CN108728835A - A kind of preparation method of electroplate material - Google Patents
A kind of preparation method of electroplate material Download PDFInfo
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- CN108728835A CN108728835A CN201710252658.5A CN201710252658A CN108728835A CN 108728835 A CN108728835 A CN 108728835A CN 201710252658 A CN201710252658 A CN 201710252658A CN 108728835 A CN108728835 A CN 108728835A
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- tannic acid
- silver
- matrix
- ferric trichloride
- solution
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
Abstract
The invention discloses a kind of preparation methods of electroplate material.Including：1) by matrix, ultrasonic wave disperses in ethanol solution or deionized water, is successively separately added into tannic acid and liquor ferri trichloridi, stirs evenly, and obtaining surface deposition has the matrix of poly- tannic acid-ferric trichloride；2) when silver nitrate solution is just disappeared with ammonia water titration to precipitation, preparation obtains silver plating solution；3) matrix of poly- tannic acid-ferric trichloride is placed in the silver plating solution of step 2) preparation the surface deposition prepared in step 1), and the stirring of polyethylene of dispersing agent pyrrolidones is added, 4) reducing agent solution is added into the solution of step 3) under stirring conditions, it reacts 1~60 minute at room temperature, obtains to surface and be covered with the matrix of silver layer.The present invention method it is easy to operate, it is used with tannic acid and ferric trichloride substantially reduce its modification time, saved cost and time, the bonding stability and electric conductivity of prepared composite material are good.
Description
Technical field
The present invention relates to conducing composite material technical fields, further say, are to be related to a kind of system of electroplate material
Preparation Method passes through tannic acid-ferric trichloride surface-functionalized matrix/silver composite material of preparing under the conditions of existing for reducing agent
Method.
Background technology
Metal-powder is electronics industry, the important source material of national defense industry.Since the density of metal is very big, it is with metal fine powder
The material of main conductive medium is difficult to avoid the generation of signs of degradation during storage and use, this will largely shadow
Ring the use of product.Metallic cover other metals either nonmetal basal body be a kind of core be polymer ceramic etc. it is nonmetallic or
Other metals, the core-shell type composite powder that surface is metal, it can assign the special electricity of matrix, magnetic, optical property and antioxygen
Change and ageing-resistant performance, can also improve the wetability of powder and metal.This patent will relate specifically to one kind can be in most of non-gold
Belong to material, metal material and composite material surface and carry out effectively modified method, mainly with glass microballoon, aluminium powder and oxidation stone
Black alkene is example.
Glass microballoon has density small and the feature of uniform particle sizes, density are much smaller than metal-powder.But common glass
Microballon is insulator, cannot function as the packing material of conductive material.Using the electro-conductive glass microballon of low-density as conductive material
The settlement issues of conducting medium can effectively be overcome.Glass microballoon chemical nickel plating on surface, copper, silver and composite coating can be used as electromagnetism
The conductive filler of shielding material and absorbing material.Due to its surface hydrophobicity, untreated glass microballoon surface and other materials
The bonding stability and binding force on surface are poor, need to be further processed, its surface is enable to form even compact
Silver layer.
Aluminium due to light specific gravity, ductility is good, metallic luster is good and cheap the advantages that, be widely used in electricity
The fields such as son, aviation and electric slurry.But aluminium powder surface-active is big, and it is extremely unstable, redox reaction easily occurs with air,
So that the advantages of losing itself.Therefore, in the application, it must be surface-treated so that treated, and aluminium powder had both kept this
The density of body is light, and the good advantage of metallic luster has good conductive property simultaneously.Silver is noble metal, close with the color of aluminium,
And its excellent conductivity while keeping aluminium powder intrinsic advantage, assigns aluminium if coating the silver of one layer of uniform and thin on aluminium powder
The good electric conductivity of powder, while being greatly reduced cost, the fields such as products obtained therefrom can be used for being electromagnetically shielded, electrocondution slurry.
