A list of representative polymers and their abbreviations.
\\n\\n
Released this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\\n\\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
Note: Edited in March 2021
\\n"}]',published:!0,mainMedia:{caption:"Highly Cited",originalUrl:"/media/original/117"}},components:[{type:"htmlEditorComponent",content:'IntechOpen is proud to announce that 191 of our authors have made the Clarivate™ Highly Cited Researchers List for 2020, ranking them among the top 1% most-cited.
\n\nThroughout the years, the list has named a total of 261 IntechOpen authors as Highly Cited. Of those researchers, 69 have been featured on the list multiple times.
\n\n\n\nReleased this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\n\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
Note: Edited in March 2021
\n'}],latestNews:[{slug:"webinar-introduction-to-open-science-wednesday-18-may-1-pm-cest-20220518",title:"Webinar: Introduction to Open Science | Wednesday 18 May, 1 PM CEST"},{slug:"step-in-the-right-direction-intechopen-launches-a-portfolio-of-open-science-journals-20220414",title:"Step in the Right Direction: IntechOpen Launches a Portfolio of Open Science Journals"},{slug:"let-s-meet-at-london-book-fair-5-7-april-2022-olympia-london-20220321",title:"Let’s meet at London Book Fair, 5-7 April 2022, Olympia London"},{slug:"50-books-published-as-part-of-intechopen-and-knowledge-unlatched-ku-collaboration-20220316",title:"50 Books published as part of IntechOpen and Knowledge Unlatched (KU) Collaboration"},{slug:"intechopen-joins-the-united-nations-sustainable-development-goals-publishers-compact-20221702",title:"IntechOpen joins the United Nations Sustainable Development Goals Publishers Compact"},{slug:"intechopen-signs-exclusive-representation-agreement-with-lsr-libros-servicios-y-representaciones-s-a-de-c-v-20211123",title:"IntechOpen Signs Exclusive Representation Agreement with LSR Libros Servicios y Representaciones S.A. de C.V"},{slug:"intechopen-expands-partnership-with-research4life-20211110",title:"IntechOpen Expands Partnership with Research4Life"},{slug:"introducing-intechopen-book-series-a-new-publishing-format-for-oa-books-20210915",title:"Introducing IntechOpen Book Series - A New Publishing Format for OA Books"}]},book:{item:{type:"book",id:"1904",leadTitle:null,fullTitle:"Automation",title:"Automation",subtitle:null,reviewType:"peer-reviewed",abstract:'This is how Dr. Kongoli views the role of Automation in the modern world: \nAutomation is closely related to the modern need for sustainable development in the 21st century. One of the principles of sustainability is "Doing More with Less" which in other words, is also one of the goals of automation. By replacing the routine part of human labor with the use of machines, automation not only increases productivity and the quality of products beyond what can be achieved by humans but also frees space, time and energy for humans to deal with the new, non-routine challenge of developing innovative and more advanced technologies. This magnificent cycle in which established developments are automated and the free resources achieved by this automation are used to develop newer technologies that are subsequently automated is one of the most successful recipes for the human race towards the goal of sustainable development.',isbn:null,printIsbn:"978-953-51-0685-2",pdfIsbn:"978-953-51-6220-9",doi:"10.5772/2327",price:159,priceEur:175,priceUsd:205,slug:"automation",numberOfPages:562,isOpenForSubmission:!1,isInWos:null,isInBkci:!1,hash:"5c36455d273d4c06b17a2ff1f239b9b9",bookSignature:"Florian Kongoli",publishedDate:"July 25th 2012",coverURL:"https://cdn.intechopen.com/books/images_new/1904.jpg",numberOfDownloads:87236,numberOfWosCitations:36,numberOfCrossrefCitations:59,numberOfCrossrefCitationsByBook:2,numberOfDimensionsCitations:77,numberOfDimensionsCitationsByBook:2,hasAltmetrics:1,numberOfTotalCitations:172,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"May 26th 2011",dateEndSecondStepPublish:"June 23rd 2011",dateEndThirdStepPublish:"October 28th 2011",dateEndFourthStepPublish:"November 27th 2011",dateEndFifthStepPublish:"March 26th 2012",currentStepOfPublishingProcess:5,indexedIn:"1,2,3,4,5,6,7",editedByType:"Edited by",kuFlag:!1,featuredMarkup:null,editors:[{id:"109973",title:"Dr.",name:"Florian",middleName:null,surname:"Kongoli",slug:"florian-kongoli",fullName:"Florian Kongoli",profilePictureURL:"https://mts.intechopen.com/storage/users/109973/images/2145_n.jpg",biography:"Dr. Florian Kongoli – Short Biography\n\nDr. Florian Kongoli, [BSc (Honors), MScA (Canada), PhD (Japan)/ MTMS, MGDMB, MCIM, MSME, MAIST,MISIJ, MSigmaXi, MIFAC, MACS, MASM, MMRS, MACerS, MECS] is CEO of FLOGEN Technologies Inc. (www.flogen.com), a high-tech technology company independently incorporated in Canada and USA, specializing among others in process control, optimization and automation as well as the development of new sustainable technologies for metallurgical, chemical and environmental industries in both non-ferrous (Ni, Cu, Zn, Pb, Fe-Ni, Fe-Cr, PGMs, etc.) extraction and processing as well as in iron and steel making and processing. \n \nHe has about 20 years of industrial research and development and academic (lecturer) experience spread across many invited engagements in Asia, Australia, Europe, North America and South America. He has a rich background in both industrial projects and pure scientific ones dealing with control, optimization and automation of processes and flowsheets; physical and thermochemical modeling; physicochemical properties mattes, slags, metals, gases, oxysulfides etc. He has worked and successfully carried out many industrial projects for more than 47 well-known metallurgical and chemical companies such as Mitsubishi Materials Corporation and Sumitomo Metal Mining (Japan), Falconbridge (now Xstrata-Canada), Western Mining Corporation (now BHP Billiton-Australia), to mention just a few. In his work he has cooperated with several well-known universities around the world such as Tohoku University (Japan), Curtin University (Australia) and University of Montreal (Canada), amongst others . \n\nDr. Kongoli has published/edited 31 books and about 90 scientific articles in the last 5 years in peer review journals and other publications dealing with process control, optimization and automation, development of novel sustainable technologies, modeling of various properties of industrial mattes, slags, metals, effect of minor components, fluxing strategies, etc. He has delivered in 20 countries around the world about 130 plenary, keynote and invited presentations as well as articles, technical reports and research presentations. The results of his work and FLOGEN’s control and automation systems have been used by several companies around the world. He has also taught several continuing education courses including 'Sulfide Smelting: Principles, Technologies and Environmental Considerations” held in San Diego, CA, 2003 and 'Modern Technologies in Non-Ferrous Smelting & Recycling: Efficiency, Control, Energy and Environmental Issues”, held in Cancun, Mexico, November 27th to December 1st 2011. \n\nHe has served in many leadership positions in national and international organizations. He has been and actually is Chair/Vice-Chair/member of about 20 professional society committees and has been a chair of about 25 technical sessions. He is Editorial/Scientific Board member of several Professional Journals including: The Minerals and Metallurgical Processing Journal (USA), Mineral Processing and Extractive Metallurgy (UK/Australia), Erzmetall (Germany), European Journal of Mineral Processing and Environmental Protection (Turkey/Europe), Journal of Metallurgy (USA/Egypt), Journal of International Environmental Application & Science (Turkey/Europe), Journal of Mining and Metallurgy (Serbia/Europe), Journal of Industrial Engineering (USA/Egypt, InTech (Croatia/Europe and Shanghai/China). He is also a peer reviewer in various professional journals. He has been member of Organizing Committees or Scientific Committees of about 50 Professional International conferences in all continents. \n\nHe is also chairman of FLOGEN STAR OUTREACH (www.flogen.org), a non-profit international organization dedicated to giving STAR power to scientists, technologists and engineers and their supporters who help them towards realizing the goal of a sustainable future . In this framework he has successfully organized and chaired several record-bearing International Symposiums dedicated to famous personalities in science and technology. Among those are: \n \nYazawa International Symposium on Metallurgical and Materials Processing: Principles and Technologies (www.flogen.org/conferences.php?spage=3) held in San Diego California, USA, March 2003 with 31 sessions and more than 3000 pages of publications from authors from 36 countries around the world - the biggest International Symposium at the time in its class.