# Electrochemical Application of Structured Color Nanotextile Materials in Garment Design

Authors: Zekai Zhang
Journal: Journal of Chemistry
 (2022)

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## Abstract

In order to improve the color saturation of textile structured chromogenic photonic crystals, this paper proposes that the dye adsorbed PSt structural elements (reactive dyes/PSt microspheres) on the outer surface can be used to construct electrochemically structured chromogenic photonic crystals on mulberry fabrics by digital printing. In this method, the adsorption conditions and adsorption model of dyes on the surface of PSt colloidal microspheres were studied. The structure and morphology of reactive dyes/PSt microspheres, the arrangement of the obtained photonic crystals, and the structural chromogenic effect were characterized. The results showed that the amount of dye adsorbed on the surface of microspheres increased significantly with the increase of adsorption temperature from 25°C to 65°C. When the adsorption temperature continued to rise to 75°C, the dye adsorption capacity on the surface of PSt microspheres did not increase significantly. The adsorption model accords with the Langmuir model; reactive dye/PSt microspheres have a typical core-shell structure, and the particle size of the microspheres is slightly larger than that before adsorption.Conclusion. The reactive dye/PSt photonic crystal chromogenic electrochemical structure constructed on the surface of white silk fabric has a regular and orderly arrangement of microspheres, showing bright structural color.


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## Body

## 1. Introduction

Textiles are mainly colored by applying dyes or pigments. In recent years, some new textile coloring technologies are emerging. Among them, the construction of photonic crystals on textile substrates, through the diffraction of light and other functions, to obtain the structural color effect to realize the ecological and environmental coloring of textiles has attracted the attention of researchers. As a typical physical color, the structural color produced by regularly arranged crystalline photonic crystals usually has the characteristics of high saturation, high brightness, and rainbow effect, which helps to enrich the pigment color and make the finishing point. However, it is challenging to construct photonic crystal electrochemistry structures on textile substrates to realize textile coloring. Textile is a kind of rough, porous, and flexible material with certain undulation, which can be divided into woven, knitted, and nonwoven kinds according to the weaving method [1]. Different weaving and processing methods will have different effects on the properties of textiles, which brings challenges to the construction of photonic crystal structures on textile substrates. At the same time, it is also difficult to prepare bright and colorful structural color films. Therefore, finding a textile substrate suitable for colloidal microsphere self-assembly to construct regular photonic crystals and obtain bright structural color effect will have good practical significance for realizing textile photonic crystal structure coloring, as shown in Figure 1.Figure 1
Clothing design process.The colloidal microsphere self-assembly method has the advantages of simple operation and good practicability. It is the most widely used method for preparing photonic crystals, mainly including the gravity sedimentation method, vertical sedimentation method, centrifugal deposition method, and electrophoretic deposition method. [2]. However, the above conventional colloidal microspheres self-assembly method has the disadvantages of low efficiency and long time, which greatly inhibits the application of photonic crystal structure color in the textile field. Therefore, there is an urgent need to develop a colloidal microsphere self-assembly method that is practical, efficient, and suitable for the preparation of good photonic crystal chromogenic electrochemical structures. As a common method in industrial production, the spraying method has the advantages of simple operation, high efficiency, and low cost and can realize large-area rapid prototyping of materials on the plane and curved surface [3]. If the spraying method and colloidal microsphere self-assembly method can be combined, it is expected to open up a large-area, rapid, and efficient way to prepare photonic crystals, which will help to promote the practical application of photonic crystal structure color. After selecting suitable textile substrates and rapidly constructing the photochromic electrochemical structure of photonic crystals, the stability of the electrochromic structure of photonic crystals will become an important bottleneck restricting the application of the electrochromic structure of photonic crystals [4]. When undergoing simple folding, bending, washing, and friction, the photonic crystal structure is easy to fall off from the substrate and the corresponding structural color effect is easy to be reduced. Therefore, how to improve the stability of the electrochemical structure of photonic crystal color generation and retain the structural color effect is a problem that researchers in the field of photonic crystal structure color generation pay close attention to.


## 2. Literature Review

Graves et al. added photosensitive pigments and thermal pigments to the spinning solution through electrospinning to prepare electrospun cellulose acetate fiber with corresponding color-changing ability, which filled the research gap of photon sensor in electrospun cellulose acetate (CA)and obtained fabrics with photothermal color changing ability [5]. Guo et al. took carbon nanotube/cotton composite yarn (CCY) as the core and nanofiber polyurethane/temperature sensitive ink as the sheath and prepared skin core nanocomposite yarn with excellent mechanical properties, electrothermal properties, and electrochromic properties; that is, color change will occur when there is a charge on the fabric [6]. J. M. et al. synthesized magnetic nanosphere with magnetochromic ability by the hydrothermal method, mixed it with resin polyethylene glycol diacrylate (PEGDA), and then irradiated it with ultraviolet light to prepare cured color fiber. This magnetochromic dispersion is a kind of magnetochromic material [7]. Duaux et al. reported the preparation of thermochromic cotton fabric, that is, its smart application in children’s clothing. However, some challenges still exist. The cost of thermochromic dyes or pigments is particularly high, the durability of thermochromic fibers is poor, and the manufacturing process is complex [8]. Therefore, it is still very necessary to develop a new method for continuously manufacturing thermochromic fibers. Dhiman et al. reported the use of a modular microfluidic system to manufacture alginate microfibers for magnetic response control of drug release and cell culture [9]. Syrek et al. continuously prepared carboxylated chitosan, polyvinyl alcohol, and hydrophobic ethylene vinyl alcohol copolymer (EVOH) spiral microfibers through microfluidic technology. Guo et al. prepared conductive PEDOT: PSS polymer hydrogel microfibers from multiflow microfluidic spinning [10]. Qu et al. used a new buoyancy-assisted vertical microfluidic device to produce a deformable hydrogel microfiber filled with bubbles. However, there are relatively few studies on manufacturing thermochromic fibers by microfluidic spinning [11].In this paper, the black reactive dye was introduced into the surface of PSt colloidal microspheres by electrostatic adsorption, and the reactive dye/PSt composite colloidal microspheres were prepared. The structured reactive dye/PSt photonic crystals were constructed on mulberry silk fabrics by digital spray printing, showing bright structural colors, in order to provide a reference for the application of structural color and pigment color coupling in textiles.


