A strontium carbonate photonic crystal pigment, its preparation method and application

Abstract

The invention discloses a strontium carbonate photonic crystal colorant and a preparation method and application thereof, and belongs to the technical field of colloidal photonic crystal assembly unit preparation and structural color development material. A chemical uniform precipitation method is adopted to prepare spherical strontium carbonate nanoparticles with uniform particle size, and spherical strontium carbonate nanoparticles of different sizes are prepared by adjusting parameters, and the spherical strontium carbonate nanoparticles are dispersed in ethanol, and strontium carbonate photonic crystal colorants of different colors are obtained after the ethanol is volatilized. The process is simple and easy to operate, can be mass-produced industrially, can be used to construct structural color coatings on the surfaces of various materials, and has broad application prospects. Compared with traditional organic colorants, the strontium carbonate photonic crystal colorant prepared by the invention has uniform size and good sphericity, and the preparation method is simple, the repeatability is strong, it is based on inorganic materials, the structure is stable, and it is not easy to fade, which solves the problem that traditional organic chemical pigments are easy to fade and a large amount of pollutants are discharged during the production process.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of colloidal photonic crystal assembly units and structural color display materials, and particularly relates to a strontium carbonate photonic crystal colorant, a preparation method thereof, and an application thereof. Background Art

[0002] The structural color of a photonic crystal originates from the interaction between a periodically arranged photonic crystal structure and light, and has the advantages of bright colors, never fading, environmental friendliness, short preparation period, etc. Compared with traditional pigments and dyes, it has the characteristics of stable color development, environmentally friendly components, and not being easily faded under sunlight. Therefore, it is more durable and has a wide application prospect in the field of color display materials. The main photonic crystal assembly units are silica, polystyrene, and methyl methacrylate. These materials have simple synthesis methods, low costs, cheap and easily available raw materials, good sphericity of colloidal particles, and uniform sizes, and are currently widely used in the preparation and application of photonic crystal functional materials. Due to the continuous expansion of the performance and uses of photonic crystal materials, inorganic nanoparticles with uniform sizes such as zinc sulfide, tin oxide, cuprous sulfide, iron oxide, and cerium oxide have gradually been successfully synthesized and used in the field of photonic crystal materials. Further expanding the range of photonic crystal assembly units helps to discover new uses of photonic crystal materials.

[0003] Strontium carbonate is mainly used for the preparation of color display glass shells, magnetic materials, etc. The reported morphologies of strontium carbonate materials currently are fibrous and needle-like. In addition, Patent CN201510291818.8 also reports a preparation method of spherical strontium carbonate, but the size of the strontium carbonate particles prepared by this method is dozens of micrometers, and this size has far exceeded the size range of photonic crystal structural color materials.

[0004] Aiming at the problem that the existing spherical strontium carbonate has a large size and cannot meet the requirements of photonic crystal structural color materials, it is urgent to find a submicron and spherical strontium carbonate nanoparticle to further meet the requirements of photonic crystal structural color materials. In addition, the corresponding strontium carbonate photonic crystal material has not been reported either. Summary of the Invention

[0005] In order to overcome the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide a strontium carbonate photonic crystal colorant, a preparation method thereof, and an application thereof, so as to solve the technical problem that the size of the existing spherical strontium carbonate nanoparticles cannot meet the requirements for the generation of structural color by photonic crystals.

[0006] In order to achieve the above purpose, the present invention adopts the following technical solutions to be realized:

[0007] The present invention discloses a strontium carbonate photonic crystal colorant, which is assembled by orderly arranging uniformly sized spherical strontium carbonate nanoparticles.

[0008] Preferably, the diameter of the spherical strontium carbonate nanoparticles is 200 - 350 nm.

[0009] The present invention also discloses a method for preparing the above-mentioned strontium carbonate photonic crystal pigment, which includes: adding a surfactant to an aqueous strontium salt solution, stirring evenly and then adding an aqueous sodium carbonate solution, continuing to stir and react, followed by centrifugation, washing, and drying to obtain spherical strontium carbonate nanoparticles, and then redispersing them in ethanol. After the solvent evaporates, a strontium carbonate photonic crystal pigment is obtained.

[0010] Preferably, the aqueous strontium salt solution is prepared by dissolving a strontium salt in water, the concentration of the aqueous strontium salt solution is 0.3 - 0.7 mol / L, the strontium salt is strontium chloride hexahydrate or strontium nitrate, the aqueous sodium carbonate solution is prepared by dissolving sodium carbonate in water, and the concentration of the aqueous sodium carbonate solution is 0.3 - 0.7 mol / L.

