Fabrication and Characterization of Meso-scale Composite Compliant Electrodes

Kuangwen Hsieha and Elisabeth Smelab

a

Department of Electrical and Computer Engineering, University of Maryland 2405 A. V. Williams Bldg. University of Maryland, College Park, MD 20742 b Department of Mechanical Engineering, University of Maryland 4107 Myers Building, 5000 College Avenue, College Park, MD 20742

Table of Contents
Fabrication and Characterization of Meso-scale Composite Compliant Electrodes .1 Table of Contents..............................................................................................................2 List of Figures....................................................................................................................2 Abstract..............................................................................................................................5 1. Introduction....................................................................................................................6 2. Experimental..................................................................................................................7 3. Results and Discussions...............................................................................................17 4. Conclusions...................................................................................................................28 5. Acknowledgements......................................................................................................29 6. References.....................................................................................................................29

List of Figures
Figure 1. Graphite and PDMS compliant electrode samples with metal contacts: Al contacts on the left and Cr and Au contacts on the right...............................................9 Figure 2. Platinum salt reduction-based composite compliant electrode: typical electrodes for conductivity measurement were 25 mm by 15 mm by 150 m...........10 Figure 3. In the case of four-point probe resistance measurement, a multimeter injects a known current across the compliant electrode from the two outside wires, and the voltage drop of the compliant electrode in the distance equivalent to between the two inside wires is measured. The resulting resistance is displayed on the multimeter. Figure obtained from [15]...................................................................11 Figure 4. Four-point probe technique was used to measure the resistance of our compliant electrodes. Two current-injecting leads and two voltage-drop leads are connected to a custom-fabricated four-point probe, which is clamped on top on the electrode being measured with two binder spring clips. Resistance was displayed on the multimeter readout. Pictures were taken by Remi Delille. .................................11 Figure 5. Different dimensions required for determining the resistivity and thus conductivity include w, t, and L; where w and t are the width and the thickness of the compliant electrode sample respectively, and L is the length in between the two inside leads of the four-point probe. Figure obtained from [15]................................12 Figure 6. Resistance measured by the multimeter was displayed in floating number, which consists of a mantissa and an exponential. The floating number presentation sometimes caused confusion during the measurements. Therefore, its display must be calibrated prior to the measurements.......................................................................14 Figure 7. A simple LED circuit was fabricated to demonstrate the conduction of our composite compliant electrodes. Two alligator clips were used to connect a sample 2

of our electrode in series with a 10 k pull up resistor and a LED. The circuit was connected to a power supply, which provided 15 volts of voltage to illuminate the LED...................................................................................................................................15 Figure 8. Youngs modulus of compliant electrodes was measured with a custommade force-strain transducer. Two pieces of transparency were glued on the electrode film being measured with Loctite 4304 and served as clamps. A strain of thin wire connected between the electrode and the arm of a 50-gram load cell, which was connected to a PC and controlled by a LabView program. The load cell arm stretched the film and the Youngs modulus was output on the PC. Pictures were courtesy of Remi Delille. ................................................................................................16 Figure 9. We could not determine relationships between either concentration by volume or the contact types and the corresponding conductivity. No percolation behavior could be observed from the graphite powder and PDMS composite electrodes. Conductivity of these compliant electrodes was also low.........................19 Figure 10. (a) The relation of electrical conductivity and platinum salt concentration by volume of composite compliant electrodes. The conductivity was displayed on a logarithmic scale. A percolation behavior could be observed. (b) Dispersed spherical platinum salt particles in the 5 % sample could be observed under SEM at 8000x magnification, rendering the electrodes nonconductive. (c) Interconnected platinum salt particles at 10% formed a path for current conduction, and the electrodes became conductive. Picture was taken under SEM at 8000x magnification. (d) A fairly uniform interconnection of platinum salt at 15% produced the most conductive electrodes. Picture was taken under SEM at 8000x magnification. SEM pictures were taken by Remi Delille. ......................................21 Figure 11. The LED experiment was successful. The green LED illuminated when the power source was switched on, as shown in (b), signifying the conductivity of our compliant electrode..........................................................................................................22 Figure 12. The relation between the Youngs modulus and the platinum salt loading by volume in two separate strain regions. In both cases, the Youngs modulus increased from 0% loading to 8% loading. At 9% loading and beyond above the percolation the modulus decreased to the same magnitude as the unloaded sample. Samples at 12% platinum salt loading were omitted from the plot. .......................24 Figure 13. The relation between the Youngs modulus and increasing number of actuations in two separate strain regions, namely 0% to 1.5 strain region, shown in (a), and 2% to 4% strain region, shown in (b). In both cases, the unloaded sample remained unchanged with increasing number of repetitive measurements. The loaded samples both below and above the percolation experienced slight increase in the modulus in the first twenty measurements; followed by a decrease in the next twenty measurements. Finally, the Youngs modulus leveled off. The modulus remained in the same order of magnitude, signifying the insensitivity of these compliant electrodes to the number of actuations. ......................................................26

Figure 14. As a result of high strain rate, Youngs modulus for 9% samples and below was unaffected while 10% samples and beyond experienced an increase. The maximum increase was 42%, corresponding to 10% platinum salt loading..............28

Abstract
In order to incorporate flexible but conductive electrodes into their micro-scale actuators, graduate students Remi Delille and Sam Moseley from the Laboratory for Micro Technology attempted fabricating novel composite compliant electrodes. Potential applications of these patternable meso-scale electrodes include electroactive polymer (EAP) devices, polymer MEMS, stretchable electronics, and nastic actuators. My task focused on assisting in the fabrication and characterization of these electrodes. Two methods for electrode fabrication are presented. Characterization focused on electrical conductivity and Youngs modulus. By the end of my placement, I completed experiments in electrical conductivity and finished most of the experiments regarding electrode Youngs modulus. The results are presented in the following report. Remi will investigate the relationship between the conductivity and strain of the compliant electrodes, as well as its lifetime in the future.

