\\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:"2296",leadTitle:null,fullTitle:"Embedded Systems - High Performance Systems, Applications and Projects",title:"Embedded Systems",subtitle:"High Performance Systems, Applications and Projects",reviewType:"peer-reviewed",abstract:'Nowadays, embedded systems - computer systems that are embedded in various kinds of devices and play an important role of specific control functions, have permeated various scenes of industry. Therefore, we can hardly discuss our life or society from now onwards without referring to embedded systems. For wide-ranging embedded systems to continue their growth, a number of high-quality fundamental and applied researches are indispensable. This book contains 13 excellent chapters and addresses a wide spectrum of research topics of embedded systems, including parallel computing, communication architecture, application-specific systems, and embedded systems projects. Embedded systems can be made only after fusing miscellaneous technologies together. Various technologies condensed in this book as well as in the complementary book "Embedded Systems - Theory and Design Methodology", will be helpful to researchers and engineers around the world.',isbn:null,printIsbn:"978-953-51-0350-9",pdfIsbn:"978-953-51-5691-8",doi:"10.5772/2684",price:119,priceEur:129,priceUsd:155,slug:"embedded-systems-high-performance-systems-applications-and-projects",numberOfPages:290,isOpenForSubmission:!1,isInWos:null,isInBkci:!1,hash:"0e7128c4252ae91952675ba2a98af9f7",bookSignature:"Kiyofumi Tanaka",publishedDate:"March 16th 2012",coverURL:"https://cdn.intechopen.com/books/images_new/2296.jpg",numberOfDownloads:56392,numberOfWosCitations:8,numberOfCrossrefCitations:8,numberOfCrossrefCitationsByBook:1,numberOfDimensionsCitations:17,numberOfDimensionsCitationsByBook:1,hasAltmetrics:0,numberOfTotalCitations:33,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:"119112",title:"Dr.",name:"Kiyofumi",middleName:null,surname:"Tanaka",slug:"kiyofumi-tanaka",fullName:"Kiyofumi Tanaka",profilePictureURL:"https://mts.intechopen.com/storage/users/119112/images/2304_n.jpg",biography:"Dr. Kiyofumi Tanaka, Associate Professor at Japan Advanced Institute of \nScience and Technology, is a researcher with a substantial experience \nin computer architecture, operating systems, and real-time embedded \nsystems fields. He was born in Japan, in 1971. He obtained B.S., M.S., \nand Ph.D. from the University of Tokyo.\n\nHe is working on two major research topics, high-performance/energy-aware \nprocessor architecture including efficient hierarchical cache memories, \nand real-time embedded systems including fast response mechanisms and \npractical real-time embedded operating systems. In his research career, \nhe developed a parallel computer with hardware-controlled distributed \nshared memories and a highly functional interconnection network, real-time \nembedded RISC processors with multi-contexts and various mechanisms for \nfast interrupt response, and a real-time embedded operating system with \nadaptive task scheduling ability.",institutionString:null,position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"2",institution:null}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"555",title:"Embedded System",slug:"computer-science-and-engineering-embedded-system"}],chapters:[{id:"31912",title:"Parallel Embedded Computing Architectures",doi:"10.5772/38478",slug:"parallel-embedded-computing-architectures",totalDownloads:5518,totalCrossrefCites:1,totalDimensionsCites:2,hasAltmetrics:0,abstract:null,signatures:"Michael Schmidt, Dietmar Fey and Marc Reichenbach",downloadPdfUrl:"/chapter/pdf-download/31912",previewPdfUrl:"/chapter/pdf-preview/31912",authors:[{id:"117475",title:"Dr",name:null,surname:"Fey",slug:"fey",fullName:"Fey"}],corrections:null},{id:"31913",title:"Determining a Non-Collision Data Transfer Paths in Hypercube Processors Network",doi:"10.5772/38168",slug:"determining-a-non-collision-data-transfer-paths-in-hypercube-processors-network",totalDownloads:2728,totalCrossrefCites:0,totalDimensionsCites:1,hasAltmetrics:0,abstract:null,signatures:"Jan Chudzikiewicz and Zbigniew Zieliński",downloadPdfUrl:"/chapter/pdf-download/31913",previewPdfUrl:"/chapter/pdf-preview/31913",authors:[{id:"115855",title:"Dr.",name:"Jan",surname:"Chudzikiewicz",slug:"jan-chudzikiewicz",fullName:"Jan Chudzikiewicz"},{id:"135626",title:"Dr.",name:"Zbigniew",surname:"Zieliński",slug:"zbigniew-zielinski",fullName:"Zbigniew Zieliński"}],corrections:null},{id:"31914",title:"Software Development for Parallel and Multi-Core Processing",doi:"10.5772/38261",slug:"software-development-for-parallel-and-multi-core-processing",totalDownloads:9762,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:null,signatures:"Kenn R. 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\r\n\r\n\tPredominantly, it is used by researchers and technocrats for accurate estimation because the main intention of it is to advance the response time. Here, quantitative data is used to fit the regression model from the experiments and for optimizing the response. So, the linear, polynomial or square functions are adopted to study the system and explore the suitable experimental condition for optimization. This book will intend to provide the reader with a comprehensive analysis of response surface methods, which is capable of being applied in all the fields of science, engineering and technology including the machine learning models in relation to the response surface method.
",isbn:"978-1-83880-299-8",printIsbn:"978-1-83880-288-2",pdfIsbn:"978-1-83880-463-3",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!0,isSalesforceBook:!1,isNomenclature:!1,hash:"a22fd44ae22d422a792470bb5c441a81",bookSignature:"Prof. Palanikumar Kayaroganam",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/11952.jpg",keywords:"Design of Experiments, Central Composite Design, Taguchi's Design, First-order Model, Second-order Model, Effect Graph, Contour Graphs, Response Optimization, Desirability Analysis, Neural Network, Fuzzy Logic, Comparison",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"April 15th 2022",dateEndSecondStepPublish:"June 22nd 2022",dateEndThirdStepPublish:"August 21st 2022",dateEndFourthStepPublish:"November 9th 2022",dateEndFifthStepPublish:"January 8th 2023",dateConfirmationOfParticipation:null,remainingDaysToSecondStep:"8 days",secondStepPassed:!0,areRegistrationsClosed:!1,currentStepOfPublishingProcess:3,editedByType:null,kuFlag:!1,biosketch:"A pioneering researcher in materials, modelling and optimization, working as head of the Institute in Sri Sairam Institute of Technology, National Best Teacher Awardee, and holder of 6 granted patents. 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Greek Nano word used for “dwarf” means one-billionth. Nanoparticles can be served as a strong bridge between the bulk materials and atomic or molecular structures. A bulk material has constant physical properties regardless of their size and shape, but at the nanoscale, the size, morphological substructure of the substance, and shape (as well as aspect ratios) are the major driving factors for changing their biological, chemical, and physical properties. Because at the nanoscale, the materials behave differently and they emerge with few novel characters in themselves, such as some of the materials become explosive (for example, aluminum) or their melting point changes (for example, silver and gold) or a new property is revealed (for example, nanosilver possess the antibacterial character and becomes an odor eater).