[0011] More preferably, the molar ratio of strontium salt to sodium carbonate is (1 - 2):1.

[0012] More preferably, the surfactant is disodium ethylenediaminetetraacetate, and the mass of the surfactant is 5% - 70% of the mass of the strontium salt.

[0013] Preferably, the rate of adding the aqueous sodium carbonate solution is 5 - 15 mL / min.

[0014] Preferably, the stirring speed of the stirring reaction is 300 - 700 r / min, and the stirring time is 20 - 40 min.

[0015] Preferably, the drying condition is to disperse the washed product in ethanol and dry it at 60 - 90 °C.

[0016] The present invention also discloses the application of the above-mentioned strontium carbonate photonic crystal pigment in a color display material.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The present invention discloses a strontium carbonate photonic crystal pigment, which is assembled by the orderly arrangement of spherical strontium carbonate nanoparticles with uniform size; the spherical strontium carbonate nanoparticles have uniform size, good sphericity, and sub-micron size, can produce bright structural colors, have stable color display, rich colors and are only related to the physical structure. As a structural color pigment, it has the advantages of environmental protection and harmlessness to the human body, and further expands the types of photonic crystal assembly units.

[0019] The present invention also discloses a preparation method of the above-mentioned strontium carbonate photonic crystal pigment. A surfactant is added to an aqueous solution of strontium salt and stirred evenly. The surfactant has a strong complexing ability with divalent metal strontium ions, and when added to the solution, it will immediately form a relatively stable complex with the free strontium particles therein. When an aqueous solution of sodium carbonate is added again, under stirring conditions, the free strontium particles, which are one of the product crystal-forming ions, can only be slowly generated through the dissociation of this complex, indirectly changing the supply mode of strontium particles and delaying the occurrence of the precipitation reaction, so that both the nucleation and growth of SrCO3 crystals are affected. Eventually, the growth habit of SrCO3 crystals is changed, and strontium salt slowly releases to react with carbonate ions to generate strontium carbonate nanoparticles. After centrifugation, washing, and drying, spherical strontium carbonate nanoparticles are obtained. Then it is redispersed in a solvent, and after the solvent slowly volatilizes, a strontium carbonate photonic crystal pigment is obtained. By introducing a surfactant to control the dissociation rate of strontium particles, the reaction progress and the size of colloidal particles are controlled, and spherical strontium carbonate nanoparticles with uniform size and in the sub-micron level are successfully prepared. When the spherical strontium carbonate nanoparticles are volatilized in the solvent, they are arranged and assembled under the driving force of capillary action to form a strontium carbonate photonic crystal pigment, producing a bright structural color, and there has been no report so far.

[0020] The present invention also discloses the application of the above-mentioned strontium carbonate photonic crystal pigment in a color display material. When the strontium carbonate photonic crystal pigment is applied in a color display material, it has the advantages of stable color display and not being prone to fading and deterioration. In addition, compared with traditional organic dyes, its production process is non-toxic and harmless, has the characteristics of environmental protection and no pollution, and responds to the requirements of the country's green production. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 XRD pattern of the strontium carbonate photonic crystal pigment prepared in Example 1 of the present invention;

[0022] Figure 2 SEM image of the strontium carbonate nanoparticles prepared in Example 2 of the present invention;

[0023] Figure 3 Digital photo of the green strontium carbonate photonic crystal pigment prepared in Example 2 of the present invention;

[0024] Figure 4 SEM image of the strontium carbonate nanoparticles prepared in Example 3 of the present invention;

[0025] Figure 5 Digital photo of the red strontium carbonate photonic crystal pigment prepared in Example 3 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0026] To enable those skilled in the art to better understand the solution of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0027] It should be noted that the terms "first", "second", etc. in the specification and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects, and do not necessarily need to be used to describe a specific order or sequence. It should be understood that such data can be interchanged under appropriate circumstances so that the embodiments of the present invention described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device including a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but may include other steps or units not clearly listed or inherent to these processes, methods, products or devices.