1. Introduction
Micro-scale compliant electrodes can be applied in fields such as electroactive polymer (EAP) devices, polymer MEMS, stretchable electronics, and microrobotics[1, 2]. In addition to these applications, members of the Laboratory for Micro Technology also seek to incorporate compliant electrodes into new actuators that are in the development stage, including nastic actuators and small-scale dielectric elastomer actuators. Despite the necessity, compliant electrodes that are micro-scale, patternable, reliable and suitable for MEMS actuators have yet to be demonstrated. Current methods for fabricating compliant electrodes include applying carbon grease [3] or graphite powder [4] to an elastomeric surface, depositing thin layers of metal on the surface of a polymer [5], and directly mixing conductive particles into a polymer matrix [6-10]. All of these methods have shortcomings. For example, applying carbon grease to a polymer surface is not compatible with microfabrication nor is it patternable. This is because the conductive material is grease and must be manually applied. Metals deposited on the surface of a polymer greatly reduced the strain capability of the polymer, rendering the electrodes unsuitable for actuators [5]. Researchers have been patterning zigzag or serpentine shaped metal thin films to circumvent the problem, as 80% of strain has been reported [5, 11]. Delaminating metal, however, presents an additional problem for this method [12]. Directly mixing conductive fillers such as carbon black, copper, silver, and conjugated polymers would significantly increase the materials Youngs modulus even at low particle loading. This method also hinders the patternability of the polymer if the polymer is UV-curable. Members of the Laboratory for Micro Technologies had been developing new composite compliant electrodes. The project was initiated by Sam Moseley and Steve Mitchell, carried on by summer research students Rachael Germansky and Colleen Gavigan from the RISE program, and continued by Remi Dellile and Dan Fang. A few different types of compliant electrodes had been developed thus far. I joined this project in the spring semester of 2005, focusing on fabrication and characterization of some of these electrodes. Refer to previous works for previous results [13, 14].

Three types of composite compliant electrodes were fabricated prior to and during my involvement in the project. These compliant electrodes include copper powder and PDMS composite electrodes, graphite powder and PDMS composite electrodes, and platinum salt and Loctite 3108 composite electrodes. I classified the two former types as conductive power-based electrodes because their fabrication was based on mixing conductive powder such as copper powder and graphite powder directly into a polymer precursor. The fabrication of the last type of compliant electrode was slightly different. The fabrication, developed by Remi and Sam, was based on ionic polymer-metal composites (IPMCs) and platinum salt reduction. The fabrication of this new composite compliant electrode includes physical impregnation of platinum salt into a UV-curable polymer precursor, polymerization under UV light, and reduction of the salt into platinum metal, thus making the electrodes conductive. Fabricated electrodes were characterized in order to understand their electrical and mechanical behaviors. Characterizations focused on electrical conductivity and Youngs modulus. In this report, I present the fabrication, measurements, and preliminary experimental results for these composite electrodes. Additional experiments would be conducted to investigate the relationship between conductivity and strain. As a result of our efforts, we plan to publish a journal paper to report the fabrication and experimental results of the novel composite compliant electrodes.

2. Experimental
2.1. Composite Compliant Electrodes Fabrication
2.1.1. Conductive Powder-based Composite Electrodes Copper powder and PDMS composite compliant electrodes, as well as some graphite powder and PDMS composite samples were made by RISE students Rachael and Colleen in summer of 2004. I do not know the procedure and recipe of these electrodes, so they are not reported in this documentation. In the spring semester of 2005, I fabricated graphite powder and PDMS composite electrodes with Remi and Sam. Compliant electrode fabrication began with mixing 1 part of PDMS (Sylgard 184, Dow Corning) curing agent with 10 parts of elastomer base by volume. Mixed PDMS was kept in a benchtop plastic desiccator for 10 7

minutes to degas the mixture. After desiccation, we filled 10 mL of PDMS into several 25-mL beakers with a syringe. Graphite powder purchased from Alfa Aesar was mixed into pre-mixed PDMS. The graphite powder has the following characteristics: 99.9995% concentration, 2.24 g/ml density, and 10 to 30 resistance. We fabricated the composite compliant electrode samples by mixing graphite powder at three different concentrations by volume 15%, 17.5%, and 20% into premixed PDMS. Graphite powder was stirred manually for more than 30 minutes because the mixture was not liquid enough to stir with a homogenizer. Well-stirred graphite and PDMS mixture was scooped into custommade molds with a stick. The mold was overfilled to ensure no air bubble was formed as the PDMS was cured in the mold. Filled molds were labeled and cured in vacuum. Typical electrodes were 5 cm long, 1 cm wide, and 1 to 2 mm thick. Three batches of graphite powder and PDMS electrode samples made by Remi, Sam and I, with 15%, 17.5%, and 20% of graphite powder by volume, respectively, along with samples made by the RISE students at 17.5% and 20% by volume were selected for measurements. There were two samples in each batch, resulting in a total of ten samples. 2.1.1.1 Metal Contacts for Conductive Powder-Based Composite Electrodes Remi and Sam fabricated metal contacts for graphite powder and PDMS composite electrodes by thermal evaporation. The fabrication was carried out in the ECE cleanroom, which is a class 1000 cleanroom. Two types of metal contacts were deposited. One type of contacts was aluminum (Al) and the other was chromium (Cr) and gold (Au). Prior to thermal evaporation, sticker labels were taped onto the middle section of each electrode. After the metallization process, the sticker was peeled off the surface of the electrode, leaving metal contacts on the electrode on each end. Figure 1 shows two graphite powder and PDMS composite compliant electrodes one with Al contacts and the other with Cr and Au contacts.