Graphene oxide has the characteristics that high form factor, high-specific surface area, using its feature, in its surface depositing homogeneous
And thin silver layer, make it that there is high conductivity in lower silver content, high conductivity is obtained under low loading to realize, drops
Low conductive filler percolation threshold obtains the good composite material film of high-strength light, electromagnet shield effect.
In the past few decades, scientists are explored and have been studied to the various methods that matrix surface metallizes,
Wherein method includes mechanical mixing, Sol-gel methods etc..These methods have powder surface modification different defects, such as
Mechanical mixing mixing is uneven, Sol-gel methods crystal grain in reducing metal oxide is easy to grow up.Therefore it selects in the invention
With the method for chemical plating.
Chemical plating be one kind in the case of no impressed current, using reducing agent by the metal ion in solution in matrix table
It is reduced into metal under the autocatalysis in face and then is deposited on the process for treating surface of matrix surface.Chemical plating is different from plating
Maximum feature is the oxidation of reduction and reducing agent that same surface is carried out at the same time two process metal ions.Chemical plating, which has, to be set
It is standby to require simple, convenient operation and control, be suitable for irregular matrix, matrix should not derivation electricity, it is at low cost the advantages that, formation
Coating has many advantages, such as uniform consistency height, thickness, corrosion resistance and excelling in abrasion resistance.Composite material obtained can apply with
Various fields can be widely used in conductive material, electronics such as in the silver-plated cladded type material for forming silver-coated copper powder of Copper Powder Surface
The fields such as slurry, electrode material, anti-biotic material, electric contact material and electromagnetic shielding material, currently used chemical plating include using
Dopamine and phenol amine are modified, but common problem is to need the time too long, needs a few hours or tens hours.
Invention content
To solve the problem in the prior art, the present invention provides a kind of preparation methods of electroplate material, lead to
The composite material that tannic acid-ferric trichloride surface modification prepares electroplate is crossed, method of the invention is easy to operate, used
The time that its modification is substantially reduced with tannic acid and ferric trichloride, cost and time are saved, prepared composite material
It bonds stability and electric conductivity is good.
The object of the present invention is to provide a kind of preparation methods of electroplate material.
Including：
1) by matrix, ultrasonic wave disperses in ethanol solution or deionized water, is successively separately added into tannic acid and ferric trichloride
Solution stirs evenly, and obtaining surface deposition has the matrix of poly- tannic acid-ferric trichloride；
The molar ratio of the tannic acid and ferric trichloride is 1:3~3:1；
2) when silver nitrate solution is just disappeared with ammonia water titration to precipitation, preparation obtains silver plating solution；
3) silver for thering is the matrix of poly- tannic acid-ferric trichloride to be placed in step 2) preparation the surface deposition prepared in step 1)
In plating solution, and the stirring of polyethylene of dispersing agent pyrrolidones is added；Its amount used is 0.5~2.0 times of silver nitrate；
4) reducing agent solution is added into the solution of step 3) under stirring conditions, reacts 1~60 minute, obtains at room temperature
The matrix of silver layer is covered with to surface.
The reducing agent is glucose solution, sodium citrate or sodium borohydride；Reducing agent dosage is 1~3 times of silver nitrate；
Wherein, preferably：
In step 1), a concentration of 0.2~6.0g/L of tannic acid；A concentration of 0.04~4.0g/L of liquor ferri trichloridi；
After tannic acid and liquor ferri trichloridi is added, it is 6~10 that Tris buffer solutions, which are added, and adjust pH.
In step 1), stir speed (S.S.) is 30~100 turns/min；Total reaction time is no more than 1min.
In step 2), a concentration of 5~40g/L of silver nitrate solution.
In step 3), mixing time is not less than 20 minutes.
In step 4), a concentration of 5~80g/L of reducing agent solution；
1~3 times of silver nitrate solution concentration in a concentration of step 2 of reducing agent solution.
Described matrix is metal, inorganic non-metallic, polymer, composite material；The form of matrix be spherical microballon, sheet,
Fiber, particle, powder.
