CN102953053A - Selective plating process for IPMC (Ionic Polymer Metal Composite) drive - Google Patents
Selective plating process for IPMC (Ionic Polymer Metal Composite) drive Download PDFInfo
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- CN102953053A CN102953053A CN2012104527043A CN201210452704A CN102953053A CN 102953053 A CN102953053 A CN 102953053A CN 2012104527043 A CN2012104527043 A CN 2012104527043A CN 201210452704 A CN201210452704 A CN 201210452704A CN 102953053 A CN102953053 A CN 102953053A
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Abstract
The invention discloses a selective plating process for an IPMC (Ionic Polymer Metal Composite) drive. The selective plating process is characterized by comprising the following steps: firstly, pretreating a substrate material; secondly, producing a non-plating region on the pretreated ion exchange membrane pretreated in the first step according to the use requirement of the drive to be isolated from a plating region; enabling an electrode not to be plated in the non-plating region in the subsequent work procedure by a mask method; when the line width is greater, directly covering by using a high-temperature-resistant electroplating adhesive tape to enable the blocked part not to be plated, and when the line width is smaller, producing a reverse covering layer by using the electroplating adhesive tape to expose a blocking line and isolating different electrode regions by generating silver chloride precipitation; and thirdly, depositing an electrode layer on the plating region by adopting soaking and reduction plating and producing a platinum, palladium, silver or copper metal electrode or a platinum-palladium composite electrode and a silver-copper composite electrode.
Description
Technical field
The present invention relates to a kind of IPMC(ion polymer-metal composite material) the selectivity plating method of driving mechanism, adopt and electroplate adhesive tape or generate silver chloride as the mask in non-plating zone by soaking, this plating method is simply efficient, can produce the driving mechanism with complicated shape, to satisfy complicated driving function.
Background technology
Ion polymer-metal composite material (IPMC) has that quality is light, snappiness good, be swift in response and the bidirectional reversible function of sensing-actuating, can be used for making produce gross distortion the electromechanical transducing devices such as driving mechanism to replace traditional piezoelectric ceramics, be that recent two decades emerges and has the novel intelligent material of very big application potential.
Make at present segmentation, multidirectional, during the Multifunctional IP MC material drivers such as combined deformation, usually can drive the function needs according to complexity, make a plurality of non-plating zones electrically isolated from one at same film material matrix and be used for powering up respectively driving.Employing laser cutting (document Yoshihiro Nakabo is arranged in the prior art, Toshiharu Mukai, Kinji Asaka.Bio-mimetic soft robots with artificial muscles[C] .Proc.of SPIE, 2004,5648:132-144) with spark cutting isolated electrode method (document JonathanRossiter, Toshiharu Mukai.Electrostatic and thermal segmentation ofmulti-segment IPMC sensor and actuctors.[C] .Proc.of SPIE, 2011,7976:C1-C8), the method of employing MEMS technique making tectum prevention electrodeposition (document Zhen Chen, Xiaobo Tan.Monolithic fabrication of ionic polymer-metal composite actuators capable ofcomplex deformation.[J] .Sensors and actuatorsA:Physical:157 (2): 246-257) etc.These methods need expensive equipment to come processing and fabricating usually, are unfavorable for promoting the use of.Among the preparation technology of Traditional IP MC, general depositing electrode comprises two reaction process, at first forms transition layer by ion-exchange-reduction, then forms well behaved electrode by electroless plating simultaneously.If only by the method depositing electrode of ion-exchange-reduction, the quality of coating of preparation is poor like this among traditional preparation method, resistivity is high, should not directly use.Further improve electrode with electroless plating, then length consuming time not only needs multiple auxiliary reagent, and temperature of reaction is had certain requirement.These shortcomings have limited popularization and the use of IPMC material to a certain extent.
