Review of Smart Material Based Actuators for Artificial Muscles

Chad Berndt, Justin DeLuca, Andrew Gilles, Mark Kopec

A thesis submitted in partial fulfillment of the requirements for the degree of

BACHELOR OF APPLIED SCIENCE

Supervisor: A.N. Sinclair

Department of Mechanical and Industrial Engineering University of Toronto

March 2007

ABSTRACT
This report is an examination of smart materials for their use in prosthetic arms. A literature review of Ionic Polymer Metal Composites (IPMC), Polyaniline, Carbon Nanotube Hydrogel, Bucky Paper, Magnetorheological materials, and Shape Memory Alloys (SMA) is included, along with some designs and applications other researchers have attempted. For each material, the physical and chemical properties, method of actuation, and microstructure are discussed in detail. Where a material showed promise for the application to human prosthetics, further investigation was conducted, examining potential fabrication techniques that have been employed. For Bucky paper, IPMC, Polyaniline, Hydrogel, and SMA samples were produced and tested. Where possible, improvements to the recipes were attempted and the results are reported. Several interesting variations were attempted such as extruding Polyaniline into a fiber and coating an IPMC with Polyaniline to improve cycle ability. The material showing the most promise for application to human prosthetics is the Shape Memory Alloys because of the large strains and forces possible. With further development, IPMCs may also be used in low force, low strain roles.

ACKNOWLEDGEMENTS
The authors wish to thank Professor Hani Naguib and Ph.D student Aaron Price for providing the opportunity, resources and guidance to explore this interesting field; John Didzbalis of C.P. Pro Prosthetics, and R.J. Clements of the Independent Living Center at Sunnybrook Hospital for sharing their resources, insight, and experience into the prosthetics field; John Ujfalusi of George Brown College for his creative and professional prosthetics fabrication; the graduate students at the Smart and Adaptive Polymers Lab for their problem solving and assistance; Kristen Facciol for her industry contacts, enthusiasm, and support.

TABLE OF CONTENTS
ACKNOWLEDGEMENTS .............................................................................................. I TABLE OF CONTENTS ................................................................................................ II LIST OF FIGURES ........................................................................................................ IV LIST OF TABLES ........................................................................................................ VII LIST OF TABLES ........................................................................................................ VII 1 INTRODUCTION.......................................................................................................... 1 2 DESIGN CRITERIA FOR ARTIFICIAL MUSCLES .............................................. 2 3 MATERIAL SELECTION AND DESIGN ................................................................. 4 3.1 IONIC POLYMER METAL COMPOSITES ........................................................................ 4 3.1.1 Macro and Micro General Descriptions............................................................ 5 3.1.2 Actuation Method ............................................................................................... 7 3.1.3 IPMC Manufacture ............................................................................................ 8 3.1.4 Testing Equipment ........................................................................................... 10 3.1.4.1 Linear Test Rig Design ............................................................................. 10 3.1.4.2 Bending Test Rig Design .......................................................................... 10 3.1.5 Testing Procedure ............................................................................................ 11 3.1.6 Results and Evaluation .................................................................................... 13 3.1.7 Future research ................................................................................................ 18 3.2 CARBON NANOTUBES .............................................................................................. 20 3.2.1 General Nanotube Characteristics .................................................................. 20 3.2.2 Actuation method ............................................................................................. 21 3.2.3 Original Recipes .............................................................................................. 24 3.2.4 Bucky Paper Properties ................................................................................... 26 3.2.5 Recipe Revisions .............................................................................................. 28 3.2.6 Testing Procedure ............................................................................................ 30 3.2.7 Results and Evaluation .................................................................................... 31 3.3 MULTI-WALL NANOTUBE HYDROGEL ..................................................................... 35 3.3.1 General Fabrication Characteristics ............................................................... 35 3.3.2 Actuation method ............................................................................................. 35 3.3.3 Original Recipes .............................................................................................. 37 3.3.4 Recipe Revisions .............................................................................................. 37 3.3.5 Testing Procedure ............................................................................................ 38 3.3.6 Results and Evaluation .................................................................................... 39 3.3.7 Suggestion of Future Work .............................................................................. 42 3.4 MAGNETORHEOLOGICAL MATERIALS ...................................................................... 43 3.4.1 Magnetorheological Elastomers ...................................................................... 43 3.4.1.1 Actuation Method ..................................................................................... 43 3.4.1.2 Recipe ....................................................................................................... 44 3.4.1.3 Recipe Improvements ............................................................................... 44 3.4.1.4 Results and Evaluation .............................................................................. 45 ii

3.4.2 Magnetorheological Fluids.............................................................................. 45 3.4.2.1 Actuation Method ..................................................................................... 45 3.4.2.2 Results and Evaluation .............................................................................. 46 3.5 CONDUCTIVE POLYMERS ......................................................................................... 47 3.5.1 Actuation method ............................................................................................. 48 3.5.2 Original recipes ............................................................................................... 50 3.5.3 Physical and Chemical Properties................................................................... 54 3.5.4 Recipe Revisions .............................................................................................. 55 3.5.5 Equipment design ............................................................................................. 58 3.5.6 Results and evaluation ..................................................................................... 60 3.6 SHAPE MEMORY ALLOYS......................................................................................... 65 3.6.1 Actuation method ............................................................................................. 65 3.6.2 recipe................................................................................................................ 67 3.6.3 Equipment Design ............................................................................................ 67 3.6.4 Results and evaluation ..................................................................................... 70 4 ARTIFICIAL ARM DESIGN AND INTEGRATION ............................................. 71 4.1 BRIEF PROSTHETICS BACKGROUND .......................................................................... 71 4.2 FINAL JOINT DESIGN ................................................................................................. 74 5 CONCLUSION ............................................................................................................ 79 6 BIBLIOGRAPHY ........................................................................................................ 81 APPENDIX: MACHINE DRAWINGS ........................................................................ 85

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LIST OF FIGURES
FIGURE 3.1.1: NAFION POLYMER CHAIN NEUTRALIZED WITH A NA+ CATION ....................... 5 FIGURE 3.1.2: TWO INTERCONNECTED CLUSTERS IN A HYDRATED POLYMER ....................... 5 FIGURE 3.1.3: TOP LEFT: SCHEMATIC DIAGRAM SHOWING THE INITIAL COMPOSITING OF PT. TOP RIGHT: A SEM MICROGRAPH OF THE INITIAL COMPOSITING. BOTTOM LEFT: SCHEMATIC DIAGRAM SHOWING THE SECONDARY COMPOSITING OF PT. BOTTOM RIGHT: A SEM MICROGRAPH OF THE SECONDARY COMPOSITING. ................................ 7 FIGURE 3.1.4: A DEMONSTRATION OF THE DEFORMATION CAPABILITY OF A 1CM X 4 CM X 0.2MM IPMC ............................................................................................................... 8 FIGURE 3.1.5: AN ILLUSTRATION DEMONSTRATING CATION AND SOLVENT MOVEMENT WITHIN THE POLYMER INFRASTRUCTURE CAUSING BENDING ACTUATION .................... 8 FIGURE 3.1.6: TRADITIONAL FABRICATION OF AN IPMC ACTUATOR ................................... 9 FIGURE 3.1.7: TEST RIG CAD MODEL ................................................................................ 10 FIGURE 3.1.8: BENDING RIG CAD MODEL ......................................................................... 11 FIGURE 3.1.9: BENDING TEST RIG SETUP ............................................................................ 12 FIGURE 3.1.10: 1ST IN-HOUSE MANUFACTURED IPMC........................................................ 14 FIGURE 3.1.11: 2ND IN-HOUSE MANUFACTURED IPMC ....................................................... 14 FIGURE 3.1.12: IPMC REPEAT ACTUATION TEST USING A 7V POTENTIAL .......................... 15 FIGURE 3.1.13: CROSS-SECTION AND SURFACE SEM IMAGES FOR ALL THREE SAMPLES .... 18 FIGURE 3.1.14: EXAMPLE OF IPMC LOCALIZED BENDING ................................................. 18 FIGURE 3.1.15: SIMPLE LINEAR DISPLACEMENT DEVICE .................................................... 19 FIGURE 3.1.16: SETUP OF IPMC ARRAY TO PRODUCE LINEAR DISPLACEMENT ................... 19 FIGURE 3.1.17: LIMITED ANGLE ROTATIONAL DEVICE ....................................................... 19 FIGURE 3.1.18: AE 801 MICRO FORCE SENSOR FROM SENSORONE .................................... 20 FIGURE 3.2.1: CNT SHEET LINEAR ACTUATION STRAIN (SUBMERGED IN ELECTROLYTE) ... 22 FIGURE 3.2.2: LINEAR ACTUATOR STRAIN FOR BUCKY PAPER SHEET ................................. 23 (-0.5V TO 1.5V, 0.1HZ, AFTER 30 CYCLES) ........................................................................ 23 FIGURE 3.2.3: LINEAR ACTUATION STRESS FOR BUCKY PAPER SHEET ................................ 23 (-0.5V TO 1.5V, 0.1HZ, AFTER 30 CYCLES) ........................................................................ 23 FIGURE 3.24: BI-STRIP/CANTILEVER STRIP ACTUATOR ...................................................... 24 FIGURE 3.2.5: BI-STRIP/CANTILEVER LINEAR CNT SHEET STRAIN ..................................... 24 FIGURE 3.2.6: BUCKY PAPER FABRICATION RECIPE ............................................................ 25 FIGURE 3.2.7: APPARATUS FOR THE FABRICATION OF BUCKY PAPER ................................. 26 FIGURE 3.2.8: BUCKY PAPER ELECTRON MICROGRAPH ...................................................... 27 FIGURE 3.2.9: BUCKY PAPER TENSILE STRESS .................................................................... 28 FIGURE 3.2.10: BUCKY PAPER FAILURE STRAIN ................................................................. 28 FIGURE 3.2.11: BUCKY PAPER REVISED RECIPE .................................................................. 30 FIGURE 3.2.12: BI-STRIP/CANTILEVER TESTING APPARATUS ............................................. 31 FIGURE 3.2.12: SAMPLE 2 FRAGMENTS .............................................................................. 32 FIGURE 3.2.13: SAMPLE 3 SHEET BENDING ........................................................................ 32 FIGURE 3.2.14 C: SAMPLE 2 EDGE ..................................................................................... 33 FIGURE 3.2.15 D: SAMPLE 3 EDGE ..................................................................................... 33 FIGURE 1.2.16 E: SAMPLE 2 SURFACE ................................................................................ 33 FIGURE 3.2.17 F: SAMPLE 3 SURFACE ................................................................................ 33 FIGURE 3.2.18 G: PURIFIED MWNT FROM CHEAPTUBES................................................... 33 iv

FIGURE 3..3.1 : NA-MWNT/PVA COMPOSITE ACTUATION ............................................... 36 FIGURE 3.3.2: MWNT/PVA HYDROGEL RECIPE ................................................................ 37 FIGURE 3.3.3 : HYDROGEL REV A ...................................................................................... 38 FIGURE 3.3.4: HYDROGEL TEST SETUP ............................................................................... 39 FIGURE 3.3.5: HYDROGEL TEST.......................................................................................... 39 FIGURE 3.3.6: HYDROGEL SAMPLE ..................................................................................... 41 FIGURE 3.3.7: HYDROGEL TEARS (MOST NOT THROUGH SAMPLE) ...................................... 41 FIGURE 3.3.8: HYDROGEL TEST SAMPLES........................................................................... 41 FIGURE 3.3.9: MWNT/PVA HYDROGEL SEM CROSS SECTION X140 ................................ 42 FIGURE 3.3.10: MWNT/PVA HYDROGEL SEM CROSS SECTION X140 .............................. 42 FIGURE 3.3.11: HYDROGEL RECIPE REV B......................................................................... 42 FIGURE 3.4.1: MICROSTRUCTURE OF CARBONYL IRON PARTICLES .................................... 43 FIGURE 3.5.1: CHANGING OXIDATION STATES THROUGH PH CHANGE OR CHARGE DISPLACEMENT .......................................................................................................... 49 FIGURE 3.5.2: TRADITIONAL FABRICATION OF A PAN ACTUATOR ...................................... 51 FIGURE 3.3: FABRICATION OF PAN ACTUATORS USING PHASE INVERSION TECHNIQUE ...... 53 FIGURE 3.5.4: DOPING OF PAN-EB TO GIVE PAN EMERALDINE SALT ................................ 54 FIGURE 3.5.5: MIXING OF POLYANILINE AND NMP USING A HOMOGENIZER ....................... 55 FIGURE 3.5.6: PRODUCTION OF POLYANILINE FILM............................................................ 56 FIGURE 3.5.7: POLYANILINE SYNTHESIZED USING THE PHASE INVERSION TECHNIQUE ....... 57 FIGURE 3.5.8: EXTRUDER DEVICE WITH PRESSURE VESSEL ASSEMBLY ON THE LEFT AND REEL ASSEMBLY ON THE RIGHT.................................................................................. 59 FIGURE 3.5.9: PRESSURE VESSEL CROSS SECTION ............................................................. 59 TABLE 3.5.1: POLYANILINE FILM (TRADITIONAL TECHNIQUE) RESULTS. ............................ 61 FIGURE 3.5.10: POLYANILINE SAMPLE MADE WITH TRADITIONAL TECHNIQUE ................... 61 FIGURE 3.5.11 SEM PHOTOGRAPH OF POLYANILINE FILM EDGE ........................................ 61 FIGURE 3.5.12: SEM OF POLYANILINE, PHASE INVERSION, SHOWING (A) OUR RESULTS AND (B) PREVIOUS RESULTS ............................................................................................... 63 FIGURE 3.5.13: IPMCS COATED WITH POLYANILINE ........................................................ 64 FIGURE 3.5.14: SEM OF CROSS SECTION OF IPMC COATED WITH POLYANILINE THROUGH SUSPENSION ............................................................................................................... 64 FIGURE 3.6.1: ATOMIC STRUCTURE OF SHAPE MEMORY ALLOYS ....................................... 65 FIGURE 3.6.2: SMA PHASE TRANSFORMATION CYCLE ....................................................... 66 FIGURE 3.6.3: SMA HEATING ASSEMBLY .......................................................................... 67 FIGURE 3.6.4: HEATING RIG PEG PATTERN ........................................................................ 68 FIGURE 3.6.5: SMA BUNDLE ............................................................................................. 68 FIGURE 3.6.6: SMA SILICONE APPLICATION ASSEMBLY .................................................... 69 FIGURE 3.6.7: DETAIL OF SILICONE APPLICATION ASSEMBLY CROSS SECTION ................... 69 FIGURE 4.1: PROSTHETIC ACTUATION THROUGH MOVEMENT OF HARNESSED TORSO ......... 72 FIGURE 4.2: CLASSIC PROSTHETIC DEVICES (A) ELBOW JOINT (B) UPPER ARM PROSTHETIC WITH HAND AND HARNESS REMOVED SHOWING ELBOW LOCK CABLE ......................... 72 FIGURE 4.3: UPPER ARM MYOELECTRIC PROSTHETIC FOR ELBOW ACTUATION ................... 73 FIGURE 4.4: LOWER ARM PROSTHETIC (A) SHOWING MYOELECTRIC HAND (B) SHOWING SENSORS IN FIBREGLASS SHELL .................................................................................. 73 FIGURE 4.5: LOWER ARM ROTATION COMPONENT FIXED TO THE DRIVE ASSEMBLY ........... 74 FIGURE 4.6: REAR CUT-AWAY VIEW OF DRIVE ASSEMBLY MOUNTED IN THE TORSO ........... 75