Following technical scheme specifically can be used in the present invention：
After the present invention by tannic acid-ferric trichloride by being deposited on matrix surface under alkaline condition, poly- (tannin will be used
Acid-ferric trichloride) surface-functionalized matrix is placed in silver plating solution, and reducing agent is added, and it prepares and bonds that stability is good, has
Matrix/silver composite material of electric conductivity, is as follows：
1) matrix after ultrasonic wave dispersion, is placed it in and is stirred evenly, tannic acid and tri-chlorination is added in ethanol solution
Concentration of iron is respectively 0.20~6.0g/L, 0.04~4.0g/L, and it is 6.0~10.0 to adjust pH, with the stirring of 30~100 turns/min
Rate stirring has the matrix of poly- (tannic acid-ferric trichloride) not higher than surface deposition for 24 hours, is obtained.The tannic acid and tri-chlorination
The molar ratio of iron is 1:3~3:1, preferred molar ratio 3:1.It is preferred that a concentration of 0.4g/L of tannic acid, ferric trichloride are a concentration of
0.12g/L, pH 8.5, mixing time 1min；
2) when the silver nitrate solution that mass concentration is 5~40g/L just being disappeared with ammonia water titration to precipitation, preparation obtains
Silver plating solution.Preferred concentration is 10g/L；
3) matrix of poly- (tannic acid-ferric trichloride) is placed in step 2) preparation the surface deposition prepared in step 1)
In silver plating solution, and dispersant is added, stirring is not less than 20 minutes；
4) glucose solution that mass concentration is 5~80g/L is added into the silver plating solution of step 3) under stirring conditions,
The volume of used glucose solution is identical as the volume of silver nitrate solution, reacts 1~60 minute at room temperature, obtains surface covering
There is the matrix of silver layer.The selection of glucose concentration and the concentration of silver plating solution are not related, but are that silver plates in concentration of glucose
Reduction effect is best at twice of liquid concentration.It is preferred that concentration of glucose is 20g/L, the reaction time is 60 minutes.
Wherein, the method described in step 1) is all suitable for the matrix of all forms, including but not limited to spherical microballon,
Sheet, fiber, particle, powder etc., while being suitable for all material type, including it is metal, inorganic non-metallic, polymer, compound
Material etc..The preferred silicon dioxide microsphere of matrix.
The principle of the present invention is：Contain a large amount of phenolic hydroxyl group in tannic acid, and phenolic hydroxyl group can fix reduction and generate
Silver particles.Meanwhile there is good cohesive stability and electric conductivity by chemically treated matrix/silver composite material,
This has been primarily due to reducing agent additional, promotes the reduction process of silver, at the same the presence of tannic acid-ferric trichloride accelerate and
Growth of the Argent grain in matrix surface is consolidated.Since tannic acid-ferric trichloride is deposited as physics in polymeric body surface
Process, it is unrelated with the surface topography of inorganic matter matrix and chemical composition in entire method, it is applicable to various forms and composition
Inorganic matter matrix.
The method of the present invention is prepared with existing compared with Conductive inorganic nonmetallic materials technology, is had the advantages that：
1) present invention is easy to operate, and matrix surface modifies the time (being no more than 1 minute) of tannic acid and ferric trichloride, cost
It is low.
2) present invention prepared by matrix surface silver layer even compact, have good conductive property (conductivity be 1.0~
1.5×105S/m) and bond stability.
3) matrix/silver composite material prepared by the present invention has higher binding force between silver layer and matrix.
4) there is no limit silver-colored attachment does not interfere with the physics of inorganic matter to pattern and composition of the present invention to inorganic matter matrix
Mechanical performance and hot property.
Description of the drawings
Fig. 1：X-ray photoelectron spectroscopy (XPS) wide range figure of 1 microballoon of embodiment, wherein Fig. 1 (a) pure silicon dioxides microballoon
X-ray photoelectron spectroscopy (XPS) wide range figure, silica surface-functionalized Fig. 1 (b) poly- (tannic acid-ferric trichloride) is micro-
X-ray photoelectron spectroscopy (XPS) wide range figure of ball, that is, silica/poly- (tannic acid-ferric trichloride) core-shell microspheres；Figure
1 (c) surface reduction has silicon dioxide microsphere i.e. silica/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres of silver
X-ray photoelectron spectroscopy (XPS) wide range figure.
