is 2:1 by the mol ratio of Co powder and Fe powder, then adds Co powder normal-temperature reaction 10h, after reaction, adjust pH to 9.5 with the 8mol/L NaOH aqueous solution, at 80 ℃, hydrothermal crystallizing 48h, cooling, filters, deionized water wash 4 times, be 1:1000 by the mol ratio of Fe powder and deionized water, with deionized water dispersion, obtain the suspension liquid of the LDHs of DL-LACTIC ACID root intercalation, at 30 ℃, leave standstill 48h, obtain the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of silicon wafer, in alkyd mixed solution, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1, silicon wafer is immersed 0.5h in alkyd mixed solution by room temperature, after taking out, use deionized water wash 10 times, add the 10mL 98wt% vitriol oil by every square centimeter of silicon wafer, again silicon wafer is immersed to 0.5h in the vitriol oil, after taking out, use deionized water wash 10 times, at N
2air drying 2min under atmosphere, obtains modified silicon wafer.
C) add by every square centimeter of modified silicon wafer the LDHs nanometer sheet aqueous solution making in 40mL step a), modified silicon wafer room temperature is soaked to 5min, take out, use deionized water wash 10 times, at N
2air drying 8min under atmosphere, obtains LDHs assembling silicon wafer.
D) add 40mL 1mg/mL aqueous solution of single-layer grapheme oxide by every square centimeter of LDHs assembling silicon wafer, the LDHs assembling silicon wafer room temperature making in step c) is soaked to 5min, take out, use deionized water wash 10 times, at N
2air drying 8min under atmosphere, obtain self-assembled film material, this self-assembled film material is pressed to the method for step c) and step d), as carrying out 5 times, primitive replaces self-assembly layer by layer take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 18nm, 8 ~ 14 mu m wavebands at 25 ℃, and the infrared emittance of this material is 0.539.
Embodiment 2:
A) be 5:1 by the mol ratio of oxalic acid and Co powder, the oxalic acid aqueous solution of 0.2mol/L and Co powder successively joined in reactor, after normal-temperature reaction 4h, at N
2under atmosphere, to the H that adds 0.5mL 30wt% in above-mentioned reaction solution by every gram of Co powder
2o
2aqueous solution chlorination reaction 0.8h, is 2:1 by the mol ratio of Mn powder and Co powder, then adds Mn powder normal-temperature reaction 4h, after reaction, adjust pH to 10 with the 8mol/L KOH aqueous solution, at 90 ℃, hydrothermal crystallizing 72h, cooling, filters, deionized water wash 6 times, be 1:2500 by the mol ratio of Co powder and deionized water, with deionized water dispersion, obtain the suspension liquid of the LDHs of oxalate intercalation, at 25 ℃, leave standstill 36h, obtain the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of quartz plate, in alkyd mixed solution, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1, quartz plate is immersed 0.8h in alkyd mixed solution by room temperature, after taking out, use deionized water wash 12 times, add the 10mL 98wt% vitriol oil by every square centimeter of quartz plate, again quartz plate is immersed to 0.8h in the vitriol oil, after taking-up, spend ion-cleaning 12 times, at N
2air drying 5min under atmosphere, obtains modification quartz plate.
C) add by every square centimeter of modification quartz plate the LDHs nanometer sheet aqueous solution making in 60mL step a), modification quartz plate room temperature is soaked to 8min, take out, use deionized water wash 7 times, at N
2air drying 3min under atmosphere, obtains LDHs assembling quartz plate.
D) add 60mL 0.7mg/mL aqueous solution of single-layer grapheme oxide by every square centimeter of LDHs assembling quartz plate, the LDHs assembling quartz plate room temperature making in step c) is soaked to 8min, take out, use deionized water wash 7 times, at N
2air drying 3min under atmosphere, obtain self-assembled film material, this self-assembled film material is pressed to the method for step c) and steps d, as carrying out 25 times, primitive replaces self-assembly layer by layer take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 103nm, 8 ~ 14 mu m wavebands at 25 ℃, and the infrared emittance of this material is 0.385.