Figure 1. Graphite and PDMS compliant electrode samples with metal contacts: Al contacts on the left and Cr and Au contacts on the right. 2.1.2. Platinum Salt Reduction-based Composite Electrodes The development of platinum salt and Loctite 3108 composite compliant electrodes were initiated by Remi and Sam in the spring semester of 2005. Remi took on the responsibility to fabricate most of these sample electrodes, using Loctite 3108 (Loctite), a UV curable polymer as the polymer matrix, tetraammineplatinum(II) chloride (Sigma-Aldrich) as the noble metal salt, and sodium borohydirde (Sigma-Aldrich) as the reducing agent. I also assisted in the fabrication. Desired platinum salt loading by volume, ranging from 2.5% to 15%, was mixed into the Loctite 3108 polymer by hand for 20 minutes, followed by homogenizing the mixture using a T18 Ultra Turrax homogenizer at 10000 rpm for two minutes. The homogenized mixture was degassed in a benchtop vacuum chamber at 20 psi for at least 5 hours. Degassed mixture was fabricated into flat films for characterization and experimentation by squeezing the mixture between two sheets of SealView (Norton Performance Plastics Corp.), with each sheet adhered to a piece of 3 inch by 2 inch glass slide. The squeezed mixture was subsequently cured using a handheld UV lamp (Spectroline, EN-180, center wavelength 365 nm) twice for 10 seconds on each side, for a total of 40 seconds of exposure. The cured films were peeled off the SealView sheets and cut to desired sizes. For the conductivity measurement, films 25 mm by 15 mm were cut. For the Youngs modulus experiments, sample size was usually 30 mm by 3 mm. Typical film thickness was 150 m. The cut films were immersed in 500 mg of sodium borohydirde dissolved in 450 mL of de-ionized water for platinum salt reduction. The 9

first round of reduction was at least 5 hours long. Then the reduction step was repeated with fresh solution for another 5 hours minimum. For all of the samples fabricated in this work, the reduction temperature was kept at 60 C. Figure 2 shows a finished sample of reduced platinum salt and cured Loctite 3108 composite compliant electrode for conductivity measurement.

Figure 2. Platinum salt reduction-based composite compliant electrode: typical electrodes for conductivity measurement were 25 mm by 15 mm by 150 m.

2.2. Characterization and Measurements

2.2.1. Electrical Conductivity Measurements 2.2.1.1 Conductive Powder-based Composite Electrodes Resistance of composite compliant electrodes at various platinum salt loading was measured with a custom-made four-point-probe and a digital multimeter (8505A, Fluke Corporation, Everett, WA) to determine their conductivity. The four-point-probe technique was used to eliminate contact resistance. The concept of four-point probe measurement is illustrated in Figure 3. Refer to the figure, a multimeter injects a known current across the compliant electrode from the two outside wires, and the voltage drop of the compliant electrode in the distance equivalent to between the two inside wires is measured. The resulting resistance is displayed on the multimeter.

10

Figure 3. In the case of four-point probe resistance measurement, a multimeter injects a known current across the compliant electrode from the two outside wires, and the voltage drop of the compliant electrode in the distance equivalent to between the two inside wires is measured. The resulting resistance is displayed on the multimeter. Figure obtained from [15]. The four-point-probe, fabricated by Mario Urdaneta, is presented in Figure 4 (a) and (b). For the measurement, the electrode sample was clamped between the four-point probe and a piece of glass with two binder spring clips so that the copper wires on the bottom side of the probe were in contact with the electrode. The electrode was placed so that the longer axis of the electrode was parallel to the copper wires. The top side of the probe is plastic so the resistance of the metal clamps was insulated from the measurements. Sample resistance was output on the readout of the multimeter. The experimental setup is shown in Figure 4 (c).
(c)

Figure 4. Four-point probe technique was used to measure the resistance of our compliant electrodes. Two current-injecting leads and two voltage-drop leads are connected to a custom-fabricated four-point probe, which is clamped on top on the electrode being measured with two binder spring clips. Resistance was displayed on the multimeter readout. Pictures were taken by Remi Delille. Once resistance was measured, resistivity was calculated from the equation R=

L , where R is the measured resistance, w and t are the width and the thickness of wt
11

the compliant electrode respectively, and L is the distance in between the two inside leads of the four-point probe. Refer to Figure 5 for different dimensions of four-point probe and compliant electrode samples. The values of w, t, and L were measured by either a caliper or a ruler. Finally, conductivity was obtained from the formula = 1 / .

Figure 5. Different dimensions required for determining the resistivity and thus conductivity include w, t, and L; where w and t are the width and the thickness of the compliant electrode sample respectively, and L is the length in between the two inside leads of the four-point probe. Figure obtained from [15]. 2.2.1.2 Platinum Salt Reduction-based Composite Electrodes In the case of platinum salt reduction-based composite electrodes, resistance measurement remained the same. Conversion from resistance to conductivity, however, was changed. Because the samples have finite dimensions, Remi Delille suggested that a resistivity correction factor should be incorporated in the electrical conductivity calculations. For our thin rectangular samples, the dimensions were first measured with a caliper. Then resistivity was calculated by the following equation, (1) where (2) G= b a t R1 , ln(2) s b