\n\nSohn International Symposium on Advanced Processing of Metals and Materials: Principles, Technologies and Industrial Practice (www.flogen.org/conferences.php?spage=2), held in San Diego California, USA, in August 2006, a new record in its class over passing the magnitude of the previous symposium with about 500 papers from authors from 80 countries and about 6000 pages of publications. \n\nFray International Symposium on Metals and Materials Processing in a Clean Environment (www.flogen.org/conferences.php?spage=1), held in Cancun, Mexico, in November-December, 2011, another record symposium in many aspects in its class with about 500 abstracts from authors from 85 countries around the world, 230 sponsoring societies and organizations worldwide, 10 Major Industrial Corporations and 3 governments financial sponsors and 7 volumes of Publications of more than 4000 pages\n\nHe was also organized and chaired other theme-based International Symposium such as 'Process Control and Optimization in Ferrous and Non-Ferrous Industry” held in Chicago, Illinois, USA in November 2003 (www.flogen.com/ControlSymposium) as well as the American Automatic Control Council/IFAC symposium of Automation in Mining, Mineral and Metals to be held in San Diego, California in 2013\n\nHe has excellent business management and organizations skills which have been instrumental in steering his company toward new ground breaking technologies.",institutionString:"FLOGEN",position:null,outsideEditionCount:null,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"1",institution:null}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"715",title:"Automotive Technology and Engineering",slug:"automotive-technology-and-engineering"}],chapters:[{id:"37986",title:"Optimization of IPV6 over 802.16e WiMAX Network Using Policy Based Routing Protocol",doi:"10.5772/50592",slug:"optimization-of-ipv6-over-802-16e-wimax-network-using-policy-based-routing-protocol",totalDownloads:2254,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:null,signatures:"David Oluwashola 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"314",title:"Regenerative Medicine and Tissue Engineering",subtitle:"Cells and Biomaterials",isOpenForSubmission:!1,hash:"bb67e80e480c86bb8315458012d65686",slug:"regenerative-medicine-and-tissue-engineering-cells-and-biomaterials",bookSignature:"Daniel Eberli",coverURL:"https://cdn.intechopen.com/books/images_new/314.jpg",editedByType:"Edited by",editors:[{id:"6495",title:"Dr.",name:"Daniel",surname:"Eberli",slug:"daniel-eberli",fullName:"Daniel Eberli"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"57",title:"Physics and Applications of Graphene",subtitle:"Experiments",isOpenForSubmission:!1,hash:"0e6622a71cf4f02f45bfdd5691e1189a",slug:"physics-and-applications-of-graphene-experiments",bookSignature:"Sergey Mikhailov",coverURL:"https://cdn.intechopen.com/books/images_new/57.jpg",editedByType:"Edited by",editors:[{id:"16042",title:"Dr.",name:"Sergey",surname:"Mikhailov",slug:"sergey-mikhailov",fullName:"Sergey Mikhailov"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1373",title:"Ionic Liquids",subtitle:"Applications and Perspectives",isOpenForSubmission:!1,hash:"5e9ae5ae9167cde4b344e499a792c41c",slug:"ionic-liquids-applications-and-perspectives",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/1373.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"51033",title:"Conductive Polymer-Based Membranes",doi:"10.5772/63560",slug:"conductive-polymer-based-membranes",body:'\nPolymers represent a larger class of organic compounds, in terms of both diversity and industrial-scale applications. They are used in the majority of industrial branches and have contributed decisively to the last century economic development. Polymers’ impact upon the human society progress showed a positive effect, but nowadays, more attention is given to the mitigation of negative environmental impact induced by their intensive use. As a consequence of exponential growth of researches in the polymers field, the macromolecular compounds’ chemistry became a distinct science within organic chemistry, a well-defined domain, in connection with other natural sciences areas. The turning point in the development of macromolecular compounds chemistry as an exact science was the transition from semi-empiric researches to rigorous experiments marked in 1925–1930 period by Staudinger and Carothers researches [1–4] that led to highlighting of polymer structures, defining the notions of macromolecule, macromolecular chain, homologous polymeric series, etc.
\nPolymers led to rapid development of plastic materials science due to their specific properties: chemical stability on acids, bases and solvents (higher than gold and platinum in some cases), high thermal stability, elasticity, plasticity, excellent mechanical strength, non-permeability to gases, low density, electrical insulation properties and also electroconductive properties. The latest characteristics referring to electroconductivity was thoroughly studied during the last 60 years, leading to the development of a new polymer chemistry subdomain, and dedicated to conductive polymers. The results, reported within research works focussed on conductive polymers, materialized in two Nobel prizes in chemistry [5]:
\nRudolph A. Marcus (1992) for his works on electron transfer theory in redox processes, with direct applications in biopolymers science and
Alan J. Heeger, Alan G. Mac Diarmid and Hideki Shirakawa (2000) for development of intrinsic electroconductive polymers through researches related to polyacetylene.
At the same time, with macromolecular compound chemistry, a new domain related to the preparation and use of membrane-type advanced materials was developed. Membrane science developed continuously as an interdisciplinary science in which polymers have a central role. With the progress of research works dedicated to conductive polymers, researches on conductive polymers membranes preparation and their application were also initiated and developed.
\nClassification of conductive polymers can be done based on various criteria. The most important criterion is related to the electric charge movement type which depends on the polymer chemical structure. Thus, two groups of electronic conductive polymers are formed:
\nRedox polymers: polymers that possess redox potential within their structure groups (reduction/oxidation capacity);
Intrinsic electroconductive polymers: polymers with conjugated п-п or p-п systems.
In the case of redox polymers, the movement of electrons is realized through reversible chemical reactions “donor-acceptor” type, in accordance with Eq. (1):\n
where “
The standard potential (E0) is determined by Eq. (2):\n
where
In the case of redox polymers, the essential condition needed for continuous electron transport, which defines the “electronic conductive polymer” property, is that groups with redox potential have to be distributed one next to the other within the macromolecular structure (its spatial configuration) in such a way that electron jump between groups is possible (Figure 1).
\nElectric charges movement within redox polymers.
Such polymers are those based on substituted nitro-styrene, quinones, dopamines and polymers which have within structure coordinative ligands based on Ir, Co, Re, Ru or Os [6].
\nThe electrons transport principle of intrinsic electroconductive polymers consists of electrons transfer from п type bonds to nearby simple σ bonds, due to repulsion effect of same type charges.
\nThe mandatory condition is that double bonds alternate with the simple ones (conjugated п-п systems), as shown in Figure 2.
\nElectric charges movement in “π-π” conjugated systems.
The same principle applies to the continuous transport of electrons in the case of polymers which contains heteroatoms N, S or O types within the macromolecular chain. Heteroatoms must be bonded to C atom that is involved in a double bond. Practically, non-participating p electrons of the heteroatom move to σ single bond, and through electrostatic repulsion effect, they further induce the movement of п electrons from the nearby double bond. That type of electrons transport is specific to conjugated p-п systems (Figure 3).
\nIntrinsic conductive polymers have the capacity to conduct electricity better than the majority of plastic materials which do not contain conjugated electron systems. For example, polyacetylene has a conductivity of 10−8–10−7 S m−1 in the form of “cis” isomer and 10−2–10−3 S m−1 in the form of “trans” isomer, compared with Teflon which has a conductivity of 10−16 S m−1. However, compared with the conductivity of metals with best electric properties (Ag and Cu), which is of order 108 S m−1, the conductivity of these polymers is very low, having semiconductor properties. Through doping process, similar with that applied to classic inorganic semiconductors, the conductivity of intrinsic conductive polymers significantly grows, being closer to metals properties. Thus, polyacetylene doping with halogen vapour made (Cl, Br, I) the conductivity grow up to 105 S m−1 [5].
\nElectric charges movement in “p-π” conjugated systems.
Doping process involves the introduction of atoms capable of extracting or providing electrons to polymer’s conjugated system, within its macromolecular chain. Introduction of such defects within the structure of macromolecule results in a more rapid jumping of electrons from created polar centres, assuring a better conductivity for the polymer. Usually, two distinct doping processes are applied [5]: oxidative doping (or p-doping) through which electrons are abstracted from the structure of polymer and reductive doping (or n-doping) through which electrons are introduced within the structure of polymer.
