CN102876287A - 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 preparation category of composite film material, be applicable to prepare the infrared low-emissivity mould material.
Background technology
The development experience of infrared low-emissivity material from the one-component to the matrix material, the development from the powder coating to mould material.So that infrared low-emissivity material is drawn close to nano-sized membrane, nanometer film is as a kind of novel infrared low-emissivity material along with the film industrial expansion, and the parameters such as composition that can be by regulating film, carrier density obtain lower infrared emittance.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 the thickness of its film is easy-regulating not, 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 relatively poor.
Layered double-hydroxide (LDHs) is a kind of layered inorganic functional materials of superior performance, its main body composition generally is made of the oxyhydroxide of two kinds of metals, its laminate structure is to replace the three-dimensional structure that packing arrangement forms by positively charged oxyhydroxide main body laminate and interlayer anion, the interlamellar spacing of LDHs changes with the laminate metal ion is different with the interlayer anion kind, LDHs is applied in plastic sheeting for farm use as infrared absorbing material, and 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 the distribution.LDHs is peeled off in peeling off solvent, and the positively charged LDHs nanometer sheet that obtains has the laminate metal ion and forms the characteristics such as adjustable sex change, laminate electric density and the adjustable sex change that distributes, and is the desirable primitive of constructing the static assembling film.Graphene is strangled the another nano level functional material of carbon family as richness, to be got by the graphene oxide reduction, except the electric property of excellence, 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, it is dispersed in water just forms the surface with the aqueous solution of single-layer grapheme oxide of negative charge.Therefore, the LDHs nanometer sheet of sheet structure and mono-layer graphite oxide alkene are carried out layer by layer self-assembly by electrostatic interaction can form novel laminated infrared film material, layer structure with 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, and internal structure in order, the 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 civilian preferably application prospect arranged.
Summary of the invention
Technical problem: the purpose 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 has preferably light transmission at nano level, 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 layer by layer self-assembly alternately take layered double-hydroxide LDHs nanometer sheet and mono-layer graphite oxide alkene as primitive, layer structure with LDHs nanometer sheet/mono-layer graphite oxide alkene order lamination, the number of plies is 2 ~ 40, the material thickness is 2 ~ 200nm, 25 ℃ of lower 8 ~ 14 mu m wavebands, 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 forms, 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.
Above-mentioned self-assembly lamination infrared film material preparation method is:
A) press carboxylic acid and M
2The mol ratio of metal is 5 ~ 10:1, with carboxylic acid aqueous solution and the M of 0.2 ~ 1.0mol/L
2Metal successively joins in the reactor, behind normal-temperature reaction 4 ~ 10h, at N
2Under the atmosphere, in above-mentioned reaction solution, press every gram M
2Metal adds the H of 0.5 ~ 5.0mL 30wt%
2O
2Aqueous solution chlorination reaction 0.5 ~ 1h presses M
1Metal and M
2The mol ratio of metal is 2:1, adds M again
1Metal normal temperature reaction 4 ~ 10h transfers pH to 9.5 ~ 10.5,70 ~ 90 ℃ lower hydrothermal crystallizing 48 ~ 72h with the 8mol/L inorganic base aqueous solution after the reaction, and cooling is filtered, and deionized water wash 4 ~ 6 times is pressed M
2The mol ratio of metal and deionized water is 1:1000 ~ 5000, disperses with deionized water, gets the suspension liquid of the LDHs of carboxylate radical intercalation, leaves standstill 24 ~ 48h under 20 ~ 30 ℃, gets 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, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1 in the alkyd mixed solution, room temperature immerses 0.5 ~ 1h in the alkyd mixed solution with substrate, use deionized water wash 10 ~ 15 times after taking out, add the 10mL98wt% vitriol oil by every square centimeter of substrate, again substrate is immersed 0.5 ~ 1h in the vitriol oil, spend ion-cleaning after the taking-up 10 ~ 15 times, at N
2Air drying 2 ~ 10min under the atmosphere gets the modification substrate.
C) add the LDHs nanometer sheet aqueous solution that makes in 40 ~ 100mL step a) by every square centimeter of modification substrate, modification substrate room temperature is soaked 5 ~ 15min, take out, use deionized water wash 5 ~ 10 times, at N
2Air drying 2 ~ 8min under the atmosphere gets 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 that makes in the step c) is soaked 5 ~ 15min, take out, use deionized water wash 5 ~ 10 times, at N
2Air drying 2 ~ 8min under the atmosphere, get the self-assembled film material, with the method for this self-assembled film material by step c) and step d), as carrying out 2 ~ 40 times, primitive replaces layer by layer self-assembly take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material.
