Preparation method of material with silver-plated surface
Technical Field
The invention relates to the technical field of conductive composite materials, in particular to a method for preparing a surface silver-plated material, which is a method for preparing a matrix/silver composite material by surface functionalization of tannic acid-ferric trichloride in the presence of a reducing agent.
Background
The metal powder is an important raw material in the electronic industry and the national defense industry. Due to the high density of metal, the material using metal micropowder as the main conductive medium is difficult to avoid the occurrence of degradation phenomenon during the storage and use process, which will affect the use of the product to a great extent. The metal coated other metal or non-metal matrix is core-shell type composite powder with core of non-metal or other metal such as high molecular ceramic and surface of metal, and it can endow the matrix with special electric, magnetic and optical properties, antioxidant and anti-aging properties, and can also improve the wettability of the powder and metal. The patent specifically relates to a method for effectively modifying the surfaces of most of non-metallic materials, metallic materials and composite materials, and mainly takes glass beads, aluminum powder and graphene oxide as examples.
The glass beads have the characteristics of small density and uniform particle size, and the density is far less than that of the metal powder. However, the common glass beads are insulators and cannot be used as filling materials of conductive materials. The conductive glass beads with low density are used as conductive materials, so that the problem of sedimentation of a conductive medium can be effectively solved. The surface of the glass microsphere is chemically plated with nickel, copper, silver and a composite coating, and the glass microsphere can be used as a conductive filler of an electromagnetic shielding material and a wave-absorbing material. Due to the surface hydrophobicity, the bonding stability and the bonding force between the surface of the untreated glass bead and the surface of other materials are poor, and further treatment is needed, so that a uniform and compact silver layer can be formed on the surface of the glass bead.
Aluminum has advantages of light specific gravity, good ductility, good metallic luster, low price and the like, and is widely applied to the fields of electronics, aviation, electronic paste and the like. However, the aluminum powder has large surface activity and is extremely unstable, and is easy to generate oxidation-reduction reaction with air, so that the advantages of the aluminum powder are lost. Therefore, in application, the aluminum powder needs to be subjected to surface treatment, so that the treated aluminum powder not only keeps the advantages of light density and good metal luster, but also has good electrical conductivity. The silver is a noble metal, the color of the silver is similar to that of aluminum, the silver has excellent conductivity, if a layer of uniform and thin silver is coated on the aluminum powder, the advantages of the aluminum powder are maintained, the aluminum powder is endowed with good conductivity, the cost is greatly reduced, and the obtained product can be used in the fields of electromagnetic shielding, conductive paste and the like.
The graphene oxide has the characteristics of high shape coefficient and high specific surface area, and a uniform and thin silver layer is deposited on the surface of the graphene oxide by utilizing the characteristics of the graphene oxide, so that the graphene oxide has high conductivity at a low silver content, high conductivity is obtained at a low filling amount, the percolation threshold of a conductive filler is reduced, and the composite material film with light weight, high strength and good electromagnetic shielding effect is obtained.
Over the past few decades, scientists have explored and studied various methods for metallizing substrate surfaces, including mechanical mixing, Sol-gel, etc. These methods have different defects for powder surface modification, such as uneven mixing by mechanical mixing, easy grain growth by Sol-gel method in reducing metal oxides, and the like. Therefore, the method of electroless plating is selected in the invention.
Electroless plating is a surface treatment technique in which metal ions in a solution are reduced to metal under the autocatalysis of a substrate surface by using a reducing agent without an external current and then deposited on the substrate surface. The biggest characteristic of chemical plating different from electroplating is that the same surface is simultaneously subjected to reduction of metal ions and oxidation of a reducing agent in two processes. The chemical plating has the advantages of simple equipment requirement, convenient operation and control, suitability for irregular matrixes, no requirement on electric conduction of the matrixes, low cost and the like, and the formed plating layer has the advantages of high density, uniform thickness, good corrosion resistance, good wear resistance and the like. The prepared composite material can be applied to various fields, such as coating materials for forming silver-coated copper powder by plating silver on the surface of the copper powder, can be widely applied to the fields of conductive materials, electronic paste, electrode materials, antibacterial materials, electric contact materials, electromagnetic shielding materials and the like, and the currently common chemical plating comprises modification by dopamine and phenol amine, but has the common problem that the time is too long, and several hours or dozens of hours are needed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a material with silver-plated surface, which prepares the composite material with silver-plated surface by surface modification of tannic acid-ferric trichloride.