\nThe two mentioned reactions are the processes for polyacetylene in Eqs (4) and (5):\n
Oxidative doping\n
In the first case, iodine is abstracting electrons from double bonds and in the second case, sodium atoms are releasing electrons to the double bonds bond resulting in their polarization. Both electric charges are migrating within the polymeric chain, adding the electric conductivity property, as shown in Eqs (4) and (5).
\nDoped intrinsic conductive polymers are obtained through one of the two main methods: chemical or electrochemical [7, 8]. Through chemical synthesis processes, monomers are polymerized/polycondensated by mixing with specific oxidative reagents such as ferric chloride or ammonium persulphate, at a specific pH. The method presents two main advantages compared with the electrochemical method: can be used to obtain polymeric powders or films that can be further processed and used at industrial level and can be used also in the synthesis of conductive polymers via electrochemical methods. Drawbacks of the methods are related to the fact that is highly sensitive, being dependent on reaction conditions (solvent nature, solvent and reagents purity, reagents’ molar ratios, temperature, mixing mode and speed, reaction time, etc.). Electrochemical synthesis method is based on polymerization/polycondensation of monomers dissolved in a specific solvent through appliance of electricity between two electrodes. The monomer solution also contains the doping agent. Through this method, polymeric films (nanometers order thickness) with controlled/predefined structure are obtained. Electrochemical synthesis can be realized through three techniques: galvanostatic, potentiostatic and potentiodynamic [8]. The method presents the following disadvantages: limited polymer doping, conductive polymer quantity and polymeric film size are limited by electrode geometry and surface, difficulties in appliance for composite materials preparation (compared with the chemical synthesis).
\nNo. | \nChemical name | \nAbbreviation | \n
---|---|---|
1 | \nPolyacetylene | \nPAc | \n
2 | \nPolyaniline | \nPANI | \n
3 | \nPolypyrrole | \nPPy | \n
4 | \nPolythiophene | \nPTh | \n
5 | \nPoly(p-phenylene) | \nPPP | \n
6 | \nPolyazulene | \nPAZ | \n
7 | \nPolyfuran | \nPFu | \n
8 | \nPolyisopren | \nPIP | \n
9 | \nPolybutadiene | \nPBD | \n
10 | \nPoly(isothianaphtene) | \nPITN | \n
11 | \nPoly(α-naphthylamine) | \nPNA | \n
A list of representative polymers and their abbreviations.
At the 2014 year level, more than 25 intrinsic conductive polymers [8] were known and used in various applications: electrochemical sensors [9–11]; gas sensors [12]; biosensors for medicine, food industry and environmental monitoring [13–15]; functionalized biomaterials with application in medicine [8, 16]; corrosion inhibitors [17]; fuel cells [18], etc. One of the main applications of conductive polymers is the development of optoelectronic devices based on electroluminescence phenomenon (field-effect transistors, FET; photodiodes; and light-emitting diodes, LEDs) [19]. The most representative polymers from those classes and their abbreviations are presented in Table 1.
\nFor each basic polymer, a larger number of derivatives with electroconductive properties suitable for various applications were studied, and the research results were reported within the literature.
\nMany of the listed conductive polymers can be used for the preparation of polymeric membranes used in advanced separation processes, which is presented in the next section.
\nMembranes are advanced materials used for separation of compounds of sizes between 0.1 nm and 1 µm (from suspensions, dissolved macromolecules to simple or complex ions) from liquid and gaseous mixtures. It is difficult to find a membrane definition that covers simultaneously the issues related to its structure, separation mechanism and utilization domain. A generally accepted definition presented within the literature is as follows:
Membranes are classified based on material type and nature, structure and application domain. Based on these criteria, membranes are as follows:
\nConsidering the pores’ form and distribution within the porous or non-porous membranes, they can be classified as
\nDepending on the separation surface, geometry membranes are plane, tubular hollow fibre type (inner diameter <0.5 mm), tubular capillary type (0.5 mm < inner diameter < 5 mm) and tubular type (inner diameter > 5 mm).
\nThere are five main methods for membrane preparation: sintering, lamination, irradiation, phase inversion and deposition on thin layers [21]. Among them, phase inversion is the most commonly used method and is applied for membrane preparation at both laboratory and industrial level. Phase inversion concept was introduced in the literature by Kesting [22], and the concept implies transformation of one homogeneous polymeric solution in a two-phase system: one rich in polymer which forms the continuous part of porous membrane and other lacking polymer which fills the pores from membrane structure. The process has three main stages: polymer solubilization in a suitable solvent, skinning of polymer solution on a plane or tubular surface and polymer precipitation (phase inversion). The stage responsible for membrane structure is the precipitation one. Frequently, one of the following techniques for polymer transformation from liquid to solid phase is used:
Membrane processes are determined by the membrane structure and differentiated after the transport mechanism of chemical species through the membrane. Passing of one component from one side of the membrane to the other is defined as
Microfiltration, ultrafiltration and reverse osmosis (
Pervaporation, gas permeation, dialysis, separation through liquid membranes (
Thermo-osmosis and membrane distillation (
Electrodialysis and electro-osmosis (
Practical realization of membrane separation processes involves specific installations for each application field, in which the core element is represented by the equipment that contains the membrane, named
Membranes and membrane process applications cover a vast area: treatment of water intended for human consumption from various sources (surface water including marine water, ground water), wastewater treatment, separation and concentration of proteins and enzymes from various natural and biosynthesis media, preparation of ultrapure water, development of medical devices (artificial kidneys, artificial lungs), development of sensors and biosensors with multiple applications, gas separations, fuel cells, ultrapure compounds via membrane distillation and pervaporation, etc.
\nRecent works in the field of membranes and membrane processes are focussing on obtaining cost reduction, improvement of separation characteristics (flow rate, selectivity, limitation of clogging) and extension of application domains at industrial scale [30]. Among these domains, the use of conductive polymer-based membranes is envisaged.
\nMembranes based on conductive polymers represent a new class of advanced materials that can be used for separation or for interphase transfer processes of some chemical species based on their electrical properties. These membranes can be obtained through the previously described processes for preparation of classic membranes, their particularities being linked to polymers’ “doping” methods in order to improve their conductive properties. Membranes of this type are obtained mainly from the polymers mentioned within Table 1, but considering the number of citations from the literature, the most used polymers are polyaniline (PANI) and polypyrrol (PPy). Apart from these polymers, during the last period, the use of functionalized polyetheretherketone (PEEK) as conductive polymer and of a considerable number of other polymers in fuel cells were thoroughly researched. Based on these facts, three main classes of conductive polymer-based membranes are presented. All the above-mentioned polymers have physical-chemical properties that do not allow the preparation of membranes using only the specific polymer but only in combination with other polymers. Such membranes usually lack conductive properties but have excellent mechanical strengths. Therefore, the majority of conductive polymer-based membranes are “composite membranes”.
\nPolyaniline (PANI) is a macromolecular compound obtained through oxidative polymerization of aniline in accordance with Eq. (6):\n
In its structure, there are structural units formed from benzene rings linked through aminic groups (-NH-) and structural units formed from a benzene ring linked with a quinone diimine. The ratio of the two structural units within polymeric chain is varying depending on its degree of oxidation. There are three particular structures of the polyaniline, which differentiate among them the function of the two structural units’ ratio (Figure 4).
\nStructural PANI forms. (a) Leucoemeraldine base, (b) pernigraniline base and (c) emeraldine base.
Thus, in the limit case of PANI containing only structural units formed from benzene rings linked through aminic groups (
PANI in the base form has properties that do not allow obtaining simple membranes (low solubility in the majority of solvents commonly used for membranes preparation, low plasticity, thermal instability at temperatures above 160°C, etc.). For this reason, PANI-based membranes are obtained through blends with other polymer (usually chemically inert) suitable for membranes preparation. Composite membranes based on PANI with conductive properties are obtained. There are a large number of inert polymers used for PANI-based composite membranes preparation, the most used being cellulose and its derivatives, polysulphone, polystyrene and polypropylene.
\nPANI-based composite membranes are used in the majority of domains mentioned for conductive polymers, mainly for selective separation processes of some chemical species from complex liquid solutions, selective separation of gases, development of biosensors, electric and electronic devices (LED, photovoltaic cells), anticorrosive films and fabrication of antistatic textile materials.