Summary of the invention
Ensureing under the IPMC material driver performance prerequisite, in order to simplify the manufacture craft of Multifunctional IP MC material driver, the present invention is directed to method for producing mask complicated in the present selectivity depositing process, and traditional plating method consuming time and characteristics that cost is high, traditional plating method is improved, provide a kind of cost low, simple and practical IPMC driving mechanism plating method.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of selectivity depositing process of IPMC driving mechanism is characterized in that, may further comprise the steps:
(1) pre-treatment of base material:, this ion-exchange membrane is carried out roughening be placed on ultrasonic cleaning under 60 ℃ the environment as base material with ion-exchange membrane, remove surface particles, then pickling and deionization poach are washed respectively;
(2) according to the service requirements of driving mechanism, make non-plating at the pretreated ion-exchange membrane of step (1) and separate from the plating district; Non-plating district requires not to be coated with electrode in subsequent handling, takes mask method to realize, but comprises two kinds of systems of selection:
1. directly make the tectum in non-plating district of the plating adhesive tape, then carry out the soaking and reducing plating of step (3);
2. pretreated ion-exchange membrane soaks in silver nitrate solution first, then makes the tectum in plating district with electroplating adhesive tape, and soak in HCl solution in exposed non-plating district, until reaction generates stable non-conductive silver nitride precipitation in non-plating district; Take the plating adhesive tape in the plating district off, then carry out the soaking and reducing plating of step (3);
(3) adopt soaking and reducing to be plated in depositing electrode floor in the plating district, make platinum, palladium, silver or copper metal electrode.
In the aforesaid method, in the described step (2), when non-plating district live width greater than 2mm, adopt in this step substep 1.; When non-plating district live width less than 2mm, adopt in this step substep 2..Wherein silver nitrate solution concentration is 0.03mo/L, soaks 1 ~ 2 hour; The HCl strength of solution is 0.1mol/L, soaks half an hour.
The concrete grammar of the described soaking and reducing plating of step (3) is:
1) utilize the corresponding metal-salt of electrode to make salts solution, the ion-exchange membrane that step (2) is generated non-plating district mask is put into metal salt solution and is soaked and carried out ion-exchange in 1 ~ 2 hour, makes the electrode metal ion enter ionic membrane; Preparation palladium or platinum electrode use Palladous chloride/platinum, dichloro two ammoniums to close palladium/platinum or dichloro four ammoniums and close palladium/platinum salt and make salts solution, and the preparation silver electrode is used silver nitrate solution or silver ammino solution; The preparation copper electrode uses copper-bath; Concentration of salt solution is 0.005 ~ 0.1mol/L, and consumption is selected 1 ~ 10mmol/cm according to the plating area
2
2) put into NaBH after processing totally with deionized water the ion-exchange membrane after the immersion of step 1) metal salt solution
4Solution stirs, and makes the interior metal ion of ion-exchange membrane be reduced the formation electrode on the film surface; For palladium or platinum electrode, NaBH
4Strength of solution is 0.5～10mmol/L, is preferably 1mmol/L; For silver or copper electrode, NaBH
4Concentration is 2 ~ 20mmol/L, is preferably 5mmol/L.
Repeat soaking and reducing plating 1 ~ 2 time.
The present invention has overcome the shortcoming that traditional IPMC preparation process is complicated, time-consuming and production cost is high, realized the technique of barrier line when a film body material is made the multi-electrode driving, the making of barrier line does not need expensive equipment, can satisfy the barrier line of different live widths making, realize the function that the complexity of material drives.Whole plating technology is simple, practical simultaneously, and selecting only needs both can obtain the good IPMC driving mechanism of driveability through for several times soaking and reducing plating after the mask process.
Description of drawings
Fig. 1 is wider shielding wire multi-electrode IPMC activation configuration figure.
Fig. 2 is thin shielding wire multi-electrode IPMC activation configuration figure.
Fig. 3 is combined electrode IPMC activation configuration figure.
In Fig. 1 ~ 3: 1 is the matrix ionic membrane, and 2 is electrode layer, and 3 is encapsulating film, and 4 is the silver chloride shielding wire, and 5 is the inner layer metal electrode layer, is generally platinum or palladium electrode, and 6 is the outer layer metal electrode layer, is generally silver or copper electrode.