Carboxylic acid described in the above-mentioned self-assembly lamination infrared film material preparation 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 ? a kind of in the 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 can be regulated, and internal structure is orderly and surfaceness is little.
Characteristics of the present invention are:
(1) LDHs of the carboxylate radical intercalation of single stage method preparation can effectively get rid of NO among traditional LDHs preparation method
3 -, Cl
-Interference Deng inorganic anion.
(2) substitute the tradition such as methane amide with water and peel off solvent, have 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) take full advantage 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 layer by layer self-assembly, and the infrared nanometer mould material of the rhythmo structure that obtains has the characteristics such as light transmission is good, infrared emittance is low.
Embodiment
Embodiment 1:
A) mol ratio by DL-LACTIC ACID and Fe powder is 8:1, the DL-LACTIC ACID aqueous solution of 0.5mol/L and Fe flour gold is belonged to successively join in the reactor, behind the normal-temperature reaction 10h, at N
2Under the atmosphere, in above-mentioned reaction solution, press the H that every gram Fe powder adds 1.2mL 30wt%
2O
2Aqueous solution chlorination reaction 0.6h is 2:1 by the mol ratio of Co powder and Fe powder, adds Co powder normal-temperature reaction 10h again, transfer pH to 9.5 with the 8mol/L NaOH aqueous solution after the reaction, 80 ℃ of lower hydrothermal crystallizing 48h, cooling is filtered, deionized water wash 4 times, mol ratio by Fe powder and deionized water is 1:1000, disperses with deionized water, gets the suspension liquid of the LDHs of DL-LACTIC ACID root intercalation, leave standstill 48h under 30 ℃, get the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of silicon wafer, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1 in the alkyd mixed solution, room temperature immerses 0.5h in the alkyd mixed solution with silicon wafer, use deionized water wash 10 times after taking out, add the 10mL 98wt% vitriol oil by every square centimeter of silicon wafer, again silicon wafer is immersed 0.5h in the vitriol oil, use deionized water wash 10 times after taking out, at N
2Air drying 2min under the atmosphere gets the modified silicon wafer.
C) add the LDHs nanometer sheet aqueous solution that makes in the 40mL step a) by every square centimeter of modified silicon wafer, modified silicon wafer room temperature is soaked 5min, take out, use deionized water wash 10 times, at N
2Air drying 8min under the atmosphere gets 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 that makes in the step c) is soaked 5min, take out, use deionized water wash 10 times, at N
2Air drying 8min under the atmosphere, get the self-assembled film material, with the method for this self-assembled film material by step c) and step d), as carrying out 5 times, primitive replaces layer by layer self-assembly take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 18nm, 25 ℃ of lower 8 ~ 14 mu m wavebands, and the infrared emittance of this material is 0.539.
Embodiment 2:
A) mol ratio by oxalic acid and Co powder is 5:1, oxalic acid aqueous solution and the Co powder of 0.2mol/L is successively joined in the reactor, behind the normal-temperature reaction 4h, at N
2Under the atmosphere, in above-mentioned reaction solution, press the H that every gram Co powder adds 0.5mL 30wt%
2O
2Aqueous solution chlorination reaction 0.8h is 2:1 by the mol ratio of Mn powder and Co powder, adds Mn powder normal-temperature reaction 4h again, transfer pH to 10 with the 8mol/L KOH aqueous solution after the reaction, 90 ℃ of lower hydrothermal crystallizing 72h, cooling is filtered, deionized water wash 6 times, mol ratio by Co powder and deionized water is 1:2500, disperses with deionized water, gets the suspension liquid of the LDHs of oxalate intercalation, leave standstill 36h under 25 ℃, get the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of quartz plate, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1 in the alkyd mixed solution, room temperature immerses 0.8h in the alkyd mixed solution with quartz plate, use deionized water wash 12 times after taking out, add the 10mL 98wt% vitriol oil by every square centimeter of quartz plate, again quartz plate is immersed 0.8h in the vitriol oil, spend ion-cleaning after the taking-up 12 times, at N
2Air drying 5min under the atmosphere gets the modification quartz plate.
