Biopolymer Composites in Electronics

Biopolymer Composites in Electronics

Edited by

K.K. Sadasivuni

Department of Mechanical and Industrial Engineering, Qatar University, Doha, Qatar

D. Ponnamma

Center for Advanced Materials, Qatar University, Doha, Qatar

J. Kim

Department of Mechanical Engineering, Inha University, Incheon, South Korea

J.-J. Cabibihan

Department of Mechanical and Industrial Engineering, Qatar University, Doha, Qatar

M.A. AlMaadeed

Center for Advanced Materials, Qatar University, Doha, Qatar

Materials Science and Technology Program, Qatar University, Doha, Qatar

Table of Contents

Cover

Title page

Copyright

Dedication

List of Contributors

Preface

Acknowledgment

1: Introduction of Biopolymer Composites: What to Do in Electronics?

Abstract

1. Introduction

2. Biopolymers and its Composites

3. Significance of Biopolymer Composites in Electronics

4. Conclusions

Acknowledgments

2: Electrical Conductivity Behavior of Biopolymer Composites

Abstract

1. Introduction

2. Poly(ɛ-Caprolactone) Polymer

3. Pure Polypyrrole

4. Polyaniline Polymer

5. Poly(3,4-Ethylenedioxythiophene): Poly(Styrene Sulfonate), PEDOT:PSS

6. Polythiophene Polymer

7. Polyacetylene

8. Conclusions

3: Biopolymer Composites With High Dielectric Performance: Interface Engineering

Abstract

1. Introduction

2. Biopolymers

3. Biodegradable Conducting Polymers

4. Methods of Synthesis of Biopolymer Composites

5. Dielectric Behavior of Polymer Composites

6. Conclusions

Acknowledgments

4: Thermal Conductivity of Biocomposite Materials

Abstract

1. Introduction

2. Biocomposites

3. Conclusions

5: Thermoelectric Properties of Biopolymer Composites

Abstract

1. Introduction

2. Thermoelectric Effect

3. Biopolymer

4. What is Biopolymer Composites?

5. Modification of Biopolymer to Biocomposites

6. Electrical Conductivity of Selected Biopolymer Composites for Making Thermoelectric Device

7. Biopolymer Composites in Thermoelectric Applications

8. Challenges and Future Trends

9. Conclusions

6: Biopolymer Composites in Fuel Cells

Abstract

1. Introduction

2. Chitosan and Its Composites Preparation Methods

3. Chitosan and Its Composite for PEM Fuel Cell Applications

4. Alginate-Based Membranes PEM Fuel Cell Applications

5. Chitosan for PEM Fuel Cell Electrode Applications

6. Biopolymers for Other Fuel Cell Membrane Applications

7. Challenges to Meet Out

8. Summary and Future Perspective

7: Biopolymer Composites in Field-Effect Transistors

Abstract

1. Introduction

2. Working of FETs

3. Applications of FETs

4. Conclusions

8: Development of Microwave Absorbers From Biopolymer Composites

Abstract

1. Introduction

2. Biopolymers Composites: An Overview

3. Natural Biopolymers Composites: A Microwave Approach

4. Synthetic Biopolymer Composites: A Microwave Approach

5. Biopolymer Composites: An Endless Source of Application

6. Conclusions

9: Biopolymer Composites for Electromagnetic Interference Shielding

Abstract

1. Introduction

2. EMI Shielding Mechanism

3. Shield Requirements and Materials for EMI Shielding

4. Conclusions

10: Biopolymer Composites in Light Emitting Diodes

Abstract

1. Introduction

2. LEDs

3. Graphene and Carbon Nanotube–Based LEDs

4. Bio-OLEDs

5. Conclusions and Challenges

11: Multifunctional Smart Biopolymer Composites as Actuators

Abstract

1. Introduction

2. EAPap

3. Ionic EAPap

4. Hybrid EAPap

5. Conclusions

Acknowledgment

12: Piezo- and Thermoelectric Materials From Biopolymer Composites

Abstract

1. Introduction

2. Basics

3. Biopolymer Nanocomposites as Piezoelectric Materials

4. Biopolymer Nanocomposites as Thermoelectric Materials

5. Conclusions

Acknowledgment

13: Development of Biosensors From Biopolymer Composites

Abstract

1. Introduction

2. Biosensors

3. Biopolymers

4. Biopolymer Composites

5. Biorecognition Element

6. Current Developments and Future Perspective

14: Development of Vapor/Gas Sensors From Biopolymer Composites

Abstract

1. Introduction

2. Fabrication of Transducers of Gas/Vapor Sensor Devices

3. Application of Biopolymer Gas/Vapor Sensors

4. Summary and Challenges

15: Biopolymers for Biocomposites and Chemical Sensor Applications

Abstract

1. Introduction

2. Cellulose

3. Starch

4. Lignin

5. Chitin and Chitosan

6. Alginate

7. Polyhydroxyalkanoates

8. Polylactic Acid

9. Pullulan

10. Collagen and Gelatin

11. Biopolymer Composites

12. Biopolymers as Chemical Sensors

13. Conclusions

16: Strain, Pressure, Temperature, Proximity, and Tactile Sensors From Biopolymer Composites

Abstract

1. Introduction

2. Synthesis and Characterization of Biopolymer Composites

3. Different Sensors From Biopolymer Composites

4. Challenges and Future Perspectives

5. Conclusions

Acknowledgment

17: Biopolymer Composites in Photovoltaics and Photodetectors

Abstract

1. Introduction

2. Photovoltaic Application of Biopolymer Composite

3. Biopolymer Composites Based UV Photodetectors

4. Conclusions

18: Application of Biopolymer Composites in Super Capacitor

Abstract

1. Introduction

2. Principle of Supercapacitors

3. Supercapacitor Materials

4. Application of Supercapacitors in Electronics

5. Conclusions

Index

Copyright

Elsevier

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Notices

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Dedication

Dedicated to a Cleaner Environment and to the Efforts in Saving it.