## 3. Research Methods

### 3.1. Experimental Materials and Instruments

Materials used included silk fabric (electric spinning, area density 45.7), commercially available; styrene (st, analytically pure); polyvinylpyrrolidone (PVP, analytically pure); azobisisobutyl ether hydrochloride (AIBA, analytical purity); deionized water (conductivity: 18 m Ω/cm), self-made in the laboratory; water-repellent EPF (industrial grade); and reactive black (industrial grade).Instruments used were Lambda-35 ultraviolet visible spectrophotometer; Brook-21 zeta potentiometer; Mastersizer-2000 Malvern laser particle sizer; Altra55 field emission scanning electron microscope; Jem2100 transmission electron microscope; 600D digital camera; KH-7700 3D video microscope; Judge-II standard light source box; and 7000 d dialysis bag.


### 3.2. Sample Preparation Method

#### 3.2.1. Pretreatment of Silk Fabric

In order to prevent the seeping phenomenon in the process of digital jet printing, the mulberry silk fabric was treated with EPF solution with a mass fraction of 1% for two dipping and two rolling processes (the rolling yield was 90%) [12]. The pretreatment of mulberry silk fabric was completed by predrying at 80°C for 3 min and 130°C for 2 min.


#### 3.2.2. Preparation of Reactive Dye/PSt Microspheres

Using the dispersion polymerization method, we weigh 1.5 g of PVP dispersant, 10.0 g of St monomer, and 90.0 g of deionized water, respectively, and add them to the three-necked flask. We place the three-necked flask in a constant temperature water bath for heating and stirring. When the temperature rises to 75°C, we add 0.15 g of AIBA (initiator) dissolved in 10.0 g of deionized water into the three-necked flask and make them react at a constant temperature for 7 hours at a speed of 300 R/min, so as to prepare positively charged PSt microspheres with a particle size of 247 nm [13]. The positively charged PSt colloidal microspheres with good monodispersity (PDI < 0.08) and particle size in the range of 180∼350 nm can be prepared by adjusting the amount of monomer and initiator. Reactive black was added to the PSt microsphere lotion of a certain concentration, stirred, and adsorbed at a specific temperature for a certain period of time, and the reactive dye/PSt microsphere was obtained after centrifugal cleaning with deionized water.


#### 3.2.3. Self-Assembly of Reactive Dye/PSt Microspheres by Spray Printing

The reactive dye/PSt colloidal microsphere lotion was sprayed onto the mulberry silk fabric with a desktop dispensing system (the nozzle diameter was 0.15 mm, and the printing pressure was 0.20 MPa). Reactive dye/PSt structure chromogenic photonic crystals can be obtained after the solvent is completely evaporated in a 60°C blast oven.


### 3.3. Testing and Characterization

#### 3.3.1. Characterization of Physical Properties of Colloidal Microspheres

The average particle size of colloidal microspheres was measured with a Malvin laser particle sizer, and the surface potential of colloidal microspheres was measured with a Zeta potentiometer. The structure and morphology of colloidal microspheres were observed by TEM and FESEM.


#### 3.3.2. Drawing of Adsorption Isotherm and Calculation of Normal Deviation

A UV visible spectrophotometer is used to test the absorbance value at the maximum absorption wavelength of reactive dye solutions with different mass fractions, and the standard working curve of dyes is drawn [14]. We determine the absorbance of dialysate of reactive dye/PSt microspheres, calculate the adsorption amount of dye on the microspheres by Lambert–Beer law, and draw the adsorption rate curve. The deviation between the experimental value and the theoretical value calculated from the adsorption equation is called the normal deviation (ND). By judging the fitting degree between the experimental point and the adsorption model, the calculation formula is as follows:(1)ND=1N∑i=1NCf,1calc−Cf,1expCf,1exp,where Cf,icalc and Cf,iexp are the calculated and experimental values of dye adsorption capacity on the microspheres, respectively, and N is the number of experimental points.


#### 3.3.3. Morphology and Color Characterization of Structured Chromogenic Photonic Crystals

The surface morphology of the structure colored photonic crystals prepared on the fabric was observed by FESEM. The photonic crystal structure color on mulberry silk fabric was observed with a digital camera and three-dimensional video microscope. The reflectance curve of the structured chromogenic photonic crystal constructed on the fabric in the range of 400∼700 nm was measured using the UV-Vis spectrophotometer.