FIGURE 4.7: CUTAWAY OF ARM SHOWING SMA CONTRACTING RESULTING IN ARM MOTION ................................................................................................................................... 76 FIGURE 4.8: A FRONT VIEW OF THE COMPLETED TORSO ASSEMBLY ................................... 77 FIGURE 4.8: ARM ACQUIRED FROM PRO PROSTHETICS THAT WAS USED FOR LOWER ARM SECTION ..................................................................................................................... 78 FIGURE 4.9: TORSO WITH BACK PANEL REMOVED SHOWN MOUNTED TO PLYWOOD BASE .. 78

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LIST OF TABLES
TABLE 3.1.1: VOLTAGE DROP ACROSS IPMC ELECTRODES ................................................ 14 TABLE 3.1.2: MAXIMUM ANGULAR DISPLACEMENT FOR EACH TEST SAMPLE AND SOLVENT EVAPORATION MEASUREMENTS ................................................................................. 16 TABLE 3.2.1: NANOTUBE PROPERTIES ................................................................................ 21 TABLE 3.2.2: BUCKY PAPER LINEAR ACTUATION PROPERTIES ............................................ 22 TABLE 3.2.3: BUCKY PAPER MECHANICAL PROPERTIES ..................................................... 27 TABLE 3.2.4: SEM AND CONDUCTIVITY ANALYSIS ............................................................ 32 TABLE 3.3.1: MWNT/PVA-HYDROGEL CONDUCTIVITY ................................................... 40 TABLE 3.5.1: POLYANILINE FILM (TRADITIONAL TECHNIQUE) RESULTS. ............................ 61 TABLE 3.5.2: MEASUREMENTS AND RESULTS FOR IPMCS COATED WITH POLYANILINE ... 65

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1 INTRODUCTION
The purpose of this thesis is to further research towards developing and integrating smart material actuators into prosthetic devices. The research conducted in this project will attempt to build off the progress made by many others in the field of smart materials. The main components of this thesis project are threefold: the first being to perform an extensive literature review on targeted smart materials. The second step is to produce, actuate and improve upon what is currently available for use as artificial muscles. Finally, we aim to produce an arm actuated solely by smart materials, which closely resembles a real human arm to attract the attention of industry professionals, inspire interest, and act as a final test of a materials performance. The report has been divided up into three main sections. The Design Criteria for Artificial Muscles section describes the current state of human prosthetics, the typical forces human muscles achieve, and the design criteria for a smart material that could be used as a replacement for electric motors in prosthetics. The next section, Materials Selection and Design, will describe in detail the physical and chemical properties of the smart materials we have targeted: Ionic PolymerMetal Composites, Bucky Paper, Carbon Nanotube Hydrogel, Magnetorheological materials, Conductive Polymers, and Shape Memory Alloys. The macro and microstructure of each material is explored and how stimuli alter this structure to achieve actuation. Recipes for fabrication of the materials are given where possible along with improvements we have discovered to refine the production process. A description of the material testing method and results are given and finally each material is evaluated in terms of its applicability to the prosthetics application. Possible future work is also mentioned. Artificial Arm Design and Integration, the final body section of the report, describes the design and construction of our prosthetics test arm as well as the potential integration of smart materials onto this test vehicle.

2 DESIGN CRITERIA FOR ARTIFICIAL MUSCLES

Everyday over 3 million people in North America go through their daily activities without the full use of one or more limbs [1]. Although small, this population has unique and demanding needs. Through technology, engineers are able to help restore mobility to people who have lost a limb to disease, accident, or war. The long-term goal of this thesis project is to advance research towards a prosthetic arm actuated by smart materials that can one day replace existing technology. The most advanced prosthetics today are known as Myoelectrics. Myoelectrically controlled arm prostheses are externally powered prostheses, which mean that they are not driven by the muscle strength of the patient, but with the aid of electric power. The two most important barriers limiting the current products functionality are weight and space. Only half of all amputees choose to get a prosthetic arm, and half of those who do, stop wearing it after a year [2]. These patients simply do not wear their prosthesis because it is too heavy or cumbersome. Increased functionality with the current technology requires a larger envelope, and a further increase in weight; an increase that is more than what is tolerable for patients. Smart materials are substances that can actuate between two or more states, effectively able to replace the gears and motors required by todays myoelectrics to achieve motion. By using smart materials instead of conventional mechanisms, it is believed that dramatic weight reduction in the prosthetic can be achieved, allowing the possibility for increased functionality and better fulfillment of the patients needs. The responses most critical in the design of actuators are stress and strain. Stress determines the amount of force the actuator can produce, and if it will move at all. Strain governs the amount of actuator movement; the displacement. It also determines the design of material and how it could be integrated into a prosthetic arm. Ideally, the smart material actuators would equal or exceed the stress and strain generated in mammalian muscle. It has been reported that human muscles can generate 350 kN/m2 of stress and strain up to 40% [19]. Smart actuators will be evaluated for their effectiveness within this frame of reference. Not all materials actuate in the same manner. Two possible modes of actuation occur: linear displacement or angular (bending) motion. With this in mind, materials must be chosen to maximize the stress and strain they produce. It is

possible to compensate for deficiencies in one area or the other through mechanical advantage. For example, a material that produces high force but low strain may be connected in series, thereby adding their respective displacements. It is also important that any substitute material not present any dangers to a potential user. For example, some classes of smart materials require massive voltages or acids for material actuation. Obviously, such a material would be impractical in a personal prosthetic.

3 MATERIAL SELECTION AND DESIGN

There are many types of smart materials, categorized according to the stimulus they respond to or the material they made from. Some examples of stimuli include temperature, stress, humidity, pH, electricity, and magnetic fields. This section will describe in detail the physical and chemical properties of the smart materials we have targeted. More specifically, the macro and microstructure of the material is explored and how stimuli alter this structure to achieve actuation. For each material, examples of other researchers designs are examined and how the given material could be used within a prosthetic arm. Finally, recipes for fabrication of the materials are given where possible. A description of the material testing method is given along with a description of the design process used to create a test rig for that purpose. Results and evaluation for each material are included. 3.1 IONIC POLYMER METAL COMPOSITES Ionic polymer metal composites (IPMC) are bending actuators that activate in the presence of an applied low voltage. They were discovered in 1992 by three researchers: K. Oguro, M. Shahinpoor, and S. Sadeghipour who have since that time contributed to the overall advancement of IPMCs as practical actuators. IPMCs are a subgroup of ionic electroactive polymers that actuate on the principal of ion diffusion across the thickness of a polymer [3]. The polymer used for IPMCs consist of hydrophilic nano-channels that allow ions to be hydrated and move within it. Oppositely charged electrodes that are chemically plated onto the polymer produce actuation. When a potential is applied, the hydrated cations within the polymer structure move towards the cathode. This displacement of hydrated cations swells the cathode side of the polymer and shrinks the anode side, which results in the polymer bending towards the anode [12]. There are several advantages to using IPMCs as artificial muscles. The main advantage of IPMCs is that they make use of a solid-state polymer that makes them stable in air. Secondly, a typical 1cm x 4cm x 0.2mm IPMC strip deforms 4cm in 0.5s [4]. This large deformation can be utilized to create linear or rotational motion depending on their arrangement. Lastly, they are inexpensive, costing only $1/cm2 and can be produced in approximately 48 hours [6].

3.1.1 MACRO AND MICRO GENERAL DESCRIPTIONS There are two types of polymers that are capable of performing the ion exchange function required for IPMCs to actuate: styrene/divinylbenzene-based polymers and perfluorinated alkenes. However, due to the rigid nature of the styrene/divinylbenzenebased polymers most research has been focused on using the perfluorinated alkenes due to their flexible properties, which is a result of their hydrophilic nature [4]. A commercially available perfluorinated alkene polymer is Nafion, which is produced by DuPont. As shown in figure 3.1.1, this type of polymer membrane has a large hydrophobic fluorocarbon backbone that determines its strength. The short side chains that are covalently bonded to the backbone end with ionic groups such as sulfonate (SO3-) which are hydrophilic [7, 9]. These ionic groups create hydrated, interconnected, cluster networks that allow cations, that neutralize the groups, to move throughout the networks [7, 9]. Figure 3.1.2 illustrates these interconnected networks when the polymer is hydrated with a solvent.

Figure 3.1.1: Nafion polymer chain neutralized with a Na+ cation [5]

Figure 3.1.2: Two interconnected clusters in a hydrated polymer [9]

Typical cations used to neutralize the ionic groups are alkali-metal cations (Li+, Na+, K+, Rb+, and Cs+) or alkyl-ammonium cations (TMA+, TEA+, TPA+, and TBA+).

Variations in size of these cations determine their mobility through the interconnected polymer networks. For example, TBA+ cations are approximately 1nm in diameter and the network connections are also 1nm in diameter. Due to their similar size the mobility of the cation is hindered [9]. Furthermore, multivalent cations such as Al3+ experience difficulty moving throughout the network, which can be attributed to their extra charges. These charges result in additional electrostatic forces associated with the cations being linked to more than one ionic group [9]. On the other hand, for smaller single charged cations such as Li+ mobility within the network is much easier. Therefore, Li+ and other similar sized and charged cations are generally used for actuating IPMCs. Polar solvents such as water and glycerol have been studied to hydrate IPMCs [7]. The volume of solvent absorbed by the IPMC is dependant on the temperature of the solvent bath during processing, which increases linearly in a temperature range of 0 C to 100 C. The amount of solvent absorbed by the IPMC determines the size of the clusters, therefore directly influencing the mobility of the cations [9]. When considering water as a solvent it is important to note that it evaporates in air and it is subject to electrolysis at electric potentials greater than 1.3V [7]. In contrast, glycerol is approximately 100 times more viscous than water, has a greater molecular weight, and experiences electrolysis at a higher applied electrical potential [7]. These solvent properties determine the stability and performance of the IPMCs in air. The last IPMC component to be discussed are the electrodes. The electrodes are chemically plated onto the polymer and consist of conducting metals such as platinum, gold, silver, carbon, graphite, carbon nanotubes, or a combination of these [4]. For the remainder of this section we will focus on platinum electrodes because the majority of IPMC research utilizes them. Electrode plating is accomplished through initial compositing and surface electrode processing [4]. During initial compositing, the inner boundary of the polymer is transformed to a metallic state up to 20 m deep. This creates a rough non-homogeneous surface with high electric resistance, as shown on the top two images in figure 3.1.3.

Figure 3.1.3: Top left: schematic diagram showing the initial compositing of Pt. Top right: a SEM micrograph of the initial compositing. Bottom left: schematic diagram showing the secondary compositing of Pt. Bottom right: a SEM micrograph of the secondary compositing. [4]

To achieve an electrode with less electric resistance secondary compositing is preformed. This creates an electrode surface that is porous which allow water flow in and out of the polymer membrane as shown in the bottom two images in figure 3.1.3. The average particle size due to platinum coagulation is 27nm [4]. 3.1.2 ACTUATION METHOD IPMCs bend in response to a small DC electric potential applied through the electrodes as seen in figure 3.1.4. According to Sia Nemat-Nasser and Yongxian Wu, this potential generates a thin boundary layer at the anode where the previously discussed interconnected clusters are depleted of their cations. The cations are attracted towards the boundary layer generated at the cathode thus filling the clusters in that region. This migration of cations creates charge imbalances that stimulate changes in the electrostatic forces and osmotic pressures within the clusters. These forces increase the volume of the clusters on the cathode side and decrease them on the anode side creating an imbalanced pressure, thus forcing the IPMC solvent to move from the anode to the cathode. This transfer in solvent swells the cathode side and creates a bending displacement towards the anode, as shown in figure 3.1.5 [9, 10].

Figure 3.1.4: A demonstration of the deformation capability of a 1cm x 4 cm x 0.2mm IPMC [4]

Figure 3.1.5: An illustration demonstrating cation and solvent movement within the polymer infrastructure causing bending actuation [4]

3.1.3 IPMC MANUFACTURE The general procedure that was followed to manufacture IPMCs is provided by Mohsen Shahinpoor in his work entitled Recent Advances in Ionic Polymer Conductor Composite Materials as Distributed Nanosensors, Nanoactuators and Artificial Muscles. The first step involved in producing an IPMC is roughening the ion-exchange polymer (Nafion) surfaces by hand sanding using a very fine grit sand paper. This step was performed to increase the surface area of the polymer. The second step in the process is to diffuse a metal salt throughout the polymer. This was achieved by placing the Nafion strip in a stirring bath of Pt(NH3)4]Cl2 solution for more than one hour. The third step is performed to produce platinum electrodes on the surfaces of the polymer. This is accomplished through chemical reduction where the metal salt diffuses to the surface of the polymer and reacts with a reducing agent to transform the platinum complex cations to a metallic state. This reduction is completed by adding a 5 wt%

solution of sodium borohydride to the Nafion strip in a water bath at 40 C for 5 hours while gradually raising the temperature of the bath to 60 C. Further development of the platinum electrodes on the surface of the polymer is completed to reduce electrode resistivity and surface pore density where a solvent can leak out. To carry out this fourth step a hydroxylamine hydrochloride solution and a hydrazine solution are added at 30 min intervals to a Pt solution at 40 C containing the Nafion strip. During this process the temperature is gradually raised up to 60 C over 4 hours. The fifth step checks to see if all of the Pt in the solution of step four has been plated onto the polymer. This can be done by taking a small sample of the solution made in step four and boiling it with sodium borohydride. If the boiled solution turns black then the fourth step should be continued until the remaining Pt has been used. If the sample solution does not change colour then the IPMC process has been completed [12]. The process diagram shown in figure 3.1.6 provides the step-by-step procedure to make an IPMC.

Cut 30cm2 sheet of Nafion polymer

IPMC
(Ionic Polymer Metal Composites)

Rinse polymer with water and place in stirring bath of 180mL of deionized water at 40 C Prepare 34mL of 5 wt% solution of sodium borohydride then add 2mL to the stirring bath every 30 min, 7 times while increasing the temperature to 60 C

Sandblast surface of polymer approx. 1 sec/cm2 or Sand with emery paper

Wash polymer using a ultrasonic cleaner

Prepare 90mL of Pt solution with 2 mg Pt/ml (excess solution is preferred) then immerse polymer Follow with the addition of 1mL of ammonium hydroxide solution (5%)

Boil polymer for 30min in dilute 2N HCl, then rinse with deionized water

Keep polymer in solution at room temperature for more than 3 hours

After 3.5hr add 20mL of sodium borohydride and stir for 1.5hr at 60 C

Boil polymer for 30min in deionized water

Rinse polymer with deionized water and Immerse in hydrochloric acid (0.1N) for 1 hour

Nafion Sheet

Prepared Base Polymer

Ion Saturated Polymer Plated Polymer

IPMC

Polymer with Electrodes

Boil polymer in 0.1N hydrochloric acid

If boiled solution turns black continue secondary plating if not then remove polymer from solution and rinse with water

Place the polymer in the Pt solution at 40 C and add 6mL of hydroxylamine hydrochloride and 3mL of hydrazine hydrate every 30min while raising the temperature up to 60 C over 4hrs.