Fig. 2：X-ray diffraction power spectrum (XRD) spectrogram of 1 microballoon of embodiment, the X of wherein Fig. 2 (a) pure silicon dioxides microballoon are penetrated
Line diffraction spectroscopy (XRD) spectrogram；The X-ray of Fig. 2 (b) silica/poly- (tannic acid-ferric trichloride) core-shell microspheres is spread out
Penetrate power spectrum (XRD) spectrogram；The X-ray of Fig. 2 (c) silica/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres is spread out
Penetrate power spectrum (XRD) spectrogram.
Fig. 3：Scanning electron microscope (SEM) image of embodiment 1, wherein the scanning electricity of Fig. 3 (a) pure silicon dioxides microballoon
Sub- microscope (SEM) image, the scanning electron of Fig. 3 (b) silica/poly- (tannic acid-ferric trichloride) core-shell microspheres
Microscope (SEM) image；The scanning electron of Fig. 3 (c) silica/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres
Microscope (SEM) image.
Fig. 4：Gained, the XPS wide range figures of Fig. 4 (a) blank aluminium powders in embodiment 8；Fig. 4 (b) tannic acid-ferric trichloride table
The XPS wide range figures of aluminium powder, that is, aluminium of face functionalization/poly- (tannic acid-ferric trichloride) core-shell microspheres；The surfaces Fig. 4 (c) are also
The XPS wide range figures of aluminium powder, that is, aluminium of original silver/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres.
Fig. 5：Gained, scanning electron microscope (SEM) image of Fig. 5 (a) blank aluminium powders in embodiment 8；Fig. 5 (b) is single
The scanning electron of the surface-functionalized aluminium powder, that is, aluminium of peaceful acid-ferric trichloride/poly- (tannic acid-ferric trichloride) core-shell microspheres
Microscope (SEM) image；Fig. 5 (c) surface reductions have aluminium powder i.e. aluminium/poly- (tannic acid-ferric trichloride)/galactic nucleus shell-type of silver compound
Scanning electron microscope (SEM) image of microballoon.
Fig. 6：Gained, scanning electron microscope (SEM) image of Fig. 6 (a) blank graphene oxides in embodiment 9；Fig. 6
(b) the surface-functionalized graphene oxide, that is, graphene oxide of tannic acid-ferric trichloride/poly- (tannic acid-ferric trichloride) nucleocapsid
Scanning electron microscope (SEM) image of formula complex microsphere；Fig. 6 (c) surface reductions have the graphene oxide i.e. graphite oxide of silver
Scanning electron microscope (SEM) image of alkene/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres.
Fig. 7 embodiments 10, scanning electron microscope (SEM) image of the pure aramid fibers of Fig. 7 (a)；Fig. 7 (b) aramid fibers/
Scanning electron microscope (SEM) image of poly- (tannic acid-ferric trichloride) core-shell microspheres；Fig. 7 (c) aramid fibers/poly-
Scanning electron microscope (SEM) image of (tannic acid-ferric trichloride)/silver-colored core-shell microspheres.
Specific implementation mode
With reference to embodiment, further illustrate the present invention.