List of Contributors

H.S. Abdo

Center of Excellence for Research in Engineering Materials (CEREM), Advanced Manufacturing Institute, King Saud University, Riyadh, Saudi Arabia

Faculty of Energy Engineering, Aswan University, Aswan, Egypt

M. Abhilash,     School of Biosciences, Mahatma Gandhi University, Kottayam, Kerala, India

A.Y. Al Haddad,     Department of Mechanical and Industrial Engineering, Qatar University, Doha, Qatar

H.F. Alharbi,     Mechanical Engineering Department, King Saud University, Riyadh, Saudi Arabia

M.A. AlMaadeed

Center for Advanced Materials

Materials Science and Technology Program, Qatar University, Doha, Qatar

M. Basheer Ahamed,     Department of Physics, B.S. Abdur Rahman University, Chennai, Tamil Nadu, India

P.R. Bhagat,     Department of Chemistry, School of Advanced Sciences, VIT University, Vellore, Tamil Nadu, India

M. Borah,     National Physical Laboratory, New Delhi, India

J.-J. Cabibihan,     Department of Mechanical and Industrial Engineering, Qatar University, Doha, Qatar

K. Chidambaram,     Department of Physics, School of Advanced Sciences, VIT University, Vellore, Tamil Nadu, India

E. Collins,     Center of Advanced Materials, Qatar University, Doha, Qatar

T.K. Das,     Department of Chemistry, Barchana Women’s College, Jaipur, Rajasthan, India

K. Deshmukh,     Department of Physics, B.S. Abdur Rahman University, Chennai, Tamil Nadu, India

R.R. Deshmukh,     Department of Physics, Institute of Chemical Technology, Mumbai, Maharashtra, India

G. Dharman,     Biomaterials in Medicinal Chemistry Laboratory, Department of Natural Product Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai, Tamil Nadu, India

A.A. Elzatahry,     Center for Advanced Materials, Qatar University, Doha, Qatar

J.P. Gogoi,     Department of Physics, The Assam Kaziranga University, Jorhat, Assam, India

S. Haque,     Department of Electrical and Computer Engineering, Sungkyunkwan University, Seoul, South Korea

H. Javed,     Department of Mechanical and Industrial Engineering, Qatar University, Doha, Qatar

M. Karkri,     CERTES Laboratory, Université Paris Est Créteil Val de Marne, Paris, France

S.K. Khadheer Pasha,     Department of Physics, School of Advanced Sciences, VIT University, Vellore, Tamil Nadu, India

K.A. Khalil

Faculty of Energy Engineering, Aswan University, Aswan, Egypt

Mechanical Engineering Department, King Saud University, Riyadh, Saudi Arabia

J. Kim,     Department of Mechanical Engineering, Inha University, Incheon, South Korea

M. Krebsz,     School of Chemical Engineering, The University of Adelaide, Adelaide, SA, Australia

B. Kumar,     Department of Mechanical and Industrial Engineering, University of Illinois at Chicago, Chicago, IL, United States

D. Losic,     School of Chemical Engineering, The University of Adelaide, Adelaide, SA, Australia

M. Mohiuddin

Department of Operations Management, American International University-Bangladesh, Dhaka, Bangladesh

School of Engineering, RMIT University, Melbourne, VIC, Australia

A. Muthumeenal,     PG and Research Department of Chemistry, Polymeric Materials Research Lab, Alagappa Government Arts College, Karaikudi, Tamil Nadu, India

A. Nagendran,     PG and Research Department of Chemistry, Polymeric Materials Research Lab, Alagappa Government Arts College, Karaikudi, Tamil Nadu, India

G.J. Ogunleye,     Center for Advanced Materials, Qatar University, Doha, Qatar

E. Okonkwo,     Nnamdi Azikiwe University, Awka

P.C. Okonkwo,     Center of Advanced Materials, Qatar University, Doha, Qatar

T. Pasinszki,     Institute of Chemistry, Eötvös Loránd University, Budapest, Hungary

S. Sundar Pethaiah,     Technische Universität München—Campus for Research Excellence and Technological Enterprise, Singapore

D. Ponnamma,     Center for Advanced Materials, Qatar University, Doha, Qatar

S. Prusty,     School of Biological Sciences, National Institute of Science Education and Research, Bhubaneswar, Odisha, India

M. Rahman,     School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, South Korea

M. Rajan,     Biomaterials in Medicinal Chemistry Laboratory, Department of Natural Product Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai, Tamil Nadu, India

K.K. Sadasivuni,     Department of Mechanical and Industrial Engineering, Qatar University, Doha, Qatar

S.N. Sawant,     Chemistry Division, Bhabha Atomic Research Centre, Mumbai, Maharashtra, India

P. Sharma,     Department of Mechanical Engineering, University of Houston, Houston, TX, United States

M.S.A. Sher Shah,     School of Chemical Engineering, Sungkyunkwan University, Suwon, South Korea

V. Subramanian,     School of Engineering & Applied Sciences (SEAS), Ahmedabad University, Ahmedabad, Gujarat, India

M. Sumathra,     Biomaterials in Medicinal Chemistry Laboratory, Department of Natural Product Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai, Tamil Nadu, India

D. Thomas,     Research & Development Centre, Bharathiar University, Coimbatore, Tamil Nadu, India

T.T. Tung,     School of Chemical Engineering, The University of Adelaide, Adelaide, SA, Australia