Prepare 48mL of 5% hydroxylamine hydrochloride and 24mL of 20% hydrazine hydrate

Sample a small amount of the Pt solution and add sodium borohydride, then boil DO NOT ADD SODIUM BOROHYDRIDE AFTER BOILING

Prepare a 240mL solution containing 120mg of Pt and 5mL of 5% ammonium hydroxide Source: http://ndeaa.jpl.nasa.gov/nasa-nde/lommas/eap/IPMC_PrepProcedure.htm

Figure 3.1.6: Traditional fabrication of an IPMC actuator

3.1.4 TESTING EQUIPMENT Two separate devices were used in the testing of our IPMC samples. One test rig has been designed and manufactured to facilitate linear displacement testing while a second device was used specifically to quantify the bending motion. 3.1.4.1 LINEAR TEST RIG DESIGN Any successfully fabricated sample needs to be quantified in terms of the actuation achieved. To accomplish this, a test rig has been designed that can measure the linear variation in a sample piece and therefore determine the strain. The sample is held in place by the two horizontal locking clamps (clamps not shown in Figure 3.1.7). One clamp is attached to the top cross beam and the other to the sheet metal carriage. The material is actuated, and as it changes size, one end of the material is free to slide along the track. A Linear Variable Displacement Transducers (LVDT) is fixed to the cross beam by a shaft support clamp and also attached to the moving carriage. As the carriage moves, the LVDT measures the relative change in position. By this method, we should be able to determine the resulting strain for any input actuation method (current, magnetic field, etc.) for a sample piece.

Figure 3.1.7: Test Rig CAD model

3.1.4.2 BENDING TEST RIG DESIGN Since IPMCs and some of the other materials we were focusing on actuate by a bending motion rather than a strict linear strain, it is necessary to quantify this bending 10

action. This was accomplished using the bending rig shown in Figure 3.1.8. Basically, a clamp, identical to the one used in the linear device, is attached to the Clamp Mount beam. The measuring device is simply a 360 protractor, cut to facilitate mounting. The sample is held from one end and left hanging down in front of the protractor. Electrical leads were placed between the beam and the sample, and between the clamp head and the sample to charge each side of the IPMC. Tinfoil was wrapped around the Clamp Mount in the sample area to increase conductivity to the samples. From this vantage point, when the material is actuated, the bending motion can be easily quantified.

Figure 3.1.8: Bending rig CAD model

3.1.5 TESTING PROCEDURE All tests performed on the in-house manufactured IPMCs and the premade IPMCs purchased from Environmental Robots Inc. were on samples measuring 27.5mm by 2.5mm. The in-house samples were cut from the larger sheets produced using the method described above using a sharp scalpel. During manufacturing all surfaces of the IPMC, including edges, are plated with platinum. Therefore, it is important to ensure that all 11

edges are cut to remove connections between the two electrode surfaces that would lead to a short circuit during testing. Once the samples were cut they were immersed in deionized water for 1 hour before testing to ensure that they were fully saturated. The angular displacements of the IPMC samples were measured using the bending rig arranged as shown in figure 3.1.9. The cathode wire was pinched directly between the right side of the IPMC and the clamp. However, the anode wire was simply touched to the tin foil that was in place between the IPMC and the bending rigs aluminum support arm. During preliminary testing it was found that just clamping the IPMC to the surface of the aluminum would result in oxidization on the surface of the aluminum when a current was passed through the support arm. This oxidation impeded current flow and contaminate the IPMC sample. Therefore, it was necessary before each test to cover the arm with a new sheet of tin foil and use that as the contact surface to the IPMC.

Figure 3.1.9: Bending test rig setup

In addition to measuring the angular displacement, the mass of solvent that evaporates during actuation was evaluated. The procedure followed for testing the IPMC samples is as follows: 1. IPMC was cut into a 27.5mm by 2.5mm strip and then immersed in de-ionized water for 1 hour. Once fully saturated the IPMCs mass was measured and then

12

the sample was placed in the bending test rig in the configuration described above. 2. A 7 volt step was applied to the sample until the displacement stopped. Once the IPMC stopped the voltage was disengaged and the sample was allowed to settle back to its relaxed position. 3. During actuation a digital multimeter was used to take readings on the IPMC electrode surfaces to determine the actual voltage applied to the sample. 4. Step 2 was repeated until change in the magnitude of angular displacement between tests was minimal. 5. The IPMC sample was removed from the test rig and then the mass was measured again. 3.1.6 RESULTS AND EVALUATION Following the above described manufacturing procedure two 30cm2 IPMC batches were produced. The first in-house sample was made using inaccurate equipment such as a basic hotplate where temperature could only be monitored using an alcohol thermometer. This made the steps that required a constant increase in solution temperature very difficult to reproduce and inconsistent with the manufacturing recipe. In addition, coarse sandpaper was used for initial surface roughing that created deep inconsistent scratched surfaces as seen in figure 3.1.10. The second in-house IPMC sample was produced using a programmable digital hotplate from Cole-Palmer, model number EW-04646-00, with a submergible temperature probe. Using this equipment temperature ramp rates and heat and stirring times given by the manufacturing recipe were followed a greater degree of accuracy. In addition, the polymer surfaces were roughened using very fine sandpaper. This allowed for greater control of the scratch depth uniformity throughout the sample as shown in figure 3.1.11.

13

Figure 3.1.10: 1st in-house manufactured IPMC

Figure 3.1.11: 2nd in-house manufactured IPMC

The IPMC samples were actuated using a 7V direct current. Most tests conducted by other researchers in the past have used small potentials in the range of 1-2V to actuate their IPMCs [4]. The reason for using such a high potential for our experiments was that during preliminary testing little to no actuation was observed with the application of a small potential, this indicated that there was very high resistance in the setup of the testing rig. Using a 7V potential and testing the voltage drop across the two electrode surfaces of the IPMC this assumption was confirmed for all three samples as shown in table 3.1.1. The samples actuated with a higher applied voltage however the potential seen by the samples was significantly less than 7V. Therefore, when the samples were actuated with a 1-2V potential the voltage drop across the electrodes was fractional which produced insignificant actuation.

In-house 1st batch Voltage drop across IPMC electrodes 4.6V

In-house 2nd batch 1.4V

Premade batch 5.8V

Table 3.1.1: Voltage drop across IPMC electrodes

Angular displacement with respect to time was recorded using a digital camera situated in front of the bending test rig. The videos produced during testing were analyzed in one-second intervals using a basic video viewing program. In general it was observed that when a DC potential was applied to the 27.5mm by 2.5mm IPMC samples there was a fast bending response toward the cathode. Once maximum displacement was reached and the circuit was shorted the IPMC returned slowly towards the anode. Figures 3.1.12 a), b), and c) display the displacement results

14

of the repeat actuation tests for all three test samples. In all the cases it was observed that the sample tips did not return to their initial starting positions. This can be attributed to low solvent content decreasing the size of cluster channels thus inhibiting the mobility of cations [11]. Therefore, it is speculated that once the cations move to one side of the IPMC they are in essence trapped in that area due to the narrow channel sizes.

a) 1st in-house manufactured IPMC

b) 2nd in-house manufactured IPMC

c) Environmental Robots Inc. premade IPMC

Figure 3.1.12: IPMC repeat actuation test using a 7V potential

When the IPMC samples were actuated multiple times in succession during a test it was found that the angular amplitude decreased with each activation, which can be seen in table 3.1.2. This correlates with findings made by other researchers that solvent evaporation increases the stiffness of a sample [8]. In addition, the amount of solvent loss in each test sample correlates to their performance. For example, as shown in table 3.1.2, the 2nd batch of in-house manufactured IPMCs lost the least amount of de-ionized water (0.0037g) throughout the test and as a result produced the largest amplitude during 15

repeated actuation. On the other hand, the premade IPMCs lost a lot of de-ionized water (0.0061g) during actuation and consequently did not perform very well.
1st activation In-house sample #1 In-house sample #2 Premade 53 53 27 2nd activation 49 57 34 3rd activation 38 57 28 4th activation 33 61 N/A 5th activation N/A 49 N/A

De-ionized water loss 0.0042g 0.0037g 0.0061g

Table 3.1.2: Maximum angular displacement for each test sample and solvent evaporation measurements

Due to the rough nature of the IMPC electrodes as shown in figure 3.1.13, resistance increases as the distance between two points on an electrode surface increases as confirmed by the work completed by Wu [14]. This increase in resistance along the surface of an IPMC explains why bending is localized to the contact points where the DC potential is applied to the sample, as shown in figure 3.1.14. Thickness is another electrode feature that has a significant impact on the actuation of an IPMC. A thick electrode increases the stiffness of a sample, which decreases actuation performance. On the other hand, a thick uniform electrode increases performance by reducing the amount of solvent that escapes the sample [4]. Therefore, to optimize IPMC performance a balance between electrode thickness and uniformity must be achieved. Evaluating the scanning electron microscope (SEM) cross-section images, the thicknesses of the first in-house manufactured, second in-house manufactured and premade IPMCs were determined to be 4m, 2.38 m, and 5.56 m respectively. The electrodes of the two in-house manufactured samples were thin in comparison to the premade sample and the surfaces were porous and uneven which should have produced poor actuation during testing. However, it was found using the SEM that the samples have a high electrode surface area that is in contact with the polymer surface in the form of grooves and spears, which were produced by sanding and reduction during manufacturing. The white areas on the SEM cross-section images indicate the platinum electrode features. This finding shows that increasing surface area improves angular

16

displacement to a greater degree then creating a uniform thick electrode to minimize solvent loss. In addition, the surfaces of the manufactured IPMCs shown in figures 3.1.13 a) and b) closely resemble samples produced by other researchers as shown in figure 3.1.3. Comparing these results it can be seen that the first in-house manufactured IPMC is the same as the bottom right image in figure 3.1.3 except shown at a different magnification. This indicates that the electrodes on the first in-house manufactured IPMC were more developed than the second in- house batch, which closely resembles the top right image in figure 3.1.3. Thus, reaffirming that thick electrodes do not improve actuation performance.

Pt electrode

Nafion

(cross-section) a) In-house manufactured IPMC, batch #1

(surface)

Nafion

Pt electrode

(cross-section) b) In-house manufactured IPMC, batch #2

(surface)

17

Pt electrode Nafion

(cross-section) c) Premade IPMC

(surface)

Figure 3.1.13: Cross-section and surface SEM images for all three samples

Figure 3.1.14: Example of IPMC localized bending

3.1.7 FUTURE RESEARCH It is difficult to make use of the bending actuation of an IPMC in its elementary form. Therefore, to facilitate their use in a prosthetic application they must be manipulated so that a useful form of actuation can be produced. Linear displacement can be achieved by connecting together two rigid nonconducting disks using several IPMCs as shown in figure 3.1.15 [12]. This configuration creates a linear displacement when the IPMCs actuate by bringing the two disks closer together. In addition, a similar design proposed by Yamakita, et al. combines several elementary IPMC units as shown in figure 3.1.16 to form an array that could potentially

18

produce large displacements. An investigation should be conducted to determine the magnitude of the forces and displacement that can be produced by both types of arrangements.

Figure 3.1.15: Simple linear displacement device [12]

Figure 3.1.16: Setup of IPMC array to produce linear displacement [56]

In addition to linear motion the concept presented in the paper entitled Limitedangle motor using ionic polymer-metal composite to achieve rotational motion [13] should be explored further. This concept mimics the actuation produced by a coiled spring in devices such as pocket watches. The device is arranged so that an IPMC strip is rigidly attached and placed into a case with the other end attached to a shaft, which is also in the case. In the casing the IMPC is loosely coiled around the shaft so that when it is activated it tightens and rotates the shaft [13]. This arrangement can be seen in figure 3.1.17.

Figure 3.1.17: Limited angle rotational device [13]

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Force measurement was a particularly difficult problem as the forces involved are extremely small and predominantly in a bending mode actuation. Several options were considered, from piezoelectric to air flow force measurement. In the end a sensor from SensorOne was determined to be capable of measuring such small forces. The AE-801 Micro Force Sensor is a cantilevered device capable of measuring up to 0.12 N (figure3.1.18). It makes use of the piezoresistive effect of silicon, employing two silicon resistors whose values change under stress. An electrical output signal is used to determine the stress. Two were purchased with the intent of incorporating them into the bending displacement and linear displacement measuring devices.

Figure 3.1.18: AE 801 Micro force sensor from SensorOne

Lastly, future work should be focused on enhancing the IPMCs material properties and performance. For example, to practically actuate a prosthetic limb the forces produced by the IPMC need to increase along with actuation and relaxation speeds. Furthermore, the capability to cycle actuation needs to be improved by addressing the solvent evaporation issues. A human limb repeats any given motion hundreds of times a day therefore the material durability and actuation repeatability is of great importance.

3.2 CARBON NANOTUBES 3.2.1 GENERAL NANOTUBE CHARACTERISTICS Carbon nanotubes have the potential of generating substantially higher mechanical stress and higher work per cycle than any actuator currently available. As of

20

yet, they have yet to live up to that potential. Nanotubes have performed two possible functions in material actuators to date. One, they may be fabricated into a macroscopic sheet, to form an actuator in and of themselves. Two, they may be used as reinforcement in other smart materials, forming composites. The immediate benefit of the composite is increased modulus of elasticity. Theoretically nanotubes are ideally suited for composite reinforcement (table 3.2.1). Their excellent electrical conductivity may also be put to use.