The invention aims to provide a preparation method of a material with silver-plated surface.
The method comprises the following steps:
1) ultrasonically dispersing the substrate in an ethanol solution or deionized water, sequentially and respectively adding a tannin solution and a ferric trichloride solution, and uniformly stirring to obtain a substrate with the surface deposited with the polytannin-ferric trichloride;
the molar ratio of the tannic acid to the ferric trichloride is 1: 3-3: 1;
2) titrating the silver nitrate solution with ammonia water until the precipitate just disappears, and preparing to obtain silver plating solution;
3) placing the substrate with the surface deposited with the polytannic acid-ferric trichloride prepared in the step 1) into the silver plating solution prepared in the step 2), adding a dispersant polyvinylpyrrolidone and stirring; the dosage of the silver nitrate is 0.5 to 2.0 times of that of the silver nitrate;
4) adding a reducing agent solution into the solution obtained in the step 3) under the condition of stirring, and reacting for 1-60 minutes at room temperature to obtain a substrate with the surface covered with a silver layer.
The reducing agent is glucose solution, sodium citrate or sodium borohydride; the dosage of the reducing agent is 1-3 times of that of silver nitrate;
among them, preferred are:
in the step 1), the concentration of the tannic acid is 0.2-6.0 g/L; the concentration of the ferric trichloride solution is 0.04-4.0 g/L; adding a tannin solution and a ferric trichloride solution, and adding a Tris buffer solution to adjust the pH value to 6-10.
In the step 1), the stirring speed is 30-100 r/min; the total reaction time is not more than 1 min.
In the step 2), the concentration of the silver nitrate solution is 5-40 g/L.
In the step 3), the stirring time is not less than 20 minutes.
In the step 4), the concentration of the reducing agent solution is 5-80 g/L;
the concentration of the reducing agent solution is 1-3 times of that of the silver nitrate solution in the step 2.
The substrate is metal, inorganic nonmetal, polymer or composite material; the matrix is in the form of spherical microbeads, flakes, fibers, particles or powder.
The invention can adopt the following technical scheme:
the invention prepares the matrix/silver composite material with good bonding stability and conductivity by depositing tannic acid-ferric trichloride on the surface of the matrix under an alkaline condition, placing the matrix functionalized by the surface of poly (tannic acid-ferric trichloride) in silver plating solution, and adding a reducing agent, and the method comprises the following specific steps:
1) the matrix is subjected to ultrasonic dispersion in an ethanol solution, then the matrix is placed and stirred uniformly, the concentrations of tannic acid and ferric trichloride are respectively 0.20-6.0 g/L and 0.04-4.0 g/L, the pH is adjusted to 6.0-10.0, and the mixture is stirred at the stirring speed of 30-100 r/min for no more than 24 hours, so that the matrix with poly (tannic acid-ferric trichloride) deposited on the surface is obtained. The molar ratio of the tannic acid to the ferric trichloride is 1: 3-3: 1, and the preferable molar ratio is 3: 1. Preferably, the concentration of tannic acid is 0.4g/L, the concentration of ferric trichloride is 0.12g/L, the pH is 8.5, and the stirring time is 1 min;
2) and titrating the silver nitrate solution with the mass concentration of 5-40 g/L by using ammonia water until the precipitate just disappears, and preparing the silver plating solution. The preferred concentration is 10 g/L;
3) placing the substrate with the poly (tannic acid-ferric trichloride) deposited on the surface, prepared in the step 1), in the silver plating solution prepared in the step 2), adding a dispersing agent, and stirring for not less than 20 minutes;
4) adding a glucose solution with the mass concentration of 5-80 g/L into the silver plating solution obtained in the step 3) under the condition of stirring, wherein the volume of the glucose solution is the same as that of the silver nitrate solution, and reacting for 1-60 minutes at room temperature to obtain a substrate with the surface covered with a silver layer. The concentration of the glucose solution is selected regardless of the concentration of the silver plating solution, but the reduction effect is best when the concentration of glucose is twice the concentration of the silver plating solution. Preferably, the glucose concentration is 20g/L and the reaction time is 60 minutes.