C) add the LDHs nanometer sheet aqueous solution that makes in the 60mL step a) by every square centimeter of modification quartz plate, modification quartz plate room temperature is soaked 8min, take out, use deionized water wash 7 times, at N
2Air drying 3min under the atmosphere gets 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 that makes in the step c) is soaked 8min, take out, use deionized water wash 7 times, at N
2Air drying 3min under the atmosphere, get the self-assembled film material, with the method for this self-assembled film material by step c) and steps d, as carrying out 25 times, primitive replaces layer by layer self-assembly take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 103nm, 25 ℃ of lower 8 ~ 14 mu m wavebands, and the infrared emittance of this material is 0.385.
Embodiment 3:
A) mol ratio by phenylformic acid and (Co powder+Fe powder) is 10:1, and wherein the mol ratio of Co powder and Fe powder is 1:4, the phenylformic acid aqueous solution and (the Co powder+Fe powder) of 1.0mol/L is successively joined in the reactor, behind the normal-temperature reaction 8h, at N
2Under the atmosphere, in above-mentioned reaction solution, press the H that every gram adds 5.0mL 30wt%
2O
2Aqueous solution chlorination reaction 0.5h is 2:1 by the mol ratio of Mg powder and (Co powder+Fe powder) metal, adds Mg powder normal-temperature reaction 8h again, transfer pH to 10 with the 8mol/LNaOH aqueous solution after the reaction, 75 ℃ of lower hydrothermal crystallizing 60h, cooling is filtered, deionized water wash 5 times, mol ratio by (Co powder+Fe powder) and deionized water is 1:3000, disperses with deionized water, gets the suspension liquid of the LDHs of benzoate anion intercalation, leave standstill 36h under 25 ℃, get the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of silicon wafer, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1 in the alkyd mixed solution, room temperature immerses 1h in the alkyd mixed solution with silicon wafer, use deionized water wash 15 times after taking out, add the 10mL 98wt% vitriol oil by every square centimeter of silicon wafer, again silicon wafer is immersed 1h in the vitriol oil, use deionized water wash 15 times after taking out, at N
2Air drying 10min under the atmosphere gets the modified silicon wafer.
C) add the LDHs nanometer sheet aqueous solution that makes in the 100mL step a) by every square centimeter of modified silicon wafer, modified silicon wafer room temperature is soaked 11min, take out, use deionized water wash 8 times, at N
2Air drying 6min under the atmosphere gets 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 that makes in the step c) is soaked 11min, take out, use deionized water wash 8 times, at N
2Air drying 6min under the atmosphere, get the self-assembled film material, with the method for this self-assembled film material by step c) and steps d, as carrying out 30 times, primitive replaces layer by layer self-assembly take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 150nm, 25 ℃ of lower 8 ~ 14 mu m wavebands, and the infrared emittance of this material is 0.407.
Embodiment 4:
A) mol ratio by acetic acid and Co powder is 6:1, carboxylic acid aqueous solution and the Co powder of 0.8mol/L is successively joined in the reactor, behind the normal-temperature reaction 7h, at N
2Under the atmosphere, in above-mentioned reaction solution, press the H that every gram Co adds 4.2mL 30wt%
2O
2Aqueous solution chlorination reaction 0.5h, the mol ratio of pressing (Zn powder+Mn powder) and Co powder is 2:1, adds Zn powder and Mn powder normal-temperature reaction 7h again, transfer pH to 10.5 with the 8mol/L KOH aqueous solution after the reaction, 80 ℃ of lower hydrothermal crystallizing 72h, cooling is filtered, deionized water wash 4 times, mol ratio by Co powder and deionized water is 1:5000, disperses with deionized water, gets the suspension liquid of the LDHs of benzoate anion intercalation, leave standstill 24h under 20 ℃, get the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of quartz plate, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1 in the alkyd mixed solution, room temperature immerses 0.5h in the alkyd mixed solution with quartz plate, use deionized water wash 10 times after taking out, add the 10mL 98wt% vitriol oil by every square centimeter of quartz plate, again substrate is immersed 0.5h in the vitriol oil, use deionized water wash 10 times after taking out, at N
2Air drying 3min under the atmosphere gets the modification quartz plate.