[0028] The present invention will be further described in detail below in conjunction with the accompanying drawings:

[0029] A preparation method of strontium carbonate photonic crystal pigment, comprising the following steps:

[0030] 1) Weigh an appropriate amount of strontium salt and add it to a beaker to prepare an aqueous strontium salt solution with a certain concentration. After fully dissolving with magnetic stirring, a uniform solution A is obtained;

[0031] 2) Weigh a certain mass of surfactant and add it to the uniform solution A prepared in step 1), and continue to stir evenly. After dissolution, a reaction precursor solution is obtained;

[0032] 3) Weigh an appropriate amount of sodium carbonate and add it to another beaker to prepare an aqueous sodium carbonate solution with a certain concentration. Stir it with magnetic force to make it fully dissolve, and a uniform solution B is obtained;

[0033] 4) Gradually add the uniform solution B prepared in step 3) to the reaction precursor solution prepared in step 2) at a certain speed. After the dropping is completed, continue to stir and react for a period of time under magnetic stirring conditions;

[0034] 5) After the reaction is completed, wash the above product by centrifugal washing, and finally dry the product in an oven to obtain strontium carbonate photonic crystal pigment.

[0035] In step 1), the strontium salt is one of strontium chloride hexahydrate and strontium nitrate, and the concentration of the strontium salt aqueous solution is 0.3 - 0.7 mol / L, preferably 0.5 mol / L.

[0036] In step 2), the surfactant is disodium ethylenediaminetetraacetate, and the mass of the surfactant is 5% - 70% of the mass of the strontium salt, preferably 20%.

[0037] In step 3), the concentration of the sodium carbonate aqueous solution is 0.3 - 0.7 mol / L, preferably 0.5 mol / L.

[0038] In step 4), the addition rate of the homogeneous solution B to the reaction precursor solution is 5 - 15 mL / min.

[0039] In step 4), the stirring reaction time is 20 - 40 min, preferably 30 min.

[0040] In step 4), the stirring speed is 300 - 700 r / min, preferably 400 r / min.

[0041] In step 5), for the washing, it is washed 2 - 4 times with deionized water, preferably 3 times.

[0042] In step 5), for the drying, the product is dispersed in a small amount of ethanol and dried in an oven.

[0043] In step 5), for the drying, the oven temperature is 60 - 90 °C, preferably 80 °C.

[0044] Example 1

[0045] A preparation method of strontium carbonate photonic crystal pigment, comprising the following steps:

[0046] 1) Weigh 5.33 g of strontium chloride hexahydrate and add it to a beaker, prepare 50 mL of a 0.4 mol / L strontium chloride hexahydrate aqueous solution, and after fully dissolving it with magnetic stirring, obtain a homogeneous solution A;

[0047] 2) Weigh 2.67 g of disodium ethylenediaminetetraacetate with a mass ratio of 50% and add it to the homogeneous solution A prepared in step 1), continue to stir evenly, and obtain a reaction precursor solution after dissolution;

[0048] 3) Weigh 2.12 g of sodium carbonate and add it to another beaker, add 50 mL of deionized water to prepare a 0.4 mol / L sodium carbonate aqueous solution, and dissolve it fully with magnetic stirring to obtain a homogeneous solution B;

[0049] 4) Gradually add the uniform solution B prepared in step 3) to the reaction precursor solution prepared in step 2) at a rate of 15 mL / min. After the addition is complete, continue to stir and react for 20 min at a stirring speed of 700 r / min under magnetic stirring conditions;

[0050] 5) After the reaction is completed, wash the above product with deionized water three times. Finally, disperse the product in ethanol and dry it in an oven at 70 °C to obtain strontium carbonate photonic crystal pigment.

[0051] See Figure 1 the XRD pattern of the strontium carbonate photonic crystal pigment prepared in Example 1 of the present invention; It can be seen from Figure 1 that the crystal form of the nano-analysis prepared by this method is strontium carbonate and the crystallization is good. The XRD test shows the successful preparation of strontium carbonate.