The method described in step 1) is applicable to all forms of substrates, including but not limited to spherical beads, flakes, fibers, particles, powders, and the like, and is applicable to all material types, including metals, inorganic non-metals, polymers, composite materials, and the like. The substrate is preferably silica microspheres.
The principle of the invention is as follows: the tannic acid contains a large amount of phenolic hydroxyl groups, and the phenolic hydroxyl groups can fix silver particles generated by reduction. Meanwhile, the matrix/silver composite material subjected to chemical treatment has good bonding stability and conductivity, mainly because a reducing agent is added to promote the reduction process of silver, and the existence of tannic acid-ferric trichloride accelerates and stabilizes the growth of silver particles on the surface of the matrix. The deposition of the tannic acid-ferric trichloride on the surface of the polymer matrix is a physical process, and the whole method is irrelevant to the surface appearance and the chemical composition of the inorganic matrix, so that the method is suitable for the inorganic matrix with various forms and compositions.
Compared with the prior art for preparing the conductive inorganic non-metallic material, the method has the following beneficial effects:
1) the method is simple and convenient to operate, the time (not more than 1 minute) for modifying the tannin and the ferric trichloride on the surface of the substrate is short, and the cost is low.
2) The silver layer on the surface of the substrate prepared by the method is uniform and compact, and has good conductivity (the conductivity is 1.0-1.5 × 10)5S/m) and adhesion stability.
3) The matrix/silver composite material prepared by the invention has higher binding force between the silver layer and the matrix.
4) The invention has no limit to the shape and the composition of the inorganic substance matrix, and the physical mechanical property and the thermal property of the inorganic substance can not be influenced by the attachment of silver.
Drawings
FIG. 1: example 1X-ray photoelectron spectroscopy (XPS) broad spectrum of microspheres, wherein fig. 1(a) X-ray photoelectron spectroscopy (XPS) broad spectrum of pure silica microspheres, and fig. 1(b) X-ray photoelectron spectroscopy (XPS) broad spectrum of poly (tannic acid-ferric trichloride) surface functionalized silica microspheres, i.e., silica/poly (tannic acid-ferric trichloride) core-shell composite microspheres; FIG. 1(c) is an X-ray photoelectron spectroscopy (XPS) broad spectrum of silica microspheres with silver reduced on the surface, i.e., silica/poly (tannic acid-ferric trichloride)/silver core-shell composite microspheres.
FIG. 2: the X-ray diffraction (XRD) pattern of the microspheres of example 1, wherein fig. 2(a) is the X-ray diffraction (XRD) pattern of pure silica microspheres; FIG. 2(b) is an X-ray diffraction (XRD) spectrum of a silica/poly (tannic acid-ferric chloride) core-shell composite microsphere; fig. 2(c) X-ray diffraction energy spectrum (XRD) spectrum of silica/poly (tannic acid-ferric chloride)/silver core-shell composite microsphere.
FIG. 3: scanning Electron Microscope (SEM) images of example 1, wherein fig. 3(a) Scanning Electron Microscope (SEM) images of pure silica microspheres, fig. 3(b) Scanning Electron Microscope (SEM) images of silica/poly (tannic acid-ferric trichloride) core-shell composite microspheres; fig. 3(c) Scanning Electron Microscope (SEM) image of silica/poly (tannic acid-ferric trichloride)/silver core-shell composite microspheres.