\nThe novel properties of nano-objects occur due to the changes in size and scale. Surface area to volume ratio of the particle depends on the size and shape of an object; here, the size of the nanoparticle is very small in at least one dimension. Nanoparticles exhibited some extra phenomenon, i.e., random motion of the small particles, quantum tunneling, discreteness of energy, uncertainty of the matter, duality nature of mass, and energy for wave particles, etc. Moreover, the gravity becomes a markedly less significant force at the nanoscale, while the Vander Waals forces became incredibly strong. Therefore, the Vander Waals forces make the materials “sticky” [1]. Due to the reduction in the spatial dimension, confinement of these quasi particles in a particular crystallographic direction within a structure generally leads to changes in physical properties of the system in that direction. Some qualities (gravitational forces, vapour pressure and boiling point) of the nanoparticles decreases with their particle size and became insignificant at nanoscale because the electromagnetic force of protons is 1036 times stronger than gravitational forces. Here, quantum mechanics dominates in place of classical mechanics. Nanomaterials are changing their electrical, optical, surface-related, mechanical, and magnetic properties at nanoscale and exhibits some prominent effects that are associated with nanoparticles, as mentioned below.
\nBecause of the electrons that cannot move freely at nanolevel and their motion became restricted, this confinement at the nanoscale resulted in the changes in electrical properties, such as the bulk conductor/semiconductor materials behaving as superconductors or conductors at nanoscale. Similarly, nanogold/nanosilver (of size less than 10 nm) cannot conduct electricity.
\nOptical properties of nanomaterials are also size dependent. Electrons cannot move freely at the nanoscale and become restricted. The confinement of the electrons causes them to react to light differently. Gold appears golden at the macroscale, but the nanosized gold particles are red. Nanosized zinc oxide particles will not scatter visible light and bulk zinc oxide particles used for sun block as they scattered visible light and appear white. Quantum dots changes in their optical appearance as the size of the particles decreases creating different colors.
\nThe surface-dominated properties such as melting point, rate of reaction, capillary action, and adhesion, are controlled by their surface area and due to high surface area of the nanomaterials, these properties show drastic changes from their bulk counter parts. At the macro scale, gold has a melting point of 1064°C, but by decreasing the particle size from 100 to 10 nm diameter, its melting temperatures drops up to 100°C. As the size reduces to about 2 nm, the melting point decreases to about half of the melting point at the macroscale level [2, 3].
\nAt nanolevel, the changes in mechanical properties of the material such as Young’s modulus, tensile strength (four times larger), lower plastic deformation, more hardness, more brittle, grain boundaries deformations, decrease in elongation, lower density of dislocation moments, short distance of dislocation moments increases, are observed.
\nFor nanomagnetic materials, each spin behaves as a small magnet for nanomaterials. The interaction between neighboring spins is dominated by the spin exchange interaction. Usually, most of the materials has J < 0 and are nonmagnetic (paramagnetic or diamagnetic) by nature. Similar to the paramagnets, the nanosuperparamagnets back to zero magnetization upon removing of the field. It happens because of their small size and not due to the inherently weak exchange between the individual moments.
\nLotus leaves are super hydrophobic due to high contact angle (122o) of water droplets to lotus leaf surface and presence of the needle-shaped wax tubes in these leaves, (a smaller-sized roughness region of 0.3–1.7 μm with
A rough surface of lotus leaves was etched into polydimethylsiloxane (PDMS) and a negative PDMS template was made, and then, the negative template was used to make a positive PDMS reproduced as a replica sheet of the original lotus leaf. These positive PDMS templates exhibit the extreme water repellency (superhydrophobic) along with the same surface structural features as the lotus leaves shown in Figure 1a–d and f. Four classes of surfaces are revealed on the grounds of surface wettability and their contact angles are shown in Figure 1g [5, 6]. The chief applications of lotus effect are in making of non-wettable rain wear/sails for boats, paints for kitchen roofs/walls that make them soot-free, windows in high-rise buildings, glass for greenhouses avoiding their expensive and cumbersome cleaning, water-repellant fibers for garments, sanitary products in bathrooms/toilets and windshields motor vehicle for reducing sticking of dirt matter and easier cleaning, etc.
\n(a) SEM images of superhydrophobic plant leave surfaces, showing the different type of epidermal cells (a–c) and various types of epicuticular wax crystals (d–f) on leaves of
When plasmonic material (nanosphere is small in comparison to the wavelength of light, and the light has a frequency close to that of the SP, then the SP will absorb energy) is exposed to sunlight, free electrons of the nanoparticle of noble metals are integrated with the photon energy that produces subwaves and conducting electrons in oscillating mode [7, 8]. These collective oscillations (excitation) offer a localized surface plasmonic resonance (LSPR). LSPR adds the benefits of the enhanced local heating effect, LSPR-powered e/h generation, enhanced UV-Vis absorption, reduced e/h diffusion length, enhanced local electric effect and molecular polarization effect, quantum tunneling effect, high catalytic effect, and to the main photocatalytic unit. Hence, NPs of noble metals act as the thermal redox reaction-active centers on the catalyst that can trap, scatter, and concentrate light [9, 10, 11], and enhance the number of active sites and the rate of electron–hole formation by providing a fast lane for charge transfer on the semiconductor surface. Cu, Ag, Au, Pt, Pd, and their alloys Cu–Ag, Cu–Au, Cu–Ag–Au, are few examples of NPs of the noble metals with SPR. This phenomenon results in numerous physical effects including tailorable absorption of light (from UV to near-IR), local heating, and proficient charge transfer. Therefore, photoexcitation leads to a smooth electron transfer between the semiconductor carrier/supports and the noble-metal NPs. NPs of Ag, or Au (< 10 nm), are the most commonly used plasmonic materials.
\nThe quantum confinement effect is observed for the particles having particle size less than the wavelength of the electron. If the motion of randomly moving electron is to be restricted in a specific energy levels (discreteness) then the motion of electron confined in three dimensions, two dimensions and one dimension, result in the particles having the shape of quantum dots, nanowire/rods and nanosheets, respectively. As the size of a particle decreases up to a nanoscale, the decrease in confining dimension makes the energy levels discrete, which widens up their band gap and band gap energy. If the size of the quantum dot is smaller than the Bohr’s radius of the charge carrier (excitons, electron, hole quasi-particles of semiconductors), then the confinement observed here leads to a transition from continuous to discrete energy levels [12]. Although the physical properties of a quantum dots are not affected by quantum confinement, their optical absorption and emission can be tuned via the quantum size effect.