Material Single wall nanotube Multi wall nanotube

Young's modulus (GPa)

Tensile Strength (GPa)

Density 3 (g/cm ) 1.331.4

Diameter (nm)

Length (m)

Resistivity (cm)

Thermal Conductivity (W/m/K)

1054 1200

150 150

1.0 - 10

1x10-4

2000

2.6 10 0.1 - 10 Table 3.2.1: Nanotube properties *Note that these values vary and are approximations only [42,43,44]

3.2.2 ACTUATION METHOD Actuation occurs in the presence of an electrolyte and under an applied voltage. Individual nanotubes undergo this actuation, translating to the macro actuation of a nanotube sheet. Applied voltage injects an electric, non-faradiac charge into the nanotubes, resulting in a geometric expansion of carbon-carbon covalent bonds [3,30]. The electrolyte compensates with the charge to form an electric double layer at the interface of the nanotube and electrolyte [29,30]. The expansion is a combination of this electrostatic (electric double layer) and quantum chemical effects (change in band layer occupation). Essentially, the carbon atoms repel each other, increasing the length of the nanotube. One group of researchers in Germany has characterized the out of plane displacement of a single sheet of bucky paper in the thickness direction. However this is of little use to us, as the actuation is very small [35]. The actuation time is approximately 3 seconds, and should be similar for other actuation modes, such as elongation along the

21

length. For paper coated in electrolyte the strain generated along the length is as high as 1% [3, 40]. Saturating the paper will result in losses of mechanical and activation properties (table 3.2.2 and table 3.2.3) [29,33,34]. Submerged, saturated paper results in strains of approximately 0.2% or less, figure 3.2.1 [34]. The stress at this value is 0.75MPa, which is twice that of human muscle. After several cycles the material will exhibit a reduction in actuation properties (figure 3.2.2, 3.2.3). However, more recent results have shown that actuation cycles much higher than those listed can be obtained without significant loss. In regards to the actuation, there is a dependency on voltage, electrolyte concentration, and the thickness of the bucky paper. The best results appear with V=1 (max before breakdown), electrolyte concentrations around 1M (for NaCl), and larger thicknesses are generally better [35, 40]. Thicknesses typically range from 15 150m, and affect the response time.

Displacement Type

Strain

Stress (linear)

In-plane, along <1% length * (<0.2%saturated) 0.75MPa Table 3.2.2: Bucky paper linear actuation properties * 32 mm long, 1-2 mm wide, 15-35 m thick paper (-0.5 to 1 .5 V vs. SCE)

Figure 3.2.1: CNT sheet linear actuation strain (submerged in electrolyte) [34]

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Figure 3.2.2: Linear actuator strain for bucky paper sheet (-0.5V to 1.5V, 0.1Hz, after 30 cycles) [39]

Figure 3.2.3: Linear actuation stress for bucky paper sheet (-0.5V to 1.5V, 0.1Hz, after 30 cycles) [39]

Making use of the elongation actuation is another important issue. The flexible bucky paper cannot withstand a compression force and will bend. Thus the CNT sheet would have to be charged until the motion was desired, the power would be turned off and the paper would contract. Due to flexibility the bucky paper sheet cannot return the system to the original state through actuation. For the single sheet actuator the setup seems to be more complicated. It appears that a counter anode would have to exist in the liquid electrolyte, in addition to the cathode and anode attached to the bucky paper [40]. Another design that has been used is the bi-strip, or cantilever strip actuator [3,29,32,37]. By laminating two pieces together, a cantilever strip actuator can be created. A strip actuator consists of two pieces of bucky paper bonded together by an electrically insulated tape, figure 3.2.4. In this form, the two pieces of bucky paper act as 23

the electrodes and the electrolyte balances the charge. For the electrolyte, 1 M of NaCl seems to be a common choice [35, 39], while Na2SO4 is also used in a 1M concentration [40]. The actuator can be dipped into the electrolyte, or submerged and actuated. A solid electrolyte paste should be applicable to this design. One sheet of bucky paper is charged negatively (with positive sodium counterions) and the other positively (with negative chloride counterions). Under an applied voltage, both CNT sheets expand, but the positive side will expand more, resulting in a bending motion [32]. For actuation 1V is required. The actuation is an expansion and bending actuation, resulting in linear length changes that seem to counteract one another. The change in the film length, as measured by the setup in figure 3.2.12 was very small (0.04%) as seen in figure 3.2.5. Considering the test setup, the value does not seem indicative of the total deformation, bending and lengthening, of the system. Experimental analysis and further research should clarify the situation and determine values for stress and strain.

Figure 3.24: Bi-strip/Cantilever strip actuator [30]

Figure 3.2.5: Bi-strip/Cantilever linear CNT sheet strain (1M NaCl, about V=0) [29]

3.2.3 ORIGINAL RECIPES Fabrication of the bucky paper is a fairly straightforward process. It is, however, dependent on the quality/type of nanotubes available. Poor quality nanotube, fibres, or bucky pearls [36] require a more extensive fabrication process. For mostly pure, untangled, nanotubes a simpler process should be sufficient. Figure 3.2.6 shows the recipe as derived from articles and journals listed on the recipe. However, changes were necessarily made to account for the materials and equipment available. Figure 3.2.7

24

illustrates the apparatus suggested for making the bucky paper, but once again it was not utilized. Note that the recipe also contains the procedure for the construction of the bistrip/cantilever strip actuator. For this project thin MWNTs (95% purity) with a COOH surface modification were obtained from Nanocyl. Pristine nanotubes are insoluble in many liquids, solvents, and resins. The surface modification, or functionalization, not only allows the nanotubes to disperse in a liquid but results in stronger bonding of the nanotubes [41]. The nanotubes were dispersed in a 1% solution of the surfactant Sodium Dodecyl Sulfate. A surfactant is used to lower the surface tension in a liquid. For the electrolyte, 1M of NaCl or a solid paste electrolyte may be utilized.

Bucky Paper
Materials MWCNT/SWCNT High Purity Sodium Dodecyl Sulfate (SDS) 10% Solution [8] Filter Paper Teflon 3.75 cm dia, 0.45m pore size [9] Deionized Water Double Sided PVC tape 1M NaCl
Add 1mg of MWNT for every mL of SDS. [8, 10] Vacuum filter through filter paper. Figure 9: Filtering Apparatus

Prepare a 50mL 1% solution of SDS Add 45mL of deionized water to 5mL of 10% SDS solution. [8]

Sonicate for 3 minutes using a step cycle (on 10s, off 10s) [11]

Heat nanotube sheet in 80C to 100C, for 3 hours or until dry [9]

Attach two strips of Bucky Paper to either side of the PVC tape. PVC tape should be slightly larger than the paper strips. [2]

Connect electrodes to power source. (Bucky paper acts as the electrodes).

Prepare Electrolyte: Liquid: 1M NaCl Paste:

Place in or coat the electrolyte onto the bucky paper

Apply 1 V for actuation

Figure 3.2.6: Bucky paper fabrication recipe

25

Figure 3.2.7: Apparatus for the fabrication of bucky paper [37]

3.2.4 BUCKY PAPER PROPERTIES Nanotubes can be used in a macroscopic structure called bucky paper. Bucky paper is a freestanding film of bundles of nanotubes [32]. These bundles or ropes of nanotubes entangle to form the paper (figure 3.2.8).

26

Figure 3.2.8: Bucky paper electron micrograph [32]

The mechanical properties of the bucky paper are dependent on the structural and interfibre bonding of the nanotubes [33]. The structural bonding includes the entanglement and bundling of the nanotubes. Interfibre bonds refer to those that occur at the points of contact between nanotubes (bundles). They may occur as chemical, physical or capillary bonds. The joint strength can be increased through functionalizing and/or welding. For bucky paper the resulting elastic modulus and tensile breaking strength ranges from 0.6 4.2 GPa and 6.3 33 Mpa, respectively [33]. One study determined the properties for MWNT paper in air and water to be those summarized in table 3.2.3, from figures 3.2.9 and 3.2.10 [33].

Bucky Paper in Air Water

Average Elastic Modulus (GPa) 2.15 1.32

Average Tensile Breaking Stress (MPa) 11.2 15.1

Table 3.2.3: Bucky paper mechanical properties [33]

27

Figure 3.2.10: Bucky paper failure strain [33] Figure 3.2.9: Bucky paper tensile stress [33]

Earlier experiments found smaller Youngs modulus and ultimate stress for SWNT to be approximately of the results above, indicating the variability in the material properties. However, the nanotubes and process in making the paper was not as refined. 3.2.5 RECIPE REVISIONS Sample 1 The first sample was made using a very close approximation to the recipe in figure 3.2.6. Two modifications were made. First, the fabrication apparatus consisted of a Nalgene Disposable Filter Unit, 7.5cm diameter, Polyethersufone filter with 0.2m pore size and water driven aspirator pump. Overall, the apparatus served the same function as that in figure 3.2.7. The second modification was made to the sonicating step. Sonicating was done for 80 minutes, since no step cycle existed. This first trial revealed two significant errors. Filtering the nanotube solution did not produce a thick enough deposit and the sonicating did not effectively break up enough of the MWNT clumps.

Sample 2 The second sample followed the previous recipe, but implemented two additional changes. First, the solution volume was increased to 200mL. Second, the nanotubes were homogenized after addition to the SDS solution, not sonicated. The homogonizer

28

was a Tissue Miser from Fisher Scientific, capable of 5000-30000 rpm. Homogonizing produced a thick foam on the surface of the solution, which was not desirable for filtering, yet did not cause any significant issues. A significant portion of the nanotubes were not deposited on the filer itself, but along the periphery: probably due to some settling that occurred while filtering the entire mixture. Upon vacuum filtering the entire Nalgene filter unit was placed in an 80C oven for 3 hours, as specified in the original recipe. The result was a slightly cracked and deformed filter. Due to this cracking, removing the nanotube sheet from the filter proved to be more difficult than just peeling it off. A scalpel was used to separate the two layers, slowly separating away the largest pieces of bucky paper possible. The results will be discussed more thoroughly in the next section.

Sample 3 A third and final sample was made from the recipe in figure 3.2.11. In the previous recipe, the solution remained very dark after filtering out the nanotubes. This indicated a high level of impurities, mostly in the form of carbon. Articles have previously mentioned that impurities severely inhibit the actuation of the bucky paper [35]. Numerous articles have used acid as a means of cleaning and functionalizing nanotubes. In some cases HCl was used to clean [35], while in others a mixture of 3:1 v/v nitricsulphuric acid was used to clean and functionalize with COOH [34, 35, 57]. It was thought that this step was unnecessary since the purchased nanotubes were functionalized with COOH. For bucky paper functionalization is not critical but aids in nanotube

bonding strength. For this sample, the nanotubes were added to a solution of 10% hydrochloric and 1M nitric acid (1:1 v/v) and brought to 80-90C. After this cleaning and likely some functionalizing, the nanotubes were filtered through standard cellulose filter paper, and rinsed with deionized water. The nanotubes were then dispersed in the SDS solution. The mixture was homogenized for 5 minutes, left to stand for 5, and then homogenized for another 5 minutes. Filtering in the Nalgene filter apparatus was done more slowly than in the previous sample. The mixture was not poured into the filter all at once. It was hoped that pouring in smaller volumes would allow less settling to occur off the filter, thus reducing wasted nanotubes. To combat the cracking of the filter, a less

29

intensive drying process was used. The Nalgene filter and nanotubes were allowed to partially dry for 15 minutes at room temperature. The filter device was placed in an 80C oven for 15 minutes, and then removed for 10min to 50C with a glass beaker placed on the sheet and weighted down. It was then allowed to cool briefly at room temperature. The process was repeated three times until sufficiently dry. The filter device was left at room temperature overnight. The uncracked/undeformed filter was removed the following day using a scalpel, much in the same way as the previous sample but with significantly improved results. The entire 7.5cm diameter sheet was removed as one piece.

Bucky Paper Revised

Materials MWNT High Purity Sodium Dodecyl Sulfate (SDS) 10% Solution [8] Filter Apparatus Nalgene Disposable Filter Unit, 7.5 cm dia Polyesthersufone, 0.2m pore size Deionized Water Double Sided PVC tape 1M NaCl
Prepare a 200mL 1% solution of SDS. Add 180mL of deionized water to 20mL of 10% SDS solution. [8] Boil in acid solution (80-90C). 10% HCL mixed with 1N Nitric acid in a 1:1 v/v ratio. Homogonize 5 minutes, stop for 5, on for another 5 minutes

Add MWNTs. 1mg for every mL of SDS. [8, 10]

Vacuum filter through Nalgene filter apparatus. Do not pour all of the mixture at once. Instead pour slowly or in stages.

Place filter apparatus in 80C oven for 15min. Remove to 50C for 10min. Cool briefly in air, and repeat x2.
Attach two strips of Bucky Paper to either side of the PVC tape. PVC tape should be slightly larger than the paper strips. [2]

Connect electrodes to power source. (Bucky paper acts as the electrodes).

Prepare Electrolyte: Liquid: 1M NaCl Or paste electrolyte.

Place in or coat the electrolyte onto the bucky paper

Apply 1 V for actuation

Figure 3.2.11: Bucky paper revised recipe

3.2.6 TESTING PROCEDURE There are a variety of options for testing the bucky paper. In this report the tests were primarily qualitative. The brittleness of the paper and observation of the filtrate are two examples. Quantitative tests include conductivity and thickness testing. Thickness was determined using a Scanning Electron Microscope (SEM). Conductivity was determined by cutting samples of specific lengths and width, measuring the resistance

30

between the two ends, and calculating the resultant conductivity. Further tests that were not conducted include tensile strength and actuator tests. The actuator can be tested for force generation using the equipment designed for this thesis. Displacement may be more difficult, but a suggested setup can be seen in figure 3.2.12.

Experimental set-up used for the measurement of the dependence of SWNT sheet length on applied potential The Bucky Paper is set on a double-sided sticky The tape is immersed into an electrolyte (salt water), the bucky paper is used as a working electrode and connected to a potentiostat,

Figure 3.2.12: Bi-strip/Cantilever testing apparatus [31]

3.2.7 RESULTS AND EVALUATION Samples 2 and 3 will be considered in the following discussion. Sample 2 produced bucky paper flakes. Only small pieces (Figure 3.2.13) could be recovered from the 7.5cm diameter filter. The pieces were extremely brittle. Sample 3 proved to be a marked improvement. The bucky paper recovered from the filter was an intact 7.5cm circle. It was also extremely flexible (Figure 3.2.14), bending tip to tip without permanent damage.

31

Figure 3.2.12: Sample 2 fragments

Figure 3.2.13: Sample 3 sheet bending

Measurements were taken as seen in table 3.2.4 to obtain values for conductivity. For the thickness, SEM images were used. The results show that the paper is extremely conductive, which was expected based on CNT properties. The conductivity values for the two samples are very close despite measuring errors, primarily in the thickness. Some interesting observations can be made from the SEM images. First, there is a clear layering effect seen in figure 3.2.14 and 3.2.15. The layers appear to be uniformly and tightly bonded, though a higher resolution SEM should be conducted. Furthermore, the surface images (figure 3.2.16, 3.2.17) also compare rather well to those from Cheap Tubes Inc (figure 3.2.18 and figure 3.2.8).

Thickness (m) Sample 2 Sample 3 50 85

Length (mm) 18.6 17.6

Width (mm) 8.64 8.45

Resistance () 27.67 23.3

Conductivity (S/m) 1556.0 1051.7

Table 3.2.4: SEM and conductivity analysis

32

Figure 3.2.14 C: Sample 2 edge

Figure 3.2.15 D: Sample 3 edge

Figure 1.2.16 E: Sample 2 surface

Figure 3.2.17 F: Sample 3 surface

Figure 3.2.18 G: Purified MWNT from Cheaptubes [59]

33

3.2.8 Suggestion of Future Work

Three components are still to be explored. First, the recipe should be refined. The effects of drying and boiling in acid should also be determined separately. Second, the bucky paper should be characterized more intently. Comparisons of tensile strength and impurities to previous papers are two examples. Finally, the actuator needs to be assembled and its performance should be characterized in terms of its force and displacement. Future designs should consider a rolled sheet of bucky paper. Rolling the paper, thus increasing the length, can produce larger actuations. An electrolyte paste should be sufficient for actuation. Nanotube actuators have high activation forces and relatively low strain. The challenge in design is to exploit the benefits and minimize their drawbacks.

