CN110982299B - Pigment system imitating spectral characteristics of natural vegetation and preparation method - Google Patents
Pigment system imitating spectral characteristics of natural vegetation and preparation method Download PDFInfo
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Abstract
The invention provides a pigment system imitating the spectral characteristics of natural vegetation and a preparation method thereof, wherein the method comprises the following steps: the layered double-hydroxyl metal hydroxide is used as a matrix, the layered plate of the layered double-hydroxyl metal hydroxide is rich in hydroxyl, and the interlayer gap is rich in crystal water and is used for simulating the spectral characteristics of the near-infrared band of water in natural vegetation cells; the colored layered double hydroxide is formed by inserting organic pigment negative charge groups between the layers of the layered double hydroxide, and the spectral characteristics of the colored layered double hydroxide in the visible light band are adjusted by adjusting the combination type and the combination proportion of the inserted organic pigment negative charge groups. The colored layered double hydroxide prepared by the method has high matching degree with the reflection spectrum curve of natural vegetation in the visible light-near infrared band range.
Description
Technical Field
The invention belongs to the field of functional coating materials, and particularly relates to a pigment system imitating spectral characteristics of natural vegetation and a preparation method thereof.
Background
The hyperspectral remote sensing technology realizes synchronous imaging of the same object in a continuous spectrum interval and simultaneously obtains data information of space dimension and spectrum dimension of the detected object. Any object has radiation, absorption, reflection and transmission of different degrees to electromagnetic waves to form unique spectral characteristics, and a spectral curve is a direct basis for distinguishing, identifying and analyzing substances. The hyperspectral detector can accurately reflect the characteristic spectrum signal of the detected object, so that a complete spectrum curve with high resolution ratio about the detected object is extracted, and the target can be easily identified in a natural background in military operations. In order to avoid hyperspectral remote sensing detection, the spectral characteristics of the surface of a detected military target need to be adjusted to be consistent with the surrounding background as much as possible.
The main working interval of the hyperspectral remote sensing technology is the 300-2500 nm waveband of an electromagnetic spectrum, and for military ground combat, vegetation is the most widely applied combat background and has a unique spectrum in the 400-2500 nm waveband, so that a spectrum material simulating the vegetation in the waveband is paid attention to by students. In recent years, a great number of beneficial attempts are made by a plurality of researchers at home and abroad, certain research progress is achieved, but a large gap exists between the practical requirements of hyperspectral camouflage/stealth. For example, the visible light spectral characteristics consistent with natural vegetation pigments can be simulated by using the metal sodium salt derivatives of chlorophyll, but the natural pigments are extremely easy to photolyze, and the spectral characteristics cannot be maintained for a long time; inspired by bionics, Li Cheng et al in south China aviation in Cr2O3The green coating is doped with a large amount of organic/inorganic high-water-content fillers such as water-absorbing cellulose and kaolin, or the water content of the coating is improved by using high-water-absorbing organic resin, so that the near infrared spectrum characteristic similar to that of natural vegetation can be prepared, but the water retention capacity of the coating is weak, and the coating is difficult to be used in a dry and high-temperature environment. On the other hand, in order to take mechanical and physical and chemical properties into consideration, the total content of various pigments and fillers in the coating cannot exceed the critical volume concentration (CPVC), and the lower content of the pigments and fillers weakens the spectrum adjusting capability of the coating. In addition, the spectral properties of various pigments and fillers can interfere with each other, which brings great difficulty to the overall spectral design of visible light-near infrared band. Therefore, a new pigment system having the typical spectral characteristics of visible light and near infrared of natural vegetation is needed to be found and used as a main functional material for regulating and controlling the spectral performance of the hyperspectral stealth coating.
Disclosure of Invention
In order to overcome the problems, the invention provides a natural vegetation imitated spectral characteristic pigment system and a preparation method thereof, and the obtained natural vegetation imitated spectral characteristic pigment system can have visible light and near-infrared typical spectral characteristics of natural vegetation and can meet the requirement of developing a hyperspectral stealth coating material.
The invention provides a preparation method of a pigment system imitating spectral characteristics of natural vegetation, which comprises the following steps:
the layered double hydroxide is adopted as a matrix, wherein a laminate of the layered double hydroxide is rich in hydroxyl, and interlayer gaps are rich in crystal water and are used for simulating the spectral characteristics of near-infrared bands of water in natural vegetation cells;
and replacing anions between the laminated dihydroxy metal hydroxide matrix layers with negative charge groups of organic pigments, so as to insert the negative charge groups of the organic pigments between the laminated dihydroxy metal hydroxide matrix layers to form the colored laminated dihydroxy metal hydroxide, wherein the spectral characteristics of the colored laminated dihydroxy metal hydroxide in a visible light band are regulated and controlled by adjusting the combination type and the combination proportion of the inserted negative charge groups of the organic pigments.