= GR,

is the resistivity correction factor for thin rectangular samples and R is the resistance measured from aforementioned measurements [16]. The term is the geometric ln(2) factor for an infinitely large slice of sample of thickness t << s, the spacing between the four-point-probe wires. The incorporation of this term was justified since the wire spacing was 5.09 mm, much greater than the typical sample thickness of 150 m. An 12

b a additional correction term R1 , is used due to the finite rectangular shape of our s b samples. The variables a is the width, and b is the length of the composites. In our b a calculations, R1 , = 0.7744 was obtained from [16]. Finally, conductivity was s b calculated from the equation, (3) 2.2.1.3 Multimeter Calibration The floating number presentation of the multimeter when it displayed the measured resistance, shown in Figure 6, presented a problem. Floating point number consists of a mantissa and an exponential that are presented in the form m 10e. As I changed the measurement range, the decimal point of the mantissa changed among 1, 10, and 100. This was indicated by the number under the LED screen. Confusion arose when the mantissa remained the same as the range of measurement was changed. Another source of confusion was the mantissa sometimes being less than 1 or larger than 10. The rule for floating number presentation indicates that the mantissa should follow the rule 1 <= m < 10. In order to determine the correct resistance measured by the multimeter, a 470 pull up resistor was used to check the displayed values of the resistance.

1 .

13

Mantissa

Exponential

Figure 6. Resistance measured by the multimeter was displayed in floating number, which consists of a mantissa and an exponential. The floating number presentation sometimes caused confusion during the measurements. Therefore, its display must be calibrated prior to the measurements. 2.2.1.4 Light Emitting Diode Experiment I also fabricated a simple light emitting diode (LED) circuit to demonstrate the electrical conduction of our composite compliant electrodes. The compliant electrode being tested was clamped by two alligator clips in series with a LED and a pull-up resistor, as shown in Figure 7. The green LED is a 5 mm LED with the following characteristics: 2.1 VDC, 25 mA, and 6.3 mcd. The red LED that is also shown in the picture has slightly different characteristics. The pull-up resistor has a resistance of 10 k. A voltage source (Lambda Electronics Corp.) supplied 15 V through the circuit to illuminate the LED. It is important to connect the LED in the correction direction in order for the circuit to work, due to the unidirectional electrical current flow of the diode. In this work, the positive lead of the power source was connected to the resistor and the negative lead to the LED. 14

Connect to power source

LEDs 3108/PlatinumCom pliant electrode

Figure 7. A simple LED circuit was fabricated to demonstrate the conduction of our composite compliant electrodes. Two alligator clips were used to connect a sample of our electrode in series with a 10 k pull up resistor and a LED. The circuit was connected to a power supply, which provided 15 volts of voltage to illuminate the LED. 2.2.2. Youngs Modulus Measurements The Youngs modulus is an important metric in evaluating the performance of compliant electrodes. Measurements were conducted with a custom-modified force strain transducer based on a 50-gram load cell purchased from Aurora Scientific (Ontario, Canada). The methodology for measurement was developed by Remi Delille and Sam Moseley. The dimensions of each sample were determined by a caliper. Typical width was between 2 to 3 mm. The thickness generally centered around 150 m. Two pieces of transparency that are 5 mm by 3 mm in size were glued on both sides of compliant electrode samples and served as clamps. The clamps prevented the soft electrode samples from breaking during the measurements. They also provided a more stable spot for tying the thin wire around the electrode sample, as described shortly. The glue was Loctite 4304, and the curing time was 40 seconds. Loctite 4304 was chosen because its Youngs modulus is higher than that of Loctite 3108, thus assuring the clamped portion of the electrode sample would not be strained by accident during the measurements and inhibit the accuracy of the experimental values. A drill bit 0.05 inch in diameter was used to manually drill a hole at the center and through the clamped portion of the compliant electrode. A strand of stainless steel 304 fine wire (California Fine Wire Company, Grover Beach, CA) was tied around the through hole. The other end of the 15

wire was tied to the load cell arm. The side of compliant electrode sample that was not tied to the thin wire was clamped on a custom-made translational stage made by Sam Moseley. The length of the compliant electrode used for the Youngs modulus calculation was the electrode portion that was not clamped by either the transparency clamps or the translational stage. The lengths were measured with a caliper and ranged from 18 mm to 27 mm. The load cell was connected to a personal computer and controlled by a LabVIEW program. The setup for Youngs modulus measurement is presented in Figure 8.

Figure 8. Youngs modulus of compliant electrodes was measured with a custom-made force-strain transducer. Two pieces of transparency were glued on the electrode film being measured with Loctite 4304 and served as clamps. A strain of thin wire connected between the electrode and the arm of a 50-gram load cell, which was connected to a PC and controlled by a LabView program. The load cell arm stretched the film and the Youngs modulus was output on the PC. Pictures were courtesy of Remi Delille. Dimensions of the compliant electrode were entered in the computer program. For each measurement, the load cell arm displaced away from the electrode sample, stretched it, and a stress versus strain curve was plotted on the LabView program. The strain rate was 0.2 mm/s for all measurements with the exception of the high strain rate experiments, which is described in section 2.2.2.2. Youngs modulus was obtained between two selected points on the linear portion of the stress versus strain curve and output on the program. In order to obtain consistent measurements, the position of the stage was adjusted so that the thin string tying the electrode sample to the load cell arm was taut between consecutive measurements. At least two samples at each platinum salt loading were measured. Each sample was measured at least five times. 16

2.2.2.1 Repetition Measurements One of the important metrics for evaluation of actuators is observing the damage to the actuator with many repetitions of actuation. Therefore, the compliant electrodes must also withstand repeated actuations. For this experiment, Youngs modulus of every sample was measured with the aforementioned method. One unloaded sample was measured for 50 repetitions. One sample of 7% platinum salt concentration just below the percolation was tested with 70 repetitions. Finally, one sample of 10% loading above the percolation threshold was repeated for 60 measurements. 2.2.2.2 High Strain Rate Measurements Because actuators may actuate at a high rate [3], Youngs modulus for composite compliant electrodes was measured at a strain rate one order of magnitude higher at 2 mm/s than the normal strain rate used for other Youngs modulus measurements. We were also interested to know whether or not the electrodes would yield under the higher actuation rate. Finally, we wanted to observe the effect of this high strain rate on the electrodes. At least five measurements were performed on one sample of each platinum salt concentration level at 2 mm/s. These samples were subsequently measured again at the normal strain rate to explore possible electrode degradation resulted from the higher strain rate. Five such measurements were performed on every sample.