D. Varade,     School of Engineering & Applied Sciences (SEAS), Ahmedabad University, Ahmedabad, Gujarat, India

W.J. Yoon,     School of Science, Technology, Engineering, & Mathematics, University of Washington, Bothell, WA, United States

Preface

Extensive scientific research is going on for keeping the environment safe, free of pollution, and reducing the waste materials. Among several ways to maintain the eco-friendly devices and biodegradable by-products, manufacturing biocomposite materials has utmost significance. The biocomposites are generally made of biopolymers and also biobased filler materials. Natural polymers like cellulose, chitosan, starch, etc. come under the biopolymer category; in addition to the synthetic biopolymers like polylactic acid, polyethylene glycol, etc. The present book is a reflection for these biopolymers and their various composites used in electronic applications. It covers the fabrication processes, testing the materials, biodegradability checking, and different uses of them in optics, fuel cells, photovoltaics, sensors, actuators, dielectrics, electromagnetic shielding, thermoelectric piezoelectrics, flexible displays, and microwave absorbers.

In this modern world, the structural characteristics and related physicochemical and functional properties of biopolymer composites are gaining interest, and the book is aimed to provide an up-to-date, coherent, and objective collection of data from eminent researchers. Other than the design, polymer assemblies, filler architecture, interfaces, and interphases are the subjects of hot study. The flexible large area panels used nowadays for monitoring purposes are made of biocomposites and their simplicity and cost of production are very feasible as compared to the highly sophisticated and expensive semiconductor micro- and nanoelectronics. Tailoring the polymer properties and the filler—both micro and nano—influence in future electronic devices is expected to be an asset to the modern technology. Many electrical, electronic, mechanical, and optical, multipurpose devices with low cost and high efficiency are envisaged.

Finally the latest ideas, most recent research and technological progress are included in a comprehensive style suitable for undergraduates, postgraduates, and academics. Using this book, the reader will be capable of gaining a consolidated view of the immense potential of biopolymers and their composites containing plant fibers, cellulose crystals, microfibrillar materials, etc. to make the world greener. In addition to the traditionally established applications, the uses that can emerge in the near future are also a matter of study of this book. The chapter authors have done a good task in reviewing the different aspects of biopolymer composites and the main challenges existing to effectively apply them in the field of electronics. A uniform reader strategy was followed throughout the book, and all points that can satisfy a variety of readers, like students, researchers, teachers in academia, professionals in industry, and government agencies, etc. are included in the discussion. In summary the efforts behind this book are immense and the investigation on biopolymer materials applicable in electronics will open a new pathway to industrialize the biodegradable, light weight, and flexible materials as electronic counterparts.

Acknowledgment

This book was made possible by two National Priority Research Program grants: NPRP 6-282-2-119 and NPRP 4-368-2-135 from the Qatar National Research Fund (a member of Qatar Foundation).

1

Introduction of Biopolymer Composites: What to Do in Electronics?

D. Ponnamma*

K.K. Sadasivuni**

M.A. AlMaadeed*,†

*    Center for Advanced Materials, Qatar University, Doha, Qatar

**    Department of Mechanical and Industrial Engineering, Qatar University, Doha, Qatar

†    Materials Science and Technology Program, Qatar University, Doha, Qatar

Abstract

Environment friendly, biodegradable and nontoxic materials especially from renewable resources are attaining great levels of attention nowadays. Biopolymers contribute a very significant division of materials through which numerous commercial products possessing the aforementioned characteristics can be made. Electronics requires lightweight and low cost components with superior properties like charge–discharge capability, dielectric properties, microwave absorption properties, actuation, transparency, etc. One of the major challenges existing in the field of electronics is the safe disposal of e-waste. The role of eco-friendly and biodegradable biopolymers and their composites in electronics is the subject of this chapter. Various biopolymers and their composites, capable of different applications in the electronics industry, are introduced here.

Keywords

biocomposites

fibers

sensor

thermal properties

energy storage

1. Introduction

Polymers and their composites have opened up a new horizon in the engineering and technology. The lightweight, easy processability, corrosion resistance, less energy requirement while assembling and integrating, higher strength, stiffness, fatigue resistance, etc. are the major advantages of such polymeric materials [1]. Since these properties vary with polymers and the fillers used to reinforce them, different kinds of polymers and nano and microfillers are generally employed depending on the basic needs [2,3]. Conducting polymer nanocomposites have much significance in fabricating flexible and transient materials and devices useful in biomedical, military, electronics, robotics, and intelligent applications. Such materials form the basis of the vast development of flexible, stretchable, wearable, and transient electronics [4,5]. However, the selection of a particular composite is usually done based on a particular requirement [6].

Smart polymer composites become more attractive if they are biocompatible and biodegradable. Now, the world is concerned about green energy and many researches are going on in the area of biodegradable polymers. The biocomposites are very helpful in biomedical field as well as in biodegradable electronics [7]. Acar et al. well illustrated the importance of biomaterials in transient and bioelectronics in their study [6]. They used polyvinyl alcohol (PVA) as a matrix and gelatin and sucrose as fillers to synthesize the composite and thus made insulating composites. Due to the triple helixes present in the structure of gelatin, its composite was much stronger. There are also reports on the electromechanical behavior of natural biopolymer chitosan filled with carbon nanotubes (CNTs). The chitosan is also capable of segregating CNTs even at very high concentration [8].

This specific chapter aims in providing a detailed information about various biopolymers, their composites, and their role in electronics. Various fields such as sensors, actuators, field effect transistors, energy harvesting devices, supercapacitors, robotics, etc. will be covered. The influence of filler geometry, shapes, concentration, and the properties of typical biopolymers on the composite properties will be investigated in brief.

