CN108871659B - Preparation method of colorimetric stress sensor based on Ag nano particle assembly - Google Patents
Preparation method of colorimetric stress sensor based on Ag nano particle assembly Download PDFInfo
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- G01L11/00—Measuring steady or quasi-steady pressure of a fluid or a fluent solid material by means not provided for in group G01L7/00 or G01L9/00
- G01L11/02—Measuring steady or quasi-steady pressure of a fluid or a fluent solid material by means not provided for in group G01L7/00 or G01L9/00 by optical means
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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Abstract
The invention relates to a preparation method of a colorimetric stress sensor based on an Ag nano-particle assembly, which comprises the following steps: dispersing the Ag nano-particle assembly in a polar solvent, adding polyethylene glycol into the solution of the film-forming polymer, uniformly stirring and defoaming to obtain a mixed solution; and drying the mixed solution to form a film, thus obtaining the colorimetric stress sensor. The visual stress color-changing film is prepared by taking the Ag nano-particle assembly as a raw material, can realize a wider range of color change from blue to yellow, and has lower cost and higher practicability compared with Au and Ag.
Description
Technical Field
The invention relates to a preparation method of a colorimetric stress sensor based on an Ag nano particle assembly, which can realize the change of macroscopic color under the action of different tensile forces and pressures, can change from blue to yellow, and belongs to the field of intelligent materials.
Background
The noble metal nano material has stronger absorption effect on visible light by virtue of stronger plasma resonance characteristics, thereby presenting different colors. The Surface Plasmon Resonance (SPR) characteristics of noble metal nanomaterials depend mainly on the size, morphology and dielectric constant of the material. In addition, in the noble metal nanoparticle assembly, the coupling effect between adjacent particles can also generate a stronger plasma resonance effect, and the regulation and control of the plasma resonance effect can be realized by regulating and controlling the spacing between the particles, so that the assembly presenting different colors in a macroscopic view is obtained. Currently, research on noble metal nanoparticle assemblies has been widely used in many areas, such as: surface enhanced Raman technology, color identification, biological treatment, chemical detection, sensors and the like. There are also many patent documents reported, for example: chinese patent document CN106415196A discloses a plasmon-based colorimetric stress sensor, in which Au nanoparticle assemblies are dispersed in PVP to prepare a film, and the film can present different colors under different pressures. However, the preparation of functional devices based on noble metal assemblies focuses mainly on Au nanoparticle assemblies, and some disadvantages exist at present. Firstly, the Au storage capacity is low, the price is high, and the cost is high; secondly, due to the limitation of the plasma resonance characteristic of the Au nanoparticles, the Au nanoparticle assembly can only change from blue to red, the color change range is narrow, and the visual application is not facilitated.
Therefore, the development of a mechanochromic film with lower price and wider color change range becomes a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a colorimetric stress sensor based on an Ag nano particle assembly.
The technical scheme of the invention is as follows:
a method for preparing a colorimetric stress sensor based on an Ag nano-particle assembly comprises the following steps:
dispersing the Ag nano-particle assembly in a polar solvent, adding polyethylene glycol into the solution of the film-forming polymer, uniformly stirring and defoaming to obtain a mixed solution;
and drying the mixed solution to form a film, thus obtaining the colorimetric stress sensor.
According to the invention, preferably, the SPR absorption range of the Ag nano particle assembly is 400-650 nm;
preferably, the Ag nanoparticle assembly is prepared as follows:
dissolving a carboxyl-containing surfactant in a glycol solvent to form a mixed solution, and raising the temperature to 150-285 ℃; and then adding silver nitrate dissolved in a glycol solvent into the mixed solution for reaction, after the reaction is finished, performing centrifugal separation, and washing the solid to obtain the Ag nano-particle assembly.
