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Ionic polymermetal composites: II. Manufacturing techniques

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2003 Smart Mater. Struct. 12 65 (http://iopscience.iop.org/0964-1726/12/1/308) View the table of contents for this issue, or go to the journal homepage for more

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INSTITUTE OF PHYSICS PUBLISHING Smart Mater. Struct. 12 (2003) 6579

SMART MATERIALS AND STRUCTURES PII: S0964-1726(03)55945-6

Ionic polymermetal composites: II. Manufacturing techniques

Kwang J Kim1 and Mohsen Shahinpoor2,3
1 Active Materials and Processing Laboratory (AMPL), Mechanical Engineering Department (MS 312), University of Nevada-Reno, Reno, NV 89557, USA 2 Articial Muscle Research Institute (AMRI), School of Engineering and School of Medicine, The University of New Mexico, Albuquerque, NM 87131, USA 3 Environmental Robots, Inc. (ERI), 909 Virginia, 205, Albuquerque, NM 87108, USA

E-mail: kwangkim@unr.edu and shah@unm.edu

Received 12 December 2001, in nal form 14 August 2002 Published 10 January 2003 Online at stacks.iop.org/SMS/12/65 Abstract This paper, the second in a series of four review papers to appear in this journal, presents a detailed description of various techniques and experimental procedures in manufacturing ionic polymermetal composites (IPMCs) that, if fully developed, can be used as effective biomimetic sensors, actuators and articial muscles as well as fully electroded with embedded electrodes for fuel cells. The performance of IPMCs manufactured by different manufacturing techniques are presented and compared. In particular, a number of issues such as force optimization using the Taguchi design of experiment technique, effects of different cations on electromechanical performance of IPMCs, electrode and particle size and distribution control, manufacturing cost minimization approaches, scaling and three-dimensional (3D) muscle production issues and heterogeneous composites by physical loading techniques are also reviewed and discussed. (Some gures in this article are in colour only in the electronic version)

1. IPMC base materials

The manufacturing of ionic polymermetal composite (IPMC) actuators, sensors and articial muscle starts with ion exchange (or permeable) polymers (often called ionomers [1, 2]). Ion exchange materials are designed and synthesized to selectively pass ions of a single or multiple charges, i.e. either cations or anions or both. Hence, depending upon the types of materials, selective passages of desirable cations or anions, or both, can be achieved, meaning that ions are mobile within the materials. Ion exchange materials are typically manufactured from organic polymers that contain covalently bonded xed ionic groups [3, 4]. Most of the popular ion exchange materials used in electrochemical industry are based upon a copolymer of styrene and divinylbenzene where the xed ionic groups are formed after polymerization. An important parameter is the ratio of styrene to divinylbenzene, which controls the crosslinking process that limits ion exchange capabilities and the water uptake. For cation exchange materials, the xed ionic

groups are usually sulfonate. The known successful fabrication of the sulfonated ion exchange membranes was based upon grinding ion exchange resins to microscale powders, mixing them with hydrophobic thermoplastic materials including polyethylene or polyvinylidineuoride and sheeting them at elevated temperatures. Recently, inclusion of a hydrophobic polymer at the formulation stage became common and known as the paste method [5]. In such a method a ne powder of hydrophobic polymer is mixed into a paste with the liquid phase monomers. The initiator and a plasticizer typically control the nal product. The basic chemistry is shown in gure 1: the co-polymerization is carried out with a predetermined ratio of styrene and divinylbenzene and occasionally with ethylstyrene. Another popular ion exchange material is peruorinated alkene: with short side-chains terminated by ionic groups (i.e. NaonTM of DuPont, typically sulfonate or carboxylate (SO 3 or COO ) for cation exchange or ammonium cations for anion exchange). Such uorocarbon polymers have linear backbones with no crosslinking and relatively few xed ionic 65

0964-1726/03/010065+15$30.00 2003 IOP Publishing Ltd Printed in the UK

K J Kim and M Shahinpoor

CH=CH 2

CH=CH 2

CH=CH 2

CH=CH 2

CH=CH 2

CH2 CH 2

SO3

Figure 1. Styrene/divinylbenzene-based ion exchange material.

+

(CF2 CF2 )n - CFO(CF - CFO)m CF CF SO 3 2 2 2

CF2 CF 3

Na

Figure 2. Popular chemical structure of peruorinated ion exchange material (Na + can be replaced by other cations). Table 1. Representative properties of a peruorinated ion exchange material NaonTM -117 (H+ form) [8]. Property Equivalent weight Thickness Conductivity Area resistance Water uptake capacity Volume expansion on hydration Value 1100 g gmol1 SO3 200 m 0.10.12 S cm1 5 cm2 Up to 30% at room temperature 1215%

Figure 3. TEM micrographs show a cross-section of an IPMC (top) and its close-up. Note that the platinum particles reside within the polymer matrix. The top micrograph shows the higher particle density toward the surface electrode.