\nThe most recent scientific researches on preparation and specific applications of PANI-based composite membranes are presented in the following paragraphs.
\nFibre-type cellulose was used in nanocomposites fabrication through oxidative in situ polymerization of aniline within fibres microstructure [31]. Polymerization was made in oxidative conditions using ammonium peroxydisulphate in hydrochloric acid aqueous solutions in which cellulose fibres impregnated with aniline are suspended. From the fibres separated at the end of the process, which contain PANI in their microporous structure, polymeric films were obtained via phase inversion process. Similarly, a composite material using nanofibrils bacterial cellulose as support material for PANI was obtained [32]. Research works showed the growth of PANI content within the composite material at the same time with the increase of its electric conductivity, with the prolonged reaction time from 30 to 90 min. Prolonging reaction time more than 90 min resulted in a decrease of electric conductivity due to aggregation of PANI particles and creation of discontinuities within nanocomposite structure. At the optimum time, a nanomaterial with the best conductivity of cca. 5.0 S m−1 was obtained. Using this composite material, a flexible film (conductive membranes) that synergetically combines PANI conductive properties with mechanical strength (Young’s modulus is 5.6 GPa and tensile strength is 95.7 MPa) provided by bacterial cellulose is obtained. The membranes obtained are applied in the field of electrochemical sensors, flexible electrodes and flexible displays. Compared with the processes in which first a nanocomposite material is obtained and then is used for conductive membrane preparation following a classic technique (phase inversion through immersion-precipitation technique), research works were conducted with the aim to obtain PANI-based composite conductive membranes following the next sequence: first, a semipermeable cellulose membrane is obtained and then on its surface, a thin layer of PANI is applied [33]. Deposition of the thin layer at membrane interface is realized via in situ polymerization of aniline with oxidative mixture containing ammonium peroxydisulphate in hydrochloric acid aqueous solutions. An aniline conversion of 80% was obtained after 24 h reaction time. At the end of the process, residual aniline was found on the active side of PANI membranes and secondary reaction products (ammonium hydrogen sulphate) obtained from ammonium peroxydisulphate were found on both sides of the membrane.
\nCellulose esters are representing another class of polymeric materials used as support in preparation of PANI-based composite membranes. Investigations on PANI deposition on the surface of some microporous cellulose ester membranes were performed using two distinct techniques: deposition of PANI layer on membrane surface through in situ aniline polymerization in liquid phase or aniline polymerization in vapour phase [34, 35].
\nIn situ polymerization of aniline in liquid phase was performed through dipping of one membrane from cellulose esters mixture in an aniline solution (PANI monomer) and FeCl3 as oxidant [34]. In other experimental variant, aniline polymerization in liquid phase is made by immersion of pre-formed cellulose esters membrane in a solution that contains aniline and HCl followed by the addition (at a certain time) of oxidative agent such as ammonium peroxydisulphate solution [35]. Aniline polymerization in vapour phase is done by soaking cellulose ester-based membrane in a solution of aniline and HCl and maintaining it in a closed tank with an oxidizing agent (ammonium peroxydisulphate and HCl solution)-saturated vapour atmosphere heated at 65–70°C [34, 35]. Cellulose acetate—PANI composite membranes with electric conductivities from 10−3 and 11 S m−1 \n(using the liquid phase polymerization) [34] and respectively 98 Sm-1 (using the vapour phase polymerization) [35] were obtained.
\nPolysulphone (Psf) is another frequently used polymer in the preparation of polymeric membranes used in membrane processes based on gradient pressure driving forces (microfiltration, ultrafiltration, reverse osmosis). This diversity of uses is due to polymers physical-chemical characteristics (chemical inertness, very good plasticity, excellent solubility in usual solvents used within phase inversion process, good mechanical strength, etc.). Psf is used as a substrate for the preparation of Psf–PANI composite membranes designed for advanced separation of compounds with polar groups from various mixtures, capitalizing the conductive properties of PANI from their structure.
\nWithin the Psf – PANI composite membranes, PANI is present in the whole membrane’s microporous structure, not only on surface. Preparation method is also a specific one and is differentiating from those already described. Thus, research works aimed to prepare Psf–PANI composite membranes through simultaneous formation of Psf-base membrane and aniline polymerization in oxidative conditions within membranes under formation pores [36]. Practically, the process consists of solubilization of Psf polymer within a specific solvent (N-methyl-pyrolidone or dimethylformamide) and aniline (PANI monomer), skinning of polymeric solution on a plane surface and immersion of polymeric film within an oxidative coagulation solution (ammonium peroxydisulphate and HCl). As the phase inversion process advances, Psf membrane is formed and within its pores PANI resulted from aniline polymerization in oxidative conditions.
\nSix types of composite membranes were obtained, using three polymeric solutions with 10, 12 and 14% Psf and two types of coagulants (distilled water and distilled water with 1.9% aniline). In all polymeric solutions, Psf was dissolved in a mixture of N-methylpyrrolidone and aniline. Obtained membranes were characterized from the point of view of flow and electroconductive properties through flows determination for solutions with variable pH (1, 3, 5, 7, 9 and 11), and selective separation properties were emphasized via determination of retention degree for standard proteins (albumin from bovine serum—BSA). BSA separation experiments proved that membranes obtained through coagulation from water and aniline solution present higher flows and retention degree compared to the membranes obtained by coagulation with only distilled water. For example, membranes obtained from 10% solution coagulated with water and aniline present a flow of 151.2 L/m2h at pH = 4.9 and 196.3 L/m2h at pH = 7.4 compared with membranes obtained from the same solution but coagulated in distilled water that showed a flow of 140.1 L/m2h at pH = 4.9 and 189.4 L/m2h at pH = 7.4. Retention degrees for membranes coagulated in water and aniline varied between 81.84 and 92.16% compared with 75.36–81.4% determined for membranes coagulated in distilled water.
\nThrough this process composite membranes with conductive properties are obtained, having separation characteristics superior to those obtained using similar polymeric conditions that contains only Psf. Performed research emphasized the dependence of Psf/aniline ratio from polymeric solution and structural and hydrodynamic characteristics of Psf–PANI composite membranes.
\nIn order to diminish the errors at laboratory level, mainly the manual skinning of polymeric solution and variation during the phase inversion process of the coagulation solution composition, Psf–PANI-based composite membrane preparation was studied in a steady-state installation [37]. That induces a modification of composite membrane preparation technology such that in one tank Psf membrane forming takes place. Psf membrane has in its pre-formed pores a certain quantity of aniline, and finalization of its structure is made in a reaction tank filled with oxidative mixture in which polymerization of aniline from pores occurs.
\nUsing a 10% Psf solution (MW = 22,000 Da) dissolved in a mixture of N-methylpyrrolidone and aniline, membranes in a continuous system in the following working conditions were prepared: thickness of the polymeric film is equal to 0.2 mm, speed of the carrier in the tanks is equal to 1 m/min, temperature of the oxidative solution is equal to 25°C and reaction time is equal to 2 h. Characterization via distilled water flow for nine samples from the same membrane led to a maximum relative deviation of flow values of 2.45%, proving that through this approach, Psf–PANI composite membranes with reproducible hydrodynamic and conductive properties both in the entire surface and from one batch to other are obtained.
\nOther polymers studied as support materials in order to develop composite membranes based on PANI, with conductive polymers, are polystyrene [38, 39] and polypropylene [40]. Thus, from blends containing PANI and polystyrene in various ratios, dissolved in N-methyl-2-pyrrolidone, flexible polymeric films were obtained via phase inversion process, phase changing taking place through precipitation in vapour phase [38]. The particularity of the method consists in the fact that PANI was obtained in a separate oxidative polymerization process: a reaction media formed from aniline and alcoholic solution of 0.1 M H2SO4 in a volumetric ratio of 1/25 is cooled to −5°C; a solution containing ammonium peroxydisulphate as initiator is slowly added in a 2-h period within the reaction mixture; obtained PANI polymer is filtered and washed with acetone and a solution of 0.1 M NH4OH and mixed for 24 h; after that the polymer is filtered again, washed with distilled water and dried at 60°C for 24h. After drying, PANI and polystyrene are dissolved in N-methyl-2-pyrrolidone, the solution being coated on a support that is heated in an oven at 60°C for 24 h. Finally, the composite membrane obtained is removed from the support and subjected to doping process by immersing in a 5 M HCl solution for 9 min and dried afterwards [38].