## 3.1. Experimental Materials and Instruments

Materials used included silk fabric (electric spinning, area density 45.7), commercially available; styrene (st, analytically pure); polyvinylpyrrolidone (PVP, analytically pure); azobisisobutyl ether hydrochloride (AIBA, analytical purity); deionized water (conductivity: 18 m Ω/cm), self-made in the laboratory; water-repellent EPF (industrial grade); and reactive black (industrial grade).Instruments used were Lambda-35 ultraviolet visible spectrophotometer; Brook-21 zeta potentiometer; Mastersizer-2000 Malvern laser particle sizer; Altra55 field emission scanning electron microscope; Jem2100 transmission electron microscope; 600D digital camera; KH-7700 3D video microscope; Judge-II standard light source box; and 7000 d dialysis bag.


## 3.2. Sample Preparation Method

### 3.2.1. Pretreatment of Silk Fabric

In order to prevent the seeping phenomenon in the process of digital jet printing, the mulberry silk fabric was treated with EPF solution with a mass fraction of 1% for two dipping and two rolling processes (the rolling yield was 90%) [12]. The pretreatment of mulberry silk fabric was completed by predrying at 80°C for 3 min and 130°C for 2 min.


### 3.2.2. Preparation of Reactive Dye/PSt Microspheres

Using the dispersion polymerization method, we weigh 1.5 g of PVP dispersant, 10.0 g of St monomer, and 90.0 g of deionized water, respectively, and add them to the three-necked flask. We place the three-necked flask in a constant temperature water bath for heating and stirring. When the temperature rises to 75°C, we add 0.15 g of AIBA (initiator) dissolved in 10.0 g of deionized water into the three-necked flask and make them react at a constant temperature for 7 hours at a speed of 300 R/min, so as to prepare positively charged PSt microspheres with a particle size of 247 nm [13]. The positively charged PSt colloidal microspheres with good monodispersity (PDI < 0.08) and particle size in the range of 180∼350 nm can be prepared by adjusting the amount of monomer and initiator. Reactive black was added to the PSt microsphere lotion of a certain concentration, stirred, and adsorbed at a specific temperature for a certain period of time, and the reactive dye/PSt microsphere was obtained after centrifugal cleaning with deionized water.


### 3.2.3. Self-Assembly of Reactive Dye/PSt Microspheres by Spray Printing

The reactive dye/PSt colloidal microsphere lotion was sprayed onto the mulberry silk fabric with a desktop dispensing system (the nozzle diameter was 0.15 mm, and the printing pressure was 0.20 MPa). Reactive dye/PSt structure chromogenic photonic crystals can be obtained after the solvent is completely evaporated in a 60°C blast oven.


## 3.2.1. Pretreatment of Silk Fabric

In order to prevent the seeping phenomenon in the process of digital jet printing, the mulberry silk fabric was treated with EPF solution with a mass fraction of 1% for two dipping and two rolling processes (the rolling yield was 90%) [12]. The pretreatment of mulberry silk fabric was completed by predrying at 80°C for 3 min and 130°C for 2 min.


## 3.2.2. Preparation of Reactive Dye/PSt Microspheres

Using the dispersion polymerization method, we weigh 1.5 g of PVP dispersant, 10.0 g of St monomer, and 90.0 g of deionized water, respectively, and add them to the three-necked flask. We place the three-necked flask in a constant temperature water bath for heating and stirring. When the temperature rises to 75°C, we add 0.15 g of AIBA (initiator) dissolved in 10.0 g of deionized water into the three-necked flask and make them react at a constant temperature for 7 hours at a speed of 300 R/min, so as to prepare positively charged PSt microspheres with a particle size of 247 nm [13]. The positively charged PSt colloidal microspheres with good monodispersity (PDI < 0.08) and particle size in the range of 180∼350 nm can be prepared by adjusting the amount of monomer and initiator. Reactive black was added to the PSt microsphere lotion of a certain concentration, stirred, and adsorbed at a specific temperature for a certain period of time, and the reactive dye/PSt microsphere was obtained after centrifugal cleaning with deionized water.


## 3.2.3. Self-Assembly of Reactive Dye/PSt Microspheres by Spray Printing

The reactive dye/PSt colloidal microsphere lotion was sprayed onto the mulberry silk fabric with a desktop dispensing system (the nozzle diameter was 0.15 mm, and the printing pressure was 0.20 MPa). Reactive dye/PSt structure chromogenic photonic crystals can be obtained after the solvent is completely evaporated in a 60°C blast oven.


## 3.3. Testing and Characterization

### 3.3.1. Characterization of Physical Properties of Colloidal Microspheres

The average particle size of colloidal microspheres was measured with a Malvin laser particle sizer, and the surface potential of colloidal microspheres was measured with a Zeta potentiometer. The structure and morphology of colloidal microspheres were observed by TEM and FESEM.


### 3.3.2. Drawing of Adsorption Isotherm and Calculation of Normal Deviation

A UV visible spectrophotometer is used to test the absorbance value at the maximum absorption wavelength of reactive dye solutions with different mass fractions, and the standard working curve of dyes is drawn [14]. We determine the absorbance of dialysate of reactive dye/PSt microspheres, calculate the adsorption amount of dye on the microspheres by Lambert–Beer law, and draw the adsorption rate curve. The deviation between the experimental value and the theoretical value calculated from the adsorption equation is called the normal deviation (ND). By judging the fitting degree between the experimental point and the adsorption model, the calculation formula is as follows:(1)ND=1N∑i=1NCf,1calc−Cf,1expCf,1exp,where Cf,icalc and Cf,iexp are the calculated and experimental values of dye adsorption capacity on the microspheres, respectively, and N is the number of experimental points.