[0052] Example 2

[0053] A preparation method of strontium carbonate photonic crystal pigment, comprising the following steps:

[0054] 1) Weigh 6.67 g of strontium chloride hexahydrate and add it to a beaker. Prepare 50 mL of 0.5 mol / L strontium chloride hexahydrate aqueous solution. After fully dissolving under magnetic stirring, obtain a uniform solution A;

[0055] 2) Weigh 3.33 g of disodium ethylenediaminetetraacetate with a mass ratio of 50% and add it to the uniform solution A prepared in step 1). Continue to stir evenly. After dissolution, obtain a reaction precursor solution;

[0056] 3) Weigh 2.68 g of sodium carbonate and add it to another beaker. Add 50 mL of deionized water to prepare a 0.5 mol / L sodium carbonate aqueous solution. Stir magnetically to dissolve it fully to obtain a uniform solution B;

[0057] 4) Gradually add the uniform solution B prepared in step 3) to the reaction precursor solution prepared in step 2) at a rate of 5 mL / min. After the addition is complete, continue to stir and react for 30 min at a stirring speed of 400 r / min under magnetic stirring conditions;

[0058] 5) After the reaction is completed, wash the above product with deionized water three times. Finally, disperse the product in ethanol and dry it in an oven at 80 °C to obtain strontium carbonate photonic crystal pigment.

[0059] See Figure 2 the SEM image of the strontium carbonate nanoparticles prepared in Example 2 of the present invention; It can be seen from Figure 2 that the strontium carbonate nanoparticles prepared by this method have uniform sizes, no agglomeration, good sphericity of the nanoparticles, meet the basic requirements of the building blocks for photonic crystal assembly, and are conducive to the self-assembly process.

[0060] See Figure 3 This is the digital photo of the green strontium carbonate photonic crystal pigment prepared in Example 2 of the present invention; it can be seen from Figure 3 that the photonic crystal pigment formed by self-assembly of the spherical strontium carbonate nanoparticles prepared by this method shows bright structural color, and can be used to replace traditional green coatings as decorative pigments, etc.

[0061] Example 3

[0062] A preparation method of a strontium carbonate photonic crystal pigment, comprising the following steps:

[0063] 1) Weigh 6.3 g of strontium nitrate and add it to a beaker, prepare 50 mL of 0.6 mol / L strontium nitrate aqueous solution, and after magnetic stirring and full dissolution, obtain a uniform solution A;

[0064] 2) Weigh 1.26 g of disodium ethylenediaminetetraacetate with a mass ratio of 20% and add it to the uniform solution A prepared in step 1), continue to stir evenly, and obtain a reaction precursor solution after dissolution;

[0065] 3) Weigh 3.21 g of sodium carbonate and add it to another beaker, add 50 mL of deionized water to prepare a 0.6 mol / L sodium carbonate aqueous solution, and magnetic stir to make it fully dissolve to obtain a uniform solution B;

[0066] 4) Gradually add the uniform solution B prepared in step 3) to the reaction precursor solution prepared in step 2) at a speed of 10 mL / min. After the addition is completed, continue to stir and react for 40 min at a stirring speed of 500 r / min under magnetic stirring conditions;

[0067] 5) After the reaction is completed, wash the above product with deionized water 3 times, and finally disperse the product in ethanol and dry it in an oven at 70 °C to obtain the strontium carbonate photonic crystal pigment.

[0068] See Figure 4 This is the SEM image of the strontium carbonate nanoparticles prepared in Example 3 of the present invention; it can be seen from Figure 4 that the spherical strontium carbonate nanoparticles prepared by this method have good sphericity, uniform size, smooth surface, high dispersion and no agglomeration, meeting the basic requirements of the composite photonic crystal assembly units and being conducive to the self-assembly process.

[0069] See Figure 5 This is the digital photo of the red strontium carbonate photonic crystal pigment prepared in Example 3 of the present invention. It can be seen from Figure 5It can be seen that the photonic crystal pigment formed by assembling spherical strontium carbonate nanoparticles prepared by this method shows a bright red color. This structural color pigment has the advantages of being environmentally friendly, pollution-free, and having stable color development, and can be used as a decorative material to replace traditional pigments.

[0070] Example 4

[0071] A preparation method of a strontium carbonate photonic crystal pigment, comprising the following steps:

[0072] 1) Weigh 3.15 g of strontium chloride hexahydrate and add it to a beaker. Prepare 50 mL of a 0.3 mol / L strontium chloride hexahydrate aqueous solution. After fully dissolving it with magnetic stirring, a uniform solution A is obtained;

[0073] 2) Weigh 0.16 g of disodium ethylenediaminetetraacetate with a mass ratio of 5% and add it to the uniform solution A prepared in step 1). Continue to stir evenly. After dissolution, a reaction precursor solution is obtained;

[0074] 3) Weigh 1.59 g of sodium carbonate and add it to another beaker. Add 50 mL of deionized water to prepare a 0.3 mol / L sodium carbonate aqueous solution. Stir it magnetically to make it fully dissolve to obtain a uniform solution B;

[0075] 4) Gradually add the uniform solution B prepared in step 3) to the reaction precursor solution prepared in step 2) at a speed of 12 mL / min. After the dropping is completed, continue to stir and react for 25 min at a stirring speed of 300 r / min under magnetic stirring conditions;

[0076] 5) After the reaction is completed, wash the above product with deionized water twice. Finally, disperse the product in ethanol and dry it in an oven at 60 °C to obtain the strontium carbonate photonic crystal pigment.

