CN109338422A - The preparation method of the preparation method of IPMC material, wherein mesosome, IPMC material - Google Patents
The preparation method of the preparation method of IPMC material, wherein mesosome, IPMC material Download PDFInfo
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- CN109338422A CN109338422A CN201811220201.7A CN201811220201A CN109338422A CN 109338422 A CN109338422 A CN 109338422A CN 201811220201 A CN201811220201 A CN 201811220201A CN 109338422 A CN109338422 A CN 109338422A
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- C25D3/00—Electroplating: Baths therefor
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- C25D3/48—Electroplating: Baths therefor from solutions of gold
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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Abstract
The present invention discloses a kind of preparation method of IPMC material, comprising the following steps: base film roughening processing occurs after base film carries out first time ion-exchange treatment and before base film progress first time reduction treatment.The invention also discloses a kind of intermediate preparations of IPMC material, a kind of IPMC material for the preparation method preparation for adopting above-mentioned IPMC material.The present invention has the adhesive force realized between enhancing electrode and base film, increases the depth for penetrating into electrode and improves the pattern for penetrating into electrode, thus the advantages of further increasing the chemical property and electromechanical properties of IPMC material.
Description
Technical field
The present invention relates to flexible intelligent ion polymer-metal composite material technical field more particularly to IPMC materials
The preparation method of preparation method, wherein mesosome, IPMC material.
Background technique
IPMC material refer to ion polymer-metal composite material (Ionic Polymer-Metal Composites,
It IPMC), is a kind of typical ionic electroactive polymer (Ionic ElectroActive Polymer, iEAP).
Due to IPMC material have light weight, deformation be big, response rapidly, flexibility is good, the unique advantages such as environmentally friendly, in biology
The various fields such as medicine, space flight and aviation, military detection, bionic mechanical have a wide range of applications.
The IPMC material of the prior art is by depositing in the upper and lower surface of ionomer base film and permeating one layer of electricity
Pole (such as platinum, gold, palladium and silver) and formed sandwich structure composite material.
A kind of preparation work at ionomer/tree-shaped interface of metal branch as disclosed in patent application 201711344832.5
Skill, including following technical step: (1) base film pretreatment (base film roughening, surface clean, removal foreign ion and swelling)；
(2) soaking and reducing plating (ion exchange and ion reduction)；(3) chemical plating or plating (increase surface electricity by oxidation-reduction process
Pole thickness)；(4) it post-processes.A kind of for another example selectivity plating work of IPMC driver disclosed in patent application 201210452704.3
Skill, after being pre-processed base material, (specifically pretreatment mode is incited somebody to action using amberplex as base material
The amberplex be cleaned by ultrasonic in the environment of roughening is placed on 60 DEG C, removes surface particles, then pickling and goes respectively
Plating area is selected in ion boiling washing) and the techniques such as progress ion reduction, ion reduction and plating in plating area.
By the above-mentioned prior art it is found that the pretreatment stage in base material occurs for its roughening of IPMC material at present.
The specific roughening technique of IPMC material matrix film a kind of as disclosed in patent application 201310385815.1, by base film into
Row roughening increases the adhesion strength between electrode layer and base film.And IPMC material is in the actual processing process, specifically in base
Body material carries out in ion exchange process, and the contraction of larger proportion can occur for basis material, influences the Effect of Pretreatment of its early period,
Leading to the effect of base material roughening early period cannot effectively play, so that the interface interaction between electrode and base film be caused to drop
It is low, good adhesion effect is mutually not achieved before, and then influence the chemical property and electromechanical properties of finished product IPMC material.
Summary of the invention
Technical problem to be solved by the present invention lies in the adhesive force how gone between enhancing electrode and base film, increase and seep
Enter the depth of electrode and improves the pattern for penetrating into electrode.
The present invention is realized by following technological means solves a kind of above-mentioned technical problem: preparation method of IPMC material,
The following steps are included: base film roughening processing occur base film carry out first time ion-exchange treatment after and base film into
Before row first time reduction treatment.
Preferably, first time reduction treatment is carried out in described matrix film and then successively carry out ion-exchange treatment, reduction
Processing, ion-exchange treatment, reduction treatment are a cycle each time, which continues repeatedly.