According to the preparation method of the Ag nanoparticle assembly of the present invention, preferably, the surfactant containing a carboxyl group is polyacrylic acid, trimercaptoacetic acid, 11-mercaptoundecanoic acid, glutamic acid, or cysteine;
the glycol solvent is ethylene glycol, diethylene glycol or triethylene glycol;
the ratio of the mass of the carboxyl group-containing surfactant to the volume of the glycol solvent in the mixed solution is 0.2 to 10 g: 50 to 500mL, more preferably 0.3 to 1.2 g: 80-120 mL;
the mass ratio of the surface active agent containing carboxyl to the silver nitrate is 0.2-10 g: 2g, more preferably 0.3 to 1.2 g: 2g of the total weight of the mixture;
the reaction time is 1-30 min. The longer the reaction time is, the larger the obtained silver nanoparticle assembly is, and the larger the red shift degree of the UV-vis absorption peak of the assembly is;
the temperature of the mixed solution was raised to 160-280 ℃. Preferred reaction temperature intervals: 180 ℃ to 240 DEG C
According to the present invention, it is preferable that the Ag nanoparticle assembly is dispersed in the polar solvent at a concentration of 1.5-10 mg/mL.
According to the present invention, preferably, the polar solvent is deionized water, N-dimethylformamide, N-dimethylmethylacetamide or dimethyl sulfoxide.
According to the present invention, preferably, the film-forming polymer is polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, cellulose-based polymer, polyacrylic acid, polyvinylidene fluoride, acrylic, polystyrene, or polyethylene terephthalate;
preferably, the mass concentration of the film-forming polymer solution is from 4 to 15%.
According to the present invention, it is preferable that the mass ratio of the Ag nanoparticle assembly to the film-forming polymer is 1 mg: 0.12-2 g;
preferably, the number average molecular weight Mn of the polyethylene glycol is 200-;
preferably, the polyethylene glycol accounts for 5-15% of the total mass of the Ag nanoparticle assembly and the film-forming polymer in the system. Polyethylene glycol is added to prevent curling of the film during drying to form a film.
According to the present invention, the mixed solution is preferably dried to form a film in a manner that: pouring the mixed solution into a mold, and drying the mixed solution into a film by a tape casting method.
The principle and the beneficial effects of the invention are as follows:
according to the Mie formula, the imaginary part of the dielectric constant of the Ag nano-particles is smaller than that of Au and Cu, so that the SPR absorption intensity of the Ag nano-particles is stronger, the peak type is sharper, and the band-to-band transition energy of the Ag nano-particles is far larger than that of the Au nano-particles, so that the SPR absorption peak of the Ag nano-particles is obviously blue-shifted and is about 400nm, and the SPR absorption peak of the Au nano-particles is about 520 nm. Therefore, the visual stress color-changing film prepared by taking the Ag nano-particle assembly as the raw material can realize the color change in a wider range from blue to yellow, and compared with Au, Ag is lower in price and has higher practicability.
Drawings
FIG. 1 is a macroscopic color change plot of a colorimetric stress sensor made in accordance with example 1 of the present invention as the amount of strain gradually increases.
FIG. 2 is a stress-strain curve of a colorimetric stress sensor made in accordance with example 1 of the present invention.
FIG. 3 shows the macroscopic color change of the colorimetric stress sensor prepared in example 1 under different pressures, wherein the pressures from left to right are 0MPa, 2MPa, 5MPa, 10MPa and 15MPa in sequence.
FIG. 4 is a photomicrograph of a composite film made according to comparative example 2 of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be further described with reference to the following examples, but is not limited thereto, in conjunction with the accompanying drawings.
The Ag nanoparticle assemblies used in the examples were prepared as follows:
(1) 0.6g of polyacrylic acid and 80mL of ethylene glycol are mixed and added into a 250mL three-necked bottle, and the mixture is heated and heated under the magnetic stirring and nitrogen protection.
(2) When the temperature rises to 190 ℃, 2g of silver nitrate dissolved in 15mL of ethylene glycol is quickly injected into the mixed solution and reacts for 6min under mechanical stirring and nitrogen protection.
(3) And after the reaction is finished, cooling to room temperature, and centrifugally washing with acetone to obtain the Ag nano-particle assembly.