\nThe phenomenon of Coulomb blockade can also be observed for a very small device (like a quantum dot) at the temperature which has to be low enough (~1 Kelvin ≅ 3 He refrigerators) so that the characteristic charging energy (the energy that is required to charge the junction with one elementary charge) is larger than the thermal energy of the charge carriers. But the small sized quantum dots of only few nanometers has quality to observe Coulomb Blockade from the liquid helium temperature up to room temperature (Figures 2a–2c) [13, 14, 15].
\n(a) Schematic diagram of typical arrangement of electrodes (quantum dot (QD) surrounded with source, drain and gate) for a single electron transistor. Energy diagram for a quantum dot, where the two tunnel barriers connected the QD to the source and drain contacts. (b) Electron transport is blocked and the dot contains a fixed number of N electrons. (b) Number of electrons on the QD can vary between N and N−1, result in rise a peak in the conductance because the gate voltage was tuned in order to align the chemical potential of the QD with that of source and drain [
During the Coulomb Blockade phenomenon, the electrons inside this quantum sized device will create a strong coulomb repulsion that prevent other electrons to flow, resulting in the device will no longer follow Ohm’s law as shown in Figures 2a–2c. When very few electrons are involved and an external static magnetic field is applied, Coulomb blockade provides the ground for spin blockade (also called Pauli blockade) and valley blockade [16, 17] which includes quantum mechanical effects due to spin and orbital interactions, respectively, between the electrons.
\nHistory of mankind is a pursuit of color. Even in the Stone Age, people made use of pigments in paintings. In the Middle Age, the ancient Egyptians used nanotechnology but they did not understand as such in detail, but they prepared colloidal dispersion as inks and other useful products like paintings, dying hair, etc. Long ago before the beginning of the “Morden nano-era,” people were well encountered with various nanosized objects and nanolevel processes, and they were using them in practice without due knowledge of the nature of these objects and processes. Thus, people were indulged in nanotechnology subconsciously, without proper understanding of the reason behind them. The secrets of nano-antiques were passed from generation to generation, without getting into the reasons behind their acquired unique properties. Thousands of primeval knew to cultivate and process the natural fabrics, such as flax, cotton, wool, and silk, in developing the fabric of typical nanoporous materials with pores size of 1–20 nm. They were able to cultivate them and process into fine fabric product. These special fabrics possessed a developed network of pores with the size of 1–20 nm, i.e., they are typical nanoporous materials. Due to their nanoporous structure, the natural fabrics possess high-utilitarian properties as they absorb sweat well, quickly swell, and dry. Since ancient times, Egyptian people were mastered with the ways of making bread, wine, beer, cheese, and other foodstuffs, where the critical fermentation processed at nanolevel. Ph. Walter conducted a study on the hair samples from ancient Egyptian burial sites. He found that the primeval Egyptians used a nanoparticle of galenite (5 nm sized PbS) made of paste of lime, lead oxide, and small amount of water to dye hair in black. The dyeing paste reacted with sulfur of keratin, to obtain a few nanometer-sized galenite particles, to provide even and steady dyeing. The British museum possess Lycurgus Cup that was made by Roman artists in the 4th century AD, as an outstanding glass work of the primordial Rome. The impression of the Tsar of Edons (Lycurgus, Figure 3a) is embossed on the bowl and it shows unusual optical properties. In natural light, the bowl is green (Figure 3b), and if illuminated from within cup, it turns red (Figure 3b). The analysis of fragments of the bowl was done in 1959, by General Electric Motors for the first time, which reflected that the bowl consists of usual soda-lime-quartz glass with about 1% of gold and silver, and also 0.5% of manganese. The researchers discovered particles of gold and silver from 50 to 100 nanometers in size using an electronic microscope (Figure 3c), responsible for the unusual coloring of the bowl. In 2007, Harry [18] explained this phenomenon by the effects of plasmon excitation of electrons with metal nanoparticles. The Medieval Age manufacturing of multi-colored-stained glass windows (due to the gold and other metal nanoparticles) of church in Europe, are also a good example of high perfection engineering. During the battles of the European knights against Muslims, they faced the extraordinary strength of the blades of Muslims warriors in fights for the first time that was made of an ultra-strong Damascus steel (nanofibrous structure). After the discovery of electron microscopy in 1857, Michal Faraday discovered the colloidal gold in different colors: ruby, green, violet, or blue [19]. Thereafter, Albert Einstein explained the existence of colloidal dispersion in terms of Brownian motion. The above theory was experimentally confirmed by Jean-Baptize Perrin, which was awarded by Nobel Prize in 1926 [20].
\n(a) Dichroic Lycrugus cup made in 4th century AD and (b) in direct light it resembles jade with an opaque greenish-yellow tone, but when light shines through the glass (transmitted light) it turns to a translucent ruby color. (c) Transmission electron microscopy (TEM) image of a silver-gold alloy particle within the glass of the Lycurgus Cup [
Metal nanoparticles (MNPs) exhibit novel and size-related physico-chemical properties significantly different from their bulk counterpart [22]. The unique properties of MNPs have been an ambassador of their potential uses in medicine, catalysis, optics, cosmetics, renewable energies, inks, microelectronics, medical imaging, environmental remediation, and biomedical devices [23, 24, 25, 26, 27, 28]. Besides, Ag-NPs exhibit a broad spectrum of bactericidal and fungicidal activity [29]. Therefore, the use of MNPs became exceptionally trendy for the wide range of consumer goods, including plastics, soaps, pastes, food, and textiles, to enhance their market value [30, 31, 32]. Among the wide range of metal nanoparticles, silver nanoparticles (Ag-NPs or nanosilver) were the most popular, due to their unique physical, chemical, and biological properties when compared to their macroscaled counterparts [33]. The advantage of the nanosilver over the other noble metals with respect to their physico-chemical properties are: small loss of the optical frequency during the surface-plasmon propagation [34], non-toxic, high electrical and thermal conductivity, stability at ambient conditions, low cost than the other noble metals such as gold and platinum, high-primitive character, wide absorption of visible and far IR region of the light, surface-enhanced Raman scattering, chemical stability, catalytic activity, and non-linear optical behavior (Figure 4a–c). Moreover, they exhibit a broad spectrum of high antimicrobial activity (bactericidal and fungicidal activity) attracting the scientists and technologists with much interest to develop nanosilver-based disinfectant products [35].