Embodiment 1
1) glass microballoon for cleaning 4g ethyl alcohol is added in the deionized water of 100ml processed, stirs evenly, then configures dense
Degree is the ferric chloride aqueous solutions of the tannic acid and 1.2g/L of 3.6g/L, and tannic acid is 3 with ferric trichloride molar ratio:1, respectively first
It is added in Matrix Solution afterwards, after being used in combination Tris-HCl buffer solutions to adjust PH to 8.5,1 point is stirred with the stir speed (S.S.) of 60 turns/min
Deposition is had the glass microballoon of poly- (tannic acid-ferric trichloride) to filter out by clock after stirring, and net, vacuum is washed with deionized water
It is dry；
2) configuration concentration is the silver nitrate solution of 10g/L, is just disappeared with ammonia water titration to precipitation, obtains silver plating solution；
3) glass microballoon after poly- (tannic acid-ferric trichloride) is surface-functionalized in step 1) will be used under stirring conditions
It is immersed in the 100ml silver plating solutions obtained in step 2), 0.05g polyethylene of dispersing agent pyrrolidones is added in this silver plating solution
(PVP) it to improve the dispersion performance of glass microballoon in the solution, stirs 20 minutes；
4) glucose solution that 100ml mass concentrations are 20g/L is added in the silver plating solution of step 3), is reacted 60 minutes
Afterwards, the glass microballoon that surface is coated with silver particles can be obtained.
After measured, glass microballoon (the silica)/galactic nucleus shell-type compounded microbeads are electrically conductive, and conductivity is 1.5 × 105S/
m。
The atomic percent of pure silicon dioxide and silicon dioxide/silver core shell-type complex microsphere surface-element contains in the present embodiment
Amount ratio is shown in Table 1.
Pure silicon dioxide microballoon XPS wide ranges figure and XRD spectra are shown in Fig. 1 (a) and Fig. 2 (a), silica/poly- (tannin respectively
Acid-ferric trichloride) core-shell microspheres XPS wide ranges figure and XRD spectra see Fig. 1 (b) and Fig. 2 (b) respectively, silica/
The XPS wide ranges figure and XRD spectra of poly- (tannic acid-ferric trichloride)/silver-colored core-shell microspheres are shown in Fig. 1 (c) and Fig. 2 (c) respectively；
Scanning electron microscope (SEM) image is shown in Fig. 3, wherein (a) pure silicon dioxide microballoon, (b) silica/poly- (tannic acid-trichlorine
Change iron) core-shell microspheres and (c) silica/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres.
It is seen in fig. 1, that in the XPS wide of Fig. 1 (b) silica/poly- (tannic acid-ferric trichloride) core-shell microspheres
Occur the ferro element not having in Fig. 1 (a) pure silicon dioxides in spectrogram, illustrates that poly- (tannic acid-ferric trichloride) has been deposited on two
Silicon oxide microsphere surface.In the XPS wide ranges of Fig. 1 (c) silica/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres
Occur silver-colored peak in figure, illustrates to deposited silver particles on silicon dioxide microsphere surface.As can be seen from Figure 2, in Fig. 2 (a) pure two
Do not have silver in the XRD spectra of silica and Fig. 2 (b) silica/poly- (tannic acid-ferric trichloride) core-shell microspheres
Peak, and there are four types of not in the XRD spectra of Fig. 2 (c) silica/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres
Silver-colored peak with lattice structure occurs, it was demonstrated that has silver particles on silicon dioxide microsphere surface.The pure dioxies of Fig. 3 (a) as can be seen from Figure 3
SiClx, Fig. 3 (b) silica/poly- (tannic acid-ferric trichloride) core-shell microspheres and Fig. 3 (c) silica/poly- (tannin
Acid-ferric trichloride)/silver-colored core-shell microspheres surface topography variation, while can be seen that and be made with chemical reduction method
Silicon dioxide/silver core shell-type complex microsphere surface silver layer it is fine and close continuous, have good electric conductivity.
Embodiment 2
For process with embodiment 1, the reaction time in step 4) is changed to 30min, 40min, 50min, 90min and 120min can
Obtain the glass microballoon that silver particles are coated with to surface.
After measured, the silicon dioxide/silver core shell-type compounded microbeads are electrically conductive, and conductivity is 1.0-1.5 × 105S/m it
Between.
Embodiment 3
The concentration of tannic acid in step 1) is changed to as 0.20g/L, 4.0g/L, 6.0g/L, accordingly with embodiment 1 by process
Ferric trichloride it is a concentration of for 0.04g/L, 2.4g/L, 4.0g/L, the glass microballoon that surface is coated with silver particles can be obtained.