Since base film is in first time ion exchange, the interface and surface of basement membrane are there are no the presence of electrode, base at this time
The shrinkage rates of film reach maximum, and roughening at this moment is selected to select the roughening when basement membrane is contracted to minimum area, subsequent progress
When ion reduction, basement membrane can be swollen, and the hole that is formed when by roughening, slot widen, and roughening effect can be reinforced.Second is carried out again
In secondary, third time or ion exchange process thereafter, electrode has been attached to basement membrane interface and surface, and basement membrane shrinkage degree subtracts
It is small, it does not need to be supplemented roughening.Furthermore for the second time, carry out roughening after ion exchange again for the third time or thereafter, it can be to preceding primary
The electrode that reduction carries out causes very big destruction.
Preferably, the period is 2~5 times.
Preferably, described matrix film roughening processing includes blasting treatment, sand paper polishing, micropin roughening, plasma etching
One kind.
Preferably, the roughening device of the micropin roughening includes micropin idler wheel or micropin plate.
Preferably, the reduction plating solution that the ion-exchange treatment uses includes containing Pd2+、Ag+、Au+、Pt+、Ni+、Cu2+'s
It is at least one that salting liquid is complexed.
Preferably, the reducing agent that the reduction treatment uses is NaBH4。
Invention additionally discloses a kind of intermediate preparations of IPMC material, comprising the following steps:
Step 1: pretreated base film is carried out first time ion-exchange treatment；
Step 2: being rinsed after the base film that step 1 is obtained carries out roughening processing；
Step 3: step 2 treated base film is carried out first time reduction treatment；
Step 4 successively carries out ion-exchange treatment, reduction treatment to step 3 treated base film, each time again
Ion-exchange treatment, reduction treatment are a cycle, which continues repeatedly.
Invention additionally discloses a kind of IPMC materials prepared by the preparation method using such as above-mentioned IPMC material.
The present invention has the advantages that technological core of the invention is to be put forward for the first time this committed step of base film roughening
It is placed in after first time ion-exchange step, so that matrix membrane material is effectively prevented in ion exchange process for the first time, Yin Ji
Body material occur larger proportion contraction, cause the surface holes formed after base film surface deformation of material and roughening, slot squeeze
Pressure is shunk, the deficiency weakened so as to cause electrode and base film interface interaction.The present invention can be enhanced between electrode and base film
Adhesive force, increase penetrate into electrode depth and improve penetrate into electrode pattern, to further increase the electricity of IPMC material
Chemical property and electromechanical properties.
The results showed that its chemical property of IPMC material and electromechanical properties for being prepared using method of the invention are all
It has been significantly improved, wherein the IPMC that opposite conventional preparation techniques obtain, capacitor can be improved 5 times, and electroluminescent dynamic deformation can mention
It is 4 times high.In addition, by this processing step adjusted, the needle electrode type IPMC actuator successfully prepared, low, high
Frequently under (0.1-20HZ) voltage, good electromechanical properties are shown, compare traditional handicraft, the high frequency for being obviously improved material is special
Property.
Detailed description of the invention
Fig. 1 is its preparation process flow schematic diagram of IPMC material of the present invention.
Fig. 2 is the VA characteristic curve figure of 1 sample of the embodiment of the present invention, 1 sample of comparative example.
Fig. 3 is the VA characteristic curve figure of 2 sample of the embodiment of the present invention, 2 sample of comparative example.
Fig. 4 is the VA characteristic curve figure of 3 sample of the embodiment of the present invention, 3 sample of comparative example.
Fig. 5 is the VA characteristic curve figure of 4 sample of the embodiment of the present invention, 4 sample of comparative example.
Fig. 6 be 1 sample of the embodiment of the present invention, 1 sample of comparative example 2V, square wave, 0.1Hz tip displacement response curve
Figure.
Fig. 7 be 2 sample of the embodiment of the present invention, 2 sample of comparative example 2V, square wave, 0.1Hz tip displacement response curve
Figure.
Fig. 8 be 3 sample of the embodiment of the present invention, 3 sample of comparative example 2V, square wave, 0.1Hz tip displacement response curve
Figure.
Fig. 9 be 4 sample of the embodiment of the present invention, 4 sample of comparative example 2V, square wave, 0.1Hz tip displacement response curve
Figure.
Figure 10 is the scanning electron microscope (SEM) photograph of 3 sample of the embodiment of the present invention, 3 sample of comparative example.