3. Results and Discussions

3.1. Electrical Conductivity Measurement
3.1.1. Multimeter Calibration The measurement results obtained from the pull-up resistor experiment are presented in Table 1. This calibration process indicated the measurement range, which was also the mantissa, was related to the resolution of the measurement rather than the magnitude and the correct reading for this multimeter was simply m 10e. Table 1. The pull-up resistor experiment helped me calibrate the multimeter display: the measurement range, which was also the mantissa, was related to the resolution of the measurement rather than the magnitude and the correct reading for this multimeter was simply m 10e.

17

Actual Resistance 470 470 470 470 470 470

Mantissa No measurement 0.46232 0.4613 0.00046 0.0004 0.000

Exponential +3 +3 +3 +6 +6 +6

Measurement Range 1 10 100 1 10 100

3.1.2. Conductive Powder-based Composite Electrodes Compliant electrode samples made of copper and PDMS composite were measured first. The resistance for electrodes that are 20% by volume ranged from 30 to 120 k, with two outliers. The resistance for one of the outliers was 1.15 M. The other outlier was not conductive at all, as no resistance could be measured. The data indicated low conductivity. Furthermore, Remi suggested that copper oxide might have formed on the surface of these electrodes so that their conductivity suffered. Due to these reasons, I did not experiment with the rest copper powder and PDMS composite compliant electrodes. Resistance of five different batches of composite compliant electrodes made of graphite powder and PDMS were also measured. During the measurement, I clipped the current injection leads from the multimeter on the metal contacts instead of the wires on the four-point probe. This is because Sam and Remi believe the thermally evaporated contacts would work better than the probe wires for current injection. The voltage drop connection remained the same. I made two separate resistance measurements to verify the consistency of the measurement. Typical resistance for these samples ranged from 200 to 2 k. Typical dimensions were w = 0.95 cm and t = 0.1 to 0.2 cm. The distance between the two voltage drop leads on the four-point probe, L, was 0.509 cm. When resistance data were converted to conductivity, consistency between two experiments was verified. We expected the conductivity to increase as the graphite powder concentration increased from 15% to 20%. Half of these data points demonstrated otherwise, as shown in Figure 9. We could not find a clear pattern from either between graphite powder loading and conductivity, or between the types of metal contacts and conductivity. We also did not find observe a sharp increase in conductivity at a certain graphite 18

concentration by volume the percolation behavior. Furthermore, the conductivity of these compliant electrodes, with the maximum conductivity less than 0.05 S/cm, was fairly low. More samples could be fabricated to further explore the conductivity of these graphite and PDMS samples. I did not do that because Remi and Sam developed the platinum salt and Loctite 3108 composite compliant electrodes that were patternable and turned out to be more conductive.
0.05 Wen, Al 0.04 0.03 0.02 0.01 0 15 16 17 18 19 20 Concentration by volume (%) Wen, Cr/Au RISE, Al RISE, Cr/Au Conductivity (S/cm) iii

Figure 9. We could not determine relationships between either concentration by volume or the contact types and the corresponding conductivity. No percolation behavior could be observed from the graphite powder and PDMS composite electrodes. Conductivity of these compliant electrodes was also low. 3.1.3. Platinum Salt Reduction-based Composite Electrodes As the result of including the resistivity correction factor in the calculations, the electrical conductivity of composite compliant electrodes increased by at least 26%. The relation between conductivity and platinum salt concentration was unaffected, since conductivity increased for all of the composites at different platinum salt concentration. Because our compliant electrodes were composed of a nonconductive polymer matrix and conductive platinum metal, we anticipated a percolation behavior. As shown in Figure 10 (a), the composites became conductive at as low as 5% platinum salt concentration by volume. Instead of jumping sharply at a particular percolation threshold, the electrical conductivity increased one order of magnitude with each increasing percent of platinum salt loading from 5% to 9%. Essentially, the composites 19

have a wide percolation threshold spanning 5% to 9% of platinum salt concentration. For the regime above the percolation, the electrical conductivity remained in the same order of magnitude despite the increase of platinum salt loading from 9% to 15%. The minimum average conductivity observed after it leveled off was 0.107 S/cm, observed at 11% platinum salt concentration. The maximum average conductivity for a particular platinum salt concentration by volume was 0.593 S/cm at 15% loading. The maximum conductivity observed from a single sample electrode was 1.076 S/cm at 15%. After the conductivity leveled off at 9%, we found the minimum conductivity of 0.001 S/cm from a sample of 9% loading. In addition to this large discrepancy among composites of varying concentrations, we observed large standard deviations for composites of the same concentration on the percolation plot, signifying a nonuniform distribution of electrical conductivity among these composites. I suppose this nonuniform distribution could be improved by homogenizing the platinum salt and polymer matrix mixture right before polymerization, but it was not tried by the completion of this report. Remi and I discussed about the percolation behavior and the nonunifrom distribution of electrical conductivity, and we hypothesized the formation of interconnections among platinum metal particles upon reduction as the cause. Referring to Figure 10 (b), at 5% of concentration by volume the lowest end of our wide percolation threshold agglomerated spherical platinum metal particles could be observed under SEM at 8000 times of magnification. The dispersed conductive particles limited the conductivity of the electrodes. On the other hand, at loadings beyond the percolation threshold, such as 10% and 15% loading, platinum metal particles formed interconnections. This formed a conduit for electrical current, and the electrodes became conductive as a result. The interconnected platinum salt particles at 10% and 15% could be clearly observed under SEM at 8000 times of magnification, as shown in Figure 10 (c) and (d), respectively. It could be seen that the interconnection of platinum salt particles at 15% was more uniform than that of the 10% sample. This explained the superior conductivity observed at 15%. However, Figure 10 (c) and (d) also demonstrated that the platinum particles were not reduced into one consistent phase throughout the film, as areas with no platinum salt could be observed. These areas with no platinum salt interconnections prevented 20