groups attached [6]. The large polymer backbones determine their mechanical strength. Short side-chains provide ionic groups that interact with water and the passage of appropriate ions. When swollen by water, NaonTM undergoes phase separation (clustering [7]) on a supermolecular structure. Their popular chemical structure and properties are given in gure 2 and table 1. Although there are several commercial ion exchange material manufacturers including Aqualitics, Asahi Chemicals, Asahi Glass, DuPont, W L Gore, Ionics, Solvay, Sybron and Tokuyama, the popular products that have been used as IPMC materials are NaonTM from DuPont, NeoseptaTM from Tokuyama, AciplexTM from Asahi Chemical, and FlemionTM or SelemionTM from Asahi Glass. At the present time all these products perform fairly well when they are properly treated by the IPMC chemical plating techniques. Since these materials exhibit ion transport intrinsically, an important process is electric charge transport through the materials by ions which can be explained in terms of an ionic ux,
i

2. Manufacturing techniques
2.1. Overview The current state-of-the-art IPMC manufacturing technique [913] incorporates two distinct preparation processes: the initial compositing process and the surface electroding process. Due to the different preparation processes, the morphologies of the precipitated platinum are signicantly different. The initial compositing process requires an appropriate platinum salt such as Pt(NH3 )4 HCl in the context of chemical reduction processes similar to the processes evaluated by a number of investigators including Takenaka [14] and Millet [15]. The principle of the compositing process is to metallize the inner surface of the material (usually, in a membrane shape, Pt nanoparticles) by a chemical reduction means such as LiBH4 or NaBH4 . The ion exchange polymer is soaked in a salt solution to allow platinum-containing cations to diffuse through via the ion exchange process. Later, a proper reducing agent such as LiBH4 or NaBH4 is introduced to platinize the materials by molecular plating. As can be seen in gure 3, the metallic platinum particles are not homogeneously formed across the material but concentrate predominantly near the interface boundaries. It has been experimentally observed that the platinum particulate layer is buried a few microns deep (typically 110 m) within the IPMC surface and is highly dispersed. The TEM image of the near-boundary region of an IPMC strip on the penetrating edge of the IPMC shows a functional particle density gradient with higher particle density toward the surface electrode. The range of average particle size was found to be around 4060 nm.

Ji ED = zi F zi F R A

(1)

where Ji is the current density (I/ A), z i is the charge on the transported ion, and F is the Faraday constant (96 485 C mol1 ). Also, E D and R A are the electric eld across the material and the area resistance of the material ( m2 ). The conductance of the material ki ( 1 m1 ) is also conveniently used, as R A = L/ki (where L = material thickness). 66

Ionic polymermetal composites

In the sequence of addition, raise the temperature up to 60 C gradually for 4 h. Note that grey metallic layers will form on the membrane surface. At the end of this process, sample a small amount of the solution and boil it with the strong reducing agent (NaBH4 ) to check the end point. Other metals (or conducting mediums) which are successfully used include palladium, silver, gold, carbon, graphite and carbon nanotubes (see gure 4). The use of electroplating was found to be very convenient [12]. 2.3. Force optimization
Figure 4. A cross-section of an IPMC showing two electrodes (top and bottom) with porous expanded graphite and dense platinum. This IPMC is manufactured by solution casting, further treatment with porous graphite and chemical reduction of platinum as effective compliant electrodes.

2.2. Recipe We describe an effective recipe to manufacture IPMC materials (for a standard size of 5 cm 5 cm of NaonTM -117) [9, 11 13, 1517]. The rst step is to roughen the material surface where it will serve as an effective electrode. This involves sandblasting or sandpapering the surface of the polymer in order to increase the surface area density where platinum salt penetration and reduction occurs, as well as ultrasonic cleaning and chemical cleaning by acid boiling (HCl or HNO3 , low concentrates). The second step is to incorporate the ion exchanging process using a metal complex solution such as tetra-amine platinum chloride hydrate as an aqueous platinum complex ([Pt(NH3 )4 ]Cl2 or [Pt(NH3 )6 ]Cl4 ) solution. Although the equilibrium condition depends on the type of charge of the metal complex, such complexes were found to provide good electrodes. The immersion and stirring time is typically more than 1 h. The third step (initial platinum compositing process) is to reduce the platinum complex cations to the metallic state in the form of nanoparticles by using effective reducing agents such as an aqueous solution of sodium or lithium borohydride (5%) at favourable temperature (i.e. 60 C). Platinum blacklike layers deposit near the surface of the material. The nal step (surface electroding process) is intended to effectively grow Pt (or other novel metals) on top of the initial Pt surface to reduce the surface resistivity. Therefore, an additional amount of platinum is plated by the following process on the deposited Pt layer: (i) Prepare a 240 ml aqueous solution of the complex ([Pt(NH3 )4 ]Cl2 or [Pt(NH3 )6 ]Cl4 ) containing 120 mg of Pt and add 5 ml of the 5% ammonium hydroxide solution (pH adjustment). (ii) The plating amount is determined by the content of Pt in the solution. Prepare a 5% aqueous solution of hydroxylamine hydrochloride and a 20% solution of hydrazine monohydrate. (iii) Place the polymer in the stirring Pt solution at 40 C. Add 6 ml of the hydroxylamine hydrochloride solution and 3 ml of the hydrazine solution every 30 min.