C) add the LDHs nanometer sheet aqueous solution that makes in the 75mL step a) by every square centimeter of modification quartz plate, modification quartz plate room temperature is soaked 15min, take out, use deionized water wash 5 times, at N
2Air drying 4min under the atmosphere gets 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 that makes in the step c) is soaked 15min, take out, use deionized water wash 5 times, at N
2Air drying 4min under the atmosphere, get the self-assembled film material, with the method for this self-assembled film material by step c) and steps d, as carrying out 40 times, primitive replaces layer by layer self-assembly take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 200nm, 25 ℃ of lower 8 ~ 14 mu m wavebands, and the infrared emittance of this material is 0.512.
Embodiment 5:
A) mol ratio by formic acid and Fe powder is 7:1, carboxylic acid aqueous solution and the Fe powder of 0.3mol/L is successively joined in the reactor, behind the normal-temperature reaction 4h, at N
2Under the atmosphere, in above-mentioned reaction solution, press the H that every gram Fe powder adds 1.4mL 30wt%
2O
2Aqueous solution chlorination reaction 0.9h, the mol ratio of pressing (Mg powder+Co powder+Mn powder) and Fe powder is 2:1, adds (Mg powder+Co powder+Mn powder) normal-temperature reaction 4 ~ 10h again, transfer pH to 10 with the 8mol/LNaOH aqueous solution after the reaction, 82 ℃ of lower hydrothermal crystallizing 50h, cooling is filtered, deionized water wash 5 times, mol ratio by Fe powder and deionized water is 1:1500, disperses with deionized water, gets the suspension liquid of the LDHs of formate intercalation, leave standstill 40h under 28 ℃, get the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of quartz plate, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1 in the alkyd mixed solution, room temperature immerses 0.9h in the alkyd mixed solution with substrate, use deionized water wash 14 times after taking out, add the 10mL 98wt% vitriol oil by every square centimeter of quartz plate, again quartz plate is immersed 0.9h in the vitriol oil, spend ion-cleaning after the taking-up 14 times, Air drying 5min under N2 atmosphere gets the modification quartz plate.
C) add the LDHs nanometer sheet aqueous solution that makes in the 85mL step a) by every square centimeter of modification quartz plate, modification quartz plate room temperature is soaked 6min, take out, use deionized water wash 10 times, at N
2Air drying 2min under the atmosphere gets 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 that makes in the step c) is soaked 6min, take out, use deionized water wash 10 times, at N
2Air drying 2min under the atmosphere, get the self-assembled film material, with the method for this self-assembled film material by step c) and step d), as carrying out 20 times, primitive replaces layer by layer self-assembly take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 96nm, 25 ℃ of lower 8 ~ 14 mu m wavebands, 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, with the L of 0.6mol/L ?(+) ?aqueous tartaric acid solution and (Co powder+Fe powder) successively join in the reactor, behind the normal-temperature reaction 4h, at N
2Under the atmosphere, in above-mentioned reaction solution, press the H that every gram (Co powder+Fe powder) adds 3.5mL 30wt%
2O
2Aqueous solution chlorination reaction 0.6h, mol ratio by (Mg powder+Co powder+Mn powder+Zn powder) and (Co powder+Fe powder) is 2:1, add again (Mg powder+Co powder+Mn powder+Zn powder) normal-temperature reaction 10h, transfer pH to 10.5 with the 8mol/L NaOH aqueous solution after the reaction, 70 ℃ of lower hydrothermal crystallizing 72h, cooling, filter, deionized water wash 6 times, mol ratio by (Co powder+Fe powder) and deionized water is 1:4500, disperses with deionized water, gets the suspension liquid of the LDHs of L ?(+) ?tartrate anion intercalation, leave standstill 30h under 22 ℃, get the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of silicon wafer, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1 in the alkyd mixed solution, room temperature immerses 0.6h in the alkyd mixed solution with silicon wafer, use deionized water wash 13 times after taking out, add the 10mL 98wt% vitriol oil by every square centimeter of silicon wafer, again silicon wafer is immersed 0.6h in the vitriol oil, spend ion-cleaning after the taking-up 13 times, at N
2Air drying 6min under the atmosphere gets the modified silicon wafer.