Adjusting the reaction time and the material ratio to obtain Ag nano-particle assemblies with different SPR absorption ranges.
Examples 1,
A method for preparing a colorimetric stress sensor based on an Ag nano-particle assembly comprises the following steps: the Ag nano-particle assembly with the SPR absorption range of 400-490 nm is dispersed in deionized water, and the preparation concentration is 5mg/mL for later use.
Polyvinyl alcohol (PVA) (Mw 130000) was dissolved by heating at 90 ℃ to prepare an aqueous PVA solution having a concentration of 10 wt.% for use.
300uL of the above Ag nanoparticle assembly solution (5mg/mL), 10g of polyvinyl alcohol (PVA) aqueous solution (10 wt.%), and 0.1g of polyethylene glycol (PEG) (Mn ═ 800) were mixed, and mixed uniformly by mechanical stirring.
And pouring the uniformly mixed PVA/Ag nano-particle assembly into a mold with the length, width and height of 6cm, 4cm and 2cm, and heating at 40 ℃ to form a film, thus obtaining the colorimetric stress sensor.
The composite film prepared in this embodiment can macroscopically change from bluish purple to red to orange to yellow as the deformation amount gradually increases under the action of tensile force, as shown in fig. 1.
Fig. 2 is a stress-strain curve of the colorimetric stress sensor obtained in this example. Colorimetric stress sensors can also produce a distinct color change under different pressures, as shown in FIG. 3. As can be seen from fig. 3, as the pressure gradually increases from 2, 5, 10 to 15MPa, the color of the colorimetric stress sensor changes from bluish purple to purplish red, orange yellow, and finally to bright yellow.
Example 2 modification of SPR absorption Range of Ag nanoparticle assemblies
As described in example 1, a method for preparing a colorimetric stress sensor based on Ag nanoparticle assembly includes the following steps:
the Ag nano-particle assembly with the SPR absorption range of 400-550 nm is dispersed in deionized water, and the preparation concentration is 5mg/mL for later use.
PVA (Mw 130000) was dissolved by heating at 90 ℃ to prepare an aqueous PVA solution having a concentration of 10 wt.% for use.
300uL of the above Ag nanoparticle assembly (5mg/mL), 10g of an aqueous polyvinyl alcohol (PVA) solution (10 wt.%), and 0.1g of polyethylene glycol (PEG) (Mn ═ 800) were mixed, and mechanically stirred and mixed uniformly. And pouring the uniformly mixed PVA/Ag nano-particle assembly into a mold with the length, width and height of 6cm, 4cm and 2cm, and heating at 40 ℃ to form a film, thus obtaining the colorimetric stress sensor.
The colorimetric stress sensor is macroscopically dark blue, can generate bright color change under the action of different pressures, and changes the color from blue to purple, red and orange yellow and finally to bright yellow along with the gradual increase of the pressure from 2, 6 and 12 to 20 MPa.
Example 3 changing PVA to polyvinylpyrrolidone PVP
As described in example 1, a method for preparing a colorimetric stress sensor based on Ag nanoparticle assembly includes the following steps:
the Ag nano-particle assembly with the SPR absorption range of 400-490 nm is dispersed in deionized water, and the preparation concentration is 5mg/mL for later use.
Polyvinylpyrrolidone (PVP) (Mw 30000) was dissolved by heating at 90 ℃ to prepare an aqueous solution having a concentration of 12 wt.% for use.
300uL of the above Ag nanoparticle assembly (5mg/mL), 10g of pvp aqueous solution (12 wt.%) and 0.1g of polyethylene glycol (PEG) (Mn ═ 800) were mixed, and mixed uniformly with mechanical stirring.
And pouring the uniformly mixed PVA/Ag nano-particle assembly into a mold with the length, width and height of 6cm, 4cm and 2cm, and heating at 60 ℃ to form a film, thus obtaining the colorimetric stress sensor.