### 3.3.3. Morphology and Color Characterization of Structured Chromogenic Photonic Crystals

The surface morphology of the structure colored photonic crystals prepared on the fabric was observed by FESEM. The photonic crystal structure color on mulberry silk fabric was observed with a digital camera and three-dimensional video microscope. The reflectance curve of the structured chromogenic photonic crystal constructed on the fabric in the range of 400∼700 nm was measured using the UV-Vis spectrophotometer.


## 3.3.1. Characterization of Physical Properties of Colloidal Microspheres

The average particle size of colloidal microspheres was measured with a Malvin laser particle sizer, and the surface potential of colloidal microspheres was measured with a Zeta potentiometer. The structure and morphology of colloidal microspheres were observed by TEM and FESEM.


## 3.3.2. Drawing of Adsorption Isotherm and Calculation of Normal Deviation

A UV visible spectrophotometer is used to test the absorbance value at the maximum absorption wavelength of reactive dye solutions with different mass fractions, and the standard working curve of dyes is drawn [14]. We determine the absorbance of dialysate of reactive dye/PSt microspheres, calculate the adsorption amount of dye on the microspheres by Lambert–Beer law, and draw the adsorption rate curve. The deviation between the experimental value and the theoretical value calculated from the adsorption equation is called the normal deviation (ND). By judging the fitting degree between the experimental point and the adsorption model, the calculation formula is as follows:(1)ND=1N∑i=1NCf,1calc−Cf,1expCf,1exp,where Cf,icalc and Cf,iexp are the calculated and experimental values of dye adsorption capacity on the microspheres, respectively, and N is the number of experimental points.


## 3.3.3. Morphology and Color Characterization of Structured Chromogenic Photonic Crystals

The surface morphology of the structure colored photonic crystals prepared on the fabric was observed by FESEM. The photonic crystal structure color on mulberry silk fabric was observed with a digital camera and three-dimensional video microscope. The reflectance curve of the structured chromogenic photonic crystal constructed on the fabric in the range of 400∼700 nm was measured using the UV-Vis spectrophotometer.


## 4. Result Analysis

### 4.1. Process Parameters of Reactive Dye/PSt Microspheres

#### 4.1.1. Dye Mass Fraction

During the polymerization of polystyrene, due to the introduction of positive initiator AIBA, the PSt colloidal microspheres synthesized in the experiment are positively charged, which can adsorb anionic reactive dyes [15]. Figure 2 shows the dye adsorption amount on the surface of PSt colloidal microspheres after adsorption at 60°C for 40 min. It can be seen that when the mass fraction of dye is less than 0.5%, the dye adsorption capacity on the surface of PSt microspheres increases significantly with the increase of the amount of dye. When the dye mass fraction was higher than 0.5%, the dye adsorption on the surface of PSt microspheres tended to be saturated and the increment was not obvious. Figure 3 shows the zeta potential curve of PSt microspheres under different dye dosages. It can be seen that the zeta potential of PSt colloidal microspheres is about +30 mV before dye adsorption. When the adsorption amount of reactive dyes increases from 0% to 0.5%, the corresponding zeta potential drops sharply. This should be driven by electrostatic attraction; many reactive dye anions are adsorbed on the surface of PSt microspheres. With the increase of dye mass fraction, the dye adsorption amount on the surface of PSt microspheres also increases. When the dye mass fraction reaches more than 0.5%, the zeta potential of the microsphere lotion tends to be stable, lower than −30 mV, showing good stability [16]. It showed that when the mass fraction of dye reached 0.5%, the adsorption of reactive dye molecules on the surface of PSt microspheres basically reached saturation. To sum up, the appropriate dye mass fraction is determined to be 0.5%.Figure 2
Dye adsorption capacity on the surface of PSt colloidal microspheres under different dye mass fractions.Figure 3
Zeta potential of PSt colloidal microspheres with different dye mass fractions.


#### 4.1.2. Adsorption Time

Figure4 shows the effect of different adsorption time periods on the dye adsorption capacity on the surface of PSt colloidal microspheres at 60°C and 0.5% dye mass fraction.Figure 4
Dye adsorption amount on the surface of PSt colloidal microspheres at different adsorption time periods.It can be seen that in the first 30 minutes of adsorption, the adsorption amount of reactive dyes on the surface of PSt microspheres increased linearly with the extension of adsorption time. If the adsorption time was prolonged, the dye adsorption capacity increased slowly. When the adsorption time was more than 40 min, the adsorption amount of dye did not increase significantly with the extension of adsorption time. This is mainly because, in the initial adsorption stage, there are a large number of positive charges on the surface of PSt microspheres, which makes a large number of anionic reactive dyes quickly adsorb to the surface of the microspheres; With the prolongation of adsorption time, the adsorption of anionic reactive dyes gradually reduced the positive electricity of the surface of the microspheres, and the subsequent increase in the amount of dye adsorption tended to moderate. In the later stage, the adsorption time continues to be extended, and the adsorption amount gradually reaches saturation and remains basically unchanged [17]. In conclusion, 40 min is a more suitable adsorption time.