\n(a) Real and (b) imaginary part of permittivities of the metal candidates Ag, Au, Na K, and Al [
LSPR region of Ag, Au, and Cu in the visible and near-infrared wavelength range of sunlight is exhibited in Figure 5a [38]. The comparative UV/Vis diffuse-reflectance spectra of AgCl, Ag@AgCl, and N-TiO2, are demonstrated by the Figure 5b that reflected the Ag@AgCl with plasmonic Ag molecules covers the wide range visible wavelength than other systems. The large effective scattering cross section, plasmon resonance with unique colors of the individual silver nanoparticles, as well as their non-bleaching properties have significant potential for single molecule labeling-based biological assays [40, 41]. Metal nanoparticles are also used in various near-field optical microscopic applications [42, 43] on the heels of augmented signal output due to their efficient scattering properties. Currently, nanosilver technologies have appeared in a variety of manufacturing processes and end products. There are many consumer products and applications which are utilizing nanosilver in consumer products (soap, shampoo, textile, disinfecting medical devices and home appliances to water treatments) with the highest degree of commercial value.
\n(a) Localized surface plasmon resonance of Ag, Au, and Cu that covers most of the visible and near-infrared wavelength range of sunlight [
During the LSPR, the light exposure in the UV-Visible wavelength range to the noble metal NPs (<10 nm), induced collective oscillations of their valence electrons [44]. The oscillating electron cloud (called localized surface plasmon/hot electrons) has the lifetime of femtoseconds order. After the lifetime, the population of hot electron started decaying via the radiative and non-radiative routes [45]. In radiative decay, they released radiations and in non-radiative decay, they were converted into photons and electron-hole pairs by inter-band/intra-band excitations that populated in conduction bands of the SP, as shown in Figure 6.
\nSchematic representation of radiative (left) and non-radiative (right) decay of the SP NP. The intra-band excitation within the conduction band results the non-radiative decay.
Surface plasmon resonance (SPR) has two different forms: (i) propagating part: surface plasmon polaritons (SPP) and (ii) stationary part: localized SPR (LSPR) [46]. The SPP traveled through resonantly excited charge oscillations on the surface of thin metal films, whereas LSPR represents the non-propagating collective oscillation of the surface electrons in metal nanostructures. By utilization of SPP and LSPR in plasmonic nanostructures, the solar energy conversion efficiency of semiconductors can be improved via two paths [46]: photonic enhancement (or light trapping) and plasmonic energy transfer enhancement. In patterned plasmonic nanostructures, multiple times efficient scattering of the incident light increases the optical path length along with the light absorption direction in thin semiconductor layers [46, 47]. The previous part (SPP) contributes to enhance the energies above the band gap of a semiconductor, whereas the latter (LSPR) can induce charge separation in the semiconductor by absorbing light at the energies below the band gap [44, 48] due to the large local-field enhancement and absorption cross-section. The LSPR-induced charge separation can occur by transferring the plasmonic energy from the metal to the semiconductor via (i) direct electron transfer (DET) [49] and/or (ii) plasmon-induced resonant energy transfer (PIRET) [48]. This is referred to as plasmonic energy transfer enhancement [46] and is strong in small metal nanoparticles with small scattering cross-sections. The efficiency of the DET process depends open the relative energy of the hot electron to the height of the Schottky barrier at the interface Therefore, the semiconductor must be in close contact with the plasmonic metal. In contrast, PIRET proceeds non-radiatively based on the near-field dipole-dipole interaction between the plasmonic metal and the semiconductor [48]. PIRET allows the light absorption and the charge separation and does not require direct contact or band alignment, but its efficiency is controlled by the spectral overlap between the semiconductor’s absorption band edge and the LSPR absorbance [48]. The good example of utilizing propagating (SPP) and localized (LSPR) plasmon modes is hematite nanorod array grown on a long-range-ordered plasmonic gold nanohole array pattern by combating the scattering/absorption trade-off, illustrated in Figure 7, where the hematite nanorods have been acted as “fiber optics miniature” to create the incarcerated modes, to trap the incident light, and to enhance the light absorption [50].
\nArchitecture and microstructure of plasmonic photoanode. (a) Scheme for the growth of the hematite nanorod array on the Au nanohole array. (b, c) Scanning electron microscopic images of the Au nanohole array without (b) and with (c) the hematite nanorods. Scale bars, 1 mm (b) and 200 nm (c) [
The size, shape, and composition of plasmonic NP affects the optical properties, i.e., absorption phenomena in the semiconductor, charge transport, and energetics of the semiconductor photoelectrodes as illustrated in Figure 8 [51].
\n(A) Normalized extinction spectra of spherical Ag-NPs (38 ± 12 nm in diameter), Au NPs (25 ± 5 nm) and CuNPs (133 ± 23 nm). The solar radiation (air mass 1.5G) spectrum was taken from the National Renewable Energy Laboratory and is shown in black (
The energy of electron-electron as well as electron-phonon coupling was ultimately being converted into heat which will further thermalize the hot electrons. In the most of the cases, nonradiative (formation of electron and holes) plasmonic decay paralyzed the thermalization process that results in the efficiency minimization of the devices [52]. It not only limits the propagation length of plasmonic waveguides but also reduces the optical absorption of the metal that declines the overall performance of the device. The hot carriers generated from nonradiative plasmon decay offers new avenues to exploit the absorption losses. Although the much efforts have been devoted to alleviate the plasmon nonradiative decay, recent research has exposed the new prospectives by utilizing this energy in the areas [44, 53] such as in photothermal heat generation [45], photovoltaic devices [53, 54], photocatalysis [55, 56], driving material phase transitions [57, 58], photon energy conversion [59, 60] and photodetection [51, 61], and solar steam generation [62, 63, 64]. Most significantly, the decay of hot electrons can lead to the localized heating in the plasmonic nanostructures and making them good candidates for nanoscale heat sources [45, 65] that can be used in cancer therapy for destroying cancer cells [66]. On the contrary, hot electrons can be captured before thermalization by an adjacent semiconductor, to provide a novel photo-electrical energy conversion or chemical energy. The transformations from Plasmon energy to chemical energy occurred in four ways to drive the chemical reactions, i.e., (i) light scattering (radiative decay, Figure 9A), (ii) hot electron injection (HEI, Figure 9B), (iii) light concentration (Figure 9C), and (iv) Plasmon-induced resonance energy transfer (PIRET, Figure 9D). Light scattering by radiative decay can enhance the effective optical path length in the semiconductor. This leads to enhance the absorption of light and generation of charge carriers that can drive the chemical reactions [65].