Preferably, the step of forming the coloured layered double hydroxide comprises:
step 1: mixing metal salt corresponding to divalent cation and metal salt corresponding to trivalent cation to prepare solution A, wherein the combination of the divalent cation and the trivalent cation is Mg-Al or Zn-Al, and the molar ratio of the divalent cation to the trivalent cation is 2: 1-4: 1;
step 2: dissolving an organic pigment in an organic solvent to prepare an organic pigment solution, slowly pouring the organic pigment solution into the solution A, and stirring, wherein the addition amount of the organic pigment accounts for 1-4% of the total mass of the metal salt corresponding to the divalent cation and the metal salt corresponding to the trivalent cation;
and step 3: adding an alkaline solution into the mixed solution of the solution A and the organic pigment solution until the pH value is 8-10, and continuously introducing N2Is stirred for a certain time to react to form a layered double hydroxide matrix, and meanwhile, the negative charge group of the organic pigment replaces anions between the layers of the layered double hydroxide matrix to form the colored layered double hydroxide；
And 4, step 4: pouring the colored layered double hydroxide solution into a reaction kettle, putting the reaction kettle into an oven, heating and reacting for a period of time at the temperature of 80-180 ℃, and crystallizing the colored layered double hydroxide solution in the reaction kettle to obtain a colored layered double hydroxide crystal;
and 5: and after cooling, pouring out the supernatant, and washing, centrifuging, filtering and drying the bottom precipitate to obtain the colored layered dihydroxy metal hydroxide powder.
Preferably, the organic pigment comprises organic blue and organic yellow, the molar ratio of the organic blue to the organic yellow is 1: 5-1: 15, and the matching degree of the reflection spectrum curve of the prepared colored layered double-hydroxy metal hydroxide and the green vegetation in the visible light-near infrared band range is higher than 96%.
Preferably, the organic pigment comprises any one or more of organic blue, organic yellow, organic red and organic green, and the matching degree of the prepared colored layered double hydroxide and various natural vegetation in the reflection spectrum curve in the visible-near infrared band range is improved by adjusting the combination type and the combination proportion of the organic pigment.
The invention provides a pigment system imitating the spectral characteristics of natural vegetation, which is a colored layered double-hydroxy metal hydroxide prepared by adopting the method, wherein the colored layered double-hydroxy metal hydroxide is formed by replacing partial anions in the layered double-hydroxy metal hydroxide with negative charge groups of organic pigments;
the colored layered double-hydroxide metal hydroxide is of a layered structure, the layered structure of the colored layered double-hydroxide metal hydroxide is formed by sharing brucite octahedrons, the layers are associated through hydrogen bonds, the laminate is rich in hydroxyl, the interlayer gaps are rich in crystal water, and the crystal water is connected with the metal hydroxide, interlayer anions and organic pigment negative charge groups through the hydrogen bonds.
Preferably, the combination of the divalent cation and the trivalent cation is Mg-Al or Zn-Al; the molar ratio of the divalent cations to the trivalent cations is 2: 1-4: 1; the addition amount of the organic pigment accounts for 1% -4% of the total mass of the metal salt corresponding to the divalent cation and the metal salt corresponding to the trivalent cation, the organic pigment comprises organic blue and organic yellow, the molar ratio of the organic blue to the organic yellow is 1: 5-1: 15, the pH value of a reaction solution system is 8-10, and the temperature of the hydrothermal reaction is 80-180 ℃.
Preferably, the combination of the divalent cation and the trivalent cation is Mg-Al or Zn-Al; the molar ratio of the divalent cations to the trivalent cations is 2: 1-4: 1; the addition amount of the organic pigment accounts for 1-4% of the total mass of the metal salt corresponding to the divalent cation and the metal salt corresponding to the trivalent cation, the organic pigment comprises any one or combination of organic blue, organic yellow, organic red and organic green, the pH value of the reaction solution system is 8-10, and the temperature of the hydrothermal reaction is 80-180 ℃.
Preferably, the matching degree of the spectrum characteristic pigment system of the imitated natural vegetation and the reflection spectrum curve of the green vegetation in the visible light-near infrared waveband range is higher than 96%.