After measured, the silicon dioxide/silver core shell-type compounded microbeads are electrically conductive, and conductivity is 1.0-1.5 × 105S/m it
Between.
Embodiment 4
Mixing time in step 1) is changed to 20 seconds, 30 seconds, 40 seconds, 50 seconds by process with embodiment 1, and surface plating can be obtained
There is the glass microballoon of silver particles.
After measured, the silicon dioxide/silver core shell-type compounded microbeads are electrically conductive, and conductivity is 1.0-1.5 × 105S/m it
Between.
Embodiment 5
Process is changed to 5g/L, 20g/L, 30g/L and 40g/L with embodiment 1, by silver nitrate concentration in step 2), accordingly
Glucose concentration is 10g/L, 40g/L, 60g/L and 80g/L, and the glass microballoon that surface is coated with silver particles can be obtained.
After measured, the silicon dioxide/silver core shell-type compounded microbeads are electrically conductive, and conductivity is 1.0-1.5 × 105S/m it
Between.
Embodiment 6
Process is adjusted to 7 respectively with embodiment 1, by the PH of tannic acid-liquor ferri trichloridi in step 1), 7.5,8,9,
9.5 and 10, the glass microballoon that surface is coated with silver particles can be obtained.
After measured, the silicon dioxide/silver core shell-type compounded microbeads are electrically conductive, and conductivity is 1.0-1.5 × 105S/m it
Between.
Embodiment 7
Process is changed to 1 with embodiment 1, by the molar ratio of tannic acid in step 1) and ferric trichloride:2,1:3,2:1 and 3:1,
The glass microballoon that surface is coated with silver particles can be obtained.
After measured, the silicon dioxide/silver core shell-type compounded microbeads are electrically conductive, and conductivity is 1.0-1.5 × 105S/m it
Between.
Embodiment 8
1) 4g is added with the aluminium powder that ethyl alcohol is cleaned into the deionized water of 100ml, is stirred evenly, then configuration concentration is
The tannic acid of 3.6g/L and the ferric chloride aqueous solutions of 1.2g/L, tannic acid are 3 with ferric trichloride molar ratio:1, it is separately added into base
It in liquid solution, after being used in combination Tris-HCl buffer solutions to adjust PH to 8.5, is stirred 1 minute with the stir speed (S.S.) of 60 turns/min, stirring knot
There is the glass microballoon of poly- (tannic acid-ferric trichloride) to filter out deposition after beam, net, vacuum drying is washed with deionized water；
2) configuration concentration is the silver nitrate solution of 10g/L, is just disappeared with ammonia water titration to precipitation, obtains silver plating solution；
3) it will under stirring conditions be impregnated with the aluminium powder of (tannic acid-ferric trichloride) poly- in step 1) after surface-functionalized
In the 100ml silver plating solutions obtained in step 2), 0.05g polyethylene of dispersing agent pyrrolidones (PVP) is added in this silver plating solution
To improve the dispersion performance of aluminium powder in the solution, stir 20 minutes；
4) glucose solution that 100ml mass concentrations are 20g/L is added in the silver plating solution of step 3), is reacted 60 minutes
Afterwards, the aluminium powder that surface is coated with silver particles can be obtained.
After measured, the aluminium/galactic nucleus shell-type composite material is electrically conductive, and conductivity is being 0.75 × 105S/m。
Fig. 4 be embodiment 8 in gained blank aluminium powder, aluminium/poly- (tannic acid-ferric trichloride) core-shell type composite material and
The XPS wide range figures of aluminium/poly- (tannic acid-ferric trichloride)/galactic nucleus shell-type composite material.Due in Fig. 4 (b) aluminium/poly- (tannic acid-
Ferric trichloride) XPS spectrum figure in there is the ferro element not having in pure aluminium powder spectrogram, illustrate to have in aluminium powder surface deposition poly- (single
Peaceful acid-ferric trichloride), there is silver-colored peak in the XPS spectrum figure of Fig. 4 (c) aluminium/poly- (tannic acid-ferric trichloride)/silver, it was demonstrated that
Aluminium powder surface deposited silver particles.