\nSchematic presentation of the transformations from Plasmon energy to chemical energy occurred in four ways (A) light scattering (radiative decay; LS), (B) hot electron injection (intra-band excitation; HEI), (C) light concentration (near field induced absorption; LC) and (D) plasmon-induced resonance energy transfer (dipole-dipole coupling; PIRET).
Recently, a combination of a chiral metamaterial with hot electron injection was demonstrated in circularly polarized light detector [62, 67], where the chiral metamaterial can perfectly absorb the circularly polarized light which is the complimentary component of the largely reflecting device. Therefore, it can be also selectively generate the hot electrons and produce a photocurrent signal depending upon the handedness of the light [62]. This ultracompact detector avoids the complexity of conventional circularly polarized light detectors, where a quarter wave-plate/polarizer were used.
\nIn order to obtain the mechanistic insights into the structure-functionality relationship of the plasmonic NP/semiconductor composites, the decoupling of plasmon-induced and non-plasmon-induced effects are promising way to improve activity. Resonant enhancement in the polarizability of the materials with a negative real dielectric function (assuming a relatively small imaginary part) is responsible for plasmonic excitations in the metal nanoparticles.
\nThe scattering cross section of a spherical gold NP is almost vanished when its radius decreased from 35 nm (Figure 10A) to 10 nm (Figure 10B), while the absorption and excitation cross section are decreased to a lesser extent for the same compound. Thus, small NPs are used for applications where only non-radiative decays are desired.
\nExtinction (black), scattering (blue) and absorption spectra (red) of a gold NP with a radius of 35 nm (A) and a radius of 10 nm (B) calculated using Mie theory. In both cases, the refractive index of the environment is 1.33 [
Recently, many techniques have been used for the synthesis of Ag-NPs by using chemical, physical, photochemical, and biological methods. Each method has its pros and cons with common problems of cost, scalability, uniform particle size, and the size distribution. Traditionally, metal nanoparticles are produced by physical methods like ion sputtering or pulsed laser ablation and chemical methods such as reduction, solvothermal synthesis, hydrothermal, sol-gel methods, and so on. However, recently, the environmentally friendly synthesis methods (by using natural products) have been developed under the branch of “green syntheses.” Depending upon the selected path of synthesis and different experimental conditions, the silver NPs of different morphology, sizes, and shapes can be obtained. Nevertheless, the most important criteria is the size distribution that should be achieved as narrow as possible for the target-specific applications [69]. Four important methods (chemical, physical, photochemical, and biological) for the synthesis of nanoparticles are discussed as follows.
\nAmong the existing methods, the chemical methods have been most common used for the production of Ag-NPs. The chemical reduction of metal ions is the most universal and easy route for the preparation of the metal nanoparticles. The chemical transformation of the silver ions into the silver nanostructures can occurred using photochemical method, [70, 71] wet chemical synthesis with [72] or without templates, [73] by employing liquid crystal, [74] polymer templates,[75] solution-based methodologies such as aspartate reduction [76] and starch-mediated reduction, etc [77]. Generally, the chemical synthesis process of the Ag-NPs in solution usually employs the following three main components: (i) metal precursors (for formation of AgNPs: AgNO3 AgClO4, AgCl, (PPh3)3AgNO3, CF3CooAg), (ii) reducing agents, and (iii) stabilizing/capping agents. Few of the representative reducing agents are: NaBH4, glucose, N,N-dimethyformamide, N2H4, sodium citrate, polyols, (such as ethylene glycol, diethylene glycol or a mixture of them), formaldehyde, etc., [78, 79, 80, 81, 82, 83]. It is known that the different reductants are powered by different degree of reducibility that can play an important role in deciding the final shape of nanostructures. Moreover, these reductants favor the growth of nanocrystals along its different facets ((100) (111) or (110) facets). Unprotected metal colloids are highly vulnerable to the irreversible aggregation due to their small size. Therefore, the protective agents such as thiols, amines, polymers (e.g., polyvinylpyrrolidone PVP, polyvinyl alcohol PVA), polyelectrolytes (sodium oleate, oleic acid, etc.) [84, 85, 86], surfactants (cetyl trimethyl ammonium bromide (CTAB), sodium dodecyl sulfate, and cetyl trimethyl ammonium chloride (CTAC)), etc., can be added to suppression aggregation. The formation of colloidal solutions from the reduction of silver salts involves four stages, i.e., nucleation, incubation, subsequent growth, and Ostwald ripening. It is also revealed that the size and the shape of synthesized Ag-NPs are strongly dependent on these stages. Furthermore, for the synthesis of monodispered Ag-NPs with uniform size distribution, all nuclei are required to form at the same time. In this case, all the nuclei are likely to have the same or similar size, and then they will have the same subsequent growth. The initial nucleation and the subsequent growth of initial nuclei can be controlled by adjusting the reaction parameters such as reaction temperature, pH, precursors, reduction agents, and stabilizing agents. These capping agents spontaneously adsorbed on the particle surface prevent their agglomeration, resulting in instable particle. In a typical experiment, aqueous 0.5 M AgNO3 (0.8 mL) was mixed well with aqueous 0.4 M poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-
(a) Polygonal (mainly triangular) silver nanoprisms were synthesized by boiling AgNO3 in
Monodispersed solution of silver nanocubes were synthesized in large quantities by reducing silver nitrate with ethylene glycol in the presence of the capping agent polyvinylpyrrolidone (PVP) [79], which is an example of the so-called polyol process. In this case, ethylene glycol served as both reducing agent and solvent. It shows that the presence of PVP and its molar ratio relative to silver nitrate along with other additive formaldehyde, NaOH, played important roles in finalizing the geometric shape and size of the product. It suggested that it is possible to tune the size of silver nanocubes by controlling the experimental conditions.
\nIn the precursor injection method, the injection rate and the reaction temperature were important factors for producing uniform-sized Ag-NPs with a reduced size [81]. The injection of the precursor solution into a hot solution is an effective mean to induce rapid nucleation in a short period of time, ensuring the fabrication of Ag-NPs with a smaller size and a narrower size distribution. Spherical Ag-NPs with a controllable size and high monodispersity were synthesized under the polyol process with the help of the modified precursor injection technique. Ag-NPs of the size 17 ± 2 nm were obtained at an injection rate of 2.5 mLs−1 along with the reaction temperature 100°C. Nearly, monodisperse Ag-NPs have been prepared in a simple oleylamine-liquid paraffin system [82] by using this technique.