Embodiment
The making of embodiment 1 wide shielding wire multi-electrode IPMC driving mechanism
To be of a size of 15cm * 0.5cm, designing 2 wide shielding wires of 3mm, material is divided into two sections multi-electrode IPMC driving mechanisms along its length is example, comprises the steps: based on the preparation method of selectivity plating
1) pre-treatment of material
With the base material of Nafion film (or adopting the Flemion ionic membrane) as material, adopt sand papering alligatoring (sand paper more than No. 600, Nafion film two surfaces of polishing gently), make surface uniform stressed during polishing as far as possible, note observing coarse uniformity coefficient, observe the surface and become muddy and do not have obvious bright spot under light, can think polishes reaches even effect.Nafion film after alligatoring ultrasonic cleaning 20 minutes after being heated to 60 ℃ is removed its surface particles; Then take out pickling, remove foreign ion by acidification; The hydrochloric acid soln that uses is about 150ml, 2mol/L, and pickling time is 30 minutes; Boil in deionized water at last and wash, remove unnecessary hydrochloric acid and other impurity, the time is about 30 minutes; Can be kept in the deionized water through pretreated Nafion film.
2) pretreated material is put into the [Pd (NH that concentration is 0.01mol/L
3)
4] Cl
2Middle immersion is taken out after 2 hours and is adopted deionized water to soak 10min, and then accepted scale is demarcated the baffle area on Nafion film surface.Utilize icking tool to carve the shielding layer measure-alike with the baffle area at high temperature resistant and plating adhesive tape acid and alkali-resistance, pattern bonded to the baffle area with carving good plating adhesive tape, and aims at compacting with the baffle area, guarantee that the plating adhesive tape does not come off in the process of follow-up soaking and reducing.
3) material is washed, then the sodium borohydride solution of putting into 500mL concentration and be 1mmol/L is sufficient reacting at normal temperatures, when when significantly bubble occurs, can think that reaction is complete, repeat soaking and reducing 1-2 time, be used for improving the electrode of material and the transition layer of body material.
4) material that soaking and reducing is good takes out, washed with de-ionized water adopts tweezers carefully to take the plating adhesive tape shielding layer that originally was bonded on the Nafion film off, can see under the sheltering of shielding layer, this subregion is not coated with the palladium metal electrode, and forming live width is the barrier line of 3mm.
5) adopt the solution of the HCl of 0.1mol/L to soak for removing inner foreign ion, the NaOH solution of rear employing 0.2mol/L soaks, and the H+ ion of replacing material inside makes the Na+ ion become inner driving ion.
6) cutting: the needs according to using cut into needed shape with the material for preparing.
7) material for well cutting carries out the potting processing, adopts the method for packing (application number: 201110255830.5), obtain IPMC multi-electrode activation configuration as shown in Figure 1 in the published patent.According to requirements, power up for the different sections of IPMC driving mechanism, the bending that the realizes driving mechanism action such as creep.
The making of embodiment 2 thin shielding wire multi-electrode IPMC material drivers
To be of a size of 6cm * 0.5cm, the barrier line width is that the multi-electrode Ag utmost point IPMC driving mechanism of 0.5mm is example, and the preparation method who plates based on selectivity comprises the steps:
1) preprocessing process of material is identical with example 1;
2) material being placed 200ml concentration is the AgNO of 0.03mo/L
3Solution soaking 1 hour, adopt acid and alkali-resistance to electroplate adhesive tape and cover pre-plating zone, exposed non-plating district, then be placed in the HCl solution of 0.1mol/L and react half an hour, non-plating district generates the AgCl shielding wire (Fig. 2) that nonconducting width is about 0.5mm, evenly firmly take the plating adhesive tape off, then deionization soaks about 10min, carries out next step soaking and reducing plating.
3) it is placed again the AgNO of 0.03mol/L
3After soaking 1-2 hour, soak among the 10min with deionized water, be placed on the NaBH that 500ml concentration is 1mmol/L
4React under the solution normal temperature, until without obvious Bubble formation, think that reaction is complete.Repeat soaking and reducing 1-2 time, improve the transition layer of base film and metal.
4) adopt the solution of the HCl of 0.1mol/L to soak for removing inner foreign ion, the NaOH solution of rear employing 0.2mol/L soaks, and the H+ ion of replacing material inside makes the Na+ ion become inner driving ion.
5) cutting: the needs according to using cut into needed shape with the material for preparing.