2. Biopolymers and its Composites

Biopolymers are polymers that biodegrade. The different properties of biopolymers include renewability, sustainability, nontoxicity, and biodegradability [4–7]. They are also neutral, noncarcinogenic, and nonimmunogenic. Depending on the materials from which the biopolymers originate, it can be classified into renewable and synthetic biopolymers. The biopolymers obtained from renewable sources are cellulose, starch, chitosan, sugar, etc. These can also be mentioned as structural biopolymers including polysaccharides, polypeptides, and polyphenols as illustrated in Fig. 1.1.

Figure 1.1   Structural biopolymers.

The global biopolymer production capacity reached 766,000 metric tons in 2009 and 1.5 million metric tons in 2011. The annual bioplastic production during the period of 2007–11 is represented in Fig. 1.2. Every year a bioplastic conference is hosted by European Union to discuss the significant growth occurring in this particular field and its growing demands in various technologies. In 2015, the conference organized a vast bioplastic focused exhibition in addition to the topics like comprehensive and insightful industry update and huge network opportunities for the biobased/nonbiodegradable polymer share [2–7].

Figure 1.2   Annual bioplastic production 2007–11.

Cellulose is the most common organic compound and biopolymer on Earth. In plants, about 33% is cellulose, its content in cotton is 90% whereas in wood, 50%. The good transparency and biocompatibility make cellulose and its derivative cellophane applicable in packaging industries. Chitosan is the second most abundant naturally occurring biomolecule and is biocompatible, low-cost, and smart with useful biological and chemical properties. Collagen is another biopolymer which is the most abundant protein in mammals. The denatured collagen known as gelatin is useful to make sausage casings, drugs, vitamins, and also have other industrial applications like photography. The protein and DNA also come in the category of biopolymers in living organisms [1,7].

However there is also another category called synthetic biopolymers, examples of which are PVA, polylactic acid (PLA), l-polylactic acid (PLLA), polybutyrals, etc. The synthetic biopolymers can be synthesized by polymerizing a specific monomer unit or by chemically modifying a naturally occurring polymer to achieve desirable properties. For instance, polyesters capable of making water-resistant bottles, cooking accessories, etc. are now produced from natural resources—like starch and sugars—through large-scale fermentation. PLA is a significant commercial polymer, useful for recyclable and biodegradable packaging, such as bottles, yoghurt cups, and candy wrappers. Other significant applications of PLA include waste bags, paper and cardboard coatings, carpets, clothing, wall covering, and also biomedical uses such as sutures, catheters, and prosthetic materials. With glass fiber reinforcement, PLA finds long-lasting durable applications in agricultural equipment, automotive parts, and construction materials. Natural biofibers like those from jute, hemp, flax, wood, and even straw or hay can replace these glass fibers and can be applied in the construction industry; it would provide a new use for an abundant, rapidly renewable agricultural commodity and at the same time conserve less rapidly renewable wood fiber [9,10].

Biopolymer nanocomposites consist of biopolymers filled with nanoparticles of 1–100 nm. Such materials exhibit much more improved properties in comparison with biopolymers because of the high aspect ratio and high surface area of the fillers employed. A list of bionanocomposites useful for packaging applications is given in a review article by Rhim et al. [9]. Table 1.1 shows a list of bionanocomposites with different biopolymer matrices and the fillers along with the process of synthesis and the most significant property emerged out of the material. If the reinforcing nanoparticles are conducting, the resultant composites generate excellent electrical and electronic applications and those composites are generally known as conductive polymer nanocomposites (CPC).

Table 1.1

Synthesis and Application for Various Bionanocomposites

An attempt to use wood-based cellulose in nanoscale for creating artificial ligaments and tendons with good mechanical properties was made by Mathew et al. [10]. The developed product was similar to or better than the natural ligaments or tendons. During the process of fabricating the artificial tendons/ligaments, major properties like biocompatibility, mechanical strength as well as resistance to in vivo moisture, temperature conditions, and cyclic loading conditions were carefully tuned. It is ideal to check the properties at human body temperature since elevated temperatures can dehydrate the specimen and affect its properties. Cherian et al. also illustrated the significance of cellulose for biomedical applications [27] especially to fabricate various versatile medical implants. Nanocellulose fibers were obtained from pineapple leaf fibers by hydrolysis and compression molding was applied to stack the nanocellulose fiber mats between polyurethane to make the specimen. The nanofibrils at 5 wt.% increased the strength of polyurethane by 300% and the stiffness by 2600%.

3. Significance of Biopolymer Composites in Electronics

In order to design and fabricate degradable and transient electronic devices for biomedical and other significant applications, thorough knowledge about the controlled degradation and material transiency is very necessary [6]. By adding gelatin or sucrose to PVA, the transiency of the resulting composite was increased/decreased by Acar et al. They have used both theoretical and experimental results to prove the effect of physical and chemical properties of the composites as well as its structure on the dissolution and transiency rate of the polymer composite film. Dissolution of the composites was correlated with the inverse exponential functions of different time constants and thus observed the transiency—the lower the time constant, the faster the transiency. In the PVA/gelatin/sucrose composites, gelatin resulted in enhanced time constants, whereas sucrose lowered the time constants.