The fabricated IPMCs can be optimized to produce a maximum force density by changing multiple process parameters including bath temperature (TR ), time-dependent concentrations of the metal containing salt, Cs (t), and the reducing agents, C R (t). The Taguchi design of experiment technique was conducted to identify the optimum process parameters [18]. The primary reaction is LiBH4 + 4[Pt(NH3 )4 ]2+ + 8OH 4Pto + 16NH3 + LiBO2 + 6H2 O. (2) The analysis technique for larger-the-better quality characteristics incorporates noise factors into an experiment involving the larger-the-better characteristics, for the maximum force generated by the manufactured IPMCs in this case. Such an analysis allows us to determine the key factors and the possible best settings for consistently good performance. The beauty of this technique is that it is just as applicable for attaining consistently high larger-thebetter responses for process performance as for end product functionality [18]. In table 2, experimental design and signalto-noise ratio (S/N) data are provided. Table 3 shows the S/N response table for the factors engaged in our experiment. Based on the S/N ratio computed for each factor and level, S/N response graphs are constructed and presented in gures 58. From our analysis, the strong effects and elements to be considered are listed in table 4. In gure 9, comparisons of 29 manufactured samples based on the Taguchi method (with two added samples, 28 and 29, for all levels 2 and 3, respectively) establishes that the force was compiled against the baseline condition (sample no 28). It is clear that the results allow one to optimize such a complicated bath process to produce a much larger blocking force that can be utilized for practical actuation applications. Another interesting point is a relationship between the measured surface resistance and platinum particle penetration within the polymer matrix. In gure 10 the measured surface resistances (left) of 29 samples are plotted against platinum penetration. The platinum penetration is measured by SEM cross-sectioning, and four-point surface resistivities (sheet resistivity) of the samples were measured by Guardian Manufacturings Model SRM-232. The surface resistivities of the samples appear to be linear despite scatters. Overall, it should be noted that the samples having low surface resistivities tend to produce larger blocking forces. The tensile testing of the samples was performed by an Instron 1011 tabletop machine. The standard sample size was 9 mm 55 mm. The strain rate was set at 2.33 (s1 ). In gure 11 tensile testing results are provided in terms of normal 67

K J Kim and M Shahinpoor

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S/N (db)

S/N (db)
0 1 2 3 4

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0 1 2 3 4

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Figure 5. S/N response graphs for factors AD.

stresses, N , and normal strain, N , for a number of samples 1, 2, 3, 28, 29, and Naon-117 (both dry and wet state). All Taguchi IPMC samples (these are wet samples) show a Young modulus of approximately 50100 MPa at a normal strain of 0.02 (at 2%), similar to that of wet NaonTM -117. The dry NaonTM -117 (H+ form) is stiffer than that of all the Taguchi samples, as expected. The approximate value of the modulus for dry NaonTM -117 is 220260 MPa at a normal strain of 0.02 (2%). The tensile strength of all the Taguchi samples is around 1013 MPa. The IPMC appears to exhibit a little more stiffness and be less yielding than as-received NaonTM -117, due primarily to the composited metal portion that interacts with the polymer matrix. The electric responses of the Taguchi samples were also investigated and are presented here in terms of the amount of charge consumed (current, I , versus time) at applied step voltages of 1, 2, 3 and 4 V for two important samples, no 3 (the best performance) and no 28 (baseline). Overall, the current responses were capacitive. This behaviour may be attributed to the double layers adjacent to platinum particles or proximate metallic layers. Also, as we increase the applied voltages, the charge consumption is signicantly increased (see gures 12 68

and 13). This means the IPMC materials utilize charges but also store them within the materials. We are currently investigating such an effect and will soon report the results. 2.4. Effects of different cations Realizing that the properties of IPMC base material differ depending upon different cations, IPMC test samples were prepared by the processes described in the previous section, with different cations. First, a batch of the IPMC articial muscle of dimensions of 10 cm 20 cm was prepared with platinum. Then, nine samples (nos 1 through 9) were cut into standard size 2 cm 10 cm strips for the ion exchange process. Each IPMC sample was treated to contain nine different counter-ions (Na+ , Li+ , K+ , H+ , Ca2+ , Mg2+ , Ba2+ , Rn NH+4n (tetrabuthylammonium and 4 tetramethylammonium, respectively)) by soaking it in an appropriate salt solution (1.5 N of NaCl, LiCl, KCl, HCl, CaCl2 , MgCl2 , BaCl2 , CH3 [CH2 ]3 NBr, [CH3 ]4 NBr, respectively) at moderate temperatures, at 30 C, for 3 days. All chemicals were obtained from Aldrich Chemical and used without further treatment. Test conditions were:

Ionic polymermetal composites

Table 2. Experimental design and S/N ratio data. (Samples 28 and 29 are prepared at levels of 2 and 3 for all factors listed.) Run 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 A 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 3 3 3 3 3 3 3 3 3 B 1 1 1 2 2 2 3 3 3 1 1 1 2 2 2 3 3 3 1 1 1 2 2 2 3 3 3 C 1 1 1 2 2 2 3 3 3 2 2 2 3 3 3 1 1 1 3 3 3 1 1 1 2 2 2 D 1 1 1 2 2 2 3 3 3 3 3 3 1 1 1 2 2 2 2 2 2 3 3 3 1 1 1 E 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 F 1 2 3 1 2 3 1 2 3 2 3 1 2 3 1 2 3 1 3 1 2 3 1 2 3 1 2 G 1 2 3 1 2 3 1 2 3 3 1 2 3 1 2 3 1 2 2 3 1 2 3 1 2 3 1 H 1 2 3 2 3 1 3 1 2 1 2 3 2 3 1 3 1 2 1 2 3 2 3 1 3 1 2 I 1 2 3 2 3 1 3 1 2 2 3 1 3 1 2 1 2 3 3 1 2 1 2 3 2 3 1 J 1 2 3 2 3 1 3 1 2 3 1 2 1 2 3 2 3 1 2 3 1 3 1 2 1 2 3 K 1 2 3 3 1 2 2 3 1 1 2 3 3 1 2 2 3 1 1 2 3 3 1 2 2 3 1 L 1 2 3 3 1 2 2 3 1 2 3 1 1 2 3 3 1 2 3 1 2 2 3 1 1 2 3 M 1 2 3 3 1 2 2 3 1 3 1 2 2 3 1 1 2 3 2 3 1 1 2 3 3 1 2 S/N (db) 46.75 33.85 52.9 46.08 43.58 46.12 45.35 39.38 37.01 47.42 43.6 33.57 45.05 46.12 46.93 45.02 43.78 44.26 42.77 44.78 37.69 37.94 50.14 35 39.75 35.93 42.27

Table 3. The S/N response along with factors engaged in our experiment. S/N response A Level 1 Level 2 Level 3 Delta A B C D E F G H I J K L M B C D E 44.01 42.35 41.75 2.37 F 43.75 41.03 43.33 2.72 G 42.96 40.23 44.93 4.7 H I J 43.64 39.48 43.16 4.16 K 44.48 42.26 41.37 3.11 L 41.03 41.63 45.54 4.51 M 41.61 42.54 43.97 2.36

43.45 42.59 43.29 43.28 43.97 44.11 42.04 43.79 40.7 41.42 42.79 41.05 3.27 2.69 1.25 2.74 Factors engaged in our experiment

42.67 42.44 41.65 42.51 43.79 43.16 2.14 0.72 Procedure

Surface roughening Boiling time in water Platinum salt concentration Stirring time (Pt-soaking) Reducing agent concentration (LiBH4)-1st Reduction bath temperature-1st Reduction/stirring time-1st Platinum salt concentration Stirring time (Pt-soaking) Reducing agent concentration (LiBH4)-2nd Reduction bath temperature-2nd Reduction/stirring time-2nd LiOH concentration Table 4. Strong effects and elements. First tier Second tier

Pretreatment Pretreatment Ion exchange Ion exchange 1st metal reduction 1st metal reduction 1st metal reduction Ion exchange Ion exchange 2nd metal reduction 2nd metal reduction 2nd metal reduction Post process/ion exchange

(G)Reducing/stirring time in the 1st reduction process, (J)Reducing agent concentration in the 2nd reduction process, and (L)Reducing/stirring time in the 2nd reduction process. (A)Surface roughening, and (K)Reduction bath temperature in the 2nd reduction process.

waveform = sinusoidal, E app = 1.2 Vrms , and frequency of 1/2 Hz. Figure 14 summarizes the test results in terms of the maximum force generated (=blocking force) by each IPMC sample (at zero displacement) containing various cations, under a given voltage of 1.2 Vrms relative to the Na+ -containing

IPMC articial muscle. A total of 13 measurements per sample were taken. The error bars in gure 14 represent their corresponding standard deviations. As observed, the Li+ -containing IPMC is superior to the others, meaning that hydration processes with respect to mobile cations play a signicant role in actuation behaviour. Also, the samples with 69

K J Kim and M Shahinpoor

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0

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Figure 6. S/N response graphs for factors EH.