#### 4.1.3. Adsorption Temperature

Figure5 shows the effect of different adsorption temperatures on the dye adsorption capacity of PSt colloidal microspheres when the dye mass fraction is 0.5% and the adsorption time is 40 min.Figure 5
Dye adsorption capacity of PSt colloidal microspheres at different adsorption temperatures.It can be seen from Figure5 that the dye adsorption amount on the surface of microspheres increased significantly with the increase of adsorption temperature from 25°C to 65°C. When the adsorption temperature continued to rise to 75°C, the dye adsorption on the surface of PSt microspheres did not increase significantly. This is because the higher the adsorption temperature is, the more intense the Brownian motion of reactive dye molecules and PSt microspheres becomes. The faster the reactive dye diffuses to the surface of microspheres, the more the dye adsorbed on the surface of microspheres. However, increasing the adsorption temperature will also accelerate the desorption rate of reactive dye on the surface of microspheres [18]. According to the comprehensive analysis, the adsorption temperature should be kept at about 65°C.


### 4.2. Adsorption Model of Dyes on PSt Colloidal Microspheres

In order to improve the controllability of the adsorption of reactive dyes on the surface of PSt colloidal microspheres and provide better theoretical guidance for its process optimization, the adsorption model of reactive dyes on the surface of PSt colloidal microspheres was further studied. Under the conditions of dye mass fraction of 0.5% and adsorption time of 40 min, the adsorption isotherms of reactive dyes on the surface of PSt colloidal microspheres at 25°C, 45°C, and 65°C were plotted. Three common theoretical adsorption models (Nernst, Langmuir, and Freundlich) were used to fit the adsorption isotherms at different temperatures by the nonlinear least square method.By comparing the corresponding normal deviation and fitting coefficient, the conformity degree of the three adsorption models is analyzed (see Table1). The specific adsorption equation is shown in equations (2) to (4).Table 1
Simulation results of adsorption isotherms of reactive dyes on PSt colloidal microspheres.
Temperature/°CNernst modelLangmuir modelFreundlich modelND%R2ND%R2ND%R22536.20.8534.10.99017.00.9434540.60.8322.30.99417.50.9436527.10.9041.10.99713.80.968


#### 4.2.1. Nernst Type

(2)Df=K1Ds.Here, Df is the concentration of dye on the fiber; Ds is the concentration of the dye in the dye solution; and K1 is the Nernst adsorption constant.


#### 4.2.2. Langmuir Type

(3)Df=K2DsSf1+KDs.Here, K2 is Langmuir adsorption constant and Sf is the dyeing saturation value of the fiber.


#### 4.2.3. Freundlich Type

(4)Df=K3Dsn.Here, K3 is Freundlich adsorption constant and n is the heterogeneity factor, 0＜n＜1.It can be seen from Table1 that under three different temperatures, the R2 of Nernst type and Freundlich type are low and the ND is large. The Langmuir model has the highest R2 , which is more than 0.99, and the corresponding ND is also the lowest [19]. Therefore, the adsorption model of reactive dyes on PSt colloidal microspheres is more in line with the Langmuir model. It can be seen that reactive dyes are localized on the surface of PSt microspheres. That is, a certain number of adsorption sites are formed on the surface of positively charged PSt colloidal microspheres, which promotes the localized adsorption of anionic reactive dyes, and there is an adsorption saturation value in the adsorption process. When the adsorption reaches a certain degree, the adsorption amount basically remains unchanged.


### 4.3. Apparent Morphology of Reactive Dye/PSt Microspheres

From the SEM and TEM photos before and after dye adsorption on the surface of PSt microspheres, it can be concluded that after dye adsorption, the reactive dye/PSt microspheres still maintain a typical core-shell structure and the sphericity is still good. The dye adsorption has no significant effect on the sphericity of colloidal microspheres. However, after adsorption of dyes, the particle size of reactive dye/PSt microspheres increased from 184.5 nm to 196.3 nm and the shell thickness increased from 30.7 nm to 36.6 nm. This may be because a large number of dye molecules are adsorbed on the surface of PSt microspheres, which can adsorb a certain amount of water molecules at the same time, resulting in a slight increase in the particle size of the microspheres.


### 4.4. Application of Reactive Dye/PSt Microspheres

From the self-assembled photonic crystal structures and corresponding structural colors of reactive dyes/PSt microspheres with different particle sizes on mulberry silk fabrics, it can be concluded that the structures of reactive dyes/PSt photonic crystals on mulberry silk fabrics are orderly arranged, showing uniform and bright structural colors; And with the decrease of the particle size of colloidal microspheres, the corresponding structural colors also show different hues such as red, orange, green, blue, and purple, and an obvious blue shift occurs [6].Reflectivity Curves of Self-Assembled Photonic Crystals with Different Particle Sizes of Reactive Dye/PSt Microspheres on White Mulberry Silk Fabric. It can be seen that as the particle size of the reactive dye/PSt microspheres decreases from 317, 298, 247, and 201 nm to 188 nm, the maximum reflection wavelength of the structure-colored photonic crystal gradually changes from 615 nm to 418 nm, which corresponds to the color phenomenon of the self-assembled photonic crystal structure of reactive dye/PSt microspheres with different particle sizes sprayed on mulberry fabric, that is, there is an obvious blue shift, which conforms to the Bragg diffraction equation.Before dye adsorption, the structure color of pure PSt microspheres on white mulberry silk fabric was dim, showing light blue and light green. After adsorbing the dye, the reactive dye/PSt photonic crystal on the same substrate shows bright blue and green and the corresponding color saturation is significantly improved. This is because the white fabric can easily reflect almost all the incident light passing through the photonic crystal layer without selectivity, diluting the structural color of the selective reflection of the photonic crystal. The black dye can significantly absorb the background stray light and make the light reflected by the photonic crystal maintain good purity and saturation without the interference of additional light [20]. The results show that the structure color effect of reactive dye/PSt photonic crystal on white mulberry silk fabric is better than that of pure PSt photonic crystal. It can be concluded that the introduction of black reactive dyes into the surface of PSt microspheres to prepare composite structural units can effectively enhance the color saturation of the structure chromogenic photonic crystals on the white substrate.