A significant level of applications is reported for biopolymers and their composites including packaging films, biomedical applications, tissue engineering, etc. However, the task here is to investigate its usefulness in the field of electronics. A large number of works are established on the applications of biopolymer composites in fabricating sensors, actuators, electromagnetic shielding materials, microwave absorbers, and so on. For example, the poly (l-lactide) is well known for its crystalline behavior and optical transparency. As mentioned earlier, PLA is a biodegradable and aliphatic linear thermoplastic polyester produced from renewable plant sources. It is nontoxic and possesses excellent mechanical, optical, thermal plasticity, and process ability especially in its composites. The dramatic improvement in the physical and mechanical properties, including stiffness and toughness, thermal stability, gas barrier properties, and electrical and thermal conductivity for the nanocomposites based on such thermoplastic biopolymers is mainly due to the high aspect ratio and high surface area of the nanofillers [28]. Though PLA possesses low degree of crystallinity, it is used for fabricating conducting polymer nanocomposites. This is done by employing conducting nanoparticles in the matrix, for instance, Kumar et al. used CNTs as the reinforcing nanoparticles to develop electrically conducting PLA composites [29]. CNTs improved both crystallinity and conductivity of PLA and its better chemo-resistive properties anticipate industrial application such as e-nose used for quick disease detection. The research also substantiates the application of PLA/CNT CPC in vapor sensing.

Very recently, cellulose paper was invented to be useful in fabricating sensors and actuators [30] and it is also termed as electro active paper (EAPap) [31]. The major advantages of this material include its lightweight, low cost, biodegradability, and low power consumption. However the low actuating frequency and output force of the EAPap demand its reinforcement with certain nanoparticles. In a group of research, homogeneous distribution of multiwalled carbon nanotubes (MWCNTs) was made in cellulose by covalent grafting as well as blending methods. The covalent grafting, in particular, overcame the disadvantages of cellulose EAPap by providing stable electron pathways for the cellulose transistor and by providing the mechanical strength. This also enhanced the resonance frequencies of the EAPap to higher band. However the authors have not paid significant attention to the piezoelectric effect occurring in cellulose [32–35] and to the effect of functional groups present on the CNTs or to the CNT alignment.

Other than cellulose, chitin is the next abundant biopolymer on earth. It is chemically defined as poly(-(1f4)-N-acetyl-d-glucosamine) and is capable of existing in both R and S forms. Chitin is present in the form of ordered crystalline microfibrils and forms many biodegradable, nontoxic, and antibacterial composites. These materials are applicable in food industry and biosensors due to its gel forming properties and are also applicable in providing reinforcement and strength. Reports explain the use of chitin as composite fillers useful for electrolytes and batteries [36,37]. The usual problems associated with the liquid electrolytes used in rechargeable lithium batteries of portable electronic devices are their high level inflammability, and these can be solved if polymers like chitin are used. It can also provide flexible shape, high energy density, and safer handling to the fabricated composites.

Activated carbons, CNTs, and graphene are established as the ideal candidates for supercapacitor electrodes because of their high specific surface area, high electrical conductivity, and accessibility to electrolytes. Supercapacitors based on such porous nanoparticles are the subject of great interest nowadays and possess excellent energy storage in addition to the rapid charge discharge capacity, high power density, and long-term stability. Deng et al. fabricated MWCNT/cellulose nanocomposite by electrospinning method using cellulose acetate/CNT solution followed by deacetylation and finally the CNFs from the precursor. The MWCNTs affected the precursor stabilization by reducing the activation energy of cellulose nanofibers from ∼230 to ∼180 kJ/mol and also enhanced the electrical conductivity and crystallite size of the activated CNFs. The nanotubes made the CNF surface rough and its electrochemical capacitance became 145 F/g at 6% of MWNTs based on the value 105 F/g for pure cellulose nanofibers at a current density of 10 A/g [38].

Organic bioelectronics mainly rests on degradable materials [7] and is a significant and new field of transient electronics [39,40]. Devices based on silicon nanomembranes [41] and peptides [42] used in biomedical devices usually degrade after a specific period unlike the long-lasting pacemakers and joints. Normally degradation duration differs based on the application, for instance the sutures should last for a few days, whereas the drug carriers should immediately break down. Therefore designing and fabricating materials with a range of degradation durability is very significant and normally the term transient stands for such programmable degradable materials. In biomedical field, transient materials are useful as nanoantibiotic/therapeutic agent to control surgical site infection [43], electrical signal detectors at the brain surface to monitor abnormal brain activities [44,45]. In an open skull procedure of detecting brain activities, Kim et al. used dissolvable flexible electronics containing microelectrodes [45] and the electrical signals from brain are collected at the electrode’s surface and then transmitted to monitoring recorder. The problems associated with open skull procedure like additional surgeries to remove biomedical devices can be eliminated in closed skull method using transient materials [46].

Flexible electronics can design special transient devices matching with the three-dimensional curved structure of the organs. However designing the interface with the nonplanar and nonstatic tissue and ensuring the biocompatibility, biodegradability, and bioresorbability of the bioelectronics device are much significant [47,48]. The mechanical properties of the materials have also been the subject of study while fabricating the transient electrodes [49,50]. Since such materials are widely used in military, biomedical, and intelligence applications and each application requires specific physicomechanical and chemical properties, typical materials and preparation methods are used to derive the final products. The most common methods of preparation include photolithography [50] and surface modification [51]. Bettinger et al. were the first to apply in biodegradable electronics by developing a field effect transistor using PVA as gate dielectric, and 5,5′-bis-(7-dodecyl-9H-fluoren-2-yl)-2,2′-bithiophene (DDFTTF) as organic semiconductor [52]. The poly(l-lactide-co-glycolide) (PLGA) is a conventional biodegradable substrate with high durability to degradation, whereas the peptide-based substrates degrade instantly especially when exposed to phosphate buffered saline [53]. There are reports on caramelized sugar-based bioelectronics devices [54,47], but with less mechanical properties. The biocompatibility and water solubility help magnesium and its derivative compounds applicable in conducting transient materials [40]. Semiconducting materials based on polymers [55], silicon nanomembranes [41], peptides [42], natural dyes [56], melanin [57], etc. are well reported. Compared to the insulating substrates conducting-insulating systems are investigated as transient substrates. Legnani et al. used bacterial cellulose membrane deposited with indium tin oxide (impart conductivity) as a platform to construct an organic light emitting diode [58]. The degradation of this flexible and biodegradable membrane took about 70 days in acidic medium. Silk fibroins as ultrathin membranes [45] and as an insulating substrate are also used for fabricating biointegrated electronics [40]. In short the field of bioelectronics needs more investigation on the structural and functional properties of the biocomposites and it is covered in this book.