Figure 11 is the end position of 4 sample of the embodiment of the present invention, 4 sample of comparative example under 2V, square wave, 0.1Hz-18Hz frequency range
Move response curve.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
It should be noted that it can directly on the other element when element is referred to as " being fixed on " another element
Or there may also be elements placed in the middle.When an element is considered as " connection " another element, it, which can be, is directly connected to
To another element or it may be simultaneously present centering elements.
The embodiment of the present invention spy carries out the introduction of its preparation process using Pd-Au-IPMC material as object, other IPMC materials
Material also should be within the scope of the present invention using preparation process of the invention.The embodiment of the present invention spy is with Dupont company
The Nafion-117 film of production be base film, the Flemion film of the base film of other prior arts such as Asahi Glass company,
Aciplex film or the Aquivion film of Solvay Solexis company of Asahi Chemical company etc. also should be in the present invention
Protection scope in.
Embodiment 1
As shown in Figure 1, the present embodiment discloses a kind of preparation process of Pd-Au-IPMC material, specifically includes the following steps:
(1) base film pre-process: base film is cut into 45mm × 45mm, in 60 DEG C of DI water (i.e. deionized water) into
Row ultrasonic cleaning 30mim, then by the basement membrane after ultrasonic cleaning successively at 100 DEG C, in the HCl solution of 2mol/L, DI water
Water-bath, which is boiled, respectively washes 30min；
(2) ion exchange: 0.162g Pd (NH is measured respectively3)4Cl2Complex salt, 66mLDI water, 8.6mLNH3H2O (content
25%~28%) solution allocation restores plating solution, and by step (1), treated that base film is put into the solution, while at 50 DEG C,
2h is impregnated under the conditions of the water-bath constant temperature oscillator of 75r/min, is rinsed matrix film surface 3 times after taking-up with DI water, and save Pd's
Salting liquid is complexed, following cycle uses；Wherein NH3H2O (content 25%~28%) solution indicates NH3Quality point in ammonium hydroxide
Number is 25%~28%.
(3) base film roughening: will be fixed by adhesive tape at four side surpluses of base film, and logical by the mold with micropin
The roller structure for crossing surface insertion micropin, in 6g/cm2Line pressure under act under, in membrane surface 25 periods of roughening back and forth,
After roughening is completed in base film upper surface, by base film turn-over, the roughening processing of lower surface is carried out, uses base film after the completion of roughening
DI water rinses 3 times；
(4) ion reduction: 186mLDI water, 1mLNH are measured respectively3H2O (content 25%~28%), 0.0076gNaBH4Match
Reducing solution is set, treated that base film is put into the solution by step (3), while at 50 DEG C, the constant temperature water bath of 75r/min vibrates
1h is restored under the conditions of device；
Circuit sequentially repetition step (2) and (4) totally 2 times, i.e., successively according to step (2), (4), (2), (4) sequence into
Row.
(5) it is electroplated: step (4) treated sample is subjected to trimming processing, selecting titanium net is anode, and pogo-pin array is
The golden water (50mL) of cathode, 1.6g/L is electrolyte, to the gold-plated processing of sample surface under the 0.1A function of current；
(6) it post-processes: the film after plating is put into 200mL, 0.2mol L-1NaOH aqueous solution in, at 50 DEG C, 600r/
2h is exchanged in the magnetic stirring apparatus of min, so that the driving ion in film is all converted to Na+。
Embodiment 2
As shown in Figure 1, the present embodiment discloses a kind of preparation process of Pd-Au-IPMC material, specifically includes the following steps:
(1) base film pre-processes: base film being cut into 45mm × 45mm, carries out ultrasonic cleaning in 60 DEG C of DI water
30mim, then by the basement membrane after ultrasonic cleaning successively at 100 DEG C, water-bath is boiled and is washed respectively in the HCl solution of 2mol/L, DI water
30min；
(2) ion exchange: 0.162g Pd (NH is measured respectively3)4Cl2Complex salt, 66mLDI water, 8.6mLNH3H2O (content
25%~28%) solution, by step (1), treated that base film is put into the solution, while at 50 DEG C, the water-bath of 75r/min
2h is impregnated under the conditions of constant temperature oscillator, is rinsed matrix film surface 2 times after taking-up with DI water, and save the complexing salting liquid of Pd, after