## 4.1. Process Parameters of Reactive Dye/PSt Microspheres

### 4.1.1. Dye Mass Fraction

During the polymerization of polystyrene, due to the introduction of positive initiator AIBA, the PSt colloidal microspheres synthesized in the experiment are positively charged, which can adsorb anionic reactive dyes [15]. Figure 2 shows the dye adsorption amount on the surface of PSt colloidal microspheres after adsorption at 60°C for 40 min. It can be seen that when the mass fraction of dye is less than 0.5%, the dye adsorption capacity on the surface of PSt microspheres increases significantly with the increase of the amount of dye. When the dye mass fraction was higher than 0.5%, the dye adsorption on the surface of PSt microspheres tended to be saturated and the increment was not obvious. Figure 3 shows the zeta potential curve of PSt microspheres under different dye dosages. It can be seen that the zeta potential of PSt colloidal microspheres is about +30 mV before dye adsorption. When the adsorption amount of reactive dyes increases from 0% to 0.5%, the corresponding zeta potential drops sharply. This should be driven by electrostatic attraction; many reactive dye anions are adsorbed on the surface of PSt microspheres. With the increase of dye mass fraction, the dye adsorption amount on the surface of PSt microspheres also increases. When the dye mass fraction reaches more than 0.5%, the zeta potential of the microsphere lotion tends to be stable, lower than −30 mV, showing good stability [16]. It showed that when the mass fraction of dye reached 0.5%, the adsorption of reactive dye molecules on the surface of PSt microspheres basically reached saturation. To sum up, the appropriate dye mass fraction is determined to be 0.5%.Figure 2
Dye adsorption capacity on the surface of PSt colloidal microspheres under different dye mass fractions.Figure 3
Zeta potential of PSt colloidal microspheres with different dye mass fractions.


### 4.1.2. Adsorption Time

Figure4 shows the effect of different adsorption time periods on the dye adsorption capacity on the surface of PSt colloidal microspheres at 60°C and 0.5% dye mass fraction.Figure 4
Dye adsorption amount on the surface of PSt colloidal microspheres at different adsorption time periods.It can be seen that in the first 30 minutes of adsorption, the adsorption amount of reactive dyes on the surface of PSt microspheres increased linearly with the extension of adsorption time. If the adsorption time was prolonged, the dye adsorption capacity increased slowly. When the adsorption time was more than 40 min, the adsorption amount of dye did not increase significantly with the extension of adsorption time. This is mainly because, in the initial adsorption stage, there are a large number of positive charges on the surface of PSt microspheres, which makes a large number of anionic reactive dyes quickly adsorb to the surface of the microspheres; With the prolongation of adsorption time, the adsorption of anionic reactive dyes gradually reduced the positive electricity of the surface of the microspheres, and the subsequent increase in the amount of dye adsorption tended to moderate. In the later stage, the adsorption time continues to be extended, and the adsorption amount gradually reaches saturation and remains basically unchanged [17]. In conclusion, 40 min is a more suitable adsorption time.


### 4.1.3. Adsorption Temperature

Figure5 shows the effect of different adsorption temperatures on the dye adsorption capacity of PSt colloidal microspheres when the dye mass fraction is 0.5% and the adsorption time is 40 min.Figure 5
Dye adsorption capacity of PSt colloidal microspheres at different adsorption temperatures.It can be seen from Figure5 that the dye adsorption amount on the surface of microspheres increased significantly with the increase of adsorption temperature from 25°C to 65°C. When the adsorption temperature continued to rise to 75°C, the dye adsorption on the surface of PSt microspheres did not increase significantly. This is because the higher the adsorption temperature is, the more intense the Brownian motion of reactive dye molecules and PSt microspheres becomes. The faster the reactive dye diffuses to the surface of microspheres, the more the dye adsorbed on the surface of microspheres. However, increasing the adsorption temperature will also accelerate the desorption rate of reactive dye on the surface of microspheres [18]. According to the comprehensive analysis, the adsorption temperature should be kept at about 65°C.