34

3.3 MULTI-WALL NANOTUBE HYDROGEL 3.3.1 GENERAL FABRICATION CHARACTERISTICS MWNT/PVA Hydrogel has two main constituents: nanotubes and poly vinyl alcohol (PVA). A technique of repeated freezing and thawing transforms the PVA from a liquid into a gel. MWNTs serve not only to reinforce the gel, making it stronger, but will yield an actuation if properly treated. For actuation to occur, the nanotubes had to be converted to sodium salts, MWNT-COONa denoted as Na-MWNTs. For this conversion to occur a carboylic acid functionalization must first be present on the nanotubes. The functionalization can be accomplished by sonicating MWNTs in a 3:1 v/v nitric-sulphuric acid solution at 50C for 5 hours [57]. However, the MWNTs ordered from Nanocyl were functionalized with carboxylic acid (COOH). MWNT-COOH was converted to sodium salts MWNT-COONa (or Na-MWNT) using a solution of NaOH [57]. Consulting with the chemistry department, it was determined that it should be possible to simply add the MWNT-COOH to a <1M solution of NaOH, resulting in Na+ ions attaching to the carboxyl chain. The NaOH solution was heated to 60C prior to MWNT addition. It was unclear whether the nanotubes should be filtered and rinsed after creating the salts. The chemistry department suggested it may not be necessary, but if so, distilled water or methanol might be appropriate. In any case, properly functionalizing with Na+ ions will result in actuation. If the MWNTs are not converted, no actuation will occur. 3.3.2 ACTUATION METHOD An electric field and electrolyte is required for actuation of the MWNT/PVA composite hydrogel. A field strength of 10V/cm and 3mM of Na2CO3 is suggested [57]. It should be noted that no actuation occurs in pure PVA gel and only minimal actuation with non-functionalized nanotubes. The Na-MWNT/PVA composite, on the other hand, results in significant and rapid actuation as seen in figure 3.3.1. The actuation mechanism is different than that for bucky paper, but is very similar to the actuation principle of IMPCs. Florys theorgy of osmotic pressure is the method of explanation [57]. Osmotic pressure is defined as The pressure exerted by the flow of water through

35

a semipermeable membrane separating two solutions with different concentrations of solute. (American Heritage Dictionaries). Florys theorgy appears to deal with the fact that polyelectrolyte gels swell and shrink at certain sections in the presence of an electric field, resulting in bending. In Na-MWNT/PVA hydrogels the MWNTCOO- serves as the polyions with negative charges, while the Na+ serve as counterions [57]. When subjected to a DC electric field the counterions inside the hydrogel strip move to the negative electrode, the polyions are immobile. Mobile ions in the surrounding solution move into the hydrogel strip, attracted by opposite charges to their counter electrode. The result is that the osmotic pressure near the positive electrode side becomes larger than that near the negative side. The positive side swells to produce a bending mode actuation (figure 3.3.1). If the field is reversed, bending will occur in the opposite direction.

Figure 3..3.1 : Na-MWNT/PVA composite Actuation (10% wt loading, 3mM Na2CO3 solution, 10V/cm electric field at a) 0 and b) 30s)

36

3.3.3 ORIGINAL RECIPES Articles were not very explicit in their description of the material fabrication, thus some inferences were required. The original recipe was derived as seen in figure 3.3.2. Once again, the nanotubes were purchased with the carboxylic acid (COOH) functionalization, but this could have been done in the lab by sonicating with 3:1 v/v nitric-sulphuric acid for 5 hours at 50C [57, 58]. This step would also help to remove impurities.

MWNT/PVA Hydrogel
Materials 10% PVA solution MWNT-COOH Glass troughs 3mM Na2CO3 Solution

Convert MWNT-COOH to sodium salts, MWNT-COONa (Na-MWNT) and aqueous NaOH

Prepare 10% PVA solution

Add 10% (w/w) of NaMWNT aqueous dispersion to 10% PVA solution

Sonicate for 10 minutes at room temperature

Heat mixture to 80C

Repeat freezing and thawing 3 times

Warm frozen mixture at room temperature for 12h

Freeze mixture for 12 hours at -20C

Pour mixture into glass troughs

Transfer mixture to a rotary evaporator at 50C for partial water evaporation. Solution should return to 10% PVA concentration

At room temp cut strips 20mm long, 5mm wide, and 0.6mm thick. (The gel will have swelled at room temp)

Prepare 3mM Na2CO3 solution (electrolyte)

Immerse strips, connect electrical connections, Apply 10V

Source: Shi J, Guo Z, Zhan B, Luo H, Li Y, Zhu D, Actuator Based on MWNT/PVA Hydrogels The Journal of Physical Chemistry Letters B (109), 14789-14791, 2005

Figure 3.3.2: MWNT/PVA hydrogel recipe

3.3.4 RECIPE REVISIONS Several adaptations to the original recipe were required, some due to a lack of information. The revised recipe is shown in figure 3.3.3. First, 5 grams of nanotubes were added to a 50mL of 0.25M NaOH. The NaOH concentration was determined based on suggestions by the chemistry department. However, the nanotubes simply absorbed the solution so another 50mL were added. A rotary evaporator was not available so the amount of NaOH solution was kept to a minimum. The nanotubes were homogenized,

37

not sonicated, forming a paste consistency. The paste was allowed to sit for approximately half an hour. Without rinsing or filtering, the paste was added to 100mL of 10% PVA solution, yielding a 2.5wt% loading of MWNTs. The mixture was then homogenized for 10 minutes and heated to 80C for 15 minutes, stirring intermittently. The mixture was poured into 3 petri dishes, 6cm in diameter and 1.5cm deep. A wax film was used to cover the top and the dish lid was placed overtop, effectively sealing the mixture. Excess mixture was put into a larger dish. The dishes were then placed into a small cooler filled with dry ice for 12 hours. After 12 hours, the samples were removed from the cooler and allowed to thaw at room temperature for 12 hours. The freezingthawing technique was repeated four more times, resulting in the hydrogel in figure 3.3.6.

MWNT/PVA Hydrogel Rev A

Materials 10% PVA solution MWNT-COOH Glass petri dishes (6cm dia, 1.5cm deep) 3mM Na2CO3 Solution 10 to 15V power supply Two copper plates (4.5cm x 4.5cm)

Add 5grams MWNT-COOH to 100mL of 0.25M NaOH, to convert to sodium salts and Na-MWNT. Homogonize. Magnetically stir for hour

Prepare 100mL 10% PVA solution.

Add Na-MWNT aqueous dispersion to 10% PVA solution to get 2.5% nanotube weighting.

Homogonize for 10 minutes

Heat mixture to 80C for 15 minutes

Repeat freezing and thawing 4 times Warm frozen sampls at room temperature for 12h Freeze mixture for 12 hours at -20C, in a cooler filled with dry ice. Pour mixture into 3 petri dishes, 1cm deep. Excess poured into larger dish

At room temp cut gel into thin strips, trying various dimensions

Prepare 100mL of 3mM Na2CO3 solution (electrolyte)

Prepare testing apparatus. Immerse copper plates 1 to 2 cm apart. Connect power supply.

Apply voltage to get 10V/cm. Actuation should occur. Reverse voltage to get actuation in opposite direction.

Source: Shi J, Guo Z, Zhan B, Luo H, Li Y, Zhu D, Actuator Based on MWNT/PVA Hydrogels The Journal of Physical Chemistry Letters B (109), 14789-14791, 2005

Figure 3.3.3 : Hydrogel Rev A

3.3.5 TESTING PROCEDURE The tests were conducted using the apparatus shown in figure 3.3.4. A piece of hydrogel was suspended in a 3mM solution of Na2CO3 between two copper plates 1cm to 2cm apart. Each plate was 4.5cm square. An electric field was created in the range of

38

7.5 to 15V/cm to produce actuation. Actuation direction can be reversed if the field is reversed.

Figure 3.3.4: Hydrogel test setup Figure 3.3.5: Hydrogel test

3.3.6 RESULTS AND EVALUATION The gel produced (figure 3.3.6) was much thicker (1cm) than those produced in other articles (0.6mm) [57]. However, it is unclear if this thickness was cut from a larger piece or if it was the as produced thickness. In any case, the surface of the gels formed many cracks/tears that went deep into the material, probably due to nonuniform cooling (figure 3.3.7). A thinner gel may not have this problem. Thin sections were cut from the large pieces (figure 3.3.8). No actuation occurred, but significant hydrolysis did. It is believed that the sodium ions were not sufficiently attached to the carboxyl chains and the presence of sodium salts may have hindered ion migration. Thus, two revisions are proposed. First, stir the MWNT-COOH into a larger volume, higher concentration of NaOH and for a much longer period of time. Second, filter and rinse the nanotubes with distilled water and methanol. If these changes have no effect, then the acid purifying and nanotube functionalizing step should be conducted with the 3:1 v/v nitric-sulphuric acid solution. In retrospect, the COOH functionalization was not verified for the purchased

39

nanotubes. Despite a lack of actuation this sample usefulness was not lost. It addressed many of the concerns associated with fabrication, thereby clarifying the steps, problems, and possible solutions. Furthermore, information was obtained on the conductivity of the MWNT/PVA Hydrogel (table 3.3.1). The SEMs, figure 3.3.9 and figure 3.3.10, taken of the MWNT cross section confirmed a fairly uniform dispersion of nanotubes, essential for strong actuation. However, the images did have enough resolution to determine if the nanotubes were dispersed as large bundles or if the clumps had broken up into small groups of individuals and strands. One other insight the SEM may offer is in regards to the small tears observed throughout the MWNT/PVA Hydrogel. These compromised the integrity of the material. For the SEM the hydrogel was broken using liquid nitrogen to reveal a clean surface. In the SEM it appears that the cross section has plateaus at varying elevations. This seems to imply the material is nonhomgeneous, either as a result of property changes in PVA or nonuniform nanotube dispersion. If the PVA is to blame, the changes may be due to the heating stage, freezing thawing technique, thickness of the material, or some combination of the aforementioned.

Thickness (m) Sample 1 Sample 2 Sample 3 Sample 4 2.5 2.6 2.0 1.5

Length (mm) 11.5 12.6 14.6 6.1

Width (mm) 8.3 6.4 6.2 5.9

Resistance (k) 123 509 298 886

Conductivity (S/m) 4.5 1.5 4.0 0.8

Table 3.3.1: MWNT/PVA-Hydrogel conductivity

40

Figure 3.3.7: Hydrogel tears (most not through sample) Figure 3.3.6: Hydrogel sample

Figure 3.3.8: Hydrogel test samples

41

Figure 3.3.9: MWNT/PVA Hydrogel SEM cross section x140

Figure 3.3.10: MWNT/PVA Hydrogel SEM cross section x140

3.3.7 SUGGESTION OF FUTURE WORK Based on the findings of the Results and Evaluation section, the recipe in figure 3.3.11 has been suggested. Once actuation has been achieved, testing of the force, and

displacement vs. time, should be conducted using the bending apparatus discussed previously.

MWNT/PVA Hydrogel Rev B

Materials 10% PVA solution MWNT-COOH Glass petri dishes (6cm dia, 1.5cm deep) 3mM Na2CO3 Solution
Functionalize MWNTs with COOH by: Sonicate 5grams of MWNT is 3:1 v/v nitric-sulphuric acid for 5 hours at 50C [A].

10 to 15V power supply Two copper plates (4.5cm x 4.5cm)

Add Na-MWNT to 10% PVA solution to get 5% nanotube weighting.

Convert to Na-MWNT by: Add 5 grams of MWNTCOOH to 300mL of 1M NaOH, to convert to sodium salts and Na-MWNT. Homogonize. Magnetically stir for 5 hours

Filter nanotubes rinse with distilled water and methanol to remove sodium salts [B, chem department].

Prepare 100mL 10% PVA solution.[A]

Homogonize for 10 minutes

Repeat freezing and thawing 4 times

Warm frozen sampls at room temperature for 12h [A]

Freeze mixture for 12 hours at -20C, in a cooler filled with dry ice.[A]

Pour mixture into 3 petri dishes, 1cm deep. Excess poured into larger dish

Heat mixture to 80C [A] for 15 minutes, stir intermittently

At room temp cut gel into thin strips, trying various dimensions

Prepare 100mL of 3mM Na2CO3 solution (electrolyte) [A]

Prepare testing apparatus. Immerse copper plates 1 to 2 cm apart. Connect power supply.

Apply voltage to get 10V/cm. Actuation should occur. Reverse voltage to get actuation in opposite direction. [A]

Source: Shi J, Guo Z, Zhan B, Luo H, Li Y, Zhu D, Actuator Based on MWNT/PVA Hydrogels The Journal of Physical Chemistry Letters B (109), 14789-14791, 2005

Figure 3.3.11: Hydrogel Recipe Rev B

42

3.4 MAGNETORHEOLOGICAL MATERIALS We examined the application of two classes of Magnetorheological materials for artificial muscles; Magnetorheological Elastomer (MRE) and Magnetorheological Fluids (MRF). A Magnetorheological material is a class of smart materials composed of two primary constituents; magnetizable particles dispersed in a matrix. 3.4.1 MAGNETORHEOLOGICAL ELASTOMERS 3.4.1.1 ACTUATION METHOD In Magnetorheological Elastomers the matrix is most often a silicone, natural, or synthetic rubber, but poly (vinyl alcohol), gelatin, and isobutylene-isoprene (UR) have also been experimented with [45, 47]. The particles used are either carbonyl iron or carbon black [47]. The magnetorheological effect is created by curing the polymerparticle mixture in the presence of a magnetic field, producing what is known as an anisotropic MRE [47]. The magnetizable particles form long chains along the field lines [45]. If a magnetic field is then applied to a completed MRE, the elastic modulus of the polymer changes with the intensity of the applied field [46]. Essentially, the magnetic field reinforces the chainlike structure of the particles within the matrix that was created during curing (see figure 29). It is this field dependent, variable elastic modulus that makes these materials so attractive for dynamic stiffness control. Applications of MREs for automotive bushings, engine mounts, brakes and dampers are already being developed by companies such as Ford and Toyota [1, 2].