TBA and TMA show much smaller force generation capability. Knowing that such hydrophobic cations have relatively large diameter and negligible hydration, the true transfer mechanism is close to electrophoretic movement without water. However, the maximum force generated at the tip of the cantilever under a given voltage of 1.2 Vrms is of the general ballpark order of the ones generated with counter-ions; Li+ Na+ > (K+ , 2+ 2+ 2+ + Ca , Mg , and Ba ) > (H , TBA, and TMA). This fact was observed for both NaonTM -based IPMC and FlemionTM based IPMC [19]. In the set of Li+ , Na+ and K+ , one should realize that Li+ is undoubtedly the smallest bare ion in the set (its radius, r [Li+ ] < r [Na+ ] < r [K+ ]) but it has the lowest mobility (the drag to its motion through the solution, u[Li+ ] < u[Na+ ] < u[K+ ]) [20, 21, 28, 29]. All these observations could be due to the hydration phenomenon (a tightly held sheath of water molecules bound under the electric eld caused by cations/anions). Thus, large organic hydrophobic ions such as TBA and TMA generate less force than Li+ -and Na+ based IPMCs. An important aspect regarding the use of such alkylammonim ions could be attributed to their large and bulky size relative to the small cations investigated. Overall, the hydration process within the membrane in connection with 70

the electrophoretic effect is fairly complex in the sense that the mobile cations experience a large viscous drag and, at the same time, exert force due to the generated strain, while they are moving through the water-containing polymer network. The situation can be interpreted as that each cation with its connected clusters [22] is shearing or rubbing past other cations and network. This could increase the viscous drag and lower the conductivity. Overall, taking consideration of the hydrated volume of each cation, v[Li+ ] v[Na + ] > (v[K+ ], 1/2v[Ca 2+ ], 1/2v[Mg 2+ ], 1/2v[Ba 2+ ]) and v[H+ ] [23], one can see a general trend of force generation; Li+ Na+ > (K+ , Ca2+ , Mg2+ and Ba2+ ) > (H+ , TBA and TMA). 2.5. Electroded particle control Based upon our manufacturing experience, controlling the electrode consisting of platinum particles (concentration and size distribution) within the polymer matrix was also found to be a non-trivial issue that can directly affect the performance of IPMCs. Here, we discuss the importance of (i) the repetitive platinum reduction process, (ii) the use of dispersing agents,

Ionic polymermetal composites

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Figure 7. S/N response graphs for factors IL.

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and (iii) the base material stretching, i.e. uniaxial mechanical stretching. First, noting that the platinum reduction is carried out in a wet batch system, repetitive platinum reduction steps [10, 11, 16, 22, 23] were found to be effective to produce IPMCs exhibiting larger force characteristics. It is our belief that increased platinum concentration within the polymer leads to higher double-layer charge capacity. In gure 15 we present the electric power consumption and current/voltage (I/ V ) behaviour under a sinusoidal wave input to an IPMC sample size of 12 mm 51 mm at different manufacturing stages. It can be clearly seen that (i) bare NaonTM has insignicant current response under an applied voltage, (ii) repetitive platinum reduction improves the current responses, and (iii) surface electroplating by gold further improves the current responses. Figure 16 shows a SEM cross-section (top) of the sample and its surface (bottom). Second, the most signicant aspect of having the porous electrode for the IPMC is that it allows effective water transport 71

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Figure 8. S/N response graphs for factors M.

K J Kim and M Shahinpoor

2.0

NafionTM-117; Cation=Li+; Reducing agent=LiBH4; 1 V Step; 1/2 Hz Width=7.2 mm; Effective Length=16.0 mm; (Note that Fmax(sample#28)~0.35 g-force)

1.5

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Fmax/Fmax(sample#28)

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0.5

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Sample Number
Figure 9. A comparison of blocking forces for 29 different samples.
150
10000

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Rs (/square)

90

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Figure 10. Four-point probe surface resistivity measurement on Taguchi samples [13].

within the electrode region so as to create effective strains (the porous nature of compliant electrodes [13, 22, 30, 31]). However, it can also cause water leakage in the form of iondriven water molecules gushing out of the porous electrode surface. This phenomenon is always visible and observable in an experiment involving wet IPMC under the inuence of an electric eld across it. This prevents the generated strains from effectively generating larger forces, similar to a leaky hydraulic jack. Therefore, a key engineering problem 72

is how to prevent such a water (solvent) leakage out of the porous electrode. Here, we describe a successfully developed technique to address such a leakage problem so as to manufacture a high output force IPMC. As discussed in [13], the nominal size of primary platinum particles of the IPMC is found to be around 50 nm, which is much larger than that of incipient particles associated with ion clusters (5 nm). This nding leads to the conclusion that incipient particles coagulate during the chemical reduction

Ionic polymermetal composites

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0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Figure 11. Tensile testing results for Taguchi samples 1, 2, 3, 28 and 29. Also, NaonTM -117 (H+ form, both dry and wet) is shown.
1.0 0.8 0.6 0.4 0.2 1.0

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Figure 12. Current responses to step voltages of 1, 2, 3 and 4 V (Taguchi sample 3).

process and eventually grow large. If so, there is a signicant potential to control this process (in term of platinum particle penetration, size and distribution). This could be achieved by introducing effective dispersing agents (additives) during the chemical reduction process. One can anticipate that the effective additives should enhance the dispersion of platinum particles within the material and nally reduce coagulation. As a result, a better platinum particle penetration into the material

can be realized. This also creates a somewhat smaller particle size with fairly good distribution. Thus, the water leakage out of the surface electrode could be signicantly reduced. In [13] we identied a number of effective dispersion agents or dispersants. The use of an effective dispersing agent during the platinum metallization process gives dramatically improved force characteristics showing a much sharper response (smaller time constants) to the input electric impetus and a dramatically 73