The colorimetric stress sensor is macroscopically blue-purple, can generate vivid color change under the action of different pressures, and the color is changed from blue-purple to purple, red, orange yellow and finally to bright yellow along with the gradual increase of the pressure from 5, 10, 17 to 25 MPa.
Example 4 change PVA to polyethylene oxide PEO
As described in example 1, a method for preparing a colorimetric stress sensor based on Ag nanoparticle assembly includes the following steps:
the Ag nano-particle assembly with the SPR absorption range of 400-490 nm is dispersed in deionized water, and the preparation concentration is 5mg/mL for later use.
Polyethylene oxide (PEO) (Mw 200000) was dissolved by heating at 90 ℃ to prepare an aqueous solution having a concentration of 3 wt.% for use.
300uL of the above Ag nanoparticle assembly (5mg/mL), 10g of pvp aqueous solution (12 wt.%) and 0.1g of polyethylene glycol (PEG) (Mn ═ 800) were mixed, and mixed uniformly with mechanical stirring.
And pouring the uniformly mixed PVA/Ag nano-particle assembly into a mold with the length, width and height of 6cm, 4cm and 2cm, heating for 1h at 80 ℃, and drying at 50 ℃ to form a film, thus obtaining the colorimetric stress sensor.
The colorimetric stress sensor is macroscopically blue-purple, can generate vivid color change under the action of different pressures, and the color is changed into purple, red and orange yellow from blue-purple along with the gradual increase of the pressure from 3, 8 and 15 to 25MPa, and finally the color is changed into bright yellow.
Comparative example 1 increasing the concentration of Ag nanoparticle Assembly
As described in example 1, Ag nanoparticle assemblies with SPR absorption range of 400-490 nm were dispersed in deionized water at a concentration of 40mg/mL for future use.
PVA (Mw 130000) was dissolved by heating at 90 ℃ to prepare an aqueous PVA solution having a concentration of 10 wt.% for use.
300uL of the above Ag nanoparticle assembly (20mg/mL), 10g of an aqueous polyvinyl alcohol (PVA) solution (10 wt.%), and 0.1g of polyethylene glycol (PEG) (Mn ═ 800) were mixed, and mechanically stirred and mixed uniformly.
And pouring the uniformly mixed PVA/Ag nano-particle assembly into a mold with the length, width and height of 6cm, 4cm and 2cm, and heating at 40 ℃ to form a film.
The prepared film is macroscopically dark blue, but the color of the film can only be changed from dark blue to purple (30MPa) along with the increase of pressure due to the excessive concentration of the Ag nano-particle assembly.
Comparative example 2 change of polyvinyl alcohol to polydimethylsiloxane PDMS with increasing concentration
As described in example 1, Ag nanoparticle assemblies with SPR absorption range of 400-550 nm were dispersed in tetrahydrofuran solution at a concentration of 20mg/mL for use. The tetrahydrofuran dispersion of the Ag nanoparticle assembly was blended with PDMS, then a certain amount of cross-linking agent was added, mechanically stirred, and cross-linked at 50 ℃ to form a film (as shown in fig. 4). However, the film showed no color change under tension and pressure.
Comparative example 3 No polyethylene glycol addition
As described in example 1, Ag nanoparticle assemblies with SPR absorption range of 400-490 nm were dispersed in deionized water at a concentration of 5mg/mL for future use.
Polyvinyl alcohol (PVA) (Mw 130000) was dissolved by heating at 90 ℃ to prepare an aqueous PVA solution having a concentration of 10 wt.% for use.
300uL of the Ag nanoparticle assembly solution (5mg/mL) and 10g of polyvinyl alcohol (PVA) aqueous solution (10 wt.%) are respectively mixed, and the mixture is mechanically stirred and uniformly mixed.
And pouring the uniformly mixed PVA/Ag nano-particle assembly into a die with the length, width and height of 6cm, 4cm and 2cm, heating at 40 ℃ to form a film, and finally obtaining the seriously curled composite film with poor stress discoloration effect.