It is continuous to be recycled；
(3) base film roughening: will be fixed by adhesive tape at four side surpluses of base film, and logical by the mold with micropin
The roller structure for crossing surface insertion micropin, in 6g/cm2Line pressure under act under, in membrane surface 50 periods of roughening back and forth,
After roughening is completed in base film upper surface, by base film turn-over, the roughening processing of lower surface is carried out, uses base film after the completion of roughening
DI water rinses 3 times；
(4) ion reduction: 186mLDI water, 1mLNH are measured respectively3H2O (content 25%~28%), 0.0076gNaBH4Match
Reducing solution is set, treated that base film is put into the solution by step (3), while at 50 DEG C, the constant temperature water bath of 75r/min vibrates
1h is restored under the conditions of device；
Circuit sequentially repetition step (2) and (4) totally 2 times；
(5) it is electroplated: step (4) treated sample is subjected to trimming processing, selecting titanium net is anode, and pogo-pin array is
The golden water (50mL) of cathode, 1.6g/L is electrolyte, to the gold-plated processing of sample surface under the 0.1A function of current；
(6) it post-processes: the film after plating is put into 200mL, 0.2mol L-1NaOH aqueous solution in, at 50 DEG C, 600r/
2h is exchanged in the magnetic stirring apparatus of min, so that the driving ion in film is all converted to Na+。
Embodiment 3
As shown in Figure 1, the present embodiment discloses a kind of preparation process of Pd-Au-IPMC material, specifically includes the following steps:
(1) base film pre-processes: base film being cut into 45mm × 45mm, carries out ultrasonic cleaning in 60 DEG C of DI water
30mim, then by the basement membrane after ultrasonic cleaning successively at 100 DEG C, water-bath is boiled and is washed respectively in the HCl solution of 2mol/L, DI water
30min；
(2) ion exchange: 0.162g Pd (NH is measured respectively3)4Cl2Complex salt, 66mLDI water, 8.6mLNH3H2O (content
25%~28%) solution, by step (1), treated that base film is put into the solution, while at 50 DEG C, the water-bath of 75r/min
2h is impregnated under the conditions of constant temperature oscillator, is rinsed matrix film surface 2 times after taking-up with DI water, and save the complexing salting liquid of Pd, after
It is continuous to be recycled；
(3) base film roughening: will be fixed by adhesive tape at four side surpluses of base film, and logical by the mold with micropin
The roller structure for crossing surface insertion micropin, in 6g/cm2Line pressure under act under, in membrane surface 75 periods of roughening back and forth,
After roughening is completed in base film upper surface, by base film turn-over, the roughening processing of lower surface is carried out, uses base film after the completion of roughening
DI water rinses 3 times；
(4) ion reduction: 186mLDI water, 1mLNH are measured respectively3H2O (content 25%~28%), 0.0076gNaBH4Match
Reducing solution is set, treated that base film is put into the solution by step (3), while at 50 DEG C, the constant temperature water bath of 75r/min vibrates
1h is restored under the conditions of device；
Circuit sequentially repetition step (2) and (4) totally 2 times；
(5) it is electroplated: step (4) treated sample is subjected to trimming processing, selecting titanium net is anode, and pogo-pin array is
The golden water (50mL) of cathode, 1.6g/L is electrolyte, to the gold-plated processing of sample surface under the 0.1A function of current；
(6) it post-processes: the film after plating is put into 200mL, 0.2mol L-1NaOH aqueous solution in, at 50 DEG C, 600r/
2h is exchanged in the magnetic stirring apparatus of min, so that the driving ion in film is all converted to Na+。
Embodiment 4
As shown in Figure 1, the present embodiment discloses a kind of preparation process of Pd-Au-IPMC material, specifically includes the following steps:
(1) base film pre-processes: base film being cut into 45mm × 45mm, carries out ultrasonic cleaning in 60 DEG C of DI water
30mim, then by the basement membrane after ultrasonic cleaning successively at 100 DEG C, water-bath is boiled and is washed respectively in the HCl solution of 2mol/L, DI water
30min；
(2) ion exchange: 0.162g Pd (NH is measured respectively3)4Cl2Complex salt, 66mLDI water, 8.6mLNH3H2O (content
25%~28%) solution, by step (1), treated that base film is put into the solution, while at 50 DEG C, the water-bath of 75r/min
2h is impregnated under the conditions of constant temperature oscillator, is rinsed matrix film surface 2 times after taking-up with DI water, and save the complexing salting liquid of Pd, after