electrical current passage and caused nonuniform electrical conductivity on the composite film surfaces. Since composite uniformity of could be hindered from any fabrication and reduction steps, our composite compliant electrodes were not uniform. This explained the scattering conductivity and large error bars associated with the percolation plot.
(a)

1 Mean

Conductivity (S/cm)

0.1

0.01

0.001

0.0001 0 2 4 6 8 10 12 14 16

Platinum Salt Concentration by Volume (%)

(b) (c) (d)

Figure 10. (a) The relation of electrical conductivity and platinum salt concentration by volume of composite compliant electrodes. The conductivity was displayed on a logarithmic scale. A percolation behavior could be observed. (b) Dispersed spherical platinum salt particles in the 5 % sample could be observed under SEM at 8000x magnification, rendering the electrodes nonconductive. (c) Interconnected platinum salt particles at 10% formed a path for current conduction, and the electrodes became conductive. Picture was taken under SEM at 8000x magnification. (d) A fairly uniform interconnection of platinum salt at 15% produced the most conductive electrodes. Picture was taken under SEM at 8000x magnification. SEM pictures were taken by Remi Delille. 21

3.1.3.1 Light Emitting Diode Experiment The LED experiment was also successful. The result of this experiment is presented in Figure 11. A sample with 9% platinum salt loading was used. The power was kept off in (a) so the LED was not lid. The power was switched on in (b), and electricity was successfully conducted through the composite electrode to illuminate the green LED.
(a) (b)

Figure 11. The LED experiment was successful. The green LED illuminated when the power source was switched on, as shown in (b), signifying the conductivity of our compliant electrode.

3.2. Youngs Modulus Measurements

3.2.1. Youngs Modulus versus Platinum Salt Loading Youngs modulus values from two separate linear stress versus strain curve regions were obtained. The two regions were from 0% to 1.5% strain and from 2% to 4% strain. Two sets of Youngs modulus were recorded because we suspected values obtained from the lower strain region might reflect the modulus of the stainless steel wire and its knots in addition to the electrode samples. This would alter the accuracy of the real sample Youngs modulus. Indeed, after repeated measurements, we observed higher Youngs modulus from the 0% to 1.5% strain region. We observed, however, that the modulus from both regimes behaved similarly. Therefore, we chose to only report the 0% to 1.5% strain values in our communication that we are currently working on, since it serves as a worst case estimate. In this report, however, I reported both sets of values. Referring to Figure 12, the Youngs modulus gradually increased from 0% to 8% loading in both cases. In the 0% to 1.5% strain case, Youngs modulus increased from 19 22

MPa at 0% loading to 32 MPa at 8% loading. At the experimental percolation of 9% loading, the modulus dropped to between 17 and 18 MPa equivalent to that of the unloaded samples and remained the same until 15% loading. A similar behavior was observed in the 2% to 4% strain region, as the sample Youngs modulus increased from 10 MPa at 0% loading to 21 MPa at 8% loading; then decreased to 10 MPa at 9% loading and remained around 10 MPa thereafter. Samples with 12% loading averaged 27 MPa in the 0% to 1.5% strain region and 16 MPa in the 2% to 4% strain region. These numbers were considered as outliers, and therefore not shown on the percolation plot. The large error bars for the 7% sample were caused by measurements taken on two different batches of samples fabricated on different occasions. Samples in the first batch averaged 28 MPa and 15 MPa in the two regions respectively. Samples from the second batch averaged 34 MPa and 25 MPa. The differences could be attributed to variations in electrode fabrication including polymerization time and platinum salt reduction duration, as well as the temperature. Another possible cause for this difference was the electrode film quality. If there were holes on the sample, the Youngs modulus would decrease as a result. Other samples at different platinum salt concentrations were also fabricated in two batches. These electrodes were made more consistently, as they had small error bars.

23

40 35

0% to 1.5% strain 2% to 4% strain

Young's Modulus (MPa)

30 25 20 15 10 5 0 0 2 4 6 8 10 12 14 16

Platinum Salt Concentration by Volume (%) Figure 12. The relation between the Youngs modulus and the platinum salt loading by volume in two separate strain regions. In both cases, the Youngs modulus increased from 0% loading to 8% loading. At 9% loading and beyond above the percolation the modulus decreased to the same magnitude as the unloaded sample. Samples at 12% platinum salt loading were omitted from the plot. Remi and Sam formulated the following explanation: at lower platinum salt loading, platinum metal particles agglomerated into small chunks and stiffened the 3108 polymer matrix. This is similar to other compliant electrode fabrication methods involving adding conductive fillers to polymers, as mentioned earlier. At high loading beyond the percolation, however, the effective spacing in the 3108 polymer for it to display its Youngs modulus was all occupied by unreduced platinum salt. Since the voids between the polymer chains were filled with unreduced platinum salt, the Youngs modulus decreased as a result. This explanation is analogous to adding too many rocks to cement in the macro scale. When too many rocks are added to cement, the Youngs modulus of the cement would decrease because there was actually not enough cement to hold all of the rocks. This explanation, however, was only a proposal. More SEM pictures of samples at both low and high platinum salt loading should allow better understanding. 24