Embodiment 3:
A) be 10:1 by phenylformic acid with the mol ratio of (Co powder+Fe powder), wherein the mol ratio of Co powder and Fe powder is 1:4, the phenylformic acid aqueous solution of 1.0mol/L and (Co powder+Fe powder) is successively joined in reactor, after normal-temperature reaction 8h, at N
2under atmosphere, in above-mentioned reaction solution by every gram of H that adds 5.0mL 30wt%
2o
2aqueous solution chlorination reaction 0.5h, is 2:1 by Mg powder with the mol ratio of (Co powder+Fe powder) metal, then adds Mg powder normal-temperature reaction 8h, after reaction, adjust pH to 10 with the 8mol/LNaOH aqueous solution, at 75 ℃, hydrothermal crystallizing 60h, cooling, filters, deionized water wash 5 times, be 1:3000 by (Co powder+Fe powder) with the mol ratio of deionized water, with deionized water dispersion, obtain the suspension liquid of the LDHs of benzoate anion intercalation, at 25 ℃, leave standstill 36h, obtain the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of silicon wafer, in alkyd mixed solution, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1, silicon wafer is immersed 1h in alkyd mixed solution by room temperature, after taking out, use deionized water wash 15 times, add the 10mL 98wt% vitriol oil by every square centimeter of silicon wafer, again silicon wafer is immersed to 1h in the vitriol oil, after taking out, use deionized water wash 15 times, at N
2air drying 10min under atmosphere, obtains modified silicon wafer.
C) add by every square centimeter of modified silicon wafer the LDHs nanometer sheet aqueous solution making in 100mL step a), modified silicon wafer room temperature is soaked to 11min, take out, use deionized water wash 8 times, at N
2air drying 6min under atmosphere, obtains LDHs assembling silicon wafer.
D) add 100mL 0.8mg/mL aqueous solution of single-layer grapheme oxide by every square centimeter of LDHs assembling silicon wafer, the LDHs assembling silicon wafer room temperature making in step c) is soaked to 11min, take out, use deionized water wash 8 times, at N
2air drying 6min under atmosphere, obtain self-assembled film material, this self-assembled film material is pressed to the method for step c) and steps d, as carrying out 30 times, primitive replaces self-assembly layer by layer take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 150nm, 8 ~ 14 mu m wavebands at 25 ℃, and the infrared emittance of this material is 0.407.
Embodiment 4:
A) be 6:1 by the mol ratio of acetic acid and Co powder, the carboxylic acid aqueous solution of 0.8mol/L and Co powder successively joined in reactor, after normal-temperature reaction 7h, at N
2under atmosphere, to the H that adds 4.2mL 30wt% in above-mentioned reaction solution by every gram of Co
2o
2aqueous solution chlorination reaction 0.5h, is 2:1 by (Zn powder+Mn powder) with the mol ratio of Co powder, then adds Zn powder and Mn powder normal-temperature reaction 7h, after reaction, adjust pH to 10.5 with the 8mol/L KOH aqueous solution, at 80 ℃, hydrothermal crystallizing 72h, cooling, filters, deionized water wash 4 times, be 1:5000 by the mol ratio of Co powder and deionized water, with deionized water dispersion, obtain the suspension liquid of the LDHs of benzoate anion intercalation, at 20 ℃, leave standstill 24h, obtain the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of quartz plate, in alkyd mixed solution, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1, quartz plate is immersed 0.5h in alkyd mixed solution by room temperature, after taking out, use deionized water wash 10 times, add the 10mL 98wt% vitriol oil by every square centimeter of quartz plate, again substrate is immersed to 0.5h in the vitriol oil, after taking out, use deionized water wash 10 times, at N
2air drying 3min under atmosphere, obtains modification quartz plate.