C) add the LDHs nanometer sheet aqueous solution that makes in the 90mL step a) by every square centimeter of modified silicon wafer, modified silicon wafer room temperature is soaked 14min, take out, use deionized water wash 8 times, at N
2Air drying 6min under the atmosphere gets 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 that makes in the step c) is soaked 14min, take out, use deionized water wash 8 times, at N
2Air drying 6min under the atmosphere, get the self-assembled film material, with the method for this self-assembled film material by step c) and step d), as carrying out 10 times, primitive replaces layer by layer self-assembly take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 37nm, 25 ℃ of lower 8 ~ 14 mu m wavebands, and the infrared emittance of this material is 0.493.
Embodiment 7:
A) mol ratio by propionic acid and (Co powder+Fe powder) is 10:1, carboxylic acid aqueous solution and (the Co powder+Fe powder) of 1.0mol/L is successively joined in the reactor, behind the normal-temperature reaction 8h, at N
2Under the atmosphere, in above-mentioned reaction solution, press the H that every gram (Co powder+Fe powder) adds 4.8mL 30wt%
2O
2Aqueous solution chlorination reaction 0.7h, the mol ratio of pressing (Mg powder+Zn powder) and (Co powder+Fe powder) is 2:1, adds (Mg powder+Zn powder) normal-temperature reaction 8h again, transfer pH to 9.5 with the 8mol/L KOH aqueous solution after the reaction, 80 ℃ of lower hydrothermal crystallizing 55h, cooling is filtered, deionized water wash 6 times, mol ratio by (Co powder+Fe powder) and deionized water is 1:2000, disperses with deionized water, gets the suspension liquid of the LDHs of carboxylate radical intercalation, leave standstill 45h under 26 ℃, get the LDHs nanometer sheet aqueous solution.
B) add 20mL alkyd mixed solution by every square centimeter of quartz plate, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1 in the alkyd mixed solution, room temperature immerses 0.5h in the alkyd mixed solution with substrate, use deionized water wash 10 times after taking out, add the 10mL 98wt% vitriol oil by every square centimeter of quartz plate, again quartz plate is immersed 0.5h in the vitriol oil, spend ion-cleaning after the taking-up 10 times, at N
2Air drying 7min under the atmosphere gets the modification quartz plate.
C) add the LDHs nanometer sheet aqueous solution that makes in the 55mL step a) by every square centimeter of modification quartz plate, modification quartz plate room temperature is soaked 15min, take out, use deionized water wash 10 times, at N
2Air drying 8min under the atmosphere gets 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 that makes in the step c) is soaked 15min, take out, use deionized water wash 10 times, at N
2Air drying 8min under the atmosphere, get the self-assembled film material, with the method for this self-assembled film material by step c) and step d), as carrying out 35 times, primitive replaces layer by layer self-assembly take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material, this material thickness is 162nm, 25 ℃ of lower 8 ~ 14 mu m wavebands, and the infrared emittance of this material is 0.475.
Claims (4)
1. self-assembly lamination infrared film material, it is characterized in that this material is to form by layer by layer self-assembly alternately take layered double-hydroxide LDHs nanometer sheet and mono-layer graphite oxide alkene as primitive, layer structure with LDHs nanometer sheet and mono-layer graphite oxide alkene order lamination, the number of plies is 2 ~ 40, and the infrared film material is thick to be 2 ~ 200nm.
2. a kind of self-assembly lamination infrared film material according to claim 1 is characterized in that the laminate metal ion of described LDHs nanometer sheet is by M
1Metal ion and M
2Metal ion forms, 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.