\nObtained polystyrene-PANI composite membranes present conductive properties depending on polystyrene/PANI ratio within the solution.
\nPolystyrene is used also in functionalized sulphonated form for the preparation of PANI-based composite materials [39]. Both polymers are obtained simultaneously in the same reaction environment consisting of aniline (PANI monomer), 4-styrene sulphonic acid sodium salt hydrate (sulphonated polystyrene monomer), ammonium peroxydisulphate and HCl (for oxidative polymerization).
\nThe working procedure is the following: within a 3.47 mM aqueous solution of 4-styrene sulphonic acid sodium salt hydrate, heated at 80°C, the oxidant ammonium peroxydisulphate (aqueous solution 4.86 M) was added drop wise in a volumetric ration of 1/7 to styrene solution, under mixing for 1 h; after that an aqueous solution of aniline chlorhydrate 0.58 M (volumetric ratio of 1/8 to mixture) is added and after another 15 min a new quantity of 4-styrene sulphonic acid sodium salt hydrate (aqueous solution with a concentration of 0.72 M in a ratio of 1/9 to reaction media) was added drop wise; the reaction media is maintained under mixing at 80°C for 3 h, and afterwards the temperature drops to ambient temperature in a 24-h period. The composite polymer is precipitated in iso-propanol for 24 h without mixing and is washed with ethanol and dried at 70°C.
\nObtained composite material contains in its structure PANI and sulphonated polystyrene macromolecular linked with chemical bonds (ionic bonds) through diimino protonated groups of PANI and sulphonic groups of sulphonated polystyrene. Due to these bonds, the conductive capacity of the composite material is lower compared with the above-presented composite materials, being practically a semiconductor. This composite material is used for polymeric membranes preparation through classic processes, dense films for antistatic packages, anticorrosive material or semiconductors.
\nPolypropylene is used as support material for preparation of PANI-based composite materials in the form of microporous membrane film through biaxial stretching technique [40]. PANI is formed within the polypropylene pores membrane through soaking of polymeric film in aniline followed by aniline oxidative polymerization using ammonium peroxydisulphate and HCl. Polypropylene—PANI composite membranes maintain the microporous structure of the support polymer, with various pores diameters and present conductive properties. These composite membranes are used in selective separation of chemical species from various liquid media through microfiltration, ultrafiltration, nanofiltration and reverse osmosis.
\nBesides polymeric materials, inorganics can be used as support for PANI-based composite materials. Thus, zeolites were used for new zeolite-PANI composite materials preparation due to their microporous structure and adsorption capacities [41]. Method consists of polymerization of aniline retained within zeolite matrix (Molecular Sieve 13X – SUPELCO Analytical) in oxidative conditions similar to those described previously (ammonium peroxydisulphate and HCl). The composite material is included within a quartz filter structure resulting in an inorganic-organic membrane with ultrafiltration flow rate properties. Conductive properties of these membranes (due to the PANI inclusion within their structure) allow separation of chemical species with high pollution potential from wastewater, such as heavy metals ions (Pb, Cu, Zn) and phenol derivatives (phenol, aminophenols or nitrophenols). Thus, retention degrees determined for heavy metal ions were 72.59% for Pb2+, 87.48% for Zn2+ and 99.55% for Cu2+. Phenol derivatives from wastewater were removed using these composite materials with efficiencies above 98% (phenol, 98.15%; aminophenol, 99.78%; nitrophenol, 99.23%).
\nPolypyrrol (PPy) is a polymer obtained by pyrrol oxidation (Py) in the form of a black powder. This polymer has poor mechanical strength and thus low processibility. Its conductive properties in natural state are very low, and it is rapidly oxidized in contact with air, changing its properties. PPy conductivity is given by the existence within its structure of π conjugated electron systems (from pyrrol ring) with p electrons available at N atom from pyrrol ring. This property is significantly improved by PPy “doping” with anions such as chloride, sulphate, perchlorate, dodecylsulphate and other organic compounds. Doped PPy is a polymer characterized by good chemical and thermal stability and better conductivity compared with other conductive polymers. Disadvantages related to PPy mechanical strength, plasticity and elasticity are improved both through doping process and by inclusion (as doped form, similar with PANI) within the polymeric and inorganic composite materials structure. PPy-based composite materials are frequently used as membranes within the processes in which driving force is no longer the pressure gradient but concentration gradient (gas separation from complex mixtures and pervaporation) and electric potential gradient (electro-dialysis).
\nDuring the last period, the research works related to PPy-based composite materials studies are focussed on their application in electro-analysis, medical field (systems for controlled release of drugs and use as biomaterial for artificial muscles) and antistatic and anticorrosive protection.
\nPPy polymerization in PPy-based composite materials is done through two methods:
Ammonium peroxydisulphate, hydrogen peroxide and various compounds based on transitional metals salts (Fe2+; Cu2+; Cr6+; Mn2+; etc.) are frequently used as oxidative agents for the polymerization through chemical oxidation.
\nThe process is presented in Eq. (7):
\nPPy polymeric chain can contain Py linked with three types of dimer sequences [8], presented in Figure 5.
\nAddition within the chemical oxidation reaction media of surfactants such as sodium dodecylbenzensulphonate and sodium alkylsulphonate and alkylnaphtalenesulphonate results in an increase of electric conductivity of the composite material and Py polymerization efficiency [42]. Electrochemical polymerization is performed in conditions mentioned within Section 1.2 based on application of an electric current between two electrodes immersed in a Py solution that contains also the dopant, in accordance with Eq. (8):
\nwhere C− is counterion.
\nDimer sequences within PPy structure. (a) α,α’, (b) α,β’ and (c) β,β’
The Py chemical oxidative polymerization was applied to obtain membranes with high permeability for gas separation. Membranes were obtained through the technique of deposition in thin layers through interfacial polymerization [43, 44]. A freestanding polymeric film, 200–300 nm thick, was obtained by Py polymerization on an inert glass support through mixing of oxidative agent aqueous solutions containing ferrous chloride (0.4 M) and ferric chloride (0.5 M) with a solution of Py dissolved in an organic solvent (n-hexane) [43]. The membranes were prepared by pouring a solution of polydimethylsiloxane dissolved in n-hexane on PPy surface, after oxidant excess removal and polymeric film washing with methanol. The contact between components was maintained for 24 h and after that the composite membrane was annealed in air at 80°C for 15 min. Finally, the composite membrane is removed from the glass surface by simple washing with water. Obtained composite membranes present high selectivity for separation of oxygen and nitrogen from various mixtures, separation ratios O2/N2 of 17.2 being reported. The permeability for O2 was 40.2 barrer. Using the same method of interfacial polymerization through chemical oxidation of Py or its derivatives (N-methylpyrrole), PPy-based conductive composite membranes with applications in the field of gas separation and pervaporation were obtained on a surface of microporous membrane supports [44]. Polymerization was performed at chamber temperature for 4 h using an aqueous 0.5 M Py solution and ferric chloride solutions (0.5, 1, 2 or 3M) as oxidative agent. The obtained membranes were washed with deionized water and stored in a 1 M HCl solution, and the operation was repeated daily for a week. In the final, membranes were stored in deionized water prior to characterization and use.
\nThe Py chemical oxidative polymerization was used also for the preparation of PPy-based composite membranes having pre-formed membranes from sulphonated poly(styrene-co-divinylbenzene) as support, with its biotechnological applications and applications in wastewater treatment through electro-dialysis [45]. PPy polymer was formed through chemical oxidation within the structure of a commercial membrane with cationic exchange properties (Selemion CMT, manufactured by Asahi Glass Co.). The process consists of immersion of commercial membrane soaked in a ferric chloride oxidant solution in a Py aqueous solution at chamber temperature for about 4 h.
\nSimilar properties related to ion exchange and possibility to apply in electro-dialysis also present PPy-based membranes obtained via Py chemical oxidative polymerization within the microporous structure of some inert polymeric supports [46] or inorganic supports [47]. In the first case [46], composite membrane is formed in one single stage through phase inversion techniques and chemical oxidation reactions. A solution of polysulphone and PPy dissolved in a N,N-dimethylformamide/methanol solvent system is coated on a plane surface and then immersed in a ferric chloride oxidant solution. At the same time, with formation of microporous polysulphone support, the chemical oxidative polymerization of Py within the preformed pores takes place. In the second case [47], the process consists of polymerization of adsorbed Py into silica through chemical oxidation, resulting in PPy inorganic-organic composite membranes.