C) add by every square centimeter of modification quartz plate the LDHs nanometer sheet aqueous solution making in 75mL step a), modification quartz plate room temperature is soaked to 15min, take out, use deionized water wash 5 times, at N
2air drying 4min under atmosphere, obtains LDHs assembling quartz plate.
D) add 75mL 0.5mg/mL aqueous solution of single-layer grapheme oxide by every square centimeter of LDHs assembling quartz plate, the LDHs assembling quartz plate room temperature making in step c) is soaked to 15min, take out, use deionized water wash 5 times, at N
2air drying 4min under atmosphere, obtain self-assembled film material, this self-assembled film material is pressed to the method for step c) and steps d, as carrying out 40 times, primitive replaces self-assembly layer by layer take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 200nm, 8 ~ 14 mu m wavebands at 25 ℃, and the infrared emittance of this material is 0.512.
Embodiment 5:
A) be 7:1 by the mol ratio of formic acid and Fe powder, the carboxylic acid aqueous solution of 0.3mol/L and Fe powder successively joined in reactor, after normal-temperature reaction 4h, at N
2under atmosphere, to the H that adds 1.4mL 30wt% in above-mentioned reaction solution by every gram of Fe powder
2o
2aqueous solution chlorination reaction 0.9h, is 2:1 by (Mg powder+Co powder+Mn powder) with the mol ratio of Fe powder, then adds (Mg powder+Co powder+Mn powder) normal-temperature reaction 4 ~ 10h, after reaction, adjust pH to 10 with the 8mol/LNaOH aqueous solution, at 82 ℃, hydrothermal crystallizing 50h, cooling, filters, deionized water wash 5 times, be 1:1500 by the mol ratio of Fe powder and deionized water, with deionized water dispersion, obtain the suspension liquid of the LDHs of formate intercalation, at 28 ℃, leave standstill 40h, obtain the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of quartz plate, in alkyd mixed solution, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1, substrate is immersed 0.9h in alkyd mixed solution by room temperature, after taking out, use deionized water wash 14 times, add the 10mL 98wt% vitriol oil by every square centimeter of quartz plate, then quartz plate is immersed to 0.9h in the vitriol oil, after taking-up, spend ion-cleaning 14 times, Air drying 5min under N2 atmosphere, obtains modification quartz plate.
C) add by every square centimeter of modification quartz plate the LDHs nanometer sheet aqueous solution making in 85mL step a), modification quartz plate room temperature is soaked to 6min, take out, use deionized water wash 10 times, at N
2air drying 2min under atmosphere, obtains LDHs assembling quartz plate.
D) add 85mL 0.9mg/mL aqueous solution of single-layer grapheme oxide by every square centimeter of LDHs assembling quartz plate, the LDHs assembling quartz plate room temperature making in step c) is soaked to 6min, take out, use deionized water wash 10 times, at N
2air drying 2min under atmosphere, obtain self-assembled film material, this self-assembled film material is pressed to the method for step c) and step d), as carrying out 20 times, primitive replaces self-assembly layer by layer take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 96nm, 8 ~ 14 mu m wavebands at 25 ℃, and the infrared emittance of this material is 0.396.