FIG. 4: XPS broad spectrum of blank aluminum powder obtained in example 8, FIG. 4 (a); FIG. 4(b) XPS broad spectrum of aluminum powder, i.e., aluminum/poly (tannic acid-ferric trichloride) core-shell composite microsphere, with tannic acid-ferric trichloride surface functionalized; FIG. 4(c) is an XPS broad spectrum of aluminum powder with silver reduced on the surface, i.e., aluminum/poly (tannic acid-ferric trichloride)/silver core-shell composite microspheres.
FIG. 5: FIG. 5(a) Scanning Electron Microscope (SEM) image of blank aluminum powder obtained in example 8; FIG. 5(b) Scanning Electron Microscope (SEM) image of tannic acid-ferric chloride surface functionalized aluminum powder, i.e., aluminum/poly (tannic acid-ferric chloride) core-shell composite microspheres; fig. 5(c) a Scanning Electron Microscope (SEM) image of aluminum powder, i.e., aluminum/poly (tannic acid-ferric trichloride)/silver core-shell type composite microspheres, with silver reduced on the surface.
FIG. 6: scanning Electron Microscope (SEM) images of blank graphene oxide obtained in example 9, fig. 6 (a); fig. 6(b) Scanning Electron Microscope (SEM) image of tannic acid-ferric chloride surface functionalized graphene oxide, i.e., graphene oxide/poly (tannic acid-ferric chloride) core-shell composite microspheres; fig. 6(c) a Scanning Electron Microscope (SEM) image of graphene oxide with silver reduced on the surface, i.e., graphene oxide/poly (tannic acid-ferric trichloride)/silver core-shell composite microspheres.
Fig. 7 a Scanning Electron Microscope (SEM) image of pure aramid fiber of example 10, fig. 7 a; fig. 7(b) Scanning Electron Microscope (SEM) image of aramid fiber/poly (tannic acid-ferric chloride) core-shell composite microsphere; fig. 7(c) Scanning Electron Microscope (SEM) image of aramid fiber/poly (tannic acid-ferric trichloride)/silver core-shell composite microsphere.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Adding 4g of glass microspheres washed by ethanol into 100ml of deionized water, stirring uniformly, then preparing tannic acid with the concentration of 3.6g/L and a ferric trichloride aqueous solution with the molar ratio of 1.2g/L to tannic acid, adding the tannic acid and ferric trichloride aqueous solution into the matrix solution in sequence respectively, adjusting the pH to 8.5 by using Tris-HCl buffer solution, stirring for 1 minute at the stirring speed of 60 revolutions per minute, filtering the glass microspheres deposited with poly (tannic acid-ferric trichloride) after stirring is finished, washing by using deionized water, and drying in vacuum;
2) preparing a silver nitrate solution with the concentration of 10g/L, and titrating with ammonia water until a precipitate just disappears to obtain a silver plating solution;
3) soaking the glass beads with the functionalized surfaces of the poly (tannic acid-ferric trichloride) in the step 1) in 100ml of silver plating solution obtained in the step 2) under the condition of stirring, adding 0.05g of dispersant polyvinylpyrrolidone (PVP) into the silver plating solution to improve the dispersion performance of the glass beads in the solution, and stirring for 20 minutes;
4) adding 100ml of glucose solution with the mass concentration of 20g/L into the silver plating solution in the step 3), and reacting for 60 minutes to obtain the glass microspheres with the surfaces plated with the silver particles.
The glass microsphere (silicon dioxide)/silver core-shell composite microsphere is determined to be conductive, and the conductivity is 1.5 × 105S/m。
The atomic percentage content ratios of the surface elements of the pure silica and the silica/silver core-shell composite microspheres in the present example are shown in table 1.