Compared with the prior art, the invention has the following advantages:
the method adopts the layered double-hydroxy metal hydroxide as a matrix, replaces anions between layers with the organic pigment negative charge groups, realizes the insertion of the organic pigment negative charge groups between the layers of the layered double-hydroxy metal hydroxide matrix, thereby realizing the dyeing of the layered double-hydroxy metal hydroxide matrix, and adjusts the types and the proportion of the organic pigments to carry out the color mixing, so that the absorption peak of the prepared colored double-hydroxy metal hydroxide material in the visible light spectrum range is highly matched with the vegetation of various colors. The laminate of the layered double hydroxide metal hydroxide is rich in hydroxyl, and the interlayer gaps are rich in crystal water, so that the laminate shows spectral characteristics similar to natural vegetation in near infrared bands, and the double hydroxide metal hydroxideThe layered structure of the material is also favorable for improving the thermal stability and the irradiation resistance of the organic pigment, and the two-dimensional pore channel structure between layers has larger inner surface and interlayer gap, is easy to accept and adsorb H2O and the like, and the stable adsorption structure can be still maintained at 150 ℃, so that the dihydroxy metal hydroxide material has higher water retention. The colored dihydroxy metal hydroxide material after the organic pigment intercalation shows the spectral characteristics similar to natural vegetation in the whole wave band range of visible light-near infrared, so that the dihydroxy metal hydroxide material after the organic pigment intercalation has good application prospect in the aspect of development of hyperspectral stealth coating materials.
Drawings
FIG. 1 is a graph of the reflectance spectrum of a sample prepared in example 1 of the present invention;
FIG. 2 is a graph of the reflectance spectrum of a sample prepared in example 2 of the present invention;
FIG. 3 is a graph of the reflectance spectrum of a sample prepared in example 3 of the present invention;
FIG. 4 is a graph of the reflectance spectrum of a sample prepared in example 4 of the present invention;
FIG. 5 is a graph of the reflectance spectrum of a sample prepared in example 5 of the present invention;
FIG. 6 is a graph of the reflectance spectrum of a sample prepared in example 6 of the present invention;
FIG. 7 is a graph of the reflectance spectrum of a sample prepared in example 7 of the present invention;
FIG. 8 is a graph of the reflectance spectrum of a sample prepared in example 8 of the present invention;
FIG. 9 is a graph of the reflectance spectrum of a sample prepared in example 13 of the present invention;
FIG. 10 is a graph of the reflectance spectrum of green vegetation (Osmanthus tree);
FIG. 11 shows the spectral matching between the samples prepared according to the embodiments of the present invention and the green vegetation (Osmanthus trees);
FIG. 12 is an XRD pattern of the layered double hydroxide and colored layered double hydroxide of the invention (example 1).
Detailed Description
Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the invention are shown in the drawings, it should be understood that the invention can be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The following examples are provided to illustrate the pigment system and the preparation method for the spectrum characteristic of the simulated natural vegetation.
In the embodiment, the layered double hydroxide is used as the matrix, wherein the layered plate of the layered double hydroxide is rich in hydroxyl, the interlayer gaps are rich in crystal water, and rich hydroxyl and interlayer crystal water can form spectral absorption peaks similar to those of natural vegetation at 1440nm, 1960nm and other positions of the near infrared spectrum of the layered double hydroxide material, so that the near infrared band spectral characteristics of the natural vegetation cell moisture can be simulated. On the basis, the present embodiment utilizes the negative charge group of the organic pigment to replace the anion between the layered double hydroxide layers, so as to insert the negative charge group of the organic pigment between the layered double hydroxide layers, and the inserted negative charge group of the organic pigment between the layered double hydroxide layers can affect the spectral characteristics of the layered double hydroxide in the visible light band, specifically, the inserted organic pigment can be any one or combination of organic blue, organic yellow, organic red and organic green, the inserted organic pigment combination and combination ratio are different, the correspondingly prepared colored layered double hydroxide can have different spectral characteristics in the visible light band, therefore, different colored layered double hydroxide can be formed by adjusting the inserted organic pigment combination and combination ratio, thereby realizing the regulation and control of the visible light wave band spectral characteristics of the layered double hydroxide. Meanwhile, the formed colored layered double-hydroxy metal hydroxide keeps the characteristics that the layered double-hydroxy metal hydroxide laminate is rich in hydroxy and the interlayer gap is rich in crystal water, so that the prepared colored layered double-hydroxy metal hydroxide can simulate the spectral characteristics of natural vegetation in the whole visible-near infrared band range.
The method comprises the following steps of forming a colored layered double hydroxide, and regulating and controlling the visible light band spectral characteristics of the layered double hydroxide, wherein the steps comprise:
step 1: mixing metal salt corresponding to divalent cation and metal salt corresponding to trivalent cation to prepare solution A, wherein the combination of the divalent cation and the trivalent cation is Mg-Al or Zn-Al, and the molar ratio of the divalent cation to the trivalent cation is 2: 1-4: 1.