4. Conclusions

Materials coming out of nonrenewable and nonbiodegradable sources have less significance in the current electronic industry. Bioderived polymers and their composites containing various particles are becoming inevitable parts of portable and transient electronics. Various biomaterials in nature include the cellulose, chitin and chitosan, amino acids, DNA, etc. which were often reinforced with silicon or magnesium nanoparticles to make electronic devices like thin film transistors. Other than the biomedical applications, transient electronic materials find uses in military field as well. The biopolymer composites possess major advantages of flexibility, biocompatibility, and tunable degradability which often make them useful for wide range of industrial products.

Acknowledgments

This chapter is made possible by NPRP grant 6-282-2-119 from the Qatar National Research Fund (a member of Qatar Foundation). The statements made herein are solely the responsibility of the authors.

References

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2

Electrical Conductivity Behavior of Biopolymer Composites

H.S. Abdo*,**

A.A. Elzatahry†

H.F. Alharbi‡

K.A. Khalil**,‡

*    Center of Excellence for Research in Engineering Materials (CEREM), Advanced Manufacturing Institute, King Saud University, Riyadh, Saudi Arabia

**    Faculty of Energy Engineering, Aswan University, Aswan, Egypt

†    Center for Advanced Materials, Qatar University, Doha, Qatar

‡    Mechanical Engineering Department, King Saud University, Riyadh, Saudi Arabia

Abstract

Interest in the study of biopolymer system has been continuously growing as a result of a variety of promising applications such as in electronics, medicine, food packaging, bioplastics, and coating. Characteristics such as being electrically conductive, biosafe, renewable, biodegradable, and carbon neutral have made application of biopolymer important in the production of environment friendly products. However, conventional polymer has been reported to have a few limitations in their properties. Biopolymer itself normally is not conductive. Inorganic nanofillers are being added to the biopolymer matrix to enhance its electrical conductivity which greatly differ from the conventional biopolymer and exhibit unexpected properties. Therefore, different types of nanofillers have been produced for this purpose. The effect of the kind of biopolymer base and also filler material on the electronic conductivity of the composite will probably be investigated and reviewed in this work.

Keywords

electrical conductivity

nanofillers

biopolymer composites

conductive polymers

1. Introduction

Biopolymer matrix mixed with different nano or microparticles of conductive metal is of interest for different scientific fields [1–9]. Electronic properties of these composites are approximately near the characteristics of metals, while the processing methods and mechanical characteristics are exactly same as nonconductive polymers [2,9]. Experimentally, it was reported that the size of particles and their shape are the most parameters affect the electrical conductivity of such polymers [9–11].

Silver (Ag) considers the most thermal and electrical conductivities among all metals [12] and silver nanoparticles have used in many purposes in antimicrobials, conductive inks, and electronics [13]. The conductivity of metal nanoparticles is similar to that of the metal powder, but the dispersion of such nanoparticles in an insulating polymer matrix prevents the conductive network formation in the nanostructured, which is substantial for increasing the electrical properties in a bulk material [14].

Today there are over 25 conductive polymer systems [15]. For a list of conductive polymers, see Table 2.1.

Table 2.1

A List of Conductive Polymers and Their Abbreviations [15]

Source: Creative Commons Attribution License (cc by).

2. Poly(ɛ-Caprolactone) Polymer

2.1. Pure PCL Polymer

Polycaprolactone is a bioresorbable semicrystalline poly(α-hydroxyester). It degrades slowly by hydrolysis due to its high crystallinity and hydrophobic nature [16,17]. It was used in many fields, such as implantable biomaterials, biodegradable materials, and microparticles for drug delivery [18,19]. The new descent of biomaterials is going to be involved and active, therefore competent at smooth linkage with encirclement tissues. Particularly, it is needed for materials, which can integrate stimulating cues. As an illustration, stimulation of healing bones, skin, and connective tissue using electrical fields have been shown [20–23].

2.2. PCL Polymer With CNT/Ag Additives

Fortunati et al. [24] have studied the effect of carbon nanotubes (CNTs) and silver nanoparticles (Ag_NP) on the multifunctional conductive biopolymer composites. They found thatAg_NP simplify the creation of conductive passageway in the presence of single-walled carbon nanotubes, statute as conductive links among nanotube bundles, and simplify the transfer of electrons (Fig. 2.1). They performed the biological test experiments on polycaprolactone + 15% silver, polycaprolactone + 1% SWCNTs, and polycaprolactone + 15% silver + 1% SWCNTs. The appropriateness of those conductive composite coatings as probable for basic human bone marrow mesenchyme system cells was exhibited displaying identical viability and cell material interaction in the tradition interval. They recommended that this strategy could serve as a design guide for other biomaterial applications of excessive effectiveness conductive biocomposites.

Figure 2.1   Electrical conductivity of different high performance conductive composites [24]. Copyright 2016. Reproduced with permission from Elsevier Ltd.