An XPS (X-ray diffraction) broad spectrum and an XRD (X-ray diffraction) spectrum of the pure silica microsphere are respectively shown in a figure 1(a) and a figure 2(a), an XPS broad spectrum and an XRD spectrum of the silica/poly (tannic acid-ferric trichloride) core-shell composite microsphere are respectively shown in a figure 1(b) and a figure 2(b), and an XPS broad spectrum and an XRD spectrum of the silica/poly (tannic acid-ferric trichloride)/silver core-shell composite microsphere are respectively shown in a figure 1(c) and a figure 2 (c); scanning Electron Microscope (SEM) images are shown in fig. 3, in which (a) pure silica microspheres, (b) silica/poly (tannic acid-ferric trichloride) core-shell composite microspheres and (c) silica/poly (tannic acid-ferric trichloride)/silver core-shell composite microspheres.
As shown in FIG. 1, the XPS broad spectrum of the silica/poly (tannic acid-ferric trichloride) core-shell composite microsphere of FIG. 1(b) shows that the pure silica of FIG. 1(a) does not contain iron, which indicates that poly (tannic acid-ferric trichloride) is deposited on the surface of the silica microsphere. In the XPS broad spectrum of the silica/poly (tannic acid-ferric trichloride)/silver core-shell composite microsphere in FIG. 1(c), a silver peak appears, which indicates that silver particles are deposited on the surface of the silica microsphere. As can be seen from fig. 2, there are no silver peaks in the XRD patterns of fig. 2(a) pure silica and fig. 2(b) silica/poly (tannic acid-ferric trichloride) core-shell type composite microspheres, while there are four silver peaks with different lattice structures in the XRD patterns of fig. 2(c) silica/poly (tannic acid-ferric trichloride)/silver core-shell type composite microspheres, which proves that there are silver particles on the surface of the silica microspheres. Fig. 3 shows the pure silica in fig. 3(a), the silica/poly (tannic acid-ferric trichloride) core-shell composite microsphere in fig. 3(b) and the silica/poly (tannic acid-ferric trichloride)/silver core-shell composite microsphere in fig. 3(c), and simultaneously shows that the silver layer on the surface of the silica/silver core-shell composite microsphere prepared by the chemical reduction method is dense and continuous and has good conductivity.
Example 2
The process is the same as that of example 1, and the glass beads with silver particles plated on the surfaces can be obtained by changing the reaction time in the step 4) to 30min, 40min, 50min, 90min and 120 min.
The silicon dioxide/silver core-shell type composite micro-bead can conduct electricity through determination, and the conductivity is 1.0-1.5 × 105And S/m.
Example 3
The process is the same as that of example 1, the concentration of tannic acid in the step 1) is changed to 0.20g/L, 4.0g/L and 6.0g/L, the concentration of ferric trichloride is correspondingly 0.04g/L, 2.4g/L and 4.0g/L, and the glass microsphere with the surface plated with silver particles can be obtained.
The silicon dioxide/silver core-shell type composite micro-bead can conduct electricity through determination, and the conductivity is 1.0-1.5 × 105And S/m.
Example 4
The process was the same as example 1, and the glass beads having silver particles plated on the surface thereof were obtained by changing the stirring time in step 1) to 20 seconds, 30 seconds, 40 seconds, and 50 seconds.
The silicon dioxide/silver core-shell type composite micro-bead can conduct electricity through determination, and the conductivity is 1.0-1.5 × 105And S/m.
Example 5
The process is the same as that of example 1, the silver nitrate concentration in the step 2) is changed into 5g/L, 20g/L, 30g/L and 40g/L, the corresponding glucose solution concentration is 10g/L, 40g/L, 60g/L and 80g/L, and the glass microsphere with the surface plated with silver particles can be obtained.
The silicon dioxide/silver core-shell type composite micro-bead can conduct electricity through determination, and the conductivity is 1.0-1.5 × 105And S/m.
Example 6
The process is the same as that of example 1, and the PH of the tannic acid-ferric trichloride solution in the step 1) is respectively adjusted to 7, 7.5, 8, 9, 9.5 and 10, so that the glass beads with silver particles plated on the surfaces can be obtained.
The silicon dioxide/silver core-shell type composite micro-bead can conduct electricity through determination, and the conductivity is 1.0-1.5 × 105And S/m.