The metal salt corresponding to the divalent cation and the metal salt corresponding to the trivalent cation may be selected according to the actual conditions, such as the nitrate Mg (NO)3)2*6H2O and Al (NO)3)3*9H2O or Zn (NO)3)2*6H2O and Al (NO)3)3*9H2O, described as Mg (NO)3)2*6H2O and Al (NO)3)3*9H2O is illustrated as an example.
Step 2: dissolving an organic pigment in an organic solvent to prepare an organic pigment solution, slowly pouring the organic pigment solution into the solution A, and stirring, wherein the addition amount of the organic pigment accounts for 1-4% of the total mass of the metal salt corresponding to the divalent cation and the metal salt corresponding to the trivalent cation.
The organic solvent can be selected from common organic solvents such as ethanol, glycol, ether and the like, the organic pigment comprises one or more of organic blue, organic yellow, organic red and organic green, and the combination of the organic pigments with different colors can finally influence the spectral characteristics of the formed colored layered double hydroxide powder.
And step 3: adding an alkaline solution into the mixed solution of the solution A and the organic pigment solution until the pH value is 8-10, and continuously introducing N2Is stirred for a certain time under the condition of (1), and the reaction forms layered double hydroxideAnd (3) a hydroxide matrix, wherein the organic pigment negative charge group replaces anions between the layers of the layered double hydroxide matrix to form the colored layered double hydroxide.
Solution A is Mg (NO)3)2And Al (NO)3)3The mixed solution of (A) and (B) can be selected from common alkaline solution, such as NaOH solution, ammonia water, etc., in Mg (NO)3)2And Al (NO)3)3Adding alkaline solution to the mixed solution of (1), Mg (NO)3)2、Al(NO3)3And alkaline solution to generate a layered double-hydroxide matrix, wherein the basic chemical formula of the layered double-hydroxide matrix is
In this embodiment M2+Represents Mg2+,M3+Represents Al2+,An-Represents NO3 -Wherein is connected to N2For the purpose of preventing CO in the air2Take part in the reaction to form CO3 2-. The dihydroxy metal hydroxide has a layered structure comprising brucite octahedron, and divalent cations (M) in the center of the octahedron and associated via hydrogen bonds between layers2+) Can be substituted by trivalent cations (M) of similar radius3+) Isomorphously substituted interlamellar anions A with excess positive charge electrostatically adsorbedn-And neutralizing to form the colored layered double hydroxide. The laminate of the colored layered double hydroxide is rich in hydroxyl, the interlayer gaps are rich in crystal water, water molecules in interlayer regions are connected with the metal hydroxide and interlayer anions through a large number of hydrogen bonds, and the rich hydroxyl and the interlayer crystal water can form a spectral absorption band similar to natural vegetation at the near-infrared spectrum position of the colored layered double hydroxide material. In addition, while the layered double hydroxide matrix is formed, the organic pigment negative charge group replaces part of anion NO between the layers of the layered double hydroxide matrix3 -A colored layered double hydroxide of a metal, in particular, in practice, a metal hydroxide of a metalHowever, the vegetation does not only include green vegetation, and the pigments contained in different natural plants are different, so that for various natural vegetation, the organic pigment can be selected from any one or a combination of organic blue, organic yellow, organic red and organic green, and the relative proportion of the organic pigment can be adjusted to perform color matching, so that the absorption peak of the colored layered double hydroxide material in the visible light spectrum range is highly matched with the spectrum of various natural vegetation, and the dyed layered double hydroxide material shows the spectral characteristics similar to the natural vegetation in the whole visible light-near infrared band range.
And 4, step 4: pouring the colored layered double hydroxide solution into a reaction kettle, putting the reaction kettle into an oven, heating and reacting for a period of time at the temperature of 80-180 ℃, and crystallizing the colored layered double hydroxide solution in the reaction kettle to obtain a colored layered double hydroxide crystal.
And 5: and after cooling, pouring out the supernatant, and washing, centrifuging, filtering and drying the bottom precipitate to obtain the colored layered dihydroxy metal hydroxide powder.
Example 1
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A from O according to the molar ratio of 3:1, and stirring the beaker on a magnetic stirring table for 5 min; adding organic blue as Mg (NO)3)2*6H2O and Al (NO)3)3*9H2Taking ethylene glycol as a solvent in an amount which is 1 percent of the total mass of O, preparing 50ml of organic pigment solution, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; then pouring the solution into a reaction kettle, reacting for 8 hours in a drying oven at 150 ℃, taking out after cooling, pouring out supernatant, washing bottom sediment for multiple times, centrifuging, filtering and drying to obtain a sample, wherein figure 1 shows that the sample is prepared in the embodiment 1 of the inventionAnd (3) a reflection spectrum graph of the sample, wherein wavelet represents Wavelength, and Reflectance represents reflectivity.