Figure 3.4.1: Microstructure of carbonyl Iron particles [46]

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3.4.1.2 RECIPE There are many possible materials from which a MRE could be created. As stated earlier, all that is required is a polymer matrix material and a magnetizable particle. One important criterion is to use particles with an average diameter of 3-5 m. The two materials should be mixed thoroughly in an ultrasonic bath. Before curing, the sample should be placed in a vacuum case for many hours to remove any air bubbles. Finally, the sample can be cured in a magnetic field according to the type of polymer used (see recipe appendix). 3.4.1.3 RECIPE IMPROVEMENTS One of the difficulties preventing more extensive use of MREs is the fact that the best performance comes when the elastomer is cured in the presence of a magnetic field. The lack of preparation technology on a mass production scale prevents more widespread use in industry. However, the MR effect is still present even if the MRE is not cured in the presence of a field. The shear modulus of a rubber filled with randomly dispersed particles has been approximated by Gran= G0(1+2.5 +14.1 modulus of the unfilled rubber and
2

) where G0 is shear

is volume fraction of the particles. One group of

researchers is trying to optimize MRE performance in an elastomer that is not cured in a field, by using silicone oil in the mixture [46]. They found that with 20% oil, the carbonyl iron particles clumped together in a grape like structure [46]. These clumps are randomly dispersed throughout the rubber matrix and when magnetized, they attempt to form a more regular structure [46]. It was determined that the oil provided lubrication to aid the movement of the clumps and resulted in a higher MR effect. Their conclusion was that the silicone oil aids in the forming of a self-assembled microstructure that an external field would normally produce during curing [46]. These same researchers also varied the percentage of carbonyl iron particles under the same conditions. Even though the MR effect increases with the percentage of particles, they determined that with 60% particles, an optimized self-assembled microstructure formed within a rubber that maintains its toughness. For 60% iron particles and 20% silicone oil, within a silicone matrix, they found the change in modulus to be G=0.14MPa, and the percentage

44

increase to be G/G0=26%, where the modulus of the unfilled silicone is G0= 0.53MPa [46]. 3.4.1.4 RESULTS AND EVALUATION MREs differ from other smart materials in that they do not technically actuate. A MRE will not undergo any significant change in dimensions in the presence of a magnetic field. However, the Youngs (elastic) modulus of a MRE does change dramatically in the presence of a magnetic field. Under fields of 1 Tesla, increases in the shear modulus have been as high as 50% [46]. When determining the strength of the magnetic field required, the minimum field with maximum results is one that just fully saturates the dispersed particles. Magnetorheological elastomers have been found to have a quick time response (<10ms), good reversibility and controllable performance due to the relationship between field strength and elastic modulus [46, 47]. Some researchers have found that the MR effect increases with percent iron particles to a maximum of 15% [47]. Since Magnetorheological Elastomers do not actuate, but only vary in their mechanical properties, they do not readily lend themselves to the application of artificial muscles and therefore we have not pursued this avenue any further.

3.4.2 MAGNETORHEOLOGICAL FLUIDS 3.4.2.1 ACTUATION METHOD A Magnetorheological Fluid (MRF) is a colloidal suspension that has the ability to change phase between liquid and solid in an applied magnetic field [46]. These fluids exhibit Newtonian-like behavior in the absence of a magnetic field, but become a weak viscoelastic solid with a certain yield stress in an applied field [47]. MR elastomers have a field dependent modulus while MR fluids have a field dependent yield stress [47]. The material matrix is composed of low permeability oil with magnetizable particles (most often carbonyl iron) suspended within. When the MRF is exposed to a magnetic field, the iron particles are magnetized and attracted to each other to form solid chains and columns in the direction of the field [46]. These columns and chains facilitate the phase

45

change and are what provides the yield stress for the material. The strength of the material is determined by the external magnetic field [46]. If the MRF is sheared beyond the yield stress, it demonstrates properties of its liquid phase. If the field is withdrawn, the material also returns to its liquid phase. 3.4.2.2 RESULTS AND EVALUATION The characteristic field-dependent yield stress makes MRFs very attractive for clutches, brakes and dampers. One problem with MRFs is that particle settlement occurs while in its liquid phase [47]. One advantage of MREs over MRFs is that the particles are not able to settle over time and therefore have a more stable MR performance [47]. Similar to the MR elastomers, we had considered using this material in some type of clutch-brake device in our rotating joint that would take up any applied load early on and release the magnetic field once our main actuators are ready. If the rotating joint was designed similar to a differential, the joint would not be able to rotate negatively while the fluid was in its solid phase. Once the field was switched off, the material would return to its liquid phase and allow our actuators to rotate the joint in the positive direction. Although, also not easily applied to artificial muscles, this class of material could be useful as a locking mechanism in further prosthetics. Magnetorheological fluids could be used as a substitute for a conventional ratchet or locking mechanism.

46

3.5 CONDUCTIVE POLYMERS Conductive polymers are a very attractive candidate for artificial muscles because of their low operating voltages, controllability, low cost and ease of manufacture. Certain conductive polymers have been reported to generate forces greater than mammalian muscle for a given cross sectional area [19]. One drawback seen in conductive polymers so far is their relatively slow reaction time. Full actuation of the material can take anywhere from 10s to 30s depending on the actuator configuration [17]. Conductive polymers are very large chain organic molecules. They are composed of a primary axis of carbon atoms connected by alternating single (one shared electron, ) and double (two shared electrons, ) bonds. In this state, the polymer is not very conductive. Conductivity is improved greatly by adding or removing electrons from the carbon chain and replacing them with positive or negative ions. These ions become imbedded into the chain to maintain neutrality. By doing this, the location of the double carbon bonds become less defined. This is known as redox doping [14]. This allows multiple double bonds to overlap in some areas, causing a delocalization of a radical cation, or polaron. When this happens in several locations, many polarons form. The polarons then pair off into more stable bipolarons. These bipolarons are spread across the polymer and become mobile in electric fields, giving rise to the polymers conductive nature [15]. Conductivities can be as high as copper at 6*107 S*m-1, but are typically three or more orders of magnitude lower in air stable materials [19]. Previously reported conductivity for polyaniline films is 0.3 S/cm [15]. Due to this conductivity, the polymer can give rise to shape change. If a potential is applied across the polymer, a charge imbalance occurs. When the polymer is in the presence of an electrolyte (a solution with free ions) and a potential is applied between the electrolyte and the polymer, ions will move into or out of the tangled polymer web in order to maintain charge balance [17]. The voltage applied is generally around 1V, but bursts up to 10V can be applied to increase power [19]. This can result in a volume increase or decrease of the polymer due to the ion mass flux. The magnitude and rate of this volume change depend on the specific sizes and charges of the dopant ions and the electrolyte used [14].

47

Various configurations of polymer and electrolyte have been explored. Two main configurations that have proven to be very effective are films and helix tube designs. Films are good because they allow for a high surface area to be in contact with the electrolyte material. This allows for fast movement of the ions once a potential is applied. Tubes have also been shown to have high strength and strain properties [15]. Tubes with a wire helix incorporated into the structure increase the conductivity along the tube and thus greatly increase activation strength and rate as compared to films [31, 32]. Electrolyte configuration is also an important consideration for actuator design. Most conductive polymers have only been tested in liquid electrolytes. However liquid electrolytes hinder the practical applications of the actuators because they require that the actuator be immersed in the corrosive liquid that must be contained and sealed. A promising solution to this is the solid polymer electrolyte (SPE). SPEs are stable in air and allow free travel of ions into the conductive polymer, similar to liquid electrolytes [23]. This allows for an actuator configuration that can be operated without special containment. Although there are many polymers that display these conductive properties after treatment most are either unstable, hard to synthesize or do not perform very well. From research done to date, polyaniline seems to show the most promise for further study. It is fairly easy to synthesize, stable in air and moisture and both shows good actuation [15]. For these reasons, we will focus on polyaniline. 3.5.1 ACTUATION METHOD Actuation of PAn arises through variation of the oxidation states. The oxidation state can be controlled electrically or chemically, although electrical control is preferred [17]. Oxidation takes place between 3 different states as electrons are removed from the polymer backbone, as shown in figure 3.5.1. Changing the oxidation state of the polymer backbone results in a charge imbalance, causing a flux of ions into or out of the polymer. The source of ions needs to be in the form of an electrolyte that is in contact with the polymer. The changes in oxidation state can be brought about by a potential of around 1V, however higher voltages may need to be applied to due resistance along the actuator [17].

48

Figure 3.5.1: Changing oxidation states through pH change or charge displacement [17]

Most designs to date use a polyaniline film immersed in an electrolyte, and apply a potential between the film and a reference electrode placed in the electrolyte in order to actuate. The electrolyte is an acidic solution of HCl, NaCl, H2SO4 HCLO4 or HNO3 with a pH <3 [30, 20]. Due to the fabrication process, it is difficult to manufacture anything other than a film. The film is usually adhered to a thin layer of either Pt film or a polypropylene film, forming a bilayer structure. When the PAn expands, it forces the bilayer actuator to bend over due to the asymmetric volume change between the two layers. This standard configuration results in properties as discussed above. Xi has outlined a process known as phase inversion that allows almost any shape to be produced [15]. This allows synthesis of PAn in a tubular form which has shown to triple the strain over film samples made with phase inversion. However, phase inversion results in a porous microstructure, which severely limits its youngs modulus. Films made with phase inversion have a youngs modulus of 3-3.5 MPa and maximum stress of 0.3 MPa [15]. However, properties of the PAn can be improved greatly by incorporating a conducting filament into the structure. One method involves adding a Platinum wire helix into the PAn tube, which results in conductivities of 244 S/m2 and strains increased from 2 to 2.7% [15].

49

Using phase inversion, PAn can also be extruded into a fibre which increases conductivity by 50 times over the tube, has a youngs modulus of 160 MPa and a maximum stress of 5MPa. However, the fibres show much less strain, almost 3 times lower than the tube [15]. 3.5.2 ORIGINAL RECIPES Two main ways have been found to produce polyaniline into a contiguous piece suitable for use as an actuator. The first is referred to as the traditional technique and the second is the phase inversion technique. According to the most recent literature review, the following steps are taken to form the PAn film using the traditional technique. First, the polyaniline powder is thoroughly dried and then added to the NMP solution by 3%wt ratio. Once fully dissolved, the solution is cast onto a smooth glass slide or Teflon mold. This is then baked in a vacuum oven at 50oC. Once the film has cured it is placed in a sonicating bath of 1M HCl for 24 hours. The film is then peeled from the glass substrate. The following steps are taken to form the HYDRIN solid polymer electrolyte and coat it on the PAn. First, a 2% wt solution of poly(epichlorohydrin-co-ethylene) is added to the tetrahydrofuran. Later Lithium perchlorate is added to the mixture and stirred for 30 minutes. This liquid mixture is then dripped onto the surface of the PAn film and allowed to dry again for 30 minutes. The final preparation involves layering parallel Pt wires across the SPE and then connecting the wires at the end of the film. More HYDRIN is then dripped over the Pt wires and allowed to cure. The PAn film is then connected as the working electrode and the Pt wires as the counter electrode and the actuator is complete. The step-by-step process can be followed in the flow chart in figure 3.5.2.

50

Polyaniline Actuator with Solid Polymer Electrolyte

(Traditional Technique)
Dried PAn EB (3 % w/w of NMP) gradually added and dissolved Mixture placed on a glass substrate or other smooth surface

Polyaniline

NMP

NMP/PAn

Materials: PAn emeraldine base (EB) (MW: 300,000) 1 M HCl NMP

PAn/NMP mixture ready for curing

PAn emeraldine salt (ES) film

doped in HCl (1 M) aqueous solution for 24 hours

Baked in oven at 50 C under vaccum

PAn with SPE coating

Add 2.5 wt% solution of (P [ECH-co-EO])

LiClO4 (0.1312 grams of LiClO4 per gram of P[ECH-co-EO]) is added and stirred for 30 minutes

Materials: poly (epichlorohydrin-co-ethylene oxide) tetrahydrofuran (THF) Lithium Perchlorate LiClO4 (THF)

(THF) + (P [ECH-co-EO])

Liquid mixture

Pan with SPE coating

Dripped onto surface of Pan and allowed to dry for 30 min

PAn All Solid Actuator

Materials: PAn with SPE coating Pt Wire Polypropylene commercial adhesive film (if wanted for substrate - bending)

Pt wires layered across SPE on PAn

SPE coated over Pt wire & cured Pan/Pt wire covered with SPE

Pan with SPE coating

Pan with SPE coating & Pt wires

Pan All Solid Actuator

Sources: [1] Kaneto, K. Improvement of electrochemical deformation of conducting polymers, strain, force and response [2] http://ndeaa.jpl.nasa.gov/nasa-nde/lommas/eap/Polypyrrole-PrepProcedure.htm

Pan connected as working electrode. Pt connected as counter electrode

Polypropylene attached if wanted

Figure 3.5.2: Traditional fabrication of a PAn actuator

51

The following steps are taken to form the PAn film using the phase inversion technique. First, Phenylhydrazine is added to the DPMU in 3% wt ratio. Then 10% PAn EB is gradually added to the solution and stirred at 0oC for 24 hrs in a water/ice bath. This is then cast onto a glass slide or coated on a Pt Wire and immersed in a water coagulation bath for 24 hours. Once removed from the water it is placed in a 1M HCl solution for 24 hours. The film is then peeled from the glass, or the wire is removed. Once this is complete, the preparation of the HYDRIN solution and the final actuator fabrication follow the steps above. The step-by-step process can be followed in the flow chart in figure 3.5.3.

52

Polyaniline Actuator with Solid Polymer Electrolyte

(Phase Inversion Technique)
Reducing agent phenylhydrazine (3 % w/w of DMPU) PAn EB (10 % w/w of DMPU) gradually added Constantly stirred for 24 hours with the temperature controlled at 0 C

Polyaniline
(phase Inversion)
DMPU

Materials: Phenylhydrazine N, N-dimethyl propylene urea (DMPU) PAn emeraldine base (EB) (MW: 300,000) HCl NMP

DMPU Stabilized from gelation

DMPU/ phenylhydrazine/PAn

PAn leucoemeraldine base (LEB)

PAn emeraldine salt (ES) State actuator

doped in HCl (1 M) aqueous solution for 24 hours

immediately immersed in a water coagulation bath for 24 hours

Cast on glass slide to form a thin layer of polymer Solution Or 250um Pt wire dipped with helix wrapped or whatever Configuration we want

PAn with SPE coating

Add 2.5 wt% solution of (P [ECH-co-EO])

LiClO4 (0.1312 grams of LiClO4 per gram of P[ECH-co-EO]) is added and stirred for 30 minutes

Materials: poly (epichlorohydrin-co-ethylene oxide) tetrahydrofuran (THF) Lithium Perchlorate LiClO4 (THF)

(THF) + (P [ECH-co-EO])

Liquid mixture

Pan with SPE coating

Dripped onto surface of Pan and allowed to dry for 30 min

PAn All Solid Actuator

Materials: PAn with SPE coating Pt Wire Polypropylene commercial adhesive film (if wanted for substrate - bending)

Pt wires layered across SPE on PAn

SPE coated over Pt wire & cured Pan/Pt wire covered with SPE

Pan with SPE coating

Pan with SPE coating & Pt wires

Pan All Solid Actuator

Sources: [1] Binbin Xi. polyaniline films and tubes prepared by phase inversion technique [2] http://ndeaa.jpl.nasa.gov/nasa-nde/lommas/eap/Polypyrrole-PrepProcedure.htm

Pan connected as working electrode. Pt connected as counter electrode

Polypropylene attached if wanted

Figure 3.3: Fabrication of PAn actuators using phase inversion technique

53

3.5.3 PHYSICAL AND CHEMICAL PROPERTIES Amorphous PAn has relatively poor intermolecular connections and thus displays no interesting properties. However, when it is transformed into a crystalline base and dopants are added, the material characteristics greatly improve [20]. The general PAn structure has the following chemical form:
[(C6H4-NH-C6H4-NH-)1-x(C6H4-N=C6H4=N-)x]n

Which gives rise to five distinct oxidation states by varying x from 0 to 1 [20]. The crystalline known as polyaniline emeraldine base (PAn EB) exists when x=0.5. PAn EB is regarded as the most useful state due to its high stability at room temperature. PAn EB is made up of a four monomer repeating chain consisting of three benzenoid rings and one quinoid ring connected by nitrogen atoms as seen in figure 3.4. The PAn - EB can then deprotonated by doping with an alkaline solution such as HCl. This increases its conductivity by up to 14 orders of magnitude [20]. The methods of fabrication discussed above result in a porous, translucent film that is stable in air at room temperature [15].