3. self-assembly lamination infrared film material preparation method 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, with carboxylic acid aqueous solution and the M of 0.2 ~ 1.0mol/L
2Metal successively joins in the reactor, behind normal-temperature reaction 4 ~ 10h, at N
2Under the atmosphere, in above-mentioned reaction solution, press every gram M
2Metal adds the H of 0.5 ~ 5.0mL 30wt%
2O
2Aqueous solution chlorination reaction 0.5 ~ 1h presses M
1Metal and M
2The mol ratio of metal is 2:1, adds M again
1Metal normal temperature reaction 4 ~ 10h transfers pH to 9.5 ~ 10.5,70 ~ 90 ℃ lower hydrothermal crystallizing 48 ~ 72h with the 8mol/L inorganic base aqueous solution after the reaction, and cooling is filtered, and deionized water wash 4 ~ 6 times is pressed M
2The mol ratio of metal and deionized water is 1:1000 ~ 5000, disperses with deionized water, gets the suspension liquid of the LDHs of carboxylate radical intercalation, leaves standstill 24 ~ 48h under 20 ~ 30 ℃, gets 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, the volume ratio of methyl alcohol and 37.5wt% concentrated hydrochloric acid is 1:1 in the alkyd mixed solution, room temperature immerses 0.5 ~ 1h in the alkyd mixed solution with substrate, use deionized water wash 10 ~ 15 times after taking out, add the 10mL98wt% vitriol oil by every square centimeter of substrate, again substrate is immersed 0.5 ~ 1h in the vitriol oil, use deionized water wash 10 ~ 15 times after taking out, at N
2Air drying 2 ~ 10min under the atmosphere gets the modification substrate;
C) add the LDHs nanometer sheet aqueous solution that makes in 40 ~ 100mL step a) by every square centimeter of modification substrate, modification substrate room temperature is soaked 5 ~ 15min, take out, use deionized water wash 5 ~ 10 times, at N
2Air drying 2 ~ 8min under the atmosphere gets 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 that makes in the step c) is soaked 5 ~ 15min, take out, use deionized water wash 5 ~ 10 times, at N
2Air drying 2 ~ 8min under the atmosphere, get the self-assembled film material, with the method for this self-assembled film material by step c) and step d), as carrying out 2 ~ 40 times, primitive replaces layer by layer self-assembly take LDHs nanometer sheet and mono-layer graphite oxide alkene, obtain self-assembly lamination infrared film material.
4. a kind of self-assembly lamination infrared film material preparation method according to claim 2, it is characterized in that the 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 ? a kind of in the tartrate, described mineral alkali is NaOH or KOH.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101950593A (en) * | 2010-09-21 | 2011-01-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite material and application thereof serving as super capacitor electrode material |
| WO2011045269A1 (en) * | 2009-10-15 | 2011-04-21 | Bayer Technology Services Gmbh | Composite materials having graphene layers and production and use thereof |
| CN102142296A (en) * | 2010-05-28 | 2011-08-03 | 南京理工大学 | Preparation method of graphene-loaded nanometre cobalt hydroxide (Co(OH)2) composite material |
| CN102509634A (en) * | 2011-10-31 | 2012-06-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene-based flexible multilayer composite film and preparing method thereof |
-
2012
- 2012-10-17 CN CN201210395414.XA patent/CN102876287B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011045269A1 (en) * | 2009-10-15 | 2011-04-21 | Bayer Technology Services Gmbh | Composite materials having graphene layers and production and use thereof |
| CN102142296A (en) * | 2010-05-28 | 2011-08-03 | 南京理工大学 | Preparation method of graphene-loaded nanometre cobalt hydroxide (Co(OH)2) composite material |
| CN101950593A (en) * | 2010-09-21 | 2011-01-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite material and application thereof serving as super capacitor electrode material |
| CN102509634A (en) * | 2011-10-31 | 2012-06-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene-based flexible multilayer composite film and preparing method thereof |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103552988A (en) * | 2013-09-30 | 2014-02-05 | 东南大学 | Layered double hydroxide based composite material with fiber hierarchical structure and preparation method thereof |
| CN105056931A (en) * | 2015-08-28 | 2015-11-18 | 齐鲁工业大学 | Zinc magnesium indium composite oxide with near-infrared light catalytic activity, and preparation method and application thereof |
| CN105056931B (en) * | 2015-08-28 | 2017-03-08 | 齐鲁工业大学 | A kind of have zinc-magnesium indium composite oxides of near infrared light catalysis activity and its preparation method and application |
| US10737302B2 (en) | 2015-12-16 | 2020-08-11 | Ecolab Usa Inc. | Peroxyformic acid compositions for membrane filtration cleaning |
| US11117172B2 (en) | 2015-12-16 | 2021-09-14 | Ecolab Usa Inc. | Peroxyformic acid compositions for membrane filtration cleaning |
| US11241009B2 (en) | 2016-04-15 | 2022-02-08 | Ecolab Usa Inc. | Performic acid biofilm prevention for industrial CO2 scrubbers |
| US11026420B2 (en) | 2016-12-15 | 2021-06-08 | Ecolab Usa Inc. | Peroxyformic acid compositions for membrane filtration cleaning in energy services |
| US11647747B2 (en) | 2016-12-15 | 2023-05-16 | Ecolab Usa Inc. | Peroxyformic acid compositions for membrane filtration cleaning in energy services |
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