Example 2
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A from O according to the molar ratio of 3:1, and stirring the beaker on a magnetic stirring table for 5 min; adding organic blue as Mg (NO)3)2*6H2O and Al (NO)3)3*9H2Preparing 50ml of organic pigment solution by using glycol as a solvent, wherein the glycol accounts for 2% of the total mass of O, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in an oven at 150 ℃, cooling, taking out, pouring out supernatant, washing the bottom precipitate for multiple times, centrifuging, filtering, and drying to obtain a sample, wherein FIG. 2 is a reflection spectrum curve of the sample prepared in the embodiment 2 of the invention, and the wavelegth represents the Wavelength and the Reflectance represents the reflectivity.
Example 3
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A from O according to the molar ratio of 3:1, and stirring the beaker on a magnetic stirring table for 5 min; adding organic blue as Mg (NO)3)2*6H2O and Al (NO)3)3*9H2Preparing 50ml of organic pigment solution by taking ethylene glycol as a solvent, wherein the content of the ethylene glycol accounts for 4% of the total mass of O, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in an oven at 150 ℃, cooling, taking out, pouring out supernatant, washing the bottom precipitate for multiple times, centrifuging, filtering, and drying to obtain a sample, wherein FIG. 3 is a reflection spectrum curve of the sample prepared in the embodiment 3 of the invention, and the wavelegth represents the Wavelength and the Reflectance represents the reflectivity.
Example 4
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A by using O according to the molar ratio of 2:1, and stirring the beaker on a magnetic stirring table for 5 min; adding organic blue as Mg (NO)3)2*6H2O and Al (NO)3)3*9H2Preparing 50ml of organic pigment solution by using glycol as a solvent, wherein the glycol accounts for 2% of the total mass of O, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in an oven at 150 ℃, cooling, taking out, pouring out supernatant, washing the bottom precipitate for multiple times, centrifuging, filtering, and drying to obtain a sample, wherein FIG. 4 is a reflection spectrum curve of the sample prepared in the embodiment 4 of the invention, and the wavelegth represents the Wavelength and the Reflectance represents the reflectivity.
Example 5
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A from O according to the molar ratio of 4:1, and stirring the beaker on a magnetic stirring table for 5 min; adding organic blue as Mg (NO)3)2*6H2O and Al (NO)3)3*9H2Preparing 50ml of organic pigment solution by using glycol as a solvent, wherein the glycol accounts for 2% of the total mass of O, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in an oven at 150 ℃, cooling, taking out, pouring out supernatant, washing the bottom precipitate for multiple times, centrifuging, filtering, and drying to obtain a sample, wherein FIG. 5 is a reflection spectrum curve of the sample prepared in the embodiment 5 of the invention, and the wavelegth represents the Wavelength and the Reflectance represents the reflectivity.
Example 6
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A from O according to the molar ratio of 3:1, and stirring the beaker on a magnetic stirring table for 5 min; then weighing Mg (NO) according to the molar ratio of 1:5 between the organic blue and the organic yellow3)26*H2O and Al (NO)3)3*9H2Preparing 100ml of organic pigment solution by taking ethylene glycol as a solvent, wherein the 2% of the total mass of O is 2%, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in an oven at 150 ℃, cooling, taking out, pouring out supernatant, cleaning bottom sediment, centrifuging, filtering, and drying to obtain a sample, wherein FIG. 6 is a reflection spectrum curve diagram of the sample prepared in the embodiment 6 of the invention, and the wavelegth represents the Wavelength and the Reflectance represents the reflectivity.
Example 7
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A from O according to the molar ratio of 3:1, and stirring the beaker on a magnetic stirring table for 5 min; then weighing Mg (NO) according to the molar ratio of 1:10 between the organic blue and the organic yellow3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of organic pigment solution by taking ethylene glycol as a solvent, wherein the 2% of the total mass of O is 2%, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in an oven at 150 ℃, cooling, taking out, pouring out supernatant, cleaning bottom sediment, centrifuging, filtering, and drying to obtain a sample, wherein FIG. 7 is a reflection spectrum curve diagram of the sample prepared in the embodiment 7 of the invention, and the wavelegth represents the Wavelength and the Reflectance represents the reflectivity.