[0077] Example 5

[0078] A preparation method of a strontium carbonate photonic crystal pigment, comprising the following steps:

[0079] 1) Weigh 7.35 g of strontium chloride hexahydrate and add it to a beaker. Prepare 50 mL of a 0.7 mol / L strontium chloride hexahydrate aqueous solution. After fully dissolving it with magnetic stirring, a uniform solution A is obtained;

[0080] 2) Weigh 5.15 g of disodium ethylenediaminetetraacetate with a mass ratio of 70% and add it to the uniform solution A prepared in step 1). Continue to stir evenly. After dissolution, a reaction precursor solution is obtained;

[0081] 3) Weigh 3.71 g of sodium carbonate and add it to another beaker. Add 50 mL of deionized water to prepare a 0.7 mol / L sodium carbonate aqueous solution. Stir it magnetically to make it fully dissolve to obtain a uniform solution B;

[0082] 4) The uniform solution B prepared in step 3) was gradually added to the reaction precursor solution prepared in step 2) at a rate of 8 mL / min. After the addition was completed, the mixture was continuously stirred and reacted for 35 min at a stirring speed of 600 r / min under magnetic stirring conditions;

[0083] 5) After the reaction was completed, the above product was washed 4 times with deionized water. Finally, the product was dispersed in ethanol and dried in an oven at 90 °C to obtain the strontium carbonate photonic crystal pigment.

[0084] The above content is only to illustrate the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution according to the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. Application of strontium carbonate photonic crystal pigment in color-displaying materials, characterized in that, The preparation method of the strontium carbonate photonic crystal pigment includes: adding a surfactant to an aqueous strontium salt solution. The surfactant has a complexing ability with divalent metal strontium ions and will immediately form a complex with free strontium ions. After stirring evenly, an aqueous sodium carbonate solution is added, and after continuous stirring and reaction, free strontium ions are generated through the dissociation of the complex, indirectly changing the supply mode of strontium ions, delaying the precipitation reaction, affecting the nucleation and growth of SrCO3 crystals, changing the growth habit of SrCO3 crystals, and the strontium salt slowly releases to react with carbonate ions to generate strontium carbonate nanoparticles. After centrifugation, washing, and drying, the strontium carbonate photonic crystal pigment is obtained; the drying condition is to disperse the washed product in ethanol and dry it at 60~90 o °C; by introducing a surfactant to control the dissociation rate of strontium ions, thereby controlling the reaction progress and the size of strontium carbonate nanocolloidal particles. When the solvent evaporates, spherical strontium carbonate nanoparticles are arranged and assembled under the drive of capillary force to form the strontium carbonate photonic crystal pigment, generating a bright structural color; The strontium carbonate photonic crystal pigment is assembled by orderly arranging spherical strontium carbonate nanoparticles with uniform size; the diameter of the spherical strontium carbonate nanoparticles is 200-350 nm; The strontium salt aqueous solution is prepared by dissolving strontium salt in water, the concentration of the strontium salt aqueous solution is 0.3-0.7 mol / L, the strontium salt is strontium chloride hexahydrate or strontium nitrate, the sodium carbonate aqueous solution is prepared by dissolving sodium carbonate in water, and the concentration of the sodium carbonate aqueous solution is 0.3-0.7 mol / L; The molar ratio of the strontium salt to sodium carbonate is 1:1; The surfactant is disodium ethylenediaminetetraacetate, and the mass of the surfactant is 5%-50% of the mass of the strontium salt.

2. The application of the strontium carbonate photonic crystal pigment according to claim 1 in a color display material, characterized in that, The rate of adding the sodium carbonate aqueous solution is 5-15 mL / min.

3. The application of the strontium carbonate photonic crystal pigment according to claim 1 in a color display material, characterized in that, The stirring speed of the stirring reaction is 300-700 r / min, and the stirring time is 20-40 min.

Images