6) material for well cutting carries out the potting processing, adopts the method for packing (application number: 201110255830.5), obtain multi-electrode IPMC activation configuration as shown in Figure 2 in the published patent.According to requirements, power up for the different sections of IPMC driving mechanism, the bending that the realizes driving mechanism action such as creep.
Considering cost and performance two aspect factors, the present invention adopts the method for Composite Coatings to prepare combined electrode also on the basis of mask (barrier line) technique, namely soaks reduction preparation combined electrode behind the various salts.Usually deposit first depositing silver or copper electrode behind platinum or the palladium electrode.
The making of embodiment 3 Composite Coatings IPMC driving mechanisms
Palladium take manufactured size as 6cm * 3cm and platinum compound electric polar form IPMC are example, and the method for Composite Coatings comprises the steps:
1) pre-treatment step of material is identical with example 1, need to consider the activity of metal when making combined electrode, thereby determines the sequencing of plating, at first selects to select first plating platinum electrode herein to the metal level a little less than Nafion film plating one deck reductibility.
2) pretreated material is placed the [Pt (NH of 0.01mol/L
3)
4] Cl
2Soaked 1-2 hour in the salt, adopt deionized water to soak about about 10min, then be placed on the NaBH that concentration is 1mmol/L
4Soaking and reducing at normal temperatures in the solution can be seen occurring bubble on the reactor vessel wall, when when significantly bubble occurs, can think that reaction is complete, and the IPMC that will plate the platinum electrode type of one deck takes out, and measures electric conductivity, basically is in half conducting state.
3) with the platinum electrode type IPMC washed with de-ionized water of above-mentioned gained, then place the [Pd (NH of 0.01mol/L
3)
4] Cl
2Soaked 1-2 hour in the salt, then be placed on the NaBH that concentration is 1mmol/L
4Soaking and reducing at normal temperatures in the solution, can see and occur bubble on the reactor vessel wall, when occurring without obvious bubble, can think that reaction is complete, so just obtained palladium platinum compound electric polar form IPMC, surface measurements conduction situation, fully conducting, repeat soaking and reducing 1-2 time, be used for improving body material and electrode transition layer.
4) aftertreatment of material
(1) drive ion-exchange: the IPMC after at first will cleaning is immersed among the HCl of 100ml, 0.1mol/L, removes foreign ion, soaks 1 hour at the HCl of new 100ml, 0.1mol/L solution after 1 hour again, then uses washed with de-ionized water.In the NaOH of 200ml, 0.2mol/L solution soaking more than 3 hours;
(2) cutting: the needs according to using cut into needed shape with the material for preparing;
(3) material for well cutting carries out the potting processing, adopts the method for packing (application number: 201110255830.5), obtain IPMC activation configuration as shown in Figure 3 in the published patent.
Claims (6)
1. the selectivity depositing process of an IPMC driving mechanism is characterized in that, may further comprise the steps:
(1) pre-treatment of base material:, this ion-exchange membrane is carried out roughening be placed on ultrasonic cleaning under 60 ℃ the environment as base material with ion-exchange membrane, remove surface particles, then pickling and deionization poach are washed respectively;
(2) according to the service requirements of driving mechanism, make non-plating at the pretreated ion-exchange membrane of step (1) and separate from the plating district; Non-plating district requires not to be coated with electrode in subsequent handling, takes mask method to realize, but comprises two kinds of systems of selection:
1. directly make the tectum in non-plating district of the plating adhesive tape, then carry out the soaking and reducing plating of step (3);
2. pretreated ion-exchange membrane soaks in silver nitrate solution first, then makes the tectum in plating district with electroplating adhesive tape, and soak in HCl solution in exposed non-plating district, until reaction generates stable non-conductive silver nitride precipitation in non-plating district; Take the plating adhesive tape in the plating district off, then carry out the soaking and reducing plating of step (3);
(3) adopt soaking and reducing to be plated in depositing electrode floor in the plating district, make platinum, palladium, silver or copper metal electrode; Perhaps platinum-palladium combined electrode, silver-copper combined electrode.
2. the selectivity depositing process of IPMC driving mechanism as claimed in claim 1 is characterized in that, in the described step (2), when non-plating district live width greater than 2mm, adopt in this step substep 1.; When non-plating district live width less than 2mm, adopt in this step substep 2..