Example 8
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A from O according to the molar ratio of 3:1, and stirring the beaker on a magnetic stirring table for 5 min; then weighing Mg (NO) according to the molar ratio of 1:15 between the organic blue and the organic yellow3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of organic pigment solution by taking ethylene glycol as a solvent, wherein the 2% of the total mass of O is 2%, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in an oven at 150 ℃, cooling, taking out, pouring out supernatant, cleaning bottom sediment, centrifuging, filtering, and drying to obtain a sample, wherein FIG. 8 is a reflection spectrum curve diagram of the sample prepared in the embodiment 8 of the invention, and the wavelegth represents the Wavelength and the Reflectance represents the reflectivity.
Example 9
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A by using O according to the molar ratio of 2:1, and stirring the beaker on a magnetic stirring table for 5 min; then weighing Mg (NO) according to the molar ratio of 1:15 between the organic blue and the organic yellow3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of organic pigment solution by taking ethylene glycol as a solvent, wherein the 2% of the total mass of O is 2%, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in a drying oven at 150 ℃, cooling, taking out, pouring out supernatant, cleaning bottom sediment, centrifuging, filtering, and drying to obtain a sample.
Example 10
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A by using O according to the molar ratio of 4:1, and stirring a beaker on a magnetic stirring table5 min; then weighing Mg (NO) according to the molar ratio of 1:15 between the organic blue and the organic yellow3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of organic pigment solution by taking ethylene glycol as a solvent, wherein the 2% of the total mass of O is 2%, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in a drying oven at 150 ℃, cooling, taking out, pouring out supernatant, cleaning bottom sediment, centrifuging, filtering, and drying to obtain a sample.
Example 11
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A from O according to the molar ratio of 3:1, and stirring the beaker on a magnetic stirring table for 5 min; then weighing Mg (NO) according to the molar ratio of 1:15 between the organic blue and the organic yellow3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of organic pigment solution by taking ethylene glycol as a solvent, wherein the 1% of the total mass of O is 1%, adding the organic pigment solution into the solution A, and continuously stirring for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in a drying oven at 150 ℃, cooling, taking out, pouring out supernatant, cleaning bottom sediment, centrifuging, filtering, and drying to obtain a sample.
Example 12
Mg(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A from O according to the molar ratio of 3:1, and stirring the beaker on a magnetic stirring table for 5 min; then weighing Mg (NO) according to the molar ratio of 1:15 between the organic blue and the organic yellow3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of organic pigment solution by taking ethylene glycol as a solvent, wherein the content of the ethylene glycol accounts for 4% of the total mass of O, and adding the organic pigment solution into the solutionStirring the solution A for 5 min; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; and then pouring the solution into a reaction kettle, reacting for 8 hours in a drying oven at 150 ℃, cooling, taking out, pouring out supernatant, cleaning bottom sediment, centrifuging, filtering, and drying to obtain a sample.
Example 13
Zn(NO3)2*6H2O and Al (NO)3)3*9H2Preparing 100ml of solution A by using O according to the molar ratio of 2:1, and stirring the beaker on a magnetic stirring table for 5 min; adding organic blue as Zn (NO)3)2*6H2O and Al (NO)3)3*9H2Preparing 50ml of organic pigment solution by taking ethylene glycol as a solvent, preparing 100ml of organic pigment solution by taking ethylene glycol as a solvent, adding the organic pigment solution into the solution A, and continuously stirring for 5min, wherein 2% of the total mass of O is ethylene glycol; finally, 2mol/L NaOH solution is prepared and is added into the solution A drop by drop until the pH value reaches about 9 and is in N2Continuously stirring for 1h under the environment; then pouring the solution into a reaction kettle, reacting for 8 hours in an oven at 150 ℃, cooling, taking out, pouring out supernatant, cleaning bottom sediment, centrifuging, filtering, and drying to obtain a sample, wherein FIG. 9 is a reflection spectrum curve diagram of the sample prepared in the embodiment 13 of the invention, and the Wavelength is represented by wavelet, and the reflectivity is represented by Reflectance.
Fig. 10 is a reflection spectrum graph of green vegetation (osmanthus tree), and fig. 11 is a spectrum matching degree between a sample prepared in an embodiment of the present invention and the green vegetation (osmanthus tree), specifically a calculated matching degree between a reflection spectrum curve of the green vegetation (osmanthus tree) in fig. 10 and a reflection spectrum curve of a corresponding sample prepared in each embodiment according to the following formula:
wherein x isikRepresenting light in the k-th wavelength band in the i-reflection spectral curveSpectral value, xjkRepresenting the spectral value of the kth wave band in the j reflection spectral curve, m representing the number of wave bands, xi representing the average value of the i reflection spectral curve, xj representing the average value of the j reflection spectral curve, rhoijRepresenting the matching degree of the i reflection spectrum curve and the j reflection spectrum curve, if the two reflection spectrum curves are completely same, then rhoijIs 1, otherwise ρijGenerally less than 1.