## 4.1.1. Dye Mass Fraction

During the polymerization of polystyrene, due to the introduction of positive initiator AIBA, the PSt colloidal microspheres synthesized in the experiment are positively charged, which can adsorb anionic reactive dyes [15]. Figure 2 shows the dye adsorption amount on the surface of PSt colloidal microspheres after adsorption at 60°C for 40 min. It can be seen that when the mass fraction of dye is less than 0.5%, the dye adsorption capacity on the surface of PSt microspheres increases significantly with the increase of the amount of dye. When the dye mass fraction was higher than 0.5%, the dye adsorption on the surface of PSt microspheres tended to be saturated and the increment was not obvious. Figure 3 shows the zeta potential curve of PSt microspheres under different dye dosages. It can be seen that the zeta potential of PSt colloidal microspheres is about +30 mV before dye adsorption. When the adsorption amount of reactive dyes increases from 0% to 0.5%, the corresponding zeta potential drops sharply. This should be driven by electrostatic attraction; many reactive dye anions are adsorbed on the surface of PSt microspheres. With the increase of dye mass fraction, the dye adsorption amount on the surface of PSt microspheres also increases. When the dye mass fraction reaches more than 0.5%, the zeta potential of the microsphere lotion tends to be stable, lower than −30 mV, showing good stability [16]. It showed that when the mass fraction of dye reached 0.5%, the adsorption of reactive dye molecules on the surface of PSt microspheres basically reached saturation. To sum up, the appropriate dye mass fraction is determined to be 0.5%.Figure 2
Dye adsorption capacity on the surface of PSt colloidal microspheres under different dye mass fractions.Figure 3
Zeta potential of PSt colloidal microspheres with different dye mass fractions.


## 4.1.2. Adsorption Time

Figure4 shows the effect of different adsorption time periods on the dye adsorption capacity on the surface of PSt colloidal microspheres at 60°C and 0.5% dye mass fraction.Figure 4
Dye adsorption amount on the surface of PSt colloidal microspheres at different adsorption time periods.It can be seen that in the first 30 minutes of adsorption, the adsorption amount of reactive dyes on the surface of PSt microspheres increased linearly with the extension of adsorption time. If the adsorption time was prolonged, the dye adsorption capacity increased slowly. When the adsorption time was more than 40 min, the adsorption amount of dye did not increase significantly with the extension of adsorption time. This is mainly because, in the initial adsorption stage, there are a large number of positive charges on the surface of PSt microspheres, which makes a large number of anionic reactive dyes quickly adsorb to the surface of the microspheres; With the prolongation of adsorption time, the adsorption of anionic reactive dyes gradually reduced the positive electricity of the surface of the microspheres, and the subsequent increase in the amount of dye adsorption tended to moderate. In the later stage, the adsorption time continues to be extended, and the adsorption amount gradually reaches saturation and remains basically unchanged [17]. In conclusion, 40 min is a more suitable adsorption time.


## 4.1.3. Adsorption Temperature

Figure5 shows the effect of different adsorption temperatures on the dye adsorption capacity of PSt colloidal microspheres when the dye mass fraction is 0.5% and the adsorption time is 40 min.Figure 5
Dye adsorption capacity of PSt colloidal microspheres at different adsorption temperatures.It can be seen from Figure5 that the dye adsorption amount on the surface of microspheres increased significantly with the increase of adsorption temperature from 25°C to 65°C. When the adsorption temperature continued to rise to 75°C, the dye adsorption on the surface of PSt microspheres did not increase significantly. This is because the higher the adsorption temperature is, the more intense the Brownian motion of reactive dye molecules and PSt microspheres becomes. The faster the reactive dye diffuses to the surface of microspheres, the more the dye adsorbed on the surface of microspheres. However, increasing the adsorption temperature will also accelerate the desorption rate of reactive dye on the surface of microspheres [18]. According to the comprehensive analysis, the adsorption temperature should be kept at about 65°C.


## 4.2. Adsorption Model of Dyes on PSt Colloidal Microspheres

In order to improve the controllability of the adsorption of reactive dyes on the surface of PSt colloidal microspheres and provide better theoretical guidance for its process optimization, the adsorption model of reactive dyes on the surface of PSt colloidal microspheres was further studied. Under the conditions of dye mass fraction of 0.5% and adsorption time of 40 min, the adsorption isotherms of reactive dyes on the surface of PSt colloidal microspheres at 25°C, 45°C, and 65°C were plotted. Three common theoretical adsorption models (Nernst, Langmuir, and Freundlich) were used to fit the adsorption isotherms at different temperatures by the nonlinear least square method.By comparing the corresponding normal deviation and fitting coefficient, the conformity degree of the three adsorption models is analyzed (see Table1). The specific adsorption equation is shown in equations (2) to (4).Table 1
Simulation results of adsorption isotherms of reactive dyes on PSt colloidal microspheres.
Temperature/°CNernst modelLangmuir modelFreundlich modelND%R2ND%R2ND%R22536.20.8534.10.99017.00.9434540.60.8322.30.99417.50.9436527.10.9041.10.99713.80.968


### 4.2.1. Nernst Type

(2)Df=K1Ds.Here, Df is the concentration of dye on the fiber; Ds is the concentration of the dye in the dye solution; and K1 is the Nernst adsorption constant.


### 4.2.2. Langmuir Type

(3)Df=K2DsSf1+KDs.Here, K2 is Langmuir adsorption constant and Sf is the dyeing saturation value of the fiber.