3. the selectivity depositing process of IPMC driving mechanism as claimed in claim 1 is characterized in that, the substep of step (2) 2. in, silver nitrate solution concentration is 0.03mo/L, soaks 1 ~ 2 hour; The HCl strength of solution is 0.1mol/L, soaks half an hour.
4. the selectivity depositing process of IPMC driving mechanism as claimed in claim 1 is characterized in that, the described soaking and reducing plating of step (3) needs to repeat 1 ~ 2 time.
5. the selectivity depositing process of IPMC driving mechanism as claimed in claim 1 is characterized in that, the concrete grammar of the described soaking and reducing plating of step (3) is:
1) utilize the corresponding metal-salt of electrode to make salts solution, the ion-exchange membrane that step (2) is generated non-plating district mask is put into metal salt solution and is soaked and carried out ion-exchange in 1 ~ 2 hour, makes the electrode metal ion enter ionic membrane; Preparation palladium or platinum electrode use Palladous chloride/platinum, dichloro two ammoniums to close palladium/platinum or dichloro four ammoniums and close palladium/platinum salt and make salts solution, and the preparation silver electrode is used silver nitrate solution or silver ammino solution; The preparation copper electrode uses copper-bath; Concentration of salt solution is 0.005 ~ 0.1mol/L, and consumption is selected 1 ~ 10mmol/cm according to the plating area
2
2) put into NaBH after processing totally with deionized water the ion-exchange membrane after the immersion of step 1) metal salt solution
4Solution stirs, and makes the interior metal ion of ion-exchange membrane be reduced the formation electrode on the film surface; For palladium or platinum electrode, NaBH
4Strength of solution is 0.5 ~ 10mmol/L, for silver or copper electrode, NaBH
4Concentration is 2 ~ 20mmol/L.
6. the selectivity depositing process of IPMC driving mechanism as claimed in claim 5 is characterized in that, for palladium or platinum electrode, NaBH
4Strength of solution is 1mmol/L; For silver or copper electrode, NaBH
4Concentration is 5mmol/L.
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Cited By (5)
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| CN104696174A (en) * | 2015-02-17 | 2015-06-10 | 哈尔滨工程大学 | Double-sheet linear driving unit made of ionic polymer metal composite |
| CN104916773A (en) * | 2014-03-14 | 2015-09-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Electro-deformation thin film array and preparation method and application thereof |
| CN109576707A (en) * | 2018-12-24 | 2019-04-05 | 河海大学常州校区 | A kind of fast preparation method of ionic artificial-muscle |
| CN109680268A (en) * | 2019-01-10 | 2019-04-26 | 西安科技大学 | A kind of preparation method of copper electrode ionomer-metallic composite artificial-muscle |
| CN111411351A (en) * | 2020-04-26 | 2020-07-14 | 吉林大学 | Preparation method of high-performance electrically-driven perfluorinated sulfonic acid IPMC flexible driver |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104916773A (en) * | 2014-03-14 | 2015-09-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Electro-deformation thin film array and preparation method and application thereof |
| CN104916773B (en) * | 2014-03-14 | 2017-10-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Electrostrictive membrane array, its preparation method and application |
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| CN109576707A (en) * | 2018-12-24 | 2019-04-05 | 河海大学常州校区 | A kind of fast preparation method of ionic artificial-muscle |
| CN109680268A (en) * | 2019-01-10 | 2019-04-26 | 西安科技大学 | A kind of preparation method of copper electrode ionomer-metallic composite artificial-muscle |
| CN109680268B (en) * | 2019-01-10 | 2020-12-01 | 西安科技大学 | Preparation method of copper electrode ionic polymer-metal composite material artificial muscle |
| CN111411351A (en) * | 2020-04-26 | 2020-07-14 | 吉林大学 | Preparation method of high-performance electrically-driven perfluorinated sulfonic acid IPMC flexible driver |
| CN111411351B (en) * | 2020-04-26 | 2021-08-27 | 吉林大学 | Preparation method of high-performance electrically-driven perfluorinated sulfonic acid IPMC flexible driver |
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