Embodiment 6:
A) by L ?(+) ?the mol ratio of tartrate and (Co powder+Fe powder) be 9:1, by the L of 0.6mol/L ?(+) ?aqueous tartaric acid solution and (Co powder+Fe powder) successively join in reactor, after normal-temperature reaction 4h, at N
2under atmosphere, to the H that adds 3.5mL 30wt% in above-mentioned reaction solution by every gram (Co powder+Fe powder)
2o
2aqueous solution chlorination reaction 0.6h, be 2:1 by (Mg powder+Co powder+Mn powder+Zn powder) with the mol ratio of (Co powder+Fe powder), add again (Mg powder+Co powder+Mn powder+Zn powder) normal-temperature reaction 10h, after reaction, adjust pH to 10.5 with the 8mol/L NaOH aqueous solution, hydrothermal crystallizing 72h at 70 ℃, cooling, filter, deionized water wash 6 times, be 1:4500 by (Co powder+Fe powder) with the mol ratio of deionized water, with deionized water dispersion, obtain the suspension liquid of the LDHs of L ?(+) ?tartrate anion intercalation, at 22 ℃, leave standstill 30h, obtain the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of silicon wafer, in alkyd mixed solution, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1, silicon wafer is immersed 0.6h in alkyd mixed solution by room temperature, after taking out, use deionized water wash 13 times, add the 10mL 98wt% vitriol oil by every square centimeter of silicon wafer, again silicon wafer is immersed to 0.6h in the vitriol oil, after taking-up, spend ion-cleaning 13 times, at N
2air drying 6min under atmosphere, obtains modified silicon wafer.
C) add by every square centimeter of modified silicon wafer the LDHs nanometer sheet aqueous solution making in 90mL step a), modified silicon wafer room temperature is soaked to 14min, take out, use deionized water wash 8 times, at N
2air drying 6min under atmosphere, obtains LDHs assembling silicon wafer.
D) add 90mL 0.6 ~ 1mg/mL aqueous solution of single-layer grapheme oxide by every square centimeter of LDHs assembling silicon wafer, the LDHs assembling silicon wafer room temperature making in step c) is soaked to 14min, take out, use deionized water wash 8 times, at N
2air drying 6min under atmosphere, obtain self-assembled film material, this self-assembled film material is pressed to the method for step c) and step d), as carrying out 10 times, primitive replaces self-assembly layer by layer take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 37nm, 8 ~ 14 mu m wavebands at 25 ℃, and the infrared emittance of this material is 0.493.
Embodiment 7:
A) be 10:1 by propionic acid with the mol ratio of (Co powder+Fe powder), the carboxylic acid aqueous solution of 1.0mol/L and (Co powder+Fe powder) successively joined in reactor, after normal-temperature reaction 8h, at N
2under atmosphere, to the H that adds 4.8mL 30wt% in above-mentioned reaction solution by every gram (Co powder+Fe powder)
2o
2aqueous solution chlorination reaction 0.7h, is 2:1 by (Mg powder+Zn powder) with the mol ratio of (Co powder+Fe powder), then adds (Mg powder+Zn powder) normal-temperature reaction 8h, after reaction, adjust pH to 9.5 with the 8mol/L KOH aqueous solution, at 80 ℃, hydrothermal crystallizing 55h, cooling, filters, deionized water wash 6 times, be 1:2000 by (Co powder+Fe powder) with the mol ratio of deionized water, with deionized water dispersion, obtain the suspension liquid of the LDHs of carboxylate radical intercalation, at 26 ℃, leave standstill 45h, obtain the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of quartz plate, in alkyd mixed solution, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1, substrate is immersed 0.5h in alkyd mixed solution by room temperature, after taking out, use deionized water wash 10 times, add the 10mL 98wt% vitriol oil by every square centimeter of quartz plate, again quartz plate is immersed to 0.5h in the vitriol oil, after taking-up, spend ion-cleaning 10 times, at N
2air drying 7min under atmosphere, obtains modification quartz plate.
C) add by every square centimeter of modification quartz plate the LDHs nanometer sheet aqueous solution making in 55mL step a), modification quartz plate room temperature is soaked to 15min, take out, use deionized water wash 10 times, at N
2air drying 8min under atmosphere, obtains LDHs assembling quartz plate.
D) add 55mL 0.7mg/mL aqueous solution of single-layer grapheme oxide by every square centimeter of LDHs assembling quartz plate, the LDHs assembling quartz plate room temperature making in step c) is soaked to 15min, take out, use deionized water wash 10 times, at N
2air drying 8min under atmosphere, obtain self-assembled film material, this self-assembled film material is pressed to the method for step c) and step d), as carrying out 35 times, primitive replaces self-assembly layer by layer take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 162nm, 8 ~ 14 mu m wavebands at 25 ℃, and the infrared emittance of this material is 0.475.