As shown in FIG. 11, when the combination of the divalent cation and the trivalent cation is Mg-Al, the organic pigments are organic blue and organic yellow, and the total mass of the organic blue and the organic yellow accounts for Mg (NO)3)2*6H2O and Al (NO)3)3*9H2When the total mass of O is 2 percent and the molar ratio of organic blue to organic yellow is 1:15, the spectral matching degree of the prepared colored layered double hydroxide and green vegetation (osmanthus tree) is the highest and can reach 97.2 percent.
From the reflectance spectrum curves of the samples prepared in the above examples, it can be seen that: the prepared colored layered double-hydroxy metal hydroxide sample forms characteristic spectral absorption peaks near 1440nm, 1960nm and other positions, and has no obvious difference from a reflection spectral curve of green vegetation (osmanthus fragrans) in a near infrared wave form, mainly because the prepared layered double-hydroxy metal hydroxide has rich hydroxyl groups and crystal water among layers, and the absorption effect of the hydroxyl groups and the crystal water in the colored layered double-hydroxy metal hydroxide on light can exactly simulate the absorption characteristic of water in natural vegetation cells on the light.
The reflection spectrum curve of the prepared colored layered double-hydroxy metal hydroxide and the reflection spectrum curve of the green vegetation (osmanthus tree) are mainly different in a visible light waveband. In examples 6 to 8, the organic blue negative charge group and the organic yellow negative charge group are intercalated in the layered double hydroxide, the coincidence degree of the reflection spectrum curve of the prepared sample and the reflection spectrum curve of the green vegetation (osmanthus tree) in the visible light band range is very high, the wave peaks in the visible light band range are all around 550nm, and in addition, the matching degree obtained by calculation according to the matching degree formula is up to 97.32%, which shows that the intercalation of the organic blue negative charge group and the organic yellow negative charge group in the layered double hydroxide can well simulate the spectrum of the green vegetation in the visible light range and the near infrared range. In each of examples 1 to 5, an organic blue negative charge group is intercalated into the layered double hydroxide, and the difference exists between the reflection spectrum curve of the obtained sample and the reflection spectrum curve of the green vegetation (osmanthus tree) in the visible light waveband, the difference is mainly that the position of the first reflection peak of the reflection spectrum curve of the green vegetation (osmanthus tree) is about 550nm, and the position of the first reflection peak of the reflection spectrum curve of the sample obtained after the organic blue negative charge group is intercalated into the layered double hydroxide is lower than 500 nm. The natural vegetation is not limited to green vegetation, the spectral characteristics of different natural vegetation can be different in the visible light band, and the reflection spectral curves of the samples in the examples 1 to 5 show that the spectral characteristics of the colored layered double hydroxide material in the visible light band can be adjusted by adjusting the types of the doped organic pigments in the practical application process, so that the effect of simulating the characteristics of different natural vegetation in the visible light-near infrared spectrum can be achieved.
FIG. 12 is an XRD pattern of a layered double hydroxide and a colored layered double hydroxide according to the present invention (example 1) wherein the layered double hydroxide was prepared under exactly the same conditions as the colored layered double hydroxide (example 1) except that no organic pigment solution was added during the preparation. As shown in fig. 12, the positions of the respective diffraction peaks of the layered double hydroxide and the colored layered double hydroxide are the same, which indicates that there is no significant change in the crystal structure of the layered double hydroxide before and after dyeing, and the intensities of the respective diffraction peaks of the layered double hydroxide and the colored layered double hydroxide are different, mainly depending on the crystallinity of the crystal and having no relation to the crystal structure.
The method for preparing the pigment system with the spectral characteristics of the simulated natural vegetation provided in the examples of the present application is described in detail above, and the embodiments are illustrated herein by using specific examples, which are only used to help understanding the present application. Meanwhile, for those skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation in the present application.
Claims (8)
1. The application of the pigment system is characterized in that the application is the spectral characteristics of simulated natural vegetation, and the preparation method of the pigment system comprises the following steps:
the layered double hydroxide is adopted as a matrix, wherein a laminate of the layered double hydroxide is rich in hydroxyl, and interlayer gaps are rich in crystal water and are used for simulating the spectral characteristics of near-infrared bands of water in natural vegetation cells;
replacing anions between the layered double hydroxide matrix layers with negative charge groups of organic pigments, so as to insert the negative charge groups of the organic pigments between the layered double hydroxide matrix layers, thereby forming the colored layered double hydroxide, wherein the spectral characteristics of the colored layered double hydroxide in a visible light band are further regulated and controlled by adjusting the combination type and the combination proportion of the inserted negative charge groups of the organic pigments;
wherein the layered double hydroxide matrix is prepared from a metal salt corresponding to a divalent cation and a metal salt corresponding to a trivalent cation, the combination of the divalent cation and the trivalent cation is Mg-Al or Zn-Al, the interlayer insertion of the layered double hydroxide matrix with an organic pigment negative charge group is carried out under hydrothermal conditions, and the organic pigment comprises: organic yellow and organic blue.