K J Kim and M Shahinpoor

1.0 0.8 0.6 0.4 0.2 1.0

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Figure 13. Current responses to step voltages of 1, 2, 3 and 4 V (Taguchi sample 28).
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Counter Ion

Figure 14. Effects of various cations on the actuation of the IPMC muscle. Comparisons were made against Na + in terms of maximum force generated at zero displacement. A sinusoidal input voltage of 1.2 Vrms and a frequency of 1/2 Hz were set for all experiments. The samples were cut in a standard size of 0.675 cm 2.54 cm. Na + was chosen as a reference since it is coordinated with four water molecules.

increased force generation. In gure 17 surface micrographs are presented for an IPMC without dispersing agent treatment and for an IPMC with dispersing agent treatment. Clearly, the effect of dispersing agent is to form uniform electroded particle surfaces. Our effort has been extended to investigate various types of dispersing agent, but results are somewhat scattered, as can be seen in gure 18. The third issue is related to the sharp diffusional resistance at the surface caused by the platinum compositing process which is the primary cause of limitation of the platinum layer growth (gure 19). One approach is to stretch the base material prior to the platinum composition process. In doing so, we expect the base materials to be plastically deformed and, as a result, larger pores (higher permeability) to be created relative to the starting materials. One approach was to stretch the base material uniaxially and carry out the routine optimal IPMC manufacturing technique. It is found that, by using such a stretching technique, the particle penetration within the material is much more effective, and forms a much denser platinum particle phase and distribution. The basic morphology of the particle formation appears different, as can be seen in gure 20. A more scattered shape (rather than a spherical form) is found in the IPMC with the material stretched prior to platinum compositing. In general, the effect of such a stretching method of manufacturing IPMCs seems to benet the IPMC performance in terms of the blocking force in a cantilever conguration. The results are presented

74

Fmax/Fmax(Na )

Ionic polymermetal composites

400
after 1st reduction after 5th reduction after gold plating (5-0-1) TM pure Nafion -117 (wet)

150 after gold plating 100 after 5th reduction after 1st reduction 50 bare Nafion-117 (no pt)

300

200 P (mW)

I (mA)
100 0 -100 0 1 2 t (sec.) 3 4 5

-50

-100

-150 -3 -2 -1 Eapp (V)

Figure 15. Time responses of an IPMC along with their current/voltage characteristics. The platinum reduction was completed ve times and nal electroplating was done with gold.

(a)

(b)

Figure 17. SEM micrographs showing surface morphologies of the IPMC sample (a) without and (b) with the use of a dispersing agent.
2.5

2.0

1.5

F/Fo
1.0 0.5 0.0 0 1 2 3 4 5 6 7

Sample Number

Figure 16. A SEM cross-section (top) of the sample and its surface (bottom). The cross-sectional view shows two platinum penetration leading edges and gold surface electrodes. The surface is fairly uniform but shows minor imperfect spots.

in gure 21. Signicantly improved generative forces were produced. 2.6. An economical approachphysical metal loading A novel fabrication process of manufacturing IPMCs equipped with physically loaded electrodes as biomimetic sensors, actuators and articial muscles that can be manufactured at about 1/10th of typical cost was developed. The underlying principle of processing these novel IPMCs is to rst physically

Figure 18. Comparisons of six different IPMC samples treated with dispersing agents. Sample no 6 is the one with no treatment. Other samples were treated by proprietary dispersing agents including PVP, PVP/PMMA, PVA/PVP, a commercial detergent and CTAB. Sample no 3, PVP treated, shows the best force generation capability.

load a conductive primary powder layer into the ionic polymer network forming a dispersed particulate layer. This primary layer functions as a major conductive medium in the composite. Subsequently, this primary layer of dispersed particles of a conductive material is further secured within the polymer network with smaller secondary particles via chemical plating, which uses reducing agents to load another phase of conductive particles within the rst layer. In turn, both 75

K J Kim and M Shahinpoor

CR

Reducing Agent

Pt Salts

Base Polymer

Figure 19. Platinum reducing process. Dark circles represent platinum particles.