Claims (2)
1. a self-assembly lamination infrared film material, it is characterized in that this material is to form by self-assembly layer by layer alternately take layered double-hydroxide LDHs nanometer sheet and mono-layer graphite oxide alkene as primitive, there is the layer structure of LDHs nanometer sheet and mono-layer graphite oxide alkene order lamination, the number of plies is 2～40, and infrared film material is thick is 2～200nm;
The laminate metal ion of described LDHs nanometer sheet is by M
1metal ion and M
2metal ion composition, wherein M
1metal ion and M
2the mol ratio of metal ion is 2:1, M
1metal ion is Mg
2+, Co
2+, Mn
2+, Zn
2+in one or more combination, M
2metal ion is Fe
3+, Co
3+in a kind of or both combination.
2. a preparation method for self-assembly lamination infrared film material as claimed in claim 1, is characterized in that its preparation method is:
A) press carboxylic acid and M
2the mol ratio of metal is 5～10:1, by the carboxylic acid aqueous solution of 0.2～1.0mol/L and M
2metal successively joins in reactor, after normal-temperature reaction 4～10h, at N
2under atmosphere, in above-mentioned reaction solution, press every gram of M
2metal adds the H of 0.5～5.0mL30wt%
2o
2aqueous solution chlorination reaction 0.5～1h, by M
1metal and M
2the mol ratio of metal is 2:1, then adds M
1metal normal temperature reaction 4～10h, adjusts pH to 9.5～10.5 with 8mol/L inorganic base aqueous solution after reaction, and hydrothermal crystallizing 48～72h at 70～90 ℃ is cooling, filters, and deionized water wash 4～6 times, by M
2the mol ratio of metal and deionized water is 1:1000～5000, disperses with deionized water, obtains the suspension liquid of the LDHs of carboxylate radical intercalation, leaves standstill 24～48h at 20～30 ℃, obtains the LDHs nanometer sheet aqueous solution;
B) add 20mL alkyd mixed solution by every square centimeter of substrate, substrate is silicon wafer or quartz plate, in alkyd mixed solution, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1, substrate is immersed 0.5～1h in alkyd mixed solution by room temperature, after taking out, use deionized water wash 10～15 times, add the 10mL98wt% vitriol oil by every square centimeter of substrate, then substrate is immersed to 0.5～1h in the vitriol oil, after taking out, use deionized water wash 10～15 times, at N
2air drying 2～10min under atmosphere, obtains modification substrate;
C) add by every square centimeter of modification substrate the LDHs nanometer sheet aqueous solution making in 40～100mL step a), modification substrate room temperature is soaked to 5～15min, take out, use deionized water wash 5～10 times, at N
2air drying 2～8min under atmosphere, obtains LDHs assembling substrate;
D) add 40～100mL0.5～1mg/mL aqueous solution of single-layer grapheme oxide by every square centimeter of LDHs assembling substrate, the LDHs assembling substrate room temperature making in step c) is soaked to 5～15min, take out, use deionized water wash 5～10 times, at N
2air drying 2～8min under atmosphere, obtain self-assembled film material, this self-assembled film material, by the method for step c) and step d), is replaced to self-assembly layer by layer take LDHs nanometer sheet and mono-layer graphite oxide alkene as primitive carries out 2～40 times, obtain self-assembly lamination infrared film material;
Carboxylic acid described in this preparation method's step a) be formic acid, acetic acid, propionic acid, oxalic acid, DL-LACTIC ACID, Pfansteihl, phenylformic acid, Whitfield's ointment, L ?(+) ?tartrate, D ?() ?tartrate, DL ?one in tartrate, described mineral alkali is NaOH or KOH.
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