Claims (6)
1. A method for preparing a colorimetric stress sensor based on an Ag nano-particle assembly comprises the following steps:
dispersing the Ag nano-particle assembly in a polar solvent, adding a film-forming polymer solution, adding polyethylene glycol, uniformly stirring and defoaming to obtain a mixed solution;
drying the mixed solution to form a film, thus obtaining the colorimetric stress sensor;
the concentration of the Ag nano-particle assembly dispersed in the polar solvent is 1.5-10mg/mL, the film-forming polymer is polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, cellulose polymer, polyacrylic acid, polyvinylidene fluoride, acrylic, polystyrene or polyethylene glycol terephthalate, the mass concentration of the film-forming polymer solution is 4-15%, the SPR absorption range of the Ag nano-particle assembly is 400-650nm, the number average molecular weight Mn of the polyethylene glycol is =200-20000, and the polyethylene glycol accounts for 5-15% of the total mass of the Ag nano-particle assembly and the film-forming polymer in the system;
the Ag nano-particle assembly is prepared by the following method:
dissolving a carboxyl-containing surfactant in a glycol solvent to form a mixed solution, and raising the temperature to 150-oC; and then adding silver nitrate dissolved in a glycol solvent into the mixed solution for reaction, after the reaction is finished, performing centrifugal separation, and washing the solid to obtain the Ag nano-particle assembly.
2. The method for preparing a colorimetric stress sensor based on Ag nanoparticle assembly according to claim 1, wherein the surfactant containing carboxyl group is polyacrylic acid, trimercaptoacetic acid, 11-mercaptoundecanoic acid, glutamic acid or cysteine;
the glycol solvent is ethylene glycol, diethylene glycol or triethylene glycol;
the ratio of the mass of the carboxyl group-containing surfactant to the volume of the glycol solvent in the mixed solution is 0.2 to 10 g: 50-500 mL;
the mass ratio of the surface active agent containing carboxyl to the silver nitrate is 0.2-10 g: 2g of the total weight.
3. The method for preparing a colorimetric stress sensor based on Ag nanoparticle assembly according to claim 1, wherein the reaction time is 1-30min, and the reaction temperature range is: 180-240oC。
4. The method of claim 1, wherein the polar solvent is deionized water, N-dimethylformamide, N-dimethylformanide, or dimethylsulfoxide.
5. The method of claim 1, wherein the mass ratio of the Ag nanoparticle assembly to the film-forming polymer is 1 mg: 0.12-2 g.
6. The method for preparing a colorimetric stress sensor based on Ag nanoparticle assembly according to claim 1, wherein the mixed solution is dried to form a film in a manner of: pouring the mixed solution into a mold, and drying the mixed solution into a film by a tape casting method.
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| CN101760147A (en) * | 2009-08-22 | 2010-06-30 | 漳立冰 | Solvent type aeolotropic nano conductive adhesive and manufacturing method thereof |
| CN103200825A (en) * | 2010-11-02 | 2013-07-10 | 印度德里技术研究院 | Blue coloured aqueous dispersion of silver nanoparticles a process for preparation and compositions thereof |
| CN106415196A (en) * | 2014-04-04 | 2017-02-15 | 加州大学评议会 | Plasmonic nanoparticle-based colorimetric stress memory sensor |
| CN106623971A (en) * | 2016-12-08 | 2017-05-10 | 中国科学院深圳先进技术研究院 | Nano-silver particles for conductive ink and preparation method of nano-silver particles |
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| CN103200825A (en) * | 2010-11-02 | 2013-07-10 | 印度德里技术研究院 | Blue coloured aqueous dispersion of silver nanoparticles a process for preparation and compositions thereof |
| CN106415196A (en) * | 2014-04-04 | 2017-02-15 | 加州大学评议会 | Plasmonic nanoparticle-based colorimetric stress memory sensor |
| CN106623971A (en) * | 2016-12-08 | 2017-05-10 | 中国科学院深圳先进技术研究院 | Nano-silver particles for conductive ink and preparation method of nano-silver particles |
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