(ii) The isopropyl alcohol is then allowed to completely evaporate (it takes approximately an hour.). (iii) The ion exchange polymer (NaonTM -117) is rst surface treated with sandpaper. The standard size of the polymer sample is about 2 2 inches. (iv) The ion exchange polymer is placed between the backing materials facing the powder-coated side. (v) Pressing is carried out at 2 ton using a temperaturecontrolled hot press (RAMCO, 50 ton capacity) at 120 130 C for a duration of 15 min. (vi) The process (i)(v) is repeated, three times. Usually, low electric surface sheet resistance is obtained (R < 1 /square by the four-probe method). (vii) The preferred process is to impregnate small noble metal particles (i.e. platinum or palladium, D p 50 nm) between the primary particles so as to further xate them within the ion exchange polymer). This process is to introduce metallic ions [Pd(NH3 )2+ ] or [Pt(NH3 )2+ ] into the ion exchange polymer initially and, later, reduce them to a metallic state. As a nal step, a conductive metallic layer (i.e. gold or palladium) is further electroplated on the top of the interlocked electrode layer. 2.7. Scaling

Figure 20. Two TEM micrographs show the intrinsic platinum particles for an IPMC mechanically stretched prior to metal compositing (left) and not stretched (right).

primary and secondary particles can be secured within the ionic polymer network and reduce the potential intrinsic contact resistances between large primary particles. Furthermore, electroplating can be applied to integrate the entire primary and secondary conductive phases and serve as another effective electrode [24]. The essence of such physically loaded and interlocked electrodes for IPMCs is depicted in gure 22. The principal idea of processing this new IPMCs is to (i) rst physically load a conductive primary powder (Ag in this case) into the polymer network forming a dispersed layer which can function as a major conductive medium near boundaries and (ii) subsequently, to further secure such primary particulate medium within the polymer network with smaller particles (Pd or Pt in this case) via a chemical plating process, so that both primary and smaller secondary particles can be secured within the polymer network. Furthermore, an electroplating process can be applied to integrate the entire conductive phase intact, serving as an effective electrode. Figures 22(a) and (b) illustrate such a process. The process developed is as follows: (i) A silver-based spherical powder (MOx-doped Ag; Superior MicroPowders EM10500X-003A; D10 < 0.8 m, D50 < 1.5 m, D90 < 2.5 m; Asur < 6 m2 g1 ) is dispersed in isopropyl alcohol (99%). Using a standard airbrush (VEGA), the powder is sprayed onto the backing material. 76

It is well understood that all commercially available (asreceived) peruorinated ion exchange polymers are in the form of hydrolyzed polymers and are semi-crystalline and may contain ionic clusters. The membrane form of these polymers has a typical thickness in the range of approximately 100 300 m. Such a thin thickness of commercially available membranes permits fast mass transfer for use in various chemical processes. Knowing that such as-received semicrystalline membranes are not melt-processable, they are not suitable for the fabrication of three-dimensional electroactive materials or other composite forms. In [25], we reported a newly developed fabrication method that can scale up or down the IPMC articial muscles in a strip size of micro-tocentimetre thickness. We have adopted a recently developed technique by Moor et al [26] for dissolving as-received ion exchange membranes in appropriate solvents. By carefully evaporating solvents out of the solution, recast ion exchange membranes were obtained [27]. A number of samples having a thickness greater than 2 mm was fabricated and tested. A test sample with a size of 2 mm thickness, 5 mm width and 15 mm length has exhibited generative forces much greater than 20 gmf with a few millimetre displacement. Figure 23 shows two IPMCs having a three-dimensional shape. 2.8. Heterogeneous compositing technique Platinum is not the only noble metal that can be produced by chemical reduction processes. Other noble metals such as palladium, gold and silver have been tried. Although there are not enough data at present regarding those noble metals as effective electroding materials, there is indication that they are also effective. A heterogeneous compositing technique, such as an alternative compositing, platinum rst and subsequently

Ionic polymermetal composites

8 7 6 5

Step Input, 1/2 Hz

Sample-C (Pt/Au) Sample-B (Pt/Au) Sample-A (Pt/Au)

Sample-C (Pt) Sample-B (Pt)

FB (g)

4 3 2 1 0 0.0 0.5 1.0 1.5 2.0 2.5

Sample-A (Pt) Sample-A (Pt/Au)

Rss (/square)

tio ven Con

nal

IPM

Cs

Sample-B (Pt/Au)

Sample-A (Pt/Au)

Eapp (V)
0

Sample

Figure 21. Measured blocking forces (left) and surface resistance of IPMC samples prepared (right). The standard sample size is 5 mm 10 mm 0.2 mm. The process information is given in terms of particles used, platinum, and the nal electroded material, gold.
(a) (b)

Ag (via physical loading) Dp~1-3 m

Pt (via chemical process) Dp~50 nm

Figure 22. (a) A schematic process illustration of the PLI-IPMCs. (b) Silver particle used [24].

Figure 23. Two IPMCs showing a spiral shape (left) and a bent beam (right). The spirally shaped IPMC can function as a linear actuator.

palladium, has been tried to control the penetration depth. Overall, those techniques are also effective. Another interesting technique is to combine conducting polymers (polypyrrole) and metals so as to create a system of the base polymer/metal/conducting polymer. We have fabricated such an IPMC system. One nding was that this procedure signicantly reduced the input power consumption while maintaining the same level of the generative blocking forces. Such an effect could be attributed to less I/ V hysteresis acting on the metal particle interacting surfaces. The results are briey presented in gure 24.

connection with IPMCs. Comparison of the performance of IPMCs manufactured by different manufacturing techniques are also presented. In particular, the issues reviewed are: force optimization, effects of different cations, electrode integrity and particle growth control, manufacturing cost minimization technique, scaling and 3D IPMC manufacturing techniques, and heterogeneous composite manufacturing techniques. The successful commercialization of the IPMC is highly dependent upon further improvement of its force density generation and manufacturing cost.