Fig. 5 be embodiment 9 in gained blank aluminium powder, aluminium/poly- (tannic acid-ferric trichloride) core-shell microspheres and
Scanning electron microscope (SEM) image of aluminium/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres.It can from Fig. 5
Go out Fig. 5 (a) pure aluminium powders, Fig. 5 (b) aluminium powders/poly- (tannic acid-ferric trichloride) core-shell microspheres and Fig. 5 (c) aluminium powders/poly- (list
Peaceful acid-ferric trichloride)/silver-colored core-shell microspheres surface topography variation, while can be seen that with chemical reduction method system
The silver layer on the aluminium/silver core-shell microspheres surface obtained is fine and close continuous, has good electric conductivity.
Embodiment 9
1) 2g is added with graphene oxide into the deionized water of 100ml, is stirred evenly, then configuration concentration is
The tannic acid of 3.6g/L and the ferric chloride aqueous solutions of 1.2g/L, tannic acid are 3 with ferric trichloride molar ratio:1, it is separately added into base
It in liquid solution, after being used in combination Tris-HCl buffer solutions to adjust PH to 8.5, is stirred 1 minute with the stir speed (S.S.) of 60 turns/min, stirring knot
There is the graphene oxide of poly- (tannic acid-ferric trichloride) to filter out deposition after beam, net, freeze-drying is washed with deionized water；
2) configuration concentration is the silver nitrate solution of 10g/L, is just disappeared with ammonia water titration to precipitation, obtains silver plating solution；
3) graphene oxide after poly- (tannic acid-ferric trichloride) is surface-functionalized in step 1) will be used in the condition of stirring
Under be immersed in the 100ml silver plating solutions obtained in step 2), in this silver plating solution be added 0.05g polyethylene of dispersing agent pyrrolidones
(PVP) it to improve the dispersion performance of graphene oxide in the solution, stirs 20 minutes；
4) glucose solution that 100ml mass concentrations are 20g/L is added in the silver plating solution of step 3), is reacted 60 minutes
Afterwards, the graphene oxide that surface is coated with silver particles can be obtained.
After measured, the graphene oxide/galactic nucleus shell-type composite material is electrically conductive, and conductivity is 1 × 105S/m。
Fig. 6 is the blank graphene oxide of gained, graphene oxide/poly- (tannic acid-ferric trichloride) nucleocapsid in embodiment 9
The scanning electron microscope of formula composite material and graphene oxide/poly- (tannic acid-ferric trichloride)/galactic nucleus shell-type composite material
(SEM) image.Fig. 6 (a) pure zirconias graphene as can be seen from Figure 6, Fig. 6 (b) graphene oxides/poly- (tannic acid-tri-chlorination
Iron) core-shell microspheres and Fig. 6 (c) graphene oxides/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres table
The variation of face pattern, while can be seen that graphene oxide/silver core-shell microspheres surface made from chemical reduction method
Silver layer it is fine and close continuous, have good electric conductivity.
Embodiment 10
1) 1.5g aramid fibers are added into the deionized water of 100ml, are stirred evenly, then configuration concentration is 3.6g/L
Tannic acid and 1.2g/L ferric chloride aqueous solutions, tannic acid and ferric trichloride molar ratio are 3:1, it is separately added into Matrix Solution
In, after being used in combination Tris-HCl buffer solutions to adjust PH to 8.5, stirred 1 minute with the stir speed (S.S.) of 60 turns/min, it will after stirring
Deposition has the aramid fiber of poly- (tannic acid-ferric trichloride) to filter out, and net, drying is washed with deionized water；
2) configuration concentration is the silver nitrate solution of 10g/L, is just disappeared with ammonia water titration to precipitation, obtains silver plating solution；
3) aramid fiber after poly- (tannic acid-ferric trichloride) is surface-functionalized in step 1) will be used under stirring conditions
It is immersed in the 100ml silver plating solutions obtained in step 2), 0.05g polyethylene of dispersing agent pyrrolidones is added in this silver plating solution
(PVP), it stirs 20 minutes；
4) glucose solution that 100ml mass concentrations are 20g/L is added in the silver plating solution of step 3), is reacted 60 minutes
Afterwards, the aramid fiber that surface is coated with silver particles can be obtained.