It is continuous to be recycled；
(3) base film roughening: will be fixed by adhesive tape at four side surpluses of base film, and logical by the mold with micropin
The roller structure for crossing surface insertion micropin, in 6g/cm2Line pressure under act under, in membrane surface 100 week of roughening back and forth
Phase after roughening is completed in base film upper surface, by base film turn-over, carries out the roughening processing of lower surface, by matrix after the completion of roughening
Film is rinsed 3 times with DI water；
(4) ion reduction: 186mLDI water, 1mLNH are measured respectively3H2O (content 25%~28%), 0.0076gNaBH4Match
Reducing solution is set, treated that base film is put into the solution by step (3), while at 50 DEG C, the constant temperature water bath of 75r/min vibrates
1h is restored under the conditions of device；
Circuit sequentially repetition step (2) and (4) totally 2 times；
(5) it is electroplated: step (4) treated sample is subjected to trimming processing, selecting titanium net is anode, and pogo-pin array is
The golden water (50mL) of cathode, 1.6g/L is electrolyte, to the gold-plated processing of sample surface under the 0.1A function of current；
(6) it post-processes: the film after plating is put into 200mL, 0.2mol L-1NaOH aqueous solution in, at 50 DEG C, 600r/
2h is exchanged in the magnetic stirring apparatus of min, so that the driving ion in film is all converted to Na+。
Pd-Au-IPMC material prepared by embodiment 1-4 is respectively labeled as A1, A2, A3, A4.In addition, being produced for specific
The difference of product material, the number specific aim that the present invention circuits sequentially repetition step (2) and (4) increase to 3~5 times, also should be
In protection scope of the present invention.
Comparative example 1
This comparative example discloses a kind of preparation process of Pd-Au-IPMC material, and the method for preparing Pd-Au-IPMC material is adopted
With the method for the prior art, embodiment 1 is compared, distinctive points are the roughening processing of base film is preposition in pretreatment stage.
Specifically includes the following steps:
Base film pretreatment: base film is cut into 45mm × 45mm, will be consolidated at four side surpluses of base film by adhesive tape
It is fixed, and by the mold with micropin by the roller structure of surface insertion micropin, in 6g/cm2Line pressure under act under,
25 periods of roughening, by base film turn-over, carry out the roughening of lower surface after roughening is completed in base film upper surface to membrane surface back and forth
Processing；Base film DI water is rinsed 3 times after the completion of roughening；Ultrasonic cleaning 30mim is carried out in 60 DEG C of DI water, then will
Basement membrane after ultrasonic cleaning is successively at 100 DEG C, and water-bath boils and washes 30min respectively in the HCl solution of 2mol/L, DI water；
(2) ion exchange: 0.162g Pd (NH is measured respectively3)4Cl2Complex salt, 66mLDI water, 8.6mLNH3H2O (content
25%~28%) solution allocation restores plating solution, and by step (1), treated that base film is put into the solution, while at 50 DEG C,
2h is impregnated under the conditions of the water-bath constant temperature oscillator of 75r/min, is rinsed matrix film surface 3 times after taking-up with DI water, and save Pd's
Salting liquid is complexed, following cycle uses；
(3) ion reduction: 186mLDI water, 1mLNH are measured respectively3H2O (content 25%~28%), 0.0076gNaBH4Match
Reducing solution is set, treated that base film is put into the solution by step (2), while at 50 DEG C, the constant temperature water bath of 75r/min vibrates
1h is restored under the conditions of device；
Circuit sequentially repetition step (2) and (3) totally 2 times；
(4) it is electroplated: the print that step (3) processing obtains being subjected to trimming processing, selecting titanium net is anode, pogo-pin array
Golden water (50mL) for cathode, 1.6g/L is electrolyte, to the gold-plated processing of sample surface under the 0.1A function of current；
(5) it post-processes: the film after plating is put into 200mL, 0.2mol L-1NaOH aqueous solution in, at 50 DEG C, 600r/
2h is exchanged in the magnetic stirring apparatus of min, so that the driving ion in film is all converted to Na+。
Comparative example 2
This comparative example discloses a kind of preparation process of Pd-Au-IPMC material, and the method for preparing Pd-Au-IPMC material is adopted
With the method for the prior art, embodiment 2 is compared, distinctive points are the roughening processing of base film is preposition in pretreatment stage.