\nPPy obtained through chemical oxidative polymerization is used as base material for medical devices [48, 49] due to its conductive properties. Py polymerization takes place in controlled conditions, a special attention being given to PPy doping and modification in order to be biocompatible. On PPy structure are engrafted biomolecules or cells (mammalian cells, endothelial cells, mesenchymal stem cells, etc.) through adsorption of covalent bonding [48]. Other studies emphasized the use of PPy incorporated in poly(ε-caprolactone) and gelatin nanofibres for cardiac tissues [49]. Performed experiments proved that increase of PPy concentration up to 30% within the composite material resulted in a reduction of average diameter of fibres from 239 ± 37 to 191 ± 45 nm, at the same time, with an increase of about six times of tensile modulus (7.9 ± 1.6 MPa initial and 50.3 ± 3.3 MPa after introduction of PPy).
\nOther applications of PPy-based composite membranes prepared through Py chemical oxidation is in the antistatic and anticorrosive materials field. Polyethylene used as natural [50] or modified [51] polymer constitutes an excellent polymeric material for the preparation of PPy composite membranes due to its properties (good mechanical strength, plasticity, elasticity) needed for membranes preparation. Thus, within the pores of polymeric films obtained through melt extrusion with subsequent annealing, uniaxial extension and thermal fixation, PPy was deposited through Py chemical oxidative polymerization [50]. Using another technique [51], polyethylene polymeric film is modified through engraftment within its structure of another polymer realized through acrylic acid irradiation with γ rays. Obtained material is highly hydrophilic which contributes to a better Py retention through surface adsorption that is further polymerized through chemical oxidation using iron chloride (III) or ammonium peroxydisulphate. Performed researches [51] were focussed on increase of electric conductivity of the composite material through increase of Py concentration within the reaction media from 0.3 to 0.9 M, but obtained results proved that this was insignificant (from 162 to 166 S m−1). Introducing a new Py polymerization phase resulted in an increase of electric conductivity from 166 to 543 S m−1.
\nPPy obtained via electrochemical method has similar application with those of PPy obtained through chemical oxidation.
\nThus, PPy membrane formed on stainless steel net is used for separation of ethanol and cyclohexane mixtures through pervaporation [52]. Electrochemical polymerization takes place in a four-cell installation with porous glass walls and three electrodes. One of the electrodes is made from stainless steel net obtained through weaving of stainless steel fibre with 25 or 18 µm diameter. Within the cell that contains this electrode, a solution of 0.1M Py, acetonitrile as solvent and a doping agent (Me4NBF4 0.05 M, Bu4NBF4 0.1 M or Bu4NPF6 0.1 M) are administered. Formed pervaporation membranes were tested in a specific installation and are proved to be selective for ethanol, permeation being dependent on Py polymerization degree and dopant type.
\nUsing a similar method, electrochemical polymerized PPy deposited onto platinum sputter-coated polyvinylidene filters was obtained [53]. Process was realized through introduction within the cell containing filters of a Py aqueous solution containing as doping agents 8-hydroxyquinoline-5-sulphonic acid (HQS) or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline disulphonic acid (BCS). PPy/BCS-type conductive membranes are permeable to a series of ions such as Co2+, Ni2+, Zn2+, K+, Mg2+, Ca2+, Mn2+, Fe3+ and Cu2+. PPy/HQS conductive membranes are not permeable to all above-mentioned ions, significant results being obtained only for K+, Co2+ and Cu2+. Moreover, ion fluxes are much higher (more than 10 times in case of Cu2+) for PPy/BCS compared with PPy/HQS membranes. Conductive membranes with permeability for Na+, K+, Ca2+ and Mg2+ ions were obtained in similar conditions with those described above with the difference that PPy was deposited onto platinum sputter-coated polyvinylidene fluoride filters and polystyrenesulphonate/dodecylbenzenesulphonate (1%) or polyvinylphosphate/dodecylbenzenesulphonate systems were used for doping [54]. It was proved that ions transport fluxes are varying in the following order: Na+ > K+ > Ca2+ >Mg2+.
\nAnother domain that was thoroughly studied in the last period and uses PPy polymers obtained in the form of membrane films via electrochemical polymerization is that of electro-analysis. Through deposition of PPy membrane on the Al2O3 surface of one electrode, amperometric sensors with multiple uses in the field of analytical chemistry is obtained [55]. PPy membrane is prepared through electrochemical polymerization of Py on the electrode surface using an aqueous solution 0.2 M Py and 0.1 M KCl (dopant) or 0.1 M Py and 0.5 M K4[Fe(CN)6] (dopant).
\nPPy based membranes applications within fuel cells domain should be mentioned also. The conductive polymers applications in the field of fuel cells are presented within the next section.
\nFuel cells are devices that generate electricity based on the free energy of a chemical reaction. A classical fuel cell consists of a porous anode fed with gas fuel that after oxidation led to electrons release; a porous cathode fed with oxidant, which generates protons and an electrolyte located between the two electrodes; and two bipolar plates and electric connectors that are linking electrodes through an exterior circuit. Chemical reactions for a classic combustion cell are presented in Eqs (9–11).\n
where E = electrical energy and H = heat.
\nType of fuel cell | \nOperating temperature (°C) | \nElectrolyte | \nReaction At the anode (A) At the cathode (C) | \n
---|---|---|---|
AFCs | \n60–90 | \nKOH (liquid) | \n(A) H2 + 2HO− = 2H2O + 2e− (C) 1/2O2 + H2O + 2e- = 2HO− | \n
PEMFCs | \n60–120 | \nPolymer–SO3H (solid) | \n(A) H2 = 2H+ + 2e− (C) 1/2O2 + 2H+ + 2e− = H2O | \n
DMFCs | \n60–120 | \nPolymer-+NR3 (liquid) | \n(A) CH3OH + 6HO- = CO2 + 5H2O + 6e− (C) 3/2O2 + 3H2O + 6e− = 6HO− | \n
PAFCs | \n160–220 | \nPhosphoric acid H3PO4 (liquid) | \n(A) H2 = 2H+ + 2e− (C) 1/2O2 + 2H+ + 2e− = H2O | \n
MCFCs | \n600–800 | \nMolten salt Li2CO3/K2CO3 (liquid) | \n(A) H2 + CO32− = H2O + CO2 + 2e− (C) 1/2O2 + CO2 + 2e- = CO32− | \n
SOFCs | \n800–1000 | \nCeramic ZrO2/Y2O3 (solid) | \n(A) H2 + O2− = H2O + 2e− (C) 1/2O2 + 2e- = O2− | \n
Main combustion cell type’s characteristics.
These devices present large spectra of applications due to the fact that global efficiencies obtained for electricity are higher than those of classical systems (thermic engines or hydroelectric turbines). At the same time, the effects induced upon the environment are less harmful than those produced by other electricity-producing systems such as fossil fuels burning.
\nFuel cells can be classified based on two main criteria: electrolyte nature (charge carriers HO−, H+, CO32− or O2−) and operation temperature. Based on the latter criterion, fuel cell types are:
Table 2 is summarizing the main combustion cell types depending on operating temperature, electrolyte nature, anode (A) and cathode (C) reactions.
\nConductive polymer membranes are thoroughly studied due to advantages offered by the fact that they function both as solid electrolytes and as selective separation barriers for the species implied in electricity generation within the fuel cells.
\nFirst applications were based on preparation and inclusion within the fuel cells structure of protons exchange membranes—Nafion, obtained from persulphonic acid and PTFE by Dupont Company 30 years ago. Nowadays researches are focussed on preparation of conductive polymers membranes with improved electric and mechanical properties. The most recent researches in preparation of both conductive membranes with protons exchange properties, applicable in PEMFCs, and conductive membranes applicable to AFCs are reviewed in the following paragraphs.
\nIn a study dedicated to this domain [56] are emphasized the large number of composite membranes based on conductive polymers used for fabrication of high temperature proton exchange membrane fuel cells. Both organic composite membranes based on polymers with electric properties such as sulphonated poly (p-phenylene), sulphonated poly(ether ether ketone), sulfonated polysulfone, sulfonated poly (arylene ether sulfone), sulfonated poly(aryl ether ether nitrile), sulfonated poly(sulphide ketone), and organic-inorganic composite membranes such as fluorinated polymer/SiO2, polyalkoxysilane/phosphotungstic acid, Nafion/PTFE/zirconium phosphate, Nafion/TiO2 and Nafion/SiO2 are reviewed.