3. Pure Polypyrrole

3.1. Pure PPy Polymer

The preparation process and polymer additives affect strongly the electronic conductivity of PPy, which is prepared chemically in aquatic solution. In addition, some of recent researches illustrate that the use of polymers could control the electrical conductivity by sterical stabilization of PPy chains [25]. To achieve this target, water soluble polymers which have molecular mass more than 22,000 g/mol such as PVAc, methyl cellulose, PEO, poly(2vinylpyridine), PVP, poly(vinylmethylether), and others were studied by Rodriguez et al. [26]. They found that, by using those additives, electrical conductivity of a wide range 10−9 : 10−12 S/cm can be achieved [26]. Specially, for polyethylene-oxide (PEO) with a molar mass of 131,000 g/mol an electrical conductivity of 2.1 × 10−3 S/cm was achieved [27–31].

3.2. PPy Polymer With PEG Additives

Using the oxidative polymerization process, Kang and Geckeler [31] have studied the effect of adding poly(ethyleneglycol) (PEG) additive on the multifunctional conductive PPy. They found that the electrical conductivity becomes greater than the PPy one that was produced without any additives (pure PPy). Exciter, there seemed to be an efficient relation between the electrical conductivity of PPy and the percentage of additives (Fig. 2.2).

Figure 2.2   Conductivity of polypyrrole (PPy) as a function of PEG additive [31]. Copyright 2016. Reproduced with permission from Elsevier Ltd.

3.3. PPy/FeCl3/Ammonium Persulfate

Ilicheva et al. [32] have proposed a technique for obtaining three-component composite materials on the basis of polyethylene (PE) substrate modified with grafted polyacrylic acid (PAA) and PPy. Iron chloride (III) or ammonium persulfate were used as oxidizers (Figs. 2.3 and 2.4). They showed that the composite materials exhibit good mechanical properties due to the presence of PE film tightly bonded with PPy through PAA. The materials thus obtained combine electronic and ionic conductivities with high mechanical strength. The ways of increasing electronic conductivity are determined [32].

Figure 2.3   Dependence of PPy content (1) and conductivity of PPy (2) on the concentration of FeCl3 [32]. Creative commons attribution license (cc by).

Figure 2.4   Dependence of PPy content (1) and conductivity of PPy (2) on the concentration of ammonium persulfate [32]. Creative commons attribution license (cc by).

The objective of their studies was focused on increasing the electrical conductivity of the PPy polymer due to increasing monomer concentration in the reaction mixture and repolymerization of pyrrole in the obtained composite material. It was established that increase of pyrrole concentration in the reaction mixture from 0.3 to 0.9 mol/dm³ did not significantly improve the electric conductivity (1.62 and 1.66 S/cm). However, under repolymerization of pyrrole, the electric conductivity increased more than three times: 1.66 and 5.43 S/cm for single and double polymerization, respectively [32].

4. Polyaniline Polymer

4.1. About PANI Polymer

PANI was primarily found by Runge in 1834, but it was generally known as black aniline [33]. In 1862, Letheby conducted some researches to characterize and analyze this new material [33]. PANI was recognized as a polymer in mixed-oxidation phase. It consisted of oxidized quinoid sets and reduced benzoid sets [34]. In 1912, Woodhead and Green [35] discovered these interesting properties of PANI. Moreover, under certain experimental conditions, it was detected that PANI had the properties of converting between a conductor and semiconductor and an insulator [36]. Since that time, PANI (PANI) has grown to be an area as well as attractive topic of impressive attraction for researching [37,38].

PANI can be created by different amalgamation of the two sets known as X and Y elements of PANI [34]. Due to this, PANI has different unique characteristics and electrical conductivity techniques that differentiate it from the other conducting polymers. As an example, the PANI conductivity differs with the degree of oxidation and the extent of protonation.

4.2. Polyaniline–Silver Nanocomposites

Varga et al. [39] have presented a brief overview of the electrical properties of conductive composites containing silver and conducting polymer–PANI. Composites were produced by oxidation of PANI with silver nitrate (AgNO3) in the existence of different acids playing the factor of doping agents. A semiconducting behavior was observed under the threshold about 21–27 vol.% of silver in composite and a metallic one above. From the temperature dependence of conductivity several charge transport mechanisms were proposed to explain experimental data with the most likely option of a superposition of the variable range hopping or the charging energy limited tunneling model with the Arrhenius-like activated transport.

Changing the proportion of silver nitrate in the reaction mixture a variability in silver content in the target product was achieved, within the range of 0–27 vol.% for salts and 0–30 vol.% for bases, respectively. A powerful reliance of the electrical conductivity on metallic silver amount was observed (Fig. 2.5) with a critical value of its volume fraction (threshold) separating two qualitatively different regions. One being under the threshold with the conductivity about 100 S/cm typical for PANI salts, showing no significant dependence on used dopant, respectively, 10−6 S/cm for bases, a value 1000 times higher than is typical for silverless deprotonated PANI. This could be ascribed to the conductivity of a granular metal system embedded in an insulating matrix. The other region with typical conductivity about 10³ S/cm is above the threshold. The high value of conductivity is believed to be a consequence of the presence of conducting paths through the material due to high amount of silver. Since the insufficient number of experimental data did not allow us to determine the exponent and the threshold, following from the percolation theory so far, we at least estimated the threshold being in the range of 21–24 vol.% for salts and 5–27 vol.% for bases [39].

Figure 2.5   The dependence of the electrical conductivity at room temperature of polyniline-silver composites (salts of MSA, deprotonated bases of MSA, salts of AC) on the silver content [39].