Example 7
The process is the same as that of example 1, and the molar ratio of the tannic acid to the ferric trichloride in the step 1) is changed to 1:2, 1:3, 2:1 and 3:1, so that the glass microspheres with silver particles plated on the surfaces can be obtained.
The silicon dioxide/silver core-shell type composite micro-bead can conduct electricity through determination, and the conductivity is 1.0-1.5 × 105And S/m.
Example 8
1) Adding 4g of aluminum powder cleaned by ethanol into 100ml of deionized water, uniformly stirring, then preparing tannic acid with the concentration of 3.6g/L and a ferric trichloride aqueous solution with the concentration of 1.2g/L, wherein the molar ratio of the tannic acid to the ferric trichloride is 3:1, respectively adding the tannic acid and the ferric trichloride aqueous solution into a matrix solution, adjusting the pH to 8.5 by using Tris-HCl buffer solution, stirring for 1 minute at the stirring speed of 60 revolutions per minute, filtering glass microspheres deposited with poly (tannic acid-ferric trichloride) after stirring is finished, cleaning by using deionized water, and drying in vacuum;
2) preparing a silver nitrate solution with the concentration of 10g/L, and titrating with ammonia water until a precipitate just disappears to obtain a silver plating solution;
3) soaking the aluminum powder with the surface functionalized by the poly (tannic acid-ferric trichloride) in the step 1) in the 100ml of silver plating solution obtained in the step 2) under the condition of stirring, adding 0.05g of dispersant polyvinylpyrrolidone (PVP) into the silver plating solution to improve the dispersion performance of the aluminum powder in the solution, and stirring for 20 minutes;
4) adding 100ml of glucose solution with the mass concentration of 20g/L into the silver plating solution in the step 3), and reacting for 60 minutes to obtain the aluminum powder with the surface plated with the silver particles.
The aluminum/silver core-shell composite material is determined to be conductive, and the conductivity is 0.75 × 105S/m。
FIG. 4 is an XPS broad spectrum of the blank aluminum powder, aluminum/poly (tannic acid-ferric trichloride) core-shell composite, and aluminum/poly (tannic acid-ferric trichloride)/silver core-shell composite obtained in example 8. Since the XPS spectrum of fig. 4(b) shows iron element not contained in the pure aluminum powder spectrum, it shows that poly (tannic acid-ferric trichloride) is deposited on the surface of aluminum powder, and the XPS spectrum of fig. 4(c) shows silver peak, which proves that silver particles are deposited on the surface of aluminum powder.
Fig. 5 is Scanning Electron Microscope (SEM) images of the blank aluminum powder, aluminum/poly (tannic acid-ferric trichloride) core-shell composite microspheres, and aluminum/poly (tannic acid-ferric trichloride)/silver core-shell composite microspheres obtained in example 9. From fig. 5, it can be seen that the pure aluminum powder in fig. 5(a), the aluminum powder/poly (tannic acid-ferric trichloride) core-shell composite microsphere in fig. 5(b) and the aluminum powder/poly (tannic acid-ferric trichloride)/silver core-shell composite microsphere in fig. 5(c) have surface morphology changes, and it can be seen that the silver layer on the surface of the aluminum/silver core-shell composite microsphere prepared by the chemical reduction method is dense and continuous, and has good conductivity.