Specifically includes the following steps:
(1) base film pre-processes: base film is cut into 45mm × 45mm, it will be at four side surpluses of base film by adhesive tape
It is fixed, and by the mold with micropin by the roller structure of surface insertion micropin, in 6g/cm2Line pressure under act under,
In membrane surface, 50 periods of roughening, by base film turn-over, carry out the rough of lower surface after roughening is completed in base film upper surface back and forth
Change processing；Base film DI water is rinsed 3 times after the completion of roughening, ultrasonic cleaning 30mim is carried out in 60 DEG C of DI water, then
By the basement membrane after ultrasonic cleaning successively at 100 DEG C, water-bath boils and washes 30min respectively in the HCl solution of 2mol/L, DI water.
(2) ion exchange: 0.162g Pd (NH is measured respectively3)4Cl2Complex salt, 66mLDI water, 8.6mLNH3H2O (content
25%~28%) solution, by step (1), treated that base film is put into the solution, while at 50 DEG C, the water-bath of 75r/min
2h is impregnated under the conditions of constant temperature oscillator, is rinsed matrix film surface 2 times after taking-up with DI water, and save the complexing salting liquid of Pd, after
It is continuous to be recycled；
(3) ion reduction: 186mLDI water, 1mLNH are measured respectively3H2O (content 25%~28%), 0.0076gNaBH4Match
Reducing solution is set, treated that base film is put into the solution by step (2), while at 50 DEG C, the constant temperature water bath of 75r/min vibrates
1h is restored under the conditions of device；
Circuit sequentially repetition step (2) and (3) totally 2 times；
(4) it is electroplated: step (3) treated sample is subjected to trimming processing, selecting titanium net is anode, and pogo-pin array is
The golden water (50mL) of cathode, 1.6g/L is electrolyte, to the gold-plated processing of sample surface under the 0.1A function of current；
(5) it post-processes: the film after plating is put into 200mL, 0.2mol L-1NaOH aqueous solution in, at 50 DEG C, 600r/
2h is exchanged in the magnetic stirring apparatus of min, so that the driving ion in film is all converted to Na+。
Comparative example 3
This comparative example discloses a kind of preparation process of Pd-Au-IPMC material, and the method for preparing Pd-Au-IPMC material is adopted
With the method for the prior art, embodiment 3 is compared, distinctive points are the roughening processing of base film is preposition in pretreatment stage.
Specifically includes the following steps:
(1) base film pre-processes: base film is cut into 45mm × 45mm, it will be at four side surpluses of base film by adhesive tape
It is fixed, and by the mold with micropin by the roller structure of surface insertion micropin, in 6g/cm2Line pressure under act under,
In membrane surface, 75 periods of roughening, by base film turn-over, carry out the rough of lower surface after roughening is completed in base film upper surface back and forth
Change processing；Base film DI water is rinsed 3 times after the completion of roughening, ultrasonic cleaning 30mim is carried out in 60 DEG C of DI water, then
By the basement membrane after ultrasonic cleaning successively at 100 DEG C, water-bath boils and washes 30min respectively in the HCl solution of 2mol/L, DI water；
(2) ion exchange: 0.162g Pd (NH is measured respectively3)4Cl2Complex salt, 66mLDI water, 8.6mLNH3H2O (content
25%~28%) solution, by step (1), treated that base film is put into the solution, while at 50 DEG C, the water-bath of 75r/min
2h is impregnated under the conditions of constant temperature oscillator, is rinsed matrix film surface 2 times after taking-up with DI water, and save the complexing salting liquid of Pd, after
It is continuous to be recycled；
(3) ion reduction: 186mLDI water, 1mLNH are measured respectively3H2O (content 25%~28%), 0.0076gNaBH4Match
Reducing solution is set, treated that base film is put into the solution by step (2), while at 50 DEG C, the constant temperature water bath of 75r/min vibrates
1h is restored under the conditions of device；
Circuit sequentially repetition step (2) and (3) totally 2 times；
(4) it is electroplated: step (3) treated sample is subjected to trimming processing, selecting titanium net is anode, and pogo-pin array is
The golden water (50mL) of cathode, 1.6g/L is electrolyte, to the gold-plated processing of sample surface under the 0.1A function of current；
(5) it post-processes: the film after plating is put into 200mL, 0.2mol L-1NaOH aqueous solution in, at 50 DEG C, 600r/
2h is exchanged in the magnetic stirring apparatus of min, so that the driving ion in film is all converted to Na+。
Comparative example 4
This comparative example discloses a kind of preparation process of Pd-Au-IPMC material, and the method for preparing Pd-Au-IPMC material is adopted
With the method for the prior art, embodiment 4 is compared, distinctive points are the roughening processing of base film is preposition in pretreatment stage.