\nOne of the most studied polymers for organic composite membranes with applications in fuel cells is poly(ether ether ketone) (PEEK), which is used in base or modified form. Thus, from sulfonated poly(ether ether ketone) (SPEEK), asymmetric microporous membranes can be obtained via phase inversion method and immersion-precipitation technique. The SPEEK polymer was obtained by dissolving PEEK in concentrated H2SO4 added in a proportion of 5 wt%, at room temperature, reaction media being maintained by mixing for 24 h. From the resulted solution, a membrane was prepared by coating on a plane glass surface, followed by immersion in a coagulation bath containing distilled water (phase inversion method, immersion-precipitation technique). The obtained membrane is modified through in situ polymerization (within membrane pores) of Py doped with iron chloride and cerium sulphate [57]. Electroconductive properties of PPy from composite membrane structure (ionic conductivity of 0.34 S m−1) made the membrane suitable for fuel cells.
\nComposite membranes are obtained, using SPEEK as base material, through inclusion within its structure of heteropolycompounds based on tungsten, molybdenum or wolfram [58]. Obtained composite membranes present a conductivity of 1 S m−1 at chamber temperature and 10 S m−1 at 100°C temperature, being used in PEMFC-type fuel cells.
\nOther studies on SPPEK applications for fuel cells showed that it can be functionalized with quaternary amine hydroxide and imidazolium hydroxide [59] (resulting membranes with 10−3 S m−1 conductivity) or by PANI inclusion within membrane structure [60].
\nPolysulfone [61] and poly(1,4-phenylene ether ether sulfone) [62] are other polymeric materials that can be used to obtain composite membranes with conductive properties for fabrication of fuel cells. Using polysulfone, asymmetric membranes can be obtained via classical process of phase inversion and afterwards functionalized through incorporating acrylamide-based ionomers having proton-conducting sulphonics groups. Incorporation process of the new polymer is based on photopolymerization [61]. At the surface of membranes prepared from poly(1,4-phenylene ether ether sulfone) modified through addition of tungstophosphoric acid, a layer of PPy polymer is applied via chemical oxidation, resulting in composite membranes used for fabrication of DMFC [62]-type fuel cells.
\nFuel cells protons exchange composite membranes, which can be used at temperature above 100°C, were obtained from poly(2,6-dimethyl-1,4-phenylene oxide), N-(3-aminopropyl)-imidazole and metal – organic frameworks [63].
\nComposite membranes with applications at high temperatures, for fuel cells, are obtained also from bi-functionalized copolymer prepared through radical copolymerization, having SiO2 [64] within in its structure.
\nAnother point of interest within the literature is represented by preparation of membranes for alkaline fuel cells. Studies performed in this domain [65, 66] classify conductive membranes for preparation of AFCs in heterogeneous and homogeneous membranes, each with their specific polymers and preparation methods. One of the most recent researches related to membranes for alkaline fuel cells is focussing on preparation of high ionic conductivity membrane from crosslinked poly(arylene ether sulphones) [67].
\nBesides traditional methods for preparation of polymeric membranes with conductive polymers (phase inversion, lamination, irradiation, etc.), a new technique was recently developed—plasma techniques both for plasma polymerization and for plasma modification of membrane surfaces [68]. Proton exchange membrane for PEMFCs and membranes for alkaline fuel cells (AFCs) can be obtained using this technique.
\nConductive polymers themselves are not forming membranes that can be used in various processes due to low mechanical strength, lack of elasticity and plasticity. For this reason, conductive polymer-based membranes are mainly composite membranes.
\nPreparation methods of composite membranes based on conductive polymers are similar to those used for simple membranes (sintering, lamination, irradiation, phase inversion, deposition on thin layers) for the formation of support polymer that confers mechanical strength and elasticity. Chemical oxidation polymerization and electrochemical polymerization are used for the inclusion within the support structure of a polymer with conductive properties. There are three ways for preparation of composite membranes presented within the literature:
\nConductive polymer is formed at the same time with support membrane; in this case, the composite membrane contains the conductive polymer in all its structure;
Conductive polymer is formed after support membrane preparation and its soaking in monomer solution followed by polymerization through chemical oxidation; in this case, composite membrane contains conductive polymer in all microporous structure;
Conductive polymer is formed only after preparation of support membrane through deposition on its surface of conductive polymeric film; in this case, composite membrane contains in its structure two different layers—sandwich type.
Conductive properties of polymers that contain conjugated electrons systems (п-п or p-п) are low compared with metals, being at the level of semiconductors. In order to obtain polymers with better conductive properties, “doping” technique is used, through introduction within polymeric chain of atoms or groups of atoms that creates “defects” within macromolecule structure as a result having more rapid “jumping” of electrons between polar centres. Doping process takes place simultaneously with conductive polymer formation within the composite membrane structure, through dopants addition within monomer solution. Doping process takes place with conductive polymer preparation in some rare cases.
\nConductive polymer-based composite membranes are used in membrane processes that generally use concentration gradient (pervaporation and gas separation) and electric potential gradient (electro-dialysis) as driving forces. There are also cases in which these membranes are used in processes that uses pressure gradient (MF, UF, RO). Many researches are focussed on conductive polymer-based composite membranes’ use for fuel cells.
\nThe contamination of food and feed crops with mycotoxigenic fungi is a persistent problem contributing to food safety and security worldwide. The infection of crops by these fungal pathogens affects crop yield and quality but of greater concern are the secondary metabolites they produce, collectively known as mycotoxins. Ingestion of mycotoxin-contaminated products has been associated with a wide range of noxious effects on humans and livestock. The major food and feed crops affected by mycotoxigenic fungi and mycotoxins include rice, maize, wheat, soybean, sorghum and groundnut, although several other crops are also affected. The association of these crops with mycotoxigenic fungi is ubiquitous, and crops are affected wherever they are produced. Three major groups of mycotoxigenic fungi are associated with mycotoxin contamination namely
More than 100 countries have established mycotoxin regulations, including 15 African countries [1, 2, 3]. The European Union and United States Food and Drug Administration established maximum allowable levels for certain food contaminants, including mycotoxins, with the aim to reduce their presence in foodstuffs to the lowest levels reasonably achievable by means of good manufacturing or agricultural practices [4]. Most of the countries have mycotoxin regulations for at least AFB1, produced predominantly by
The management of mycotoxigenic fungi and their subsequent mycotoxins is therefore vital towards ensuring sustainable, safe food and feed production. Integrated management practises that reduce the incidence of mycotoxigenic fungi as well as the management of abiotic factors that contribute to mycotoxin contamination are required before and following harvest. However, preharvest management is considered the most important in limiting the overall contamination of crops. Therefore, the use of tolerant varieties is deemed the most proficient and environmentally sound approach to manage fungi and their toxins. In addition, several other management approaches such as optimal plant production, cultural practises, chemical control and the management of mycotoxigenic fungi by atoxigenic strains or bacteria could further reduce fungal incidence and subsequent mycotoxin contamination.
\nManaging mycotoxigenic fungi and their mycotoxins in crop plants requires a proper understanding of the biology, epidemiology and genetics/genomics of the fungus and host plant. Major crops vary significantly in susceptibility to mycotoxigenic fungi and subsequent mycotoxin contamination. Maize is widely considered to be among the most susceptible of major crops to mycotoxins, while rice is considered among the least susceptible crop [7, 8, 9].