The tendency of PANI morphology controlled by customizing the production circumstance has led to the generation of PANI of different structural forms including nanoparticles, nanorods, and nanotubes. These different structural forms which alienable with PANI are created achievable by the use of dopants like has large MW sulfonic-acids. So that, the differences in the molecular aggregation of the polymer imply that an array of electronic characteristics is realizable with doped PANI. Thence enables the polymer to possess an extensive in biosensors and electrochemistry application [39].

5. Poly(3,4-Ethylenedioxythiophene): Poly(Styrene Sulfonate), PEDOT:PSS

5.1. Pure (PEDOT:PSS) Polymer

As guaranteeing materials for electrodes in optoelectronic applications, PEDOT:PSS has surfaced. It has a lot of merits greater than further conducting polymers, like excellent thermal stability. It can be processed in watery solution [40,41]. Subsequently, it is often commonly used as a material for inkjet printing and as an electrodes buffer layer in organic chemistry [42,43]. Latterly, it was discovered that the electrical conductivity of poly(3,4 -ethylenedioxythiophene):poly(styrene sulfonate) coatings is generally developed by the inclusion of polyalcohols in high dielectric-solvents, like DMSO and DMF, to a PEDOT:PSS mixture [44–46].

5.2. Improvement of (PEDOT:PSS) Conductivity

Kim et al. [47] have measured the direct current conductivity (σDC) of PEDOT doped with PSS with different organic solvents. They reported the improvement of σDC in the PEDOT/PSS mixture by means of the modification of solvent conductivity from ∼0.8 to ∼80 S/cm−1. The temperature reveals that the PEDOT/PSS system achieves the essential system once some of the natural solvents like THF, DMSO, and DMF are used (Fig. 2.6).

Figure 2.6   Temperature dependence of σ DC (T) of PEDOT/PSS layers using different natural solvents [47].

6. Polythiophene Polymer

6.1. Pure PTh Polymer

PTh has been commonly used in thermally stable conjugated and environmentally biopolymer materials since 1980 [48]. It is used as optical and chemical sensors, DNA detectors, molecular devices, and many other applications [49–53]. Different polymerization approaches of thiophene are already documented in the publications. The first approach is electro-polymerization, second is chemical oxidative polymerization, and the third is metalcatalyzed coupling reactions. In 1983, Waltman et al. [54] successfully produced high conductive PTh thin layers by the first technique, but it is rarely used in electroluminescent materials preparation. Lin and Dudek [55] have documented the polycondensation of PTh catalyzed by Ni (bipy) Cl2, and identical outputs were also reported by Yamamoto et al. [48]. Latterly, Kim and his researchers [56–61] produced PTh in watery dispersion solution and characterized its characteristics.

6.2. Polythiophene/TiO2 Nanocomposites

Uygun et al. [62] have possessed a core–shell structure from a mixture of PTh polymer and nanoparticles of titanium-dioxide (TiO2), It was produced using oxidative-polymerization of thiophene using iron chloride in the existence of three various surfactants: cationic, nonionic, and anionic. In the presence of surfactant materials, the electrical properties of the nanocomposites were scrutinized, and the best semiconductor features were reported for PTh/TiO2 anionic regime.

Fig. 2.7A–D shows the electrical conductivity of the nanocomposites using a log σ T versus 1/T plot. It is clearly proportional to temperature up to 21–26° C. Over these temperature ranges and up to 36°C, the electrical conductivity unexpectedly dropped down [62].

Figure 2.7   Temperature dependence of total electrical cond. (rT) polythiophene/TiO2 composite system.

(A) NaDBS-doped polythiophene/TiO2, (B) dedoped polythiophene/TiO2, (C) TTAB-doped polythiophene/TiO2, and (D) Tween 20–doped polythiophene/TiO2 [62]. Copyright 2016. Reproduced with permission from Elsevier Ltd.

7. Polyacetylene

7.1. About PAc Polymer

Conducting biopolymers are the topic of current fundamental and industrial research [63,64]. The characteristic benefit of those kinds of materials is the conjugated dual link. Polyacetylene, (CH)x, is the least restrictive as well as the most significant representative of these different types of substance. The thermodynamically stable temperature conductivity of polyacetylene can be varied over more than 16 rules of importance making CH recommended for several purposes, like solar cells [65], rechargeable batteries [66], and also as a part of the future computers [67]. To try to answer these questions, Ehinger et al. [63] have performed DC and microwave conductivity measurements in the temperature scale of 10–330 K at doping degrees where the magnetic vulnerability is not high [68]; they find, however, that they can describe their results by conventional transporter between disturbance-induced centralized states. The theory that they apply there was originally developed for amorphous inorganic semiconductors [69] and probably will not take advantage of the solitonic benefits of the defects [63].

7.2. Polyacetylene/SWCNT Composite

Ku et al. [70] have synthesized water soluble SWCNT-poly-acetylene [single-walled carbon nanotube-PA, single-walled carbon nanotube-P(2EPy-MeTf)] nanocomposites via surface initiated grafting-from method. The loading of single-walled carbon nanotube in the SWNT grafted ionic poly-acetylenes was estimated to be 21%. The SWNT-poly-acetylene mixture showed high water solubility (8 mg/mL). According to their results, the electrical conductivity at room temperature of the doped single-walled carbon nanotube-poly-acetylene composites was reported to be within the range of 1023–1024 S/cm.

They observed that the single-walled carbon nanotube poly-acetylene composites are highly water soluble and the electrical conductivity of the doped single-walled carbon nanotube poly-acetylene composites is 2 degrees of magnitude higher than the previously recorded values for poly-acetylene composites. [70]

8. Conclusions

A review