### 4.2.3. Freundlich Type

(4)Df=K3Dsn.Here, K3 is Freundlich adsorption constant and n is the heterogeneity factor, 0＜n＜1.It can be seen from Table1 that under three different temperatures, the R2 of Nernst type and Freundlich type are low and the ND is large. The Langmuir model has the highest R2 , which is more than 0.99, and the corresponding ND is also the lowest [19]. Therefore, the adsorption model of reactive dyes on PSt colloidal microspheres is more in line with the Langmuir model. It can be seen that reactive dyes are localized on the surface of PSt microspheres. That is, a certain number of adsorption sites are formed on the surface of positively charged PSt colloidal microspheres, which promotes the localized adsorption of anionic reactive dyes, and there is an adsorption saturation value in the adsorption process. When the adsorption reaches a certain degree, the adsorption amount basically remains unchanged.


## 4.2.1. Nernst Type

(2)Df=K1Ds.Here, Df is the concentration of dye on the fiber; Ds is the concentration of the dye in the dye solution; and K1 is the Nernst adsorption constant.


## 4.2.2. Langmuir Type

(3)Df=K2DsSf1+KDs.Here, K2 is Langmuir adsorption constant and Sf is the dyeing saturation value of the fiber.


## 4.2.3. Freundlich Type

(4)Df=K3Dsn.Here, K3 is Freundlich adsorption constant and n is the heterogeneity factor, 0＜n＜1.It can be seen from Table1 that under three different temperatures, the R2 of Nernst type and Freundlich type are low and the ND is large. The Langmuir model has the highest R2 , which is more than 0.99, and the corresponding ND is also the lowest [19]. Therefore, the adsorption model of reactive dyes on PSt colloidal microspheres is more in line with the Langmuir model. It can be seen that reactive dyes are localized on the surface of PSt microspheres. That is, a certain number of adsorption sites are formed on the surface of positively charged PSt colloidal microspheres, which promotes the localized adsorption of anionic reactive dyes, and there is an adsorption saturation value in the adsorption process. When the adsorption reaches a certain degree, the adsorption amount basically remains unchanged.


## 4.3. Apparent Morphology of Reactive Dye/PSt Microspheres

From the SEM and TEM photos before and after dye adsorption on the surface of PSt microspheres, it can be concluded that after dye adsorption, the reactive dye/PSt microspheres still maintain a typical core-shell structure and the sphericity is still good. The dye adsorption has no significant effect on the sphericity of colloidal microspheres. However, after adsorption of dyes, the particle size of reactive dye/PSt microspheres increased from 184.5 nm to 196.3 nm and the shell thickness increased from 30.7 nm to 36.6 nm. This may be because a large number of dye molecules are adsorbed on the surface of PSt microspheres, which can adsorb a certain amount of water molecules at the same time, resulting in a slight increase in the particle size of the microspheres.


## 4.4. Application of Reactive Dye/PSt Microspheres

From the self-assembled photonic crystal structures and corresponding structural colors of reactive dyes/PSt microspheres with different particle sizes on mulberry silk fabrics, it can be concluded that the structures of reactive dyes/PSt photonic crystals on mulberry silk fabrics are orderly arranged, showing uniform and bright structural colors; And with the decrease of the particle size of colloidal microspheres, the corresponding structural colors also show different hues such as red, orange, green, blue, and purple, and an obvious blue shift occurs [6].Reflectivity Curves of Self-Assembled Photonic Crystals with Different Particle Sizes of Reactive Dye/PSt Microspheres on White Mulberry Silk Fabric. It can be seen that as the particle size of the reactive dye/PSt microspheres decreases from 317, 298, 247, and 201 nm to 188 nm, the maximum reflection wavelength of the structure-colored photonic crystal gradually changes from 615 nm to 418 nm, which corresponds to the color phenomenon of the self-assembled photonic crystal structure of reactive dye/PSt microspheres with different particle sizes sprayed on mulberry fabric, that is, there is an obvious blue shift, which conforms to the Bragg diffraction equation.Before dye adsorption, the structure color of pure PSt microspheres on white mulberry silk fabric was dim, showing light blue and light green. After adsorbing the dye, the reactive dye/PSt photonic crystal on the same substrate shows bright blue and green and the corresponding color saturation is significantly improved. This is because the white fabric can easily reflect almost all the incident light passing through the photonic crystal layer without selectivity, diluting the structural color of the selective reflection of the photonic crystal. The black dye can significantly absorb the background stray light and make the light reflected by the photonic crystal maintain good purity and saturation without the interference of additional light [20]. The results show that the structure color effect of reactive dye/PSt photonic crystal on white mulberry silk fabric is better than that of pure PSt photonic crystal. It can be concluded that the introduction of black reactive dyes into the surface of PSt microspheres to prepare composite structural units can effectively enhance the color saturation of the structure chromogenic photonic crystals on the white substrate.


## 5. Conclusion

(1)
In this paper, reactive dye/polystyrene (PSt) composite colloidal microspheres were prepared by electrostatic adsorption. The optimum conditions for dye adsorption were determined: dye mass fraction was 0.5%, adsorption temperature was 65°C, and adsorption time was 40 min.(2)
The adsorption of active black B on positively charged PSt colloidal microspheres conforms to the Langmuir model and belongs to localized adsorption.(3)
Using the digital spray printing method and the reactive dye/PSt composite colloidal microspheres as the structural elements, the structured three-dimensional photonic crystals can be directly constructed on the white mulberry silk fabric, showing bright and beautiful structural colors, which have certain reference significance for the application of the coupling of structural colors and pigment colors in textiles.



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*Source: 2044265-2022-08-25.xml*