\nCrops with resistance to numerous mycotoxigenic fungi have been documented [10, 11, 12], but none of these are immune. Resistance to mycotoxigenic fungi therefore appears to be quantitative rather than qualitative. Breeding programmes at both public and private institutions are initiating and expanding their efforts to develop disease-resistant inbred and hybrid materials [13]. A number of international institutions such as the International Maize and Wheat Improvement Centre (CIMMYT) and the International Institute of Tropical Agriculture (IITA) in African countries including Kenya and Nigeria have established breeding programmes with the primary focus on producing inbred lines with improved resistance to
Diallel analysis to determine the general combinability (GC) and specific combinability (SC) of resistant genotypes has been reported for
Inbred lines with resistance to aflatoxin contamination were evaluated for GCA and SCA for resistance to fumonisin accumulation, and two lines with resistance to FUM and AF were registered [25]. That research demonstrated the ability to breed resistance to multiple mycotoxigenic fungi and/or their mycotoxins. Furthermore, improved resistance to
Quantitative trait loci (QTL) associated with resistance to mycotoxigenic fungi has been mapped in maize and wheat and can be used for marker-assisted selection [15, 16, 32, 33, 34, 35, 36]. Some QTLs, however, displayed pleiotropic effects, sometimes resulting in resistance to both traits [15, 32, 37]. QTL analyses have also demonstrated pleiotropic effects for resistance to other mycotoxigenic fungi and/or their associated mycotoxins. In QTL studies involving multiple ear rot pathogens, maize resistant to FER and FUM accumulation was also resistant to
Genetically modified crops are plants of which the DNA has been altered through the introduction of a foreign gene to express a trait not inherent to the modified plant. Three transgene-mediated strategies have been proposed for the management of mycotoxigenic fungi and mycotoxins in maize [48]. These include (1) the reduction of fungal infection, (2) the degradation of mycotoxins and (3) interfering with the mycotoxin biosynthetic pathway. To reduce infection by the fungus, the incorporation of antifungal and/or resistance genes, as well as the overexpression of defence-related genes, is required. Catabolic enzymes from microbes have been used to detoxify certain mycotoxins both
Exposure of seeds or other heritable materials to chemicals or radiation with the purpose to induce DNA changes (mutations) is known as mutation breeding. Nuclear technology for crop improvement makes use of ionising radiation, which causes induced mutations with a high mutation frequency in plants [57]. These mutations might be beneficial and alter physiological characters of plants, including plant height, ear height and improved root architecture [58, 59]. The radiation of seeds may also cause genetic variability that enables breeders to select new genotypes with improved grain yield and quality [60]. Mutation breeding has been successfully used to generate genetic variation in cereal crops, including maize, for a number of aspects including enhanced yield and productivity, altered ear length, drought tolerance and enhanced stem structure [61, 62, 63]. It can thus potentially provide an attractive means for generating tolerance to mycotoxigenic fungi and their mycotoxins.
\nThe planting of disease-resistant plants is an effective, affordable and environmentally sound strategy to control ear rot diseases and mycotoxin accumulation [64]. Commercial hybrids differ in their ability to accumulate mycotoxins [64], while hybrids grown outside of their adapted range are more susceptible to mycotoxins than those grown within their adapted range [18]. Determining host-plant resistance to mycotoxigenic fungi and mycotoxin accumulation is a fundamental step towards developing commercially tolerant plant varieties. Several factors require careful consideration when screening materials for resistance to mycotoxigenic fungi and their mycotoxins. Inoculation technique significantly contributes to the efficacy of the screening protocol and should, therefore, be appropriate, produce consistent results and consider the disease cycle of the pathogen. Numerous studies relating to different crops report on the importance of screening for resistance under variable environmental conditions since genotype by environment interactions (GEI) plays such a vital role in disease development and mycotoxin contamination. Furthermore, GEI and stability indicators provide for the selection of material tolerant across a broad range of environments or alternatively exhibiting tolerance in specific environments.
\nVarious countries have reported on the tolerance levels of maize and wheat cultivars to mycotoxigenic fungi and associated mycotoxins [65, 66, 67]. However, focus has been placed on the characterisation of inbred lines for the identification of appropriate breeding material towards resistance to mycotoxigenic fungi and their toxins [68, 69, 70, 71, 72, 73, 74]. Genetically modified maize, expressing
Adhering to planting dates and planting plants at lower or optimal densities reduces mycotoxin accumulation during production [75, 76, 77]. Plants should be planted at recommended row widths and densities to specifically reduce water stress [78] and ensure optimal nutrient availability. Maize ears should be harvested from the field as soon as possible because favourable conditions for ear rot and/or mycotoxin accumulation may occur if harvest is delayed, thus leading to elevated mycotoxin levels [79, 80].
\nThe primary objective of cultural control of mycotoxigenic fungi is to minimise factors that result in plant stress. Inoculum build-up on plant residues can be reduced by crop rotation practices, such as the rotation of maize with non-host crops [75, 81, 82]. Crop rotation with legumes, brassicas and potato could also significantly reduce
Field preparation and cultivation practices play a central role in the management of
Limiting plant stress to increase plant vigour by adhering to optimum plant dates, preventing drought stress and the optimal use of fertilisers have reduced
Fungicides have been shown to significantly reduce FHB and DON contamination of wheat grain. Triazole fungicides such as metconazole and tebuconazole have been shown to control FHB and DON contamination in wheat [96]. However, fungicides are neither effective in reducing
Reduced FHB severity and mycotoxin contamination of wheat under field conditions using tannic acid and the botanicals, Chinese galls and buckthorn, have been shown [100]. These researchers also reported disease and mycotoxin reduction efficacy close to that observed with a synthetic fungicide, thereby demonstrating the potential use of natural compounds in managing mycotoxigenic fungi and their toxins. Furthermore, several studies report on a reduced fungal growth and mycotoxin contamination for
The use of biological control agents to manage mycotoxigenic fungi has been reported. Atoxigenic
An epidemic can be described as a ‘change in disease intensity in a host population over time and space’ [108]. Mathematical modelling of crop disease is a rapidly expanding discipline within plant pathology [109] with the first models developed by Van der Plank [110, 111]. In epidemiology, modelling aims to understand the main determinants of epidemic development in order to address disease management in a sustainable and efficient manner. It can, therefore, serve as an instrument to monitor and assess the risk of mycotoxin contamination in crops that would drive agronomic decisions during cultivation, in order to enhance management strategies [112].
\nMost research regarding disease forecasting of mycotoxigenic fungi has focussed on FHB of wheat. This disease is considered well suited for risk assessment modelling because of the severity of epidemics, compound losses resulting from mycotoxin contamination and relatively narrow time periods of pathogen sporulation, inoculum dispersal and host infection [113]. This can be seen from the online forecasting model FusaProg [114], which is a threshold-based tool to control
Field-based models to predict FUM B1 contamination in maize grain have been elusive, most probably due to the complexity of interactions between numerous abiotic and biotic disease factors [115]. The concentration and severity of FUM produced by
A risk assessment model (FUMAgrain) developed for FUM contamination of maize grain in Italy gives an initial risk alert at the end of flowering based on meteorological conditions [118]. A second alert follows at kernel maturation following assessments of grain moisture, European corn borer damage and FUM synthesis risk. FUMAgrain could simulate FUM synthesis in maize accounting for 70% of the variation for calibration and 71% for validation. The importance of meteorological conditions at flowering and the growth of
Food and feed crops are consistently threatened by mycotoxigenic fungi and compound their infection by depositing toxic metabolites, including mycotoxins. Preharvest management of mycotoxin contamination is vital to maintaining contamination levels below economically feasible and legislated thresholds. Planting genotypes with enhanced host resistance is considered the most practical, affordable and environmentally sound method of controlling mycotoxigenic fungi and their mycotoxins. However, integrating resistant varieties with good agricultural practises such as crop rotation, chemical/biological control and other strategies that optimise plant production by minimising stressors may further reduce the risks associated with mycotoxin contamination. Resistance to mycotoxigenic fungi exists and has been identified in appropriate breeding materials but such resistance needs to be introduced in high-yielding and locally adapted hybrids. To date, conventional breeding has not been able to introgress disease and/or mycotoxin resistance into important staple crops like maize. Therefore, further research is required into factors with a greater efficacy to reduce mycotoxigenic fungi and mycotoxins preharvest as resistant varieties are being developed.
\nThe South African Maize Trust and the National Research Foundation (NRF) of South Africa (Thuthuka; South Africa—Kenya Research Partnership Programme Bilateral); the MAIZE Competitive Grants Initiative, International Maize and Wheat Improvement Centre (CIMMYT), and CGIAR, the National Commission for Science, Technology and Innovation (NACOSTI) of Kenya; the Agricultural Research Council of South Africa are all acknowledged for funding.
\nThe authors declare no conflict of interest.
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\n\nIMPORTANT: You must be a member or grantee of the listed funders in order to apply for their Open Access publication funds. Do not attempt to contact the funders if this is not the case.
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