\nIn the physical synthesis process of Ag-NPs, usually, the physical energies (thermal, ac power, and arc discharge) are utilized to produce Ag-NPs with a narrow size particle distribution. This approach can permit us to produce large quantities of Ag-NPs samples in a single process. Under the physical methods, the metallic NPs can be generally fabricated by evaporation-condensation process that could be carried out in a tube furnace at atmospheric pressure. The large space of tube furnace, consumption of large amount of energy, raising the environmental temperature around the source material and a lot of time for achieving thermal stability, are the few drawbacks of the method. Another physical method of synthesis of Ag-NPs is a thermal decomposition method that used to synthesize the powdered Ag-NPs [90]. In particular case, Ag-NPs (particles with particle size of 9.5 nm with a standard deviation of 0.7 nm) were formed by thermal decomposition of a Ag1+–oleate complex, at high temperature of 290°C. This indicates that the Ag-NPs were prepared with a very narrow size distribution. Jung et al. [91] reported a small ceramic heater (with a local heating area) for synthesizing the metal NPs and by evaporating the source materials under the flow of carrier gas, i.e., air. It had been reported that the geometric mean diameter, the geometric standard deviation, and the total concentration of spherical NPs without agglomeration increases with the temperature of the surface of the heater. The testimony given by Tien et al. [92] reveal the fabrication technique for the Ag-NPs by employing the electrical discharge machining (EDM) without addition of any surfactants. Where, pure silver wires were submerged in deionized water and treated as electrodes. The stability of suspension, concentration of particles, particle size, solution properties, electric conductivity, and pH are the factors that may affect the synthesis of NPs by enhancing the complex interactions to the nanofluid, in the form of van der Waals combination force and electrostatic Coulomb repulsion force. Metallic Ag-NPs of the 10 nm size and ionic silver of approximate concentrations 11–19 ppm were obtained by silver rod at the consumption rate ~ 100mgmin−1. More recently, Siegel et al. [93] reported an unconventional approach for the physical synthesis of gold-NPs and Ag-NPs by the direct metal sputtering into the liquid medium (glycerol-to-water).
\nThe photo-induced synthesis of Ag-NPs has two main approaches: that is the photophysical (top down) and photochemical (bottom up) ones. In former way, NPs could be prepared by the fragmentation of the bulk metals and followed by generation of the NPs from ionic precursors. The NPs are formed by the direct photoreduction of a metal ion using photo-chemically generated intermediates, such as excited molecules and radicals, which are often known as photosensitization of NPs [94, 95]. The main advantages of the photo-induced process are: clean process, high spatial resolution, convenience of use, the controllable in-situ reducing agents generation; the formation of NPs can be triggered by the photo irradiation, (iii) enables one to fabricate the NPs in various mediums including emulsion, surfactant micelles, polymer films, glasses, cells, etc [94]. The direct photo-reduction process of AgNO3 takes place in the presence of sodium citrate (NaCit) using different light thermal sources (UV, white, blue, cyan, green, and orange) at room temperature [96]. This light-induced process results in a metallic colloid with size and shape powered distinctive optical properties of the particles. Reproducible UV photo-activation method is used for the preparation of the stable Ag-NPs in aqueous TritonX-100 (TX-100) [97], where TX-100 molecules play a dual role: (i) as an reducing agent and (ii) as a NPs stabilizer through template/capping action. The addition of surfactant solution to TX-100 and silver precursor helps in carrying out the NPs growth process by controlling the diffusion (by decreasing the diffusion/mass transfer coefficient of the system) to improve the NPs size distributions (by increasing the surface tension at the solvent–NPs interface). The Ag-NPs (size 2–8 nm) can also be synthesized in a basic aqueous AgNO3 solution and carboxymethylated chitosan (CMCTS) under UV light irradiation. CMCTS is a biocompatible water-soluble derivative of chitosan and served as a reducing agent for silver cation and a stabilizing agent for Ag-NPs (stable for more than 6 months), simultaneously [98]. This method is used to fabricate a high-yield metal nanostructures and composite materials at low cost. Few alternative approaches, such as laser ablation at the solid?liquid interface and combination of the reducing agent and sunlight, are also used for metal nanostructure fabrication. The three-dimensional metal NPs are produced using laser ablation and are applicable in the field of a light-driven actuator, bioimaging, and three-dimensional processing [99]. The photo-induced silver nanoprisms/nanodecahedrons have been the synthesis by controlling the concentration of sodium citrate and sunlight (ultraviolet light). At the lower concentration of citrate (⩽5.0 × 10−4 M), silver nanoprisms are converted into nanodecahedrons silver by increasing the concentration of citrate as shown in Figure 12. Although the intensity of light affects the shape of the NPs, the lighting power density did not influence the shape conversion except for reaction rate [100].
\nPhoto-induced synthesis of silver nanoprisms and nanodecahedrons by controlling the concentration of sodium citrate and sunlight [
Usually, wet-chemical or physical method is used to prepare the metal nanoparticles. However, the chemicals used in pbhysical and chemical methods are generally expensive, harmful and inflammable but the bogenic methods are a cost effective, energy saver and having enviornmentally benign protocols technique for green synthesis of silver nanoparticles from different microorganisms (yeast, fungi and bacteria, etc) and plant tissues (leaves, fruit, latex, peel, flower, root, stem, etc) as shown in Figure 13. Pytochemicals (lipids, protiens, polyphenols, carboxylic acids, saponins, aminoacids, polysachccarides amino cellulose, enzymes, etc.) present in plants are used as reducing and capping agent. The use of agro waste and micro-orgamisms materials not only reduces the cost of synthesis but also minimizes the need of using hazardous chemicals and stimulates “green synthesis“ way for synthesizing nanoparticles [101, 102].
\nBiogenic synthesis of metal nanoparticle of various shape and size using microorganisms and plant tissues extracts.
This method of biosynthesis is very simple, requiring less time and energy in comparison to the physical and chemical methods with predictable mechanisms. The other advantages of biological methods are the availability of a vast array of biological resources, a decreased time requirement, high density, stability, and the ready-to-soluble as-prepared nanoparticles in water [103]. Therefore, biogenic synthesis of metal NPs unwraps up enomorus opportunities for the use of biodegradable or waste materials.