3.2.2. Youngs Modulus versus Repetitions In fifty measurements, Youngs modulus of the unloaded sample remained unchanged between 20 and 23 MPa in the 0% to 1.5% strain region and 9 MPa and 12 MPa in the 2% to 4% strain region. This is shown in both Figure 13 (a) and (b). For loaded samples both below and above the percolation in both strain regions, the Youngs modulus showed similar pattern. In the 0% to 1.5% strain region, the modulus of the 7% loading sample increased from 28 MPa to almost 30 MPa in the first ten measurements. Then it gradually decreased to slightly above 22 MPa in the next thirty repetitions before it finally leveled off at above 22 MPa. The modulus of the 10% loading sample also increased from 29 MPa to 31 MPa in the first twenty measurements, followed by a gradual but steady decrease to up to the fortieth measurement. In the last twenty measurements, Youngs modulus scattered between 26 and 28 MPa, but seemed to level off around these values. In the 2% to 4% strain regime, the modulus of the 7% sample remained slightly above 18 MPa for the first ten measurements. The decrease in the Youngs modulus took place between the tenth and the thirtieth measurement, from 18 MPa to slightly below 15 MPa. The Youngs modulus of this sample seemed to level off at 14 MPa by the end of seventieth measurement. Finally, the modulus of the 10% loading sample also remained relatively steady at 21 MPa before the first twenty measurements. The subsequent decrease occurred between the twentieth and the fortieth measurement, from 21 MPa to 18 MPa. In the last twenty measurements, the modulus centered between 17 MPa and 19 MPa.

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30

10% 7% 0%

24 22

10% 7% 0%

Young's Modulus (MPa)

Young's Modulus (MPa)

0 10 20 30 40 50 60 70

20 18 16 14 12 10

28

26

24

22

20

8 0 10 20 30 40 50 60 70

Strain Repetitions (times)

Strain Repetitions (times)

Figure 13. The relation between the Youngs modulus and increasing number of actuations in two separate strain regions, namely 0% to 1.5 strain region, shown in (a), and 2% to 4% strain region, shown in (b). In both cases, the unloaded sample remained unchanged with increasing number of repetitive measurements. The loaded samples both below and above the percolation experienced slight increase in the modulus in the first twenty measurements; followed by a decrease in the next twenty measurements. Finally, the Youngs modulus leveled off. The modulus remained in the same order of magnitude, signifying the insensitivity of these compliant electrodes to the number of actuations. These results signified that Youngs modulus of the conductive composite electrodes experienced minor strain softening. The largest observed decrease was only 30%, which occurred for the 7% sample in the 2% to 4 % strain region. Furthermore, all of the modulus values remained in the same order of magnitude. These composite compliant electrodes showed insensitivity to repetitive actuations, showing the possibility for them to be used as reliable compliant electrodes. A couple of things that are not shown from the experimental plots must be noted. First, both of the loaded samples were also used in the Youngs modulus versus platinum salt loading experiment. Therefore, ten measurements were taken on these samples prior to the repetition measurements. The Youngs moduli from these first ten measurements were not exactly the same as those obtained in the first couple of measurements in the repetition measurement due to setup uncertainties. This was a problem in our measurement metrology that is yet unsolved. Those data points were therefore omitted because they would be misleading for the real effect of repetitive actuations on the 26

Youngs modulus of the electrodes. Second, the film with 10% loading actually had higher Youngs modulus than the 7% sample. This was due to the fact that the particular 10% sample was an outlier. Finally, even though only up to seventy measurements were taken, we believed that the measurements were enough to show the effect of many repeating actuations. It was difficult to obtain many data points in this experiment because the sample electrode film must relax to the unstressed state between consecutive measurements. This relaxation took at least three minutes, making the experiment timeconsuming. Furthermore, an experiment for one sample, corresponding to at least fifty measurements in this report, must be finished once it started. This is because the Youngs modulus might change as the result of new measurement setups. These two factors limited the number of measurements in this experiment. In order to efficiently observe the effect of repetitions on the Youngs modulus, the LabVIEW program should be modified so that the experiment could be automated. 3.2.3. Youngs Modulus versus High Strain Rate Considerably higher Youngs modulus for every sample across the platinum salt loading range was observed, though all of the modulus measurements remained in the same order of magnitude. In the 0% to 1.5% strain region, the largest increase was found at 10% loading from 19 MPa at 200 m per second to 41 MPa at 2 mm per second a 116% increase in the modulus. Despite the increase in modulus, none of these samples yielded under the much higher strain rate. In the subsequent measurements under the normal strain rate, the Youngs modulus of samples below 10% platinum salt loading remained relatively unchanged. In this regime, the largest change in Youngs modulus was the 15% decrease observed at 6% loading. This decrease, however, could be caused by experimental setup and not from the high strain rate. At 10% loading or higher, however, we observed at least 28% of increase in Youngs modulus. The largest increase that we found was at 10% loading. The Youngs modulus increased from 19 MPa to 27 MPa, or 42 % of increase. Above results correspond to the 0% to 1.5% strain region, which is shown in Figure 14. Similar results were observed in the 2% to 4% strain region.