Figure 3.5.4: Doping of PAn-EB to give PAn emeraldine salt [24]

Physical properties of polyaniline can vary greatly depending on different recipes, configurations and electrolyte materials. As a basis for comparison, we will use numbers generated by K. Kaneto in his report Improvement of electrochemical deformation of conducting polymers, strain, force and response due to the fact that his fabrication process is widely used today. In an aqueous electrolyte of Ph <3, the strain in a PAn sample was found to be 5-6% with 0.5V. This strain gave a stress of 10MPa [25]. Time response of the actuator can vary from 18s to 30s for similar samples [17]. 54

3.5.4 RECIPE REVISIONS Several changes were made to the proposed recipes either due to equipment constraints or design changes. The procedure that was followed in the lab will be outlined in this section. For the synthesis of polyaniline film using the traditional technique, polyaniline (MW 20,000) was available in the lab, having previously been purchased. Hydrochloric acid, Nitric acid and NMP were purchased from Sigma-Aldrich. For a standard sample, 5mL of NMP was added into a small 20 mL test tube containing 150mg of polyaniline powder. The mixture was then homogenized with a manual homogenizer at a maximum RPM of 30,000 for 5 minutes. This was done using a rig as seen in figure 3.5.5.

Figure 3.5.5: mixing of polyaniline and NMP using a homogenizer

While this was done, a glass Petri dish with a 9 cm diameter was wiped with a mold release agent and allowed to dry. After mixing, the solution was then transferred using a pipette into the glass Petri disk to avoid contamination of the film with unhomoginized material. The Petri dish was then swirled by hand to allow the solution to coat the entire bottom surface of the dish. The dish was then placed in a vacuum oven at 170 oC and 25 InHg. The solution was allowed to dry, while periodically opening the oven door and allowing moisture to escape and be wiped off the oven window. This

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usually involved 3-4 cycles and took approximately 45 minutes. The film was then allowed to cure and soaked in water. The film was peeled away from the dish carefully using a scoopula and then immersed in a 1 M solution of HCl for 24 hours. Cutting a small square 1cm X 3cm from the film and adhering it to a piece of scotch tape completed the bilayer actuator. Actuation was tested first with the use of liquid electrolyte. The actuator was then immersed in a 1 M solution of nitric acid and connected to a DC electric circuit with the connection above the waterline. A copper counter electrode was then inserted in the solution, and a voltage applied. The process is summarized in figure 3.5.6.

Figure 3.5.6: Production of Polyaniline film

The above changes were made for several reasons. Firstly, the sonicating called for in the initial recipe was not sufficient to properly mix the polyaniline with the NMP, therefore physical means was necessary. Also, some recipes called for centrifuging the mixture after homogenizing, but this was found to be unnecessary because the amount of particles left was insufficient to justify separation by centrifugal force. Mold release was added to the glass substrate to aid in removal from the glass substrate. It was found that 56

difficulty in film removal was greatly reduced by using the mold release agent. The temperature was increased to 170 oC because it was found that at a lower temperature the film cracked into many pieces and a contiguous film could not be formed. Finally, the solid polymer electrolyte was never attempted because actuation in the liquid electrolyte was found to be insufficient to justify further development of the actuator. For the synthesis of the polyaniline using the phase inversion technique, the same polyaniline available was used. 100 mL of Phenylhydrazine and 100 mL DMPU were purchased from Sigma Aldrich. Dry ice was obtained from the medical science supply store. The recipe followed for the phase inversion technique was not altered although ideal conditions were not met due to equipment constraints in the lab. The 24 hour 0 oC cooling period was difficult to maintain, and there was always a small period where the temperature was either too cold or too hot. The mixing solution was kept cold by first putting the 50 mL mixing vessel within another 150 mL beaker all placed in a 1.5 L Tupperware container. The Tupperware container was then filled with dry ice and wrapped with parafilm to slow evaporation and aid in insulation. This kept the solution quite cold for several hours. Once the dry ice had been evaporated, ice was added to the Tupperware container for the duration of the cooling cycle. The final procedure is outlined in figure 3.5.7.

Figure 3.5.7: Polyaniline synthesized using the phase inversion technique

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Once the cooling phase was completed, the coagulation through immersion in water was not completely successful. While the liquid polymer did coagulate, it was not solid enough to continue with testing as a solid polymer actuator. A final recipe was conducted using integration between the polyaniline traditional film and the IPMC discussed in chapter 3.2. It was postulated that since the IPMC dehydrates and loses its ability to move through actuation, it might benefit from a waterproof coating. Whatever this coating may be it must also be conductive to allow the IPMC to receive electrical charge to actuate. A thin layer of polyaniline coating the IPMC may serve this function. The IPMC was synthesized as it was outlined earlier in the chapter. The polyaniline was then made as it was outlined for synthesis under the traditional technique; however, before entering the oven, one sample of IPMC was coated with the liquid solution of PANi and suspended horizontally between two alligator clips on a small stand. A second sample was placed in a smaller 4 cm Petri dish and completely immersed in the PANi solution. Both these were entered in the oven at a temperature of 130 oC and -25 InHg, well below the maximum operating temperature of the nafion of 170 oC. The polyaniline was allowed to dry as before, except that each time the oven door was opened, the IMPCs were re-painted with the polyaniline to ensure an even coating. 3.5.5 EQUIPMENT DESIGN To extrude the Pani into fibers a special apparatus was designed and manufactured. The device has two separate assemblies that work in conjunction, the Pressure Vessel Assembly and the Reel Assembly (Figure 3.5.8). Polyaniline produced by the phase-inversion method is poured into the Pressure vessel, which is made up of three subcomponents; the cap, vessel, and extruder (see Figure 3.5.9). The steel vessel is then pressurized to ~100 psi with inert nitrogen gas, forcing the viscous Pani mixture out through the 1 mm hole in the extruder. The entire assembly is placed in a water bath, with the Pressure vessel just above the waterline, so that the fiber extrudes directly into the coagulating bath. The fixture supporting the pressure vessel is made of Delrin because of its water resistant properties, while steel was chosen for the pressure vessel components because of its high yield strength. The cap can be removed to facilitate

58

pouring while the extruder can also be removed to allow for creation of different fiber thicknesses.

Figure 3.5.8: Extruder device with Pressure vessel assembly on the left and Reel assembly on the right

Figure 3.5.9: Pressure Vessel cross section

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The purpose of the Reel assembly is to collect the fiber into a convenient spool for later use. The entire assembly is composed of a base, motor mount, spindle and reel, and is placed in the same water bath as the Pressure Vessel assembly. An electric motor is attached to the motor mount (above the waterline) and a belt is run from the motor to the reel. As the fiber is extruded, it is slowly wound onto the rotating reel. The reel is submerged in water so that coagulation of the polyaniline can take place over twenty four hours. Delrin was once again chosen for these components because of the constant contact with water. Unfortunately, at the time of this report we had not been able to extrude any fibers due to delays manufacturing the components. However, this device provides the future capability to create polyaniline fibers.

3.5.6 RESULTS AND EVALUATION Although the various configurations were not successful at actuating, several interesting results were still obtained. Primarily, data was collected on the thickness, weight and conductivity of the samples. None of the samples actuated enough for proper measurements to be taken. The thickness of the samples was measured by use of scaled SEM photographs. The conductivity was measured using a digital multimeter to measure electrical resistance at several points on the sample with the probes separated at defined distances. The resistance measurement was then used to calculate the resistivity using the following equation:

The inverse of the resistivity is then taken to find the conductivity. Masses were taken before and after doping to determine the addition of doping materials during the process. For the polyaniline made with the traditional technique, the conductivity and doped weights were measured carefully, as well as analysis of the film thickness under an electron microscope. The conductivity of the sample was determined to be 0.166 S/cm. This matches very closely with other reported results. The mass before and after doping was 2.5 mg and 3.4 mg respectively. This shows a significant addition of Cl into the structure during doping. This leads us to believe that the doping process was successful 60

and that the polyaniline base film was transformed into the emeraldine salt state. This was also confirmed by the high change on conductivity of the sample before and after doping. Results can be found in table 3.5.1.
Polyaniline Film Thickness Length Width 10 m Pre Doped Mass Resistance Conductivity 0 Post Doped Mass Resistance Conductivity 3.4 mg 10 K 0.166 S/cm

18 mm 9 mm 2.5 mg

Table 3.5.1: Polyaniline film (traditional technique) results.

The film also appeared to be quite uniform, with a smooth, metallic blue surface. This contradicts previous reports, which stated that the film would be translucent. The film can be seen in figure 3.5.10. SEM photographs were taken of the film, and can be seen in figure 3.5.11.

Figure 3.5.10: Polyaniline sample made with traditional technique

Figure 3.5.11 SEM photograph of polyaniline film edge

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The failure of the material to actuate can be attributed to several causes. First, the molecular weight used was 20,000, whereas all other reports suggested a MW of 300,000. This higher weight gives the material a denser network through which to actuate. With our low MW, it is probable that the material was actuating, but was not measurable. Another reason could be the thickness of our sample. Our sample was very thin compared to the samples reviewed in the literature review. The increased thickness may add to the structures ability to actuate by giving it a greater area through which strain can take place. Synthesis of thicker films was attempted by simply adding more solution to a smaller diameter Petri dish, but this resulted in an inconsistent structure with crusted edges and cracked interior. Finally, our electrical setup may have not been ideal due to the connection to the PANi film. The alligator clip used caused a bend in the film that could not be avoided while still maintaining good electrical connection. This bend may have prevented the film from being able to actuate freely. Future work on the polyaniline film may include devising a way to cure thicker films with a consistent surface, as well as variation on the electrical setup. Also, future research may include investment in a higher weight polyaniline to determent the difference the MW has on the final product. The synthesis of polyaniline film using the phase inversion technique was not as successful as outlined in the literature review. SEM photographs taken of our sample show a much more irregular structure than that of previous work. This can be seen in figure 3.5.12. After coagulation in water, the structure of the material never hardened beyond a crumbly substance that could not be handled easily without destroying it. This material had the consistency of dried mud. This could once again be attributed to two major reasons. The first is the inconsistency during the cooling process. The setup used made it difficult to maintain the proper temperature. It was found that upon starting, the dry ice caused the sample to be well below zero, and by morning the sample had reached nearly room temperature. The process was tried several times and it was observed that when the temperature was kept cooler, the final solution was much more viscous, and coagulated into a more solid structure. Future work will include obtaining polyaniline with a higher MW, and also devising a way to keep the cooling cycle at a consistent temperature. Another variable that may be worthy of investigation is the temperature of the coagulation bath. Coagulation may be accelerated by a heated or cooled water bath.

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(a)

(b)

Figure 3.5.12: SEM of polyaniline, phase inversion, showing (a) our results and (b) previous results

The coating of polyaniline onto the surface of the IPMC was highly successful. The results of the two different methods of coating were slightly different. The sample that was suspended had a more consistent surface, however the mass was lower, indicating that less polyaniline coated the sample. The immersed sample had two areas of inconsistency where it made contact with the glass substrate. The samples can be seen in figure 3.5.13 From SEM images, the thickness of the coating was measured to be 5 m on the suspended sample. Thickness of the immersed sample could not be measured directly due to the SEM photographs being out of focus. However, for conductivity calculations, the thickness will be estimated as 10 m due to the similarity of production with the traditional film. The polyaniline can be seen as a thin black line between the bright outer surface and the light grey diffused Pt layer. This can be seen in figure 3.5.14. The conductivity of the samples was quite good, and was very similar to each other, with both being much higher than the polyaniline film. The conductivity of the suspended sample was slightly higher than the immersed sample. This could be because the layer is so thin; conductivity of the Pt layer could also be being measured in parallel. Results can be found in table 3.5.2. Actuation of the samples was tested as outlined in chapter 3.1.5. The suspended sample did actuate, but not nearly as much as an uncoated IPMC. This could be due to poor electrical connection through the PANi layer, or improper ionizing of the nafion

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layer. However, no dehydration of the sample was witnessed during actuation. The immersed sample did not actuate at all. This may be due to the inconsistent surface finish causing stiffness that the IPMC cannot overcome. Future research should include investigating ways to coat the samples without impeding the actuation of the IPMC. The potential for polyaniline to increase the IPMCs cycling ability is high as long as a coating method can be applied that does not impede actuation.

Coated Polyaniline through suspension

Coated Polyaniline through immersion

Figure 3.5.13: IPMCs coated with polyaniline

PANi coating Pt layer

Nafion

Figure 3.5.14: SEM of cross section of IPMC coated with polyaniline through suspension

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IPMC coated with Polyaniline Film IPMC coated with Polyaniline Film Suspended curing Immersed curing 5 m N/A Pre Doped Thickness L W Mass 20 mm 6 mm 51 mg 20 mm 7 mm 57 mg Resistance 2.4 K 3 K Conductivity 2.1 S/cm 0.7 S/cm Mass 53.3 mg 61.2 mg Resistance 0.55 K 0.75 K Conductivity 9 S/cm 2.8 S/cm Post Doped

Table 3.5.2: Measurements and results for IPMCs coated with polyaniline

3.6 SHAPE MEMORY ALLOYS 3.6.1 ACTUATION METHOD Shape memory alloys (SMAs) are metals, most often NiTi, CuZnAl, and CuAlNi, which demonstrate two unique properties, pseudo-elasticity, and the shape memory effect [1]. Pseudo-elasticity (or super-elasticity) is the materials ability to fully recover a large induced strain when it is austenite phase [2]. The shape memory effect is the materials ability to be severely deformed, and then return to its original shape when heated [1]. These unique properties are made possible through a reversible solid-state phase change from a martensite atomic structure to an austenite structure. A transformation between these phases can be induced by either a temperature change or an applied stress state [2]. Martensite exists at lower temperatures, and is softer and more easily deformed. The molecular structure of matensite is twinned as shown in Figure 3.6.1 [1]. Sufficient loading of the material produces large strains and seemingly plastic deformation [2].