2. Use of a pigment system according to claim 1, wherein the step of forming the coloured layered double hydroxide comprises:
step 1: mixing metal salt corresponding to divalent cation and metal salt corresponding to trivalent cation to prepare solution A, wherein the combination of the divalent cation and the trivalent cation is Mg-Al or Zn-Al, and the molar ratio of the divalent cation to the trivalent cation is 2: 1-4: 1;
step 2: dissolving an organic pigment in an organic solvent to prepare an organic pigment solution, slowly pouring the organic pigment solution into the solution A, and stirring, wherein the addition amount of the organic pigment accounts for 1-4% of the total mass of the metal salt corresponding to the divalent cation and the metal salt corresponding to the trivalent cation;
and step 3: adding an alkaline solution into the mixed solution of the solution A and the organic pigment solution until the pH value is 8-10, and continuously introducing N2Stirring for a certain time under the condition of (1) to react to form a layered double hydroxide matrix, and simultaneously replacing anions between the layers of the layered double hydroxide matrix with organic pigment negative charge groups to form colored layered double hydroxide;
and 4, step 4: pouring the colored layered double hydroxide solution into a reaction kettle, putting the reaction kettle into an oven, heating and reacting for a period of time at the temperature of 80-180 ℃, and crystallizing the colored layered double hydroxide solution in the reaction kettle to obtain a colored layered double hydroxide crystal;
and 5: and after cooling, pouring out the supernatant, and washing, centrifuging, filtering and drying the bottom precipitate to obtain the colored layered dihydroxy metal hydroxide powder.
3. The application of the pigment system according to claim 1, wherein the organic pigment comprises organic blue and organic yellow, the molar ratio of the organic blue to the organic yellow is in a range of 1:5 to 1:15, and the matching degree of the prepared colored layered double hydroxy metal hydroxide and the reflection spectrum curve of green vegetation in a visible light-near infrared band is higher than 96%.
4. The use of a pigment system according to claim 1, wherein the organic pigments comprise any one or more of organic blue, organic yellow, organic red and organic green, and the matching degree of the prepared colored layered double hydroxide with the reflection spectrum curve of various natural vegetation in the visible-near infrared band is improved by adjusting the combination type and combination proportion of the organic pigments.
5. Use of a pigment system according to claim 1, wherein the coloured layered double hydroxide is formed by replacing part of the anions in the layered double hydroxide by negatively charged groups of an organic pigment;
the colored layered double-hydroxide metal hydroxide is of a layered structure, the layered structure of the colored layered double-hydroxide metal hydroxide is formed by sharing brucite octahedrons, the layers are associated through hydrogen bonds, the laminate is rich in hydroxyl, the interlayer gaps are rich in crystal water, and the crystal water is connected with the metal hydroxide, interlayer anions and organic pigment negative charge groups through the hydrogen bonds.
6. Use of a pigment system according to claim 1, characterized in that the combination of said divalent cations and said trivalent cations is Mg-Al or Zn-Al; the molar ratio of the divalent cations to the trivalent cations is 2: 1-4: 1; the addition amount of the organic pigment accounts for 1% -4% of the total mass of the metal salt corresponding to the divalent cation and the metal salt corresponding to the trivalent cation, the organic pigment comprises organic blue and organic yellow, the molar ratio of the organic blue to the organic yellow is 1: 5-1: 15, the pH value of a reaction solution system is 8-10, and the temperature of the hydrothermal reaction is 80-180 ℃.
7. Use of a pigment system according to claim 1, characterized in that the combination of said divalent cations and said trivalent cations is Mg-Al or Zn-Al; the molar ratio of the divalent cations to the trivalent cations is 2: 1-4: 1; the addition amount of the organic pigment accounts for 1-4% of the total mass of the metal salt corresponding to the divalent cation and the metal salt corresponding to the trivalent cation, the organic pigment comprises any one or combination of more of organic blue, organic yellow, organic red and organic green, the pH value of the reaction solution system is 8-10, and the temperature of the hydrothermal reaction is 80-180 ℃.
8. The use of a pigment system according to claim 1, wherein the degree of matching of the spectral characteristics of the pigment system for imitating natural vegetation with the reflection spectral curve of green vegetation in the visible-near infrared band is higher than 96%.
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