\nAt the nanoscale, particle-particle interactions are either dominated by weak Vander Waals forces, stronger polar and electrostatic interactions or covalent interactions. Characterization of nanoparticles is vital part of determination of the phase purity, shape, size, morphology, electronic transition plasmonic character, atomic environment and surface charge, etc. By using advanced analytical techniques such as electron microscopic techniques (atomic force microscopy (AFM), electron energy loss spectroscopy (EELS), surface enhanced Raman scattering (SERS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and their corresponding energy-dispersive X-ray spectroscopy (EDX), and selected area electron diffraction (SAED for crystallinity). Properties like surface morphology, size, and overall shape are determined by electron microscopy techniques and elemental composition by SEM-/TEM-/EELS-supported EDX. Optical analysis techniques such as Fourier transform infrared (FTIR) spectroscopy, fluorescence correlation spectroscopy (FCS, diffusion coefficients, hydrodynamic radii, average concentrations, and kinetic chemical reaction), X-ray diffraction (XRD for phase purity with crystal parameters and particle size), diffuse light scattering (DLS can probe the size distribution of small particles), UV-Vis spectroscopy (band gap, particle size electronic interaction), XPS (X-ray photon spectroscopy, surface environment of elemental arrangement), Raman spectroscopy (it provides submicron spatial resolution average size and size distribution through analysis of the spectral line broadening and shift), nuclear magnetic resonance (NMR can detect structure, compositions, diffusivity of nanomaterials, dynamic interaction of species under investigation), small-angle X-ray scattering (SAXS; from 0.1° to 3° can evaluate the size distribution, shape, orientation, and structure of a variety of polymers and nanomaterials), zeta potential with a value of ±30 mV is generally chosen to infer particle stability. Above analysis can be used to determine the properties of nanomaterials such as the size distribution, dispersibility, average particle diameter, charge affect the physical stability and the in vivo distribution of the nanoparticles. Few of above are discussed below.
\nThe crystalline structure, size, and shape of the unit cell and the crystallite size of a material can be determined using X-ray diffraction spectroscopy (XRD). Usually, X-ray diffraction peaks were observed at 2θ = 38.00°, 44.16°, 64.40°, and 77.33°, which correspond to (111), (200), (220), and (311) Bragg’s reflections of the face-centered cubic (fcc) structure of metallic silver, respectively (standard JCPDS card No. 04-0783 or 87-0597). The crystalline size of the particulate can be estimated by using the Debye-Scherrer formula d = 0.89λ βcosθ, where d is the particle size, λ is the wavelength of X-ray radiation (1.5406 Å), β is the full-width at half-maxima (FWHM) of the strongest peak (in radians) of the diffraction pattern and 2θ is the Bragg angle [104].
\nIn this technique the whole sample is analyzed by scanning with a focused fine beam of electrons and electrostatic or electromagnetic lenses to generate images of much higher resolution. Surface morphology of the sample is determined by the help of the secondary electrons emitted from the sample surface.
\nIn TEM analysis, an incident beam of electrons is transmitted through an ultra-thin sample which interacts with the sample and transforms into unscattered electrons, elastically scattered electrons, or inelastically scattered electrons. The scattered or unscattered electrons are focused by a series of electromagnetic lenses and then projected on a screen to generate a electron diffraction, amplitude-contrast image, a phase-contrast image, or a shadow image of varying darkness according to the density of unscattered electron. Transmission electron microscopy techniques can provide direct imaging, diffraction and spectroscopic information, chemical composition, either simultaneously or in a serial manner, of the specimen with an atomic or a sub-nanometer spatial resolution. High-resolution TEM imaging, when combined with nanodiffraction, scanning tunneling microscopy (STM), atomic resolution electron energy-loss spectroscopy, and nanometer resolution X-ray energy dispersive spectroscopy techniques, is critical to the fundamental studies of importance to nanoscience and nanotechnology.
\nDifferent surface structures can be obtained from various synthesis routes. Surface morphology of the nano-structural features of silver are examined using above electron microscopic techniques. Electron microscopy images of single-crystal Ag-NPs (cubes, bars, wires, and bipyramids) grown in ethylene glycol in the presence of PVP and Br− at different proportions, are demonstrated in the Figure 14A–D. Silver triangular nanoplates, prepared by are demonstrated by the Figure 14E and F Asymmetric Silver “Nanocarrot” Structures, were synthesized by using wet chemical method using CF3COOAg as precursor, PEG as reducing agent, and PVP as capping agent are depicted in the Figure 14G–I [105, 106].
\nElectron microscopy images of single-crystal Ag nanocrystals: (A) nanocubes prepared in ethylene glycol with PVP as a capping agent in DMF; (B) nanobars prepared in ethylene glycol in the presence of PVP and Br−; (C) pentagonal nanowires prepared in ethylene glycol in the presence of PVP in DMF; (D) bipyramids prepared in ethylene glycol in the presence of PVP, where TEM image represented by E, F, and G and the EELS spectrum of the asymmetric silver nanocarrot, were represented by H&I [
STM uses quantum tunneling current to generate electron density images at the atomic scale for conductive/semiconductive surfaces and biomolecules attached on conductive substrates [107]. A sharp scanning tip, an xyz-piezo scanner controlling the lateral and vertical movement of the tip, a coarse control unit positioning the tip close to the sample within the tunneling range, a vibration isolation stage and feedback regulation electronics are the basic parts of the STM instrumentation. Its working on the generic principle for, i.e., to bring a susceptible probe in close proximity to the surface of an object measured to monitor the reactions of the probe [108].
\nThe AFM can investigate the size, shape, structure, sorption, dispersion, and aggregation of nanomaterials. It is based on a physical scanning of samples at sub-micron level (contact or noncontact mode) using a probe tip of atomic scale and offers ultra-high resolution (>100 times better than the optical diffraction) in particle size measurement. One of the principal advantages of this nondestructive technique is that it felicitates the imaging of the non-conducting samples without any specific pretreatment and without causing appreciable harm to the surface. The major drawbacks of this technique is (i) the size of the cantilever tip is generally larger than the dimensions of the nanomaterials to be examined that led to unfavorable overestimation of the lateral dimensions of the samples [109, 110], (ii) AFM also lacks the capability of the detecting or locating specific molecules; however, this disadvantage has been eliminated by recent progress in single-molecule force spectroscopy with an AFM cantilever tip carrying a ligand.
\nIn looking to the better understanding of the atomic processes in solids, their emerging demand for new imaging, diffraction and spectroscopy methods with high-spatial resolution. That demand has been reinforced by the growing interest of human being in nanomaterials. Although, the transmission electron microscopy (TEM) can provide the structural information with excellent spatial resolution (down to atomic dimensions) through high-resolution TEM imaging and electron diffraction technique, electron energy-loss spectroscopy offers unique possibilities for the nanoscale thin materials (plasmonic) analysis. Due to the broad range of inelastic interactions of the high energy electrons with the specimen atoms, ranging from phonon interactions to ionization processes, EELS and their combination with TEM offers the facility to map the elemental composition of a specimen for studying the physical and chemical properties of a wide range of biological and non-biological materials. Moreover, the energy distribution of all the inelastically scattered electrons provides the information [111] about the local environment of the atomic electrons for the universal dispersions of surface plasmons in flat nanostructures, [112] 3D distribution of the surface plasmons around a metal nanoparticle [113] and exotic nanostructures are shown in Figure 15 [114].