3. Conclusions
This paper, the second in a series of four review papers, presents a detailed description of various manufacturing techniques in

Acknowledgments
This work was partially supported by US NRL/DARPA. The authors thank the laboratory work done by Environmental Robots, Inc. and the Articial Muscle Research Institute of the 77

K J Kim and M Shahinpoor

2.00 70

1.75

Nafion -117 (5Pt-1Pt) =0.1 Hz, Eapp=1.92 V Dimension=7.5 x 15.0 mm

TM

60

Nafion -117, =1/2 Hz Dimension=7.5 x 70 mm Wave=Triangular

TM

1.50 50

Pyrrole Treated IPMC

1.25

Conventional IPMC Pin (mW) FT (g)

1.00

40

Conventional IPMC
30

0.75

Pyrrole Treated IPMC

20

0.50 10 0.25

0.00

-0.25 8 9 10 11 12 13 14 15 16 17 18 19 20 21

-10 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6

T (sec)

T (sec)

Figure 24. Force characteristics and input power consumptions of IPMCs (Conventional IPMC and pyrrole-treated IPMC). Polymerization of pyrrole was carried with the presence of a catalyst, Fe, within Naon.

University of New Mexico. Discussions with Professor P G De Gennes at the College de France were helpful.

References
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[13] Shahinpoor M and Kim K J 2001 Ionic polymermetal compositesI. Fundamentals Smart Mater. Struct. 10 81933 [14] Takenaka H, Torikai E, Kwami Y and Wakabayshi N 1982 Solid polymer electrolyte water electrolysis Int. J. Hydrogen Energy 7 397403 [15] Millet P, Pineri M and Durand R 1989 New solid polymer electrolyte composites for water electrolysis J. Appl. Electrochem. 19 1626 [16] Oguro K 2001 Recipe-IPMC ed Y Bar-Cohen posted at http://ndeaa.jpl.nasa.gov/nasande/lommas/eap/IPMC PrepProcedure.htm [17] Shahinpoor M, Bar-Cohen Y, Simpon J O and Smith J 1998 Ionic polymermetal composites (IPMC) as biomimetic sensors and structuresa review Smart Mater. Struct. 7 1530 [18] Peace G S 1993 Taguchi MethodsA Hands-On Approach (New York: Addison-Wesley) [19] Noh T G, Tak Y, Nam J D, Jeon J W, Kim H M, Choi H R and Bae S 2001 Development of large-surface Naonmetal composite actuator and its electrochemical characterization Proc. Smart Structures and Materials 2001: Electroactive Polymer Actuators and Devices vol 4329 pp 45865 [20] Moor W 1972 Physical Chemistry 4th edn (Englewood Cliffs, NJ: Prentice-Hall) [21] Atkins P W 1982 Physical Chemistry 2nd edn (London: Oxford University Press) [22] de Gennes P G, Okumura K, Shahinpoor M and Kim K J 2000 Mechanoelectric effects in ionic gels Europhys. Lett. 50 5138 [23] Onishi K, Sewa S, Asaka K, Fujiwara N and Oguro K 2000 Bending response of polymer electrolyte actuator Proc. Smart Structures and Materials 2001: Electroactive Polymer Actuators and Devices vol 3987 pp 1218 [24] Shahinpoor M and Kim K J 2002 A novel physically-loaded and interlocked electrode developed for ionic polymermetal composites (IPMCs) Actuator Sensors A 96 12532 [25] Kim K J and Shahinpoor M 2002 Development of three dimensional ionic polymermetal composites as articial muscles Polymer 43 797802 [26] Moor R B, Cable K M and Croley T L 1992 Barriers to ow in semicrystalline ionomer a procedure for preparing melt-processes peruorosulfonate ionomer lms an membranes J. Membrane Sci. 75 714 [27] Gebel G, Aldebert P and Pineri M 1987 Structure and related

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properties of solution-case peruosulfonate ionomer lms Macromolecules 20 14258 [28] Komoroski R A and Mauritz K A 1982 Nuclear Magnetic Resonance Studies and the Theory of Ion Pairing in Peruorinated Ionomers in (ACS Symp. Series vol 180)(Washington, DC: American Chemical Society) [29] Bhattacharya K, Li J and Xiao Y 2001 Electromechanical models for optimal design and effective behavior of

electroactive polymers Electroactive Polymer (EAP) Actuators as Articial Muscles ed Y Bar-Cohen (Washington, DC: SPIE Optical Engineering Press) [30] Shahinpoor M, Kim K J and Leo D 2003 Ionic polymermetal composites as multifunctional materials Polym. Compos. 24 [31] Shahinpoor M and Kim K J 2002 Mass transfer induced hydraulic actuation in ionic polymermetal composites J. Intell. Mater. Systems Struct. 13 36976

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