After measured, the aramid fiber/galactic nucleus shell-type composite material is electrically conductive, and conductivity is 1.2 × 105Between S/m.
Fig. 7 is the blank aramid fiber of gained, aramid fiber/poly- (tannic acid-ferric trichloride) core-shell type in embodiment 10
The scanning electron microscope of composite material and aramid fiber/poly- (tannic acid-ferric trichloride)/galactic nucleus shell-type composite material
(SEM) image.The pure aramid fibers of Fig. 7 (a) as can be seen from Figure 7, Fig. 7 (b) aramid fibers/poly- (tannic acid-ferric trichloride) core
The surface topography of shell-type complex microsphere and Fig. 7 (c) aramid fibers/poly- (tannic acid-ferric trichloride)/silver core-shell microspheres
Variation, while can be seen that the silver layer on graphene oxide/silver core-shell microspheres surface made from chemical reduction method causes
It is close continuous, have good electric conductivity.
Pure silicon dioxide and silica/poly- (tannic acid-ferric trichloride)/galactic nucleus shell-type are compound micro- in 1 embodiment 1 of table
The relative atomic percent of ball surface element
Claims (7)
1. a kind of preparation method of electroplate material, it is characterised in that the method includes：
1) by matrix, ultrasonic wave disperses in ethanol solution or deionized water, is successively separately added into tannic acid and ferric trichloride is molten
Liquid stirs evenly, and obtaining surface deposition has the matrix of poly- tannic acid-ferric trichloride；
The molar ratio of the tannic acid and ferric trichloride is 1:3~3:1；
2) when silver nitrate solution is just disappeared with ammonia water titration to precipitation, preparation obtains silver plating solution；
3) silver plating solution for thering is the matrix of poly- tannic acid-ferric trichloride to be placed in step 2) preparation the surface deposition prepared in step 1)
In, and the stirring of polyethylene of dispersing agent pyrrolidones is added, amount used is 0.5~2.0 times of silver nitrate；
4) reducing agent solution is added into the solution of step 3) under stirring conditions, reacts 1~60 minute at room temperature, obtains table
Face is covered with the matrix of silver layer；
The reducing agent is glucose, sodium citrate or sodium borohydride；
Reducing agent dosage is 1~3 times of silver nitrate.
2. the preparation method of electroplate material as described in claim 1, it is characterised in that：
In step 1), a concentration of 0.2~6.0g/L of tannic acid；A concentration of 0.04~4.0g/L of liquor ferri trichloridi；It is added
After tannic acid and liquor ferri trichloridi, it is 6~10 that Tris buffer solutions, which are added, and adjust pH.
3. the preparation method of electroplate material as claimed in claim 2, it is characterised in that：
In step 1), stir speed (S.S.) is 30~100 turns/min；Total reaction time is no more than 1min.
4. the preparation method of electroplate material as described in claim 1, it is characterised in that：
In step 2), a concentration of 5~40g/L of silver nitrate solution.
5. the preparation method of electroplate material as described in claim 1, it is characterised in that：
In step 3), mixing time is not less than 20 minutes.
6. the preparation method of electroplate material as described in claim 1, it is characterised in that：
In step 4), a concentration of 5~80g/L of reducing agent solution；
1~3 times of silver nitrate concentration in a concentration of step 2) of reducing agent solution.
7. the preparation method of the electroplate material as described in one of claim 1~6, it is characterised in that：
Described matrix is metal, inorganic non-metallic, polymer, composite material；The form of matrix be spherical microballon, sheet, fiber,
Particle, powder.
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