\nEELS data and corresponding electrodynamic calculation for rod. (a) Annular dark field (ADF) image of rod with high aspect ratio 9.6, (b) multivariate statistical analysis (MVSA)) score images, (c) discrete dipole approximation (DDA) calculated electric field plots displaying the field generated by a plane wave optical excitation at the energies and polarization given on each plane, and (d) summed EEL spectrum [
In decades past, synthesis of silver nanostructures has been an active research area because of their excellent optical properties such as surface-enhanced Raman scattering (SERS) and surface plasmonic resonance, which strongly depend on size, shape, and composition, and can be checked by the help of the optical analyses like XPS and UV-Visible spectroscopy analysis. Although, the change in color of precursor silver ion to silver nanoparticles was visually observed, the absorption measurements were carried out using UV-Visible spectrophotometer to check the stability of silver nanoparticles. Characteristic UV-Vis spectrum peak of bulk Ag appears at 320 nm due to the inter-band 4d → 5sp transitions [87]; and the red shift in this peak to around 420 nm was observed due to the occurring of the plasmonic resonance phenomenon in the nano-dispersion of silver metal. Effect of shape and size on optical properties of the silver nanoparticle is reflected by Figure 16.
\n(a) optical spectra of the individual silver nanoparticles of different shape spherical (Blue emission), pentagon (Green emission) and triangular (Red emission) as reflected from their typical high resolution TEM images. (b) Plot of the lateral size of TEM images vs the wavelength of the plasmonic resonance spectral peak for a spherical (dark circle; 85%) pentagon (empty rectangle; 5%) and triangular (dark triangle; 5%) particles [
UV-Vis spectroscopy also used for particle size determination of silver nanoparticles, using Mie scattering theory. The full width at half maxima of the optical spectra (Lorentz-shaped peak; Ω) can be used to calculate the particle size of stable suspension by using following equation [116, 117]:
\nwhere,
SERS can be employed as a sensitive and selective technique for identification of molecules. Strong electromagnetic fields are generated due to the localized surface plasmon resonance (LSPR) of nano-noble metals, when they are exposed to visible light. If the Raman scatterer is placed near these intensified electromagnetic fields of nano-noble metals, the induced-dipole increases that results in the increase of intensity of the inelastic scattering. Similar relations can hold-good for the extinction and scattering cross sections of the nanoparticle. If the extinction and scattering cross sections of the nanoparticle at resonant wavelengths are maximized, it represents the spectroscopic signature of exciting the LSPR. A SER spectrum also provides the accurate information about molecular structure and the local environment in condensed phases than any other electronic spectroscopy technique.
\nA typical example of the surface-enhanced Raman scattering (SERS) is reflected by Figure 17, where the coupling effect still dominates the SERS and the flower-like silver mesoparticle dimer image with the large hot areas is ≈10 to 100 times greater than the individual mesoparticles [118].
\nSEM images of a self-assembled dimmer of flower-like silver mesoparticles along with their corresponding Raman images at the axis parallel to the dimer axis of the detected particles with high SERS quality [
Metal nanocatalysts of different shapes and sizes like quantum dots, nanotubes, nanofibres, nanolithographs, self-assemble processing devices, nanoparticles, and nanofibres, have immense significance. They have bright future in broad research areas of high-tech applications in the field of information of storage, computing, medical and biotechnology, energy, sensors, photonics, communication, and smart materials. The size and shape of the nanometal is a critical criteria to target-specific applications that may be achieved by keeping size distribution as narrow as possible. Nanometals has enormous potential to serve all facets of life for building big future from small things, as they acquire the goodness of both homogeneous and heterogeneous catalysts. At present, the pretty command over the morphologies of silver nanoparticles has received immense attention of researchers due to their considerable budding applications in almost all fields. In the present context, they have attracted the interest of the people due to their unique physical, chemical, and biological properties in compared to their massive counterparts. Silver nanoparticles are also studied by material scientists who investigate their integration into other materials in order to obtain enhanced properties, for example, in solar cells where silver nanoparticles are used as plasmonic light traps. These properties make them valuable in other applications such as catalyst [119, 120], inks, microelectronics, medical, imaging, health products, and waste management. Antifungicidal activities making them extremely popular in a diverse range of consumer/medical products, including plastics, soaps, pastes, food, cosmetics, medicine, highly sensitive surface-enhanced Raman spectroscopy (SERS) application [121, 122, 123], water treatment and textiles, etc., that boost their market value [124]. Moreover, the nanofibre can be very effective in attracting and trapping small particles because it is “sticky” due to its large surface area. This makes nanofibres excellent materials for use in filtration [125]. Moreover, silver nanoparticles accounts for more than 23% of available nano-products in the market. It includes the share of different facets of life, i.e., 52.61% health and fitness, 10.44% cleaning, 10.04% food, 6.02% household equipments, 4.02% medicine, 3.21% electronic devices, 2.01% toys, and 11.65% others [126]. Out of the versatile applications of nanosilver in diverse phases of life, few are discussed below.
\nThe silver nanoparticles exhibit a broad spectrum of antibactericidal, antiviral, anti-inflmmatory, antiangiogenic, anti-tumor, and anti-oxidativeproperties along with the biological and chemical sensing, imaging, drug carrier, and diagnosis of the cancer/HIV/AIDS [127, 128, 129, 130, 131]. When the researchers directed near-infrared laser light through the mice’s skin and at the tumors, the resonant absorption of energy in the embedded nanoshells raised the temperature of the cancerous tissues from about 37°C to about 45°C. The photothermal heating killed the cancer cells while leaving the surrounding healthy tissue unharmed. In the mice treated with nanoshells, all signs of cancer disappeared within 10 days; in the control groups, the tumors continued to grow rapidly [132].
\nSilver nanotechnology, emerging as a fast growing technology in the field of orthopedics due to its antimicrobial properties. Therefore, silver nanoparticles can be used in orthopedic applications such as trauma implants, tumor prostheses, bone cement, and hydroxyapatite coatings to prevent the biofilm formation. Bio film formation is a major source of morbidity in orthopedic surgery. The promising results with
Silver nanoparticles are already utilized for various applications in areas such as food supplements, food packaging, and functional food ingredients. To protect the food from dust, gases (O2, CO2), light, pathogens, moisture nanocomposite LDPE films containing Ag and ZnO nanoparticles packaging, would be a safer, inert; cheaper to produce, easy to dispose and reuse-way. Nanocomposite LDPE films containing Ag and ZnO nanoparticles were prepared by melt mixing in a twin screw extruder. Packages prepared from the above films were used to carry/store fresh orange juice, fresh meat (highly perishable commodity) to avoid the proliferation of undesirable microorganisms and also to provide desired texture to the food, encapsulate food components (e.g., control the release