Example 9
1) Adding 2g of graphene oxide into 100ml of deionized water, uniformly stirring, preparing a tannic acid solution with the concentration of 3.6g/L and a ferric trichloride solution with the concentration of 1.2g/L, wherein the molar ratio of the tannic acid to the ferric trichloride solution is 3:1, respectively adding the tannic acid solution to the base solution, adjusting the pH to 8.5 by using a Tris-HCl buffer solution, stirring for 1 minute at the stirring speed of 60 revolutions per minute, filtering the graphene oxide deposited with poly (tannic acid-ferric trichloride) after stirring is finished, washing with the deionized water, and freeze-drying;
2) preparing a silver nitrate solution with the concentration of 10g/L, and titrating with ammonia water until a precipitate just disappears to obtain a silver plating solution;
3) soaking the graphene oxide with the functionalized surface of the poly (tannic acid-ferric trichloride) in the step 1) in 100ml of silver plating solution obtained in the step 2) under the condition of stirring, adding 0.05g of dispersant polyvinylpyrrolidone (PVP) into the silver plating solution to improve the dispersion performance of the graphene oxide in the solution, and stirring for 20 minutes;
4) adding 100ml of glucose solution with the mass concentration of 20g/L into the silver plating solution in the step 3), and reacting for 60 minutes to obtain the graphene oxide with the silver particles plated on the surface.
The graphene oxide/silver core-shell composite material can conduct electricity through determination, and the conductivity is 1 × 105S/m。
Fig. 6 is a Scanning Electron Microscope (SEM) image of the blank graphene oxide, the graphene oxide/poly (tannic acid-ferric trichloride) core-shell composite, and the graphene oxide/poly (tannic acid-ferric trichloride)/silver core-shell composite obtained in example 9. Fig. 6 shows the pure graphene oxide in fig. 6(a), the graphene oxide/poly (tannic acid-ferric trichloride) core-shell composite microsphere in fig. 6(b) and the graphene oxide/poly (tannic acid-ferric trichloride)/silver core-shell composite microsphere in fig. 6(c), and it can be seen that the silver layer on the surface of the graphene oxide/silver core-shell composite microsphere prepared by the chemical reduction method is dense and continuous, and has good conductivity.
Example 10
1) Adding 1.5g of aramid fiber into 100ml of deionized water, uniformly stirring, then preparing tannic acid with the concentration of 3.6g/L and a ferric trichloride aqueous solution with the concentration of 1.2g/L, wherein the molar ratio of the tannic acid to the ferric trichloride is 3:1, respectively adding the tannic acid and the ferric trichloride aqueous solution into a matrix solution, adjusting the pH to 8.5 by using Tris-HCl buffer solution, stirring for 1 minute at the stirring speed of 60 revolutions per minute, filtering the aramid fiber deposited with poly (tannic acid-ferric trichloride) after stirring is finished, washing with the deionized water, and drying;
2) preparing a silver nitrate solution with the concentration of 10g/L, and titrating with ammonia water until a precipitate just disappears to obtain a silver plating solution;
3) soaking the aramid fiber with the functionalized surface of the poly (tannic acid-ferric trichloride) in the step 1) in 100ml of silver plating solution obtained in the step 2) under the condition of stirring, adding 0.05g of dispersant polyvinylpyrrolidone (PVP) into the silver plating solution, and stirring for 20 minutes;
4) adding 100ml of glucose solution with the mass concentration of 20g/L into the silver plating solution in the step 3), and reacting for 60 minutes to obtain the aramid fiber with the silver particles plated on the surface.
The aramid fiber/silver core-shell composite material can conduct electricity through determination, and the conductivity is 1.2 × 105And S/m.
Fig. 7 is a Scanning Electron Microscope (SEM) image of the bare aramid fiber, aramid fiber/poly (tannic acid-ferric trichloride) core-shell composite, and aramid fiber/poly (tannic acid-ferric trichloride)/silver core-shell composite obtained in example 10. Fig. 7 shows that the surface morphology of the pure aramid fiber of fig. 7(a), the aramid fiber/poly (tannic acid-ferric trichloride) core-shell type composite microsphere of fig. 7(b) and the aramid fiber/poly (tannic acid-ferric trichloride)/silver core-shell type composite microsphere of fig. 7(c) is changed, and meanwhile, the silver layer on the surface of the graphene oxide/silver core-shell type composite microsphere prepared by the chemical reduction method is dense and continuous, and has good conductivity.
Table 1 relative atomic percentages of surface elements of pure silica and silica/poly (tannic acid-ferric chloride)/silver core-shell composite microspheres of example 1