Figure 3.6.1: Atomic structure of shape memory alloys

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However, due to the shape memory effect this deformation can be recovered if the material is heated to its high temperature austenite structure [2]. If an external load is applied to the SMA during the phase change from matensite to austenite, work can be done during the heating process. If the SMA is then allowed to cool the material will return to its low temperature martensite configuration (see Figure 3.6.2). In this way actuation can be achieved.

Figure 3.6.2: SMA phase transformation cycle [1]

The pseudo-elastic effect occurs in shape memory alloys when the alloy is at higher temperatures and therefore completely composed of Austenite [1]. If an increasing external load is applied to the shape memory alloy, eventually the Austenite becomes transformed into stress-induced Martensite (Figure 3.6.2). The loading is absorbed by the softer Martensite, but as soon as the loading is decreased a reverse phase transformation occurs, returning the material to its high temperature Austenite phase [1, 2]. In this way large strains can be recovered. Unlike the shape memory effect, pseudoelasticity occurs without a change in temperature.

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3.6.2 RECIPE For production of artificial muscles, the SMAs must be coated in silicone to insulate the wires, both to decrease the heat transfer and for safety. Mechanical advantage is also required to maximize the achievable strain. In a figure-eight configuration, A. Price et al achieved a strain of 31.6% [2]. We will follow the procedure used in that work, but not the wire configuration. Shape memory alloys most often come in the form of a wire, which heats up quickly and is easy to work with. Flexinol wire (NiTi) is the shape memory alloy chosen for this application. 3.6.3 EQUIPMENT DESIGN Two pieces of equipment were needed to produce the bands of shape memory alloy actuators. As previously described, the shape memory effect is dependent on the material being heat activated. To reset the memory of the material and absolve any residual stresses, the Flexinol wires must be bent into the desired shape and heated to 600C for 1 hour [2]. To accomplish this, a heating rig that could withstand the high temperatures and provide the structure to bend the wire was necessary. The device we designed and used is shown in Figure 3.6.3.

Figure 3.6.3: SMA heating assembly

The base plate has M8 taps to allow shoulder bolts to be installed. These shoulder bolts will provide the surface to wrap our wire around in an S type pattern. The rig has two separate sets of shoulder bolts to increase capacity. The SMA wires are wound around the pegs and pinched at each end by socket head cap screws threaded into the

67

plate. This 10 peg S-pattern will produce individual wires approximately 320 mm in length (see Figure 3.6.4). This length was chosen to provide sufficient strain while conforming to the limiting dimensions of our testing arm and torso.

Figure 3.6.4: Heating rig peg pattern

The actual length that will actuate is 260 mm (see Firgure3.6.5) based on the calculation:
Actuating Length (# pegs)( 1 2 peg circumference) (# gaps)( gap length) (10 pegs)( 1 2 10mm) (9 gaps)(11.2mm) 258mm Total Length Actuating Length Fastening Length (258mm) 2(30mm) 318mm

Figure 3.6.5: SMA bundle

The theoretical compressed length of the wire would be simply the distance from the outer diameter of the first peg to the last peg, which is measured as 145mm, yielding a theoretical strain of 44%, assuming the wire returns to its original configuration. This is a best-case estimate since the silicone coating required to increase resistance and produce heat will resist actuation. The device used to coat the wires in silicone has two sets of six grooves machined out of an aluminum plate (Figure 3.6.6). The grooves are circular with a radius of 1.5 68

mm and a depth of (Figure 3.6.7). At each end the groove is raised to hold a taut wire up from the bottom and a clamp is used to hold the wires in place. Silicone can then be applied in large amounts and smoothed over the upheld wires coating all surfaces. Once curing is complete the bundles of six wires in parallel can be pealed off the aluminum. The ends of the wires are left exposed and soldered together using a special flux, Indalloy #2. The bundles are now ready for actuation and integration onto our testing arm.

Figure 3.6.6: SMA silicone application assembly

Figure 3.6.7: Detail of silicone application assembly cross section

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3.6.4 RESULTS AND EVALUATION Unfortunately, we were unable to complete the testing of our SMA bundles in time for this report. Hopefully, this design can be tested and implemented as part of a future work.

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4 ARTIFICIAL ARM DESIGN AND INTEGRATION

This section will outline our design and fabrication of the arm rig as well as give a brief background in modern prosthetic devices. Design requirements state that the arm mimic the motion of a human arm during an arm wrestling competition. Therefore, the primary goal of arm design will be to fabricate a rig that will allow our smart materials to actuate a prosthetic arm about the shoulder joint. The arm design will consist of a standalone rig that will allow motion of an arm necessary for arm wrestling. The rig will also house the smart materials as well as any auxiliary equipment necessary for actuation. A secondary goal will be to have the rig appear as lifelike as possible and thus gain attention for further research. 4.1 BRIEF PROSTHETICS BACKGROUND Modern prosthetics fall into two main categories: classic prosthetics and myoelectric prosthetics. Aside from improvements in materials, classic prosthetic devices have not changed greatly in the past few decades [51]. Classic prosthetic devices consist of a fibreglass shell that is fitted to the patients stump through inverse casting [50]. The Shell is then fastened to an aluminum wrist and elbow joint. The wrist can be attached to a metallic hook or cosmetic hand, depending on the users requirements. The elbow joint consists of a mechanism that allows for 11 locking positions through angles from 10o to 135o of elbow flexion [50]. The elbow and hook are actuated through a cable system attached to a harnessed body part. When the patient shrugs or moves the harnessed body part, the cable is tensioned causing actuation of the prosthetic [51]. The elbow can be locked and unlocked by tugging on the elbow joint cable. Classic prosthetic devices are easy to use, lightweight and simple, making them the most popular option amongst most amputees.

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Figure 4.1: Prosthetic actuation through movement of harnessed torso [51]

(a)

(b)

Figure 4.2: Classic Prosthetic devices (a) Elbow joint (b) Upper arm prosthetic with hand and harness removed showing elbow lock cable [4]

Recent innovations have been made in the field of advanced prosthetics, with the invention of sensors that can allow patients to activate prosthetics through the flexion of existing muscles. These are known as myoelectric devices. Myoelectric prosthetic devices consist of a metal or plastic chassis that contain DC electric motors and gears used for actuation. The chassis is then connected to a fibreglass shell, which is formed around the patients stump. Sensors that detect current during the flexion of patients muscles are placed in the fibreglass shell as to make close contact with muscle groups close to the skin surface. Myoelectric devices allow for lifelike movement of the prosthetic without the need for cables and harnesses, which makes them very appealing for day-to-day use. Devices made by Otto-Bock can actuate at speeds up to 300mm/s 72

[52]. However, the devices are quite heavy and require battery packs due to the electric motors and gears, which severely limits their usability. [53, 54]

Figure 4.3: Upper arm myoelectric prosthetic for elbow actuation [53]

Myoelectric sensors

Figure 4.4: Lower arm prosthetic (a) showing myoelectric hand (b) showing sensors in fibreglass shell [53]

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4.2 FINAL JOINT DESIGN Design of the Rig has involved two phases. First, a mode of actuation for the arm was decided and second, the method by which the material causes actuation was decided. The actuation mode refers to the way in which the rig will simulate the motion of a human arm during an arm wrestling match. This motion has been simulated through the rotation of a single component consisting of an arm ending just above the elbow. This piece is rigidly connected to a drive shaft that is connected around the shoulder joint with a universal joint. The drive shaft is then connected to a series of pulleys, which the smart materials actuate upon. The drive shaft components can be seen in figure 4.5. A shell covering the upper arm mechanism is connected as the base around which the lower arm rotates. The drive shaft is held in place within the torso by two housings as shown in figure 4.6.

Figure 4.5: Lower arm rotation component fixed to the drive assembly

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Figure 4.6: Rear cut-away view of drive assembly mounted in the torso

The smart memory alloy actuators, fabricated as SASMAC actuators, are connected in pairs to each of the four pulleys, and are strung vertically to connect with the bottom base of the torso. The pulleys allow for connections on opposite sides that allow the actuator to be pulling on the tangent of the pulley for the entire movement. As the SASMAC contracts, the pulleys are rotated, which turns the rest of the drive mechanism and thus the arm turns. This can be seen in figure 4.7.

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Figure 4.7: Cutaway of arm showing SMA contracting resulting in arm motion

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Figure 4.8: A front view of the completed torso assembly

To save time, used prosthetic arms have been acquired and have been adapted to fit our design. Pro Prosthetics has donated two used upper arm prosthetics to us, and they have fit into the design nicely. The best arm has a fully functioning locking elbow joint, and is in good mechanical condition. The arm was taken apart just above the elbow joint and re-drilled to fit the lower arm drive shaft. A male torso was acquired from A Fiber Inc. A panel has been cut out of the back of the torso to allow for insertion and access to the various components. Velcro tabs are used to allow fast replacement and removal of the rear access panel. The torso is mounted on two perpendicular plywood plates, which have been cut to fit the contours of the torso. The plywood plates have been used to mount all the inner components. A rubber pas has also been attached to the plywood base to insulate the wood from the SMA during actuation. John Ujfalusi from George Brown College fabricated the upper arm shell, which supports the lower arm. For detailed machine drawings, refer to appendix A.

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Figure 4.8: Arm acquired from Pro Prosthetics that was used for lower arm section

Figure 4.9: Torso with back panel removed shown mounted to plywood base

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5 CONCLUSION
The purpose of this thesis was to further research towards developing and integrating smart material actuators into prosthetic devices. The research conducted in this project has attempted to build off the progress made by many others in the field of smart materials. Through the literature review, possible candidate materials were identified as potentially meeting the design criteria for our prosthetic application. These materials included Ionic Polymer-Metal Composites, Bucky Paper, Carbon Nanotube Hydrogel, Magnetorheological materials, Conductive Polymers, and Shape Memory Alloys. Previous research had shown that they operated within practical constraints and were able to actuate with adequate stress and strain. For each of these materials, physical and chemical properties were researched as well as means of actuation and methods of synthesis. From this, Ionic Polymer-Metal Composites, Bucky Paper, Carbon Nanotube Hydrogel, Conductive Polymers, and Shape Memory Alloys were investigated further. Each material was synthesized and tested for its ability to fulfill the design requirements. This was done through a variety of experiments and through the use of custom designed equipment. A prosthetic arm test vehicle was constructed as a final tool to evaluate a materials ability to duplicate human performance. Initial test results prompted refinement to our fabrication techniques. The IPMCs produced the largest bending motion close to 90 for some samples; however the forces involved for this motion were not sufficient for application to prosthetics. Improvements to the recipe for Carbon Nanotube Bucky paper produced physical characteristics far superior to our original results in terms of flexibility, resilience, and sample quality. The Multi-walled Carbon Nanotube Hydrogel did not produce any actuation, but the principles of fabrication were tested and confirmed. Polyaniline samples were also unable to actuate, but showed improvements in conductivity upon doping. Variations of the Polyaniline as a coating for IPMCs improved its actuation and it is hoped that an extruded fiber will also show promise. Final results showed that although these materials may, after further research and development, be able to fulfill the design requirements, at present the technology is still in its infancy.

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As discussed in each section of this report, there are recommendations for continued work. This project has achieved a strong base for which to refine, develop, characterize, and implement smart materials. However, the methods by which these materials are fabricated require refinement. Suggested process revisions were discussed in Recipe Revision sections and should be explored. Additional sources, as they become available, should be consulted for further improvement. The materials should be further characterized using tensile, SEM, and conductivity assessments. Actuation can be characterized by the bending and linear displacement measuring equipment developed. In regards to the bending and linear test rigs, modifications should be made to accommodate the two AE 801 Micro Force Sensor purchased from SensorOne. These rigs can then be used to determine the forces exerted by the actuating materials. Once sufficient strength and displacement are achieved, the materials should be integrated into devices such as the arm developed in this project. It may be beneficial to determine the exact forces required for actuating specific equipment, including the arm. Further development of these and other materials into functional devices is encouraged.

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6 BIBLIOGRAPHY
[1] AASRA, AB. Membership in the Alberta Amputee Sport and Recreation Association, Retrieved on 11/13/2006 from: http://www.aasra.ab.ca/member.htm Advanced Arm Dynamics Inc. Retrieved on 11/10/2006 from: http://www.armdynamics.com/home.html Bar-Cohen Y., Biomimetics: Biologically Inspired Technologies, CRC (2005), pp. 267-287. Shahinpoor M., Kim K.J., Ionic polymer-metal composites. Part I. Fundamentals, Smart Mater. Struct. 10 (2001), pp. 819-833. Shahinpoor M., Kim K.J., Leo D., Ionic Polymer-Metal Composites as Multifunctional Materials, Polymer Composites 24 (2003), pp. 24-33. Shahinpoor M., Kim K.J., Novel ionic polymer-metal composites equipped with physically loaded particulate electrodes as biomimetic sensors, actuators and artificial muscles, Sensors and Actuators A-Physical 96 (2002), pp. 125-132. Zamani S., Nemat-Nasser S., Experimental Study of Nafion-based Ionic Polymer-metal Composites (IPMCs) with Glycerol as Solvent, Proc. of SPIE 5757 (2005), pp. 165- 169. Nemat-Nasser S., Wu Y., Comparative Experimental Study if Ionic Polymer-metal Composites with Different Backbone Ionomers and in Various Cation Forms, Journal of Applied Physics 93 (2003), pp. 5255-5267. Nemat-Nasser S., Wu Y., Tailoring the Actuation of Ionic Polymer-metal Composites, Smart Materials and Structures 15 (2006), pp. 909-923. Nemat-Nasser S., Zamani S., Modeling of electrochemomechanical response of ionic polymermetal composites with various solvents, Journal of Applied Physics 10 (2006). Nam B., Yoo Y., Study on Bending Behavior of Ionic Polymer Metal Composites with Various Organic Solvents and Cationic Species, Proc. of SPIE 5759 (2005), pp. 525-533. Shahinpoor M., Recent Advances in Ionic Polymer Conductor Composites Materials as Distributed Nanosensors, Nanoactuators and Artificial Muscles, Proc. of SPIE 5759 (2005), pp. 49-63. Takagi K., Luo Z., Asaka K., Tahara K., Limited-angle Motor Using Ionic Polymer-metal Composite, Proc. of SPIE 5759 (2005), pp. 487-496. Malone, E., Lipson, H., Freeform Fabrication of Electroactive Polymer Actuators and Electromechanical Devices , 15th Solid Freeform Fabrication Symposium, Austin TX, 2004, pp.697-708. Xi, B., Novel conducting polymer structures for electrochemical actuators, University of Wollongong, 2005, pp. 30-38. Diaz, A. F, Logan, A., Electroanalytical Chemistry, 1980, p. 111. Smela, E., W. Lu, and B. R. Mattes, "Polyaniline Actuators, Part 1: PANI(AMPS) in HCl," Synthetic Metals, 2005.

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