Specifically includes the following steps:
(1) base film pre-processes: base film is cut into 45mm × 45mm, it will be at four side surpluses of base film by adhesive tape
It is fixed, and by the mold with micropin by the roller structure of surface insertion micropin, in 6g/cm2Line pressure under act under,
In membrane surface, 100 periods of roughening, by base film turn-over, carry out lower surface after roughening is completed in base film upper surface back and forth
Roughening processing rinses base film DI water 3 times after the completion of roughening；Ultrasonic cleaning 30mim is carried out in 60 DEG C of DI water, so
Afterwards by the basement membrane after ultrasonic cleaning successively at 100 DEG C, water-bath boils and washes 30min respectively in the HCl solution of 2mol/L, DI water；
(2) ion exchange: 0.162g Pd (NH is measured respectively3)4Cl2Complex salt, 66mLDI water, 8.6mLNH3H2O (content
25%~28%) solution, by step (1), treated that base film is put into the solution, while at 50 DEG C, the water-bath of 75r/min
2h is impregnated under the conditions of constant temperature oscillator, is rinsed matrix film surface 2 times after taking-up with DI water, and save the complexing salting liquid of Pd, after
It is continuous to be recycled；
(3) ion reduction: 186mLDI water, 1mLNH are measured respectively3H2O (content 25%~28%), 0.0076gNaBH4Match
Reducing solution is set, treated that base film is put into the solution by step (2), while at 50 DEG C, the constant temperature water bath of 75r/min vibrates
1h is restored under the conditions of device；
Circuit sequentially repetition step (2) and (3) totally 2 times；
(4) it is electroplated: step (3) treated sample is subjected to trimming processing, selecting titanium net is anode, and pogo-pin array is
The golden water (50mL) of cathode, 1.6g/L is electrolyte, to the gold-plated processing of sample surface under the 0.1A function of current；
(5) it post-processes: the film after plating is put into 200mL, 0.2mol L-1NaOH aqueous solution in, at 50 DEG C, 600r/
2h is exchanged in the magnetic stirring apparatus of min, so that the driving ion in film is all converted to Na+。
Pd-Au-IPMC material prepared by comparative example 1-4 is respectively labeled as A1-R*, A2-R*, A3-R*, A4-R*；Wherein
A1-R* is the control sample of A1, and A2-R* is the control sample of A2, and A3-R* is the control sample of A3, and A4-R* is the control sample of A4.
Embodiment 5
Under identical testing conditions to the sample of the sample of above-mentioned each embodiment 1-4, comparative example 1-4, it carries out than electricity
Capacitance test, test result are shown in Fig. 2-5.
It is learnt by the data analysis of Fig. 2-5, using its ratio of the Pd-Au-IPMC material of preparation method preparation of the invention
Capacitance is 4-5 times for using its specific capacitance value of the Pd-Au-IPMC material of conventional method preparation.The present invention electrode and tradition
The discrete particle difference of preparation process preparation is that needle electrode is made of fine and close electrode particle.Around at the top of the pin hole,
Grain presses together to form long continuous conductor, is deep into polymer, and IPMC material itself is equivalent to an easy electricity
Structure of container, therefore the presence of needle electrode to penetrate into electric depth and greatly increases, and shortens the interstructural distance of sandwiching electrodes,
Therefore its chemical property is significantly improved.
Embodiment 6
Under identical testing conditions to the sample of the sample of above-mentioned each embodiment 1-4, comparative example 1-4, end is carried out
The test of shift value, test result are shown in Fig. 6-9.
It is learnt by the data analysis of Fig. 6-9, its end of Pd-Au-IPMC material prepared using preparation method of the invention
End movement value is 2-4 times for using its tip displacement value of the Pd-Au-IPMC material of conventional method preparation.
Since IPMC material is under voltage effect, internal cation can generate displacement, the imbalance point of internal soundness
Cloth can and then macroscopically generate Centimeter Level bending deformation.Internal infiltration electrode is deeper, it is meant that electric field is to material internal
Removable cation adsorption capacity it is bigger, more increase the coherent condition of its internal cation, therefore its end movement value
Increase.