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iiiiiii Change in Young's Modulus (%) 50 40 30 20 10 0 -10 -20 0 2 4 6 8 10 12 14 16 Platinum Salt Concentration by Volume (%)

Figure 14. As a result of high strain rate, Youngs modulus for 9% samples and below was unaffected while 10% samples and beyond experienced an increase. The maximum increase was 42%, corresponding to 10% platinum salt loading. As proposed in section 3.2.1, our composite electrodes reduced to either disperse platinum metal particles or agglomerated interconnections. For films below the percolation, more disperse platinum metal particles were present and the modulus of composite electrodes was dominated by the polymer matrix. Since the unloaded 3108 sample was not affected by the high strain rate, samples that were below the percolation displayed the similar characteristics. This explained the samples that were unaffected by the high strain rate. At higher platinum salt concentrations, the high strain rate could have broken the agglomerated and interconnected platinum metal particles into disperse particles or smaller agglomerated chunks. The altered particle distribution resembled that of the samples with lower loading, which explained the increased modulus. It is important to note that the 9% sample did not experience such increase in Youngs modulus. This result suggested that electrodes made with a concentration much higher than the percolation threshold might be undesirable, as its Youngs modulus would be affected by higher actuation rates.

4. Conclusions
In the spring and summer semesters of 2005, I assisted graduate students Remi Delille and Sam Moseley on the fabrication and the characterization of novel composite compliant electrodes. Specifically, we obtained satisfying results from compliant 28

electrodes based on platinum salt reduction. The experiments on sample conductivity were finished. In addition, most of the Youngs modulus experiments were finished. More data points from these experiments might be necessary to ensure the validity of the conclusions that we have drawn thus far. For example, more repetitions could be taken to investigate the effect of hundreds of actuations on the compliant electrodes. Upcoming tasks include modifying the LabVIEW program to complete this task, as well as finishing conductivity versus strain experiments. Based on the preliminary data gathered thus far, we think we have a type of very conductive compliant electrode that is fairly stretchable. Our experimental results indicated maximum conductivity of 1.08 S/cm and Youngs modulus in the range of 30 MPa. Furthermore, Youngs modulus of electrodes that were tested under high strain rate and many actuations remained in the same order of magnitude after these experiments, signifying their insensitivity to high strain rate and high number of actuation. We are currently working on a publication describing the fabrication method and experimental results of our new composite compliant electrodes. The work will near complete we obtained and analyzed the data from the conductivity versus strain experiment. Upon the completion of characterizations, we expect to incorporate these electrodes in novel nastic actuators that are currently being developed in the Laboratory for Micro Technology. More work may follow in order to shrink these meso-scale electrodes to micro-scale so that they can be incorporated in small-scale dielectric elastomer actuators that are also being developed in our lab.

5. Acknowledgements
The author appreciates Remi Delille and Sam Moseley for supervision and discussions. The author would like to acknowledge Mario Urdaneta for debugging the LabVIEW program used for the Youngs modulus experiments. The author would like to thank Dr. Elisabeth Smela for guidance and direction. The research opportunity and funding was made possible by the ASPIRE program and MTECH.

6. References
[1] R. Pelrine, P. Sommer-Larsen, R. Kornbluh, R. Heydt, G. Kofod, Q. Pei, and P. Gravesen, "Applications of dielectric elastomer actuators," presented at Smart 29

[2]

[3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16]

Structures and Materials 2001: Electroactive Polymer Actuators and Devices (EAPAD), 2001. H. R. Choi, S. M. Ryew, K. M. Jung, H. M. Kim, J. W. Jeon, J. D. Nam, R. Maeda, and K. Tanie, "Micro robot actuated by soft actuators based on dielectric elastomer," presented at International Conference on Intelligent Robots and Systems, Lausanne, Switzerland, 2002. R. Pelrine, R. Kornbluh, Q. B. Pei, and J. Joseph, "High-speed electrically actuated elastomers with strain greater than 100%," Science, vol. 287, pp. 836839, 2000. R. Heydt, R. Kornbluh, R. Pelrine, and V. Mason, "Design and performance of an electrostrictive-polymer-film acoustic actuator," J. Sound Vib., vol. 215, pp. 297311, 1998. R. Pelrine, R. Kornbluh, J. Joseph, and R. Heydt, "High-field deformation of elastomeric dielectrics for actuators," Mat. Sci. Eng. C, vol. 11, pp. 89-100, 2000. K. Yamaguchi, J. J. C. Busfield, and A. G. Thomas, "Electrical and mechanical behavior of filled elastomers. I. The effect of strain," J. Polym. Sci. Pt. B-Polym. Phys., vol. 41, pp. 2079-2089, 2003. S. Jiguet, A. Bertsch, H. Hofmann, and P. Renaud, "Conductive SU8-silver composite photopolymer," presented at 17th IEEE International Conference on Micro Electro Mechanical Systems, Maastricht, The Netherlands, 2004. D. W. Marshall, "Copper-based conductive polymers: a new concept in conductive resins," J. Adhesion, vol. 74, pp. 301-315, 2000. D. I. Kang, W. J. Cho, and C. S. Ha, "Structure and electrochemical properties of electrically conductive composites," Mol. Cryst. Liq. Cryst., vol. 280, pp. 199204, 1996. R. Faez, W. A. Gazotti, and M.-A. De Paoli, "An elastomeric conductor based on polyaniline prepared by mechanical mixing," Polymer, vol. 40, pp. 5497-5503, 1999. D. S. Gray, J. Tien, and C. S. Chen, "High-conductivity elastomeric electronics," Adv. Mater., vol. 16, pp. 393-397, 2004. T. Li, Z. Y. Huang, Z. C. Xi, S. P. Lacour, S. Wagner, and Z. Suo, "Delocalizing strain in a thin metal film on a polymer substrate," Mech. Mater., vol. 37, pp. 261273, 2005. K. Hsieh, "Conductivity and Young's modulus measurements for compliant electrodes," University of Maryland, College Park, MD, 2005. K. Hsieh, "Characterization of Composite Compliant Electrodes Based on Platinum Salt Reduction," University of Maryland, College Park, MD, 2005. S. Mitchell, "Conductive polymer composites," University of Maryland, College Park, MD, 2003. H. Topsoe, Geometric factors in four point resistivity measurement, 1968.

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