Above-described embodiment 3 is respectively adopted, the Pd-Au-IPMC material that the preparation method of comparative example 3 is prepared, section electricity
Pole pattern is as shown in Figure 10, the needle electrode type Pd- that wherein Figure 10 (a) successfully prepares for the preparation method of above-described embodiment 3
Au-IPMC material, and there is also particulate electrodes around needle electrode；10 (b) prepare for the preparation method of above-mentioned comparative example 3
Needle electrode type Pd-Au-IPMC material out, only a small amount of particulate electrode exist, the absolutely not presence of needle electrode.
Embodiment 7
The present embodiment to the sample of the sample of above-mentioned each embodiment 4, comparative example 4 under identical testing conditions, Yu Gao
Under frequency, it is tested for the property experiment, test result is shown in Figure 11.Wherein for electric actuation test sample size be unified for 35mm ×
The sample of 5mm clamps one end to form cantilever beam structure, drift 30mm.
It is learnt by the data analysis of Figure 11, the Pd-IPMC material and tradition prepared using preparation method of the invention is made
The IPMC that standby technique obtains also has been significantly improved compared to performance in high frequency.
The present invention is that acicular texture is very succinct with dendritic structure difference, not complicated branch.In addition, branch
Shape electrode is tightly attached to each other, and there are a certain distance between needle electrode.Its rigidity is smaller than the IPMC of dendroid electrode, tool
There is the material of needle electrode more soft.Compared with the IPMC of conventional preparation techniques preparation, the presence of needle electrode to penetrate into
Electrode depth obviously increases, and material is under alternating voltage effect, and cation is in polymeric inner cation towards movable cathode
Distance is reduced, and electrode is bigger to the attraction of cation, so being conducive to it all has large deformation under low, high frequency.
In conclusion technological core of the invention is to be put forward for the first time, by base film roughening, this committed step is placed in first
After secondary ion exchange step, so that matrix membrane material is effectively prevented in ion exchange process for the first time, because basis material is sent out
The contraction of raw larger proportion causes its surface deformation of matrix membrane material and leads to the deficiency of interface interaction decrease.To enhance electrode
Adhesive force between base film increases the depth for penetrating into electrode and improves the pattern for penetrating into electrode, to further increase
The chemical property and electromechanical properties of IPMC material.
It should be noted that, in this document, such as first and second or the like relational terms are used merely to one if it exists
A entity or operation with another entity or operate distinguish, without necessarily requiring or implying these entities or operation it
Between there are any actual relationship or orders.Moreover, the terms "include", "comprise" or its any other variant are intended to
Cover non-exclusive inclusion, so that the process, method, article or equipment for including a series of elements not only includes those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or setting
Standby intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that
There is also other identical elements in the process, method, article or apparatus that includes the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of preparation method of IPMC material, which comprises the following steps: base film roughening processing occurs in matrix
Film carries out first time ion-exchange treatment later and before base film progress first time reduction treatment.
2. the preparation method of IPMC material according to claim 1, which is characterized in that carried out for the first time in described matrix film
Reduction treatment and then successively carry out ion-exchange treatment, reduction treatment, each time ion-exchange treatment, reduction treatment one
A period.
3. the preparation method of IPMC material according to claim 2, which is characterized in that the period is 2~5 times.
4. the preparation method of IPMC material according to claim 1, which is characterized in that described matrix film roughening, which is handled, includes
Blasting treatment, sand paper polishing, micropin roughening, plasma etching one kind.
5. the preparation method of IPMC material according to claim 4, which is characterized in that the roughening device of the micropin roughening
Including micropin idler wheel or micropin plate.
6. the preparation method of IPMC material according to claim 1, which is characterized in that the ion-exchange treatment used
Reduction plating solution includes containing Pd2+、Ag+、Au+、Pt+、Ni+、Cu2+Complexing salting liquid it is at least one.
7. the preparation method of IPMC material according to claim 1, which is characterized in that the reduction that the reduction treatment uses
Agent is NaBH4。
8. a kind of intermediate preparation of IPMC material, which comprises the following steps:
Step 1: pretreated base film is carried out first time ion-exchange treatment；
Step 2: being rinsed after the base film that step 1 is obtained carries out roughening processing；
Step 3: step 2 treated base film is carried out first time reduction treatment；
Step 4 successively carries out ion-exchange treatment, reduction treatment, each secondary ion to step 3 treated base film again
Exchange processing, reduction treatment are a cycle, which continues repeatedly.
9. the intermediate preparation of IPMC material according to claim 8, which is characterized in that the period continues 2~5
It is secondary.
10. a kind of IPMC material prepared by the preparation method using IPMC material as described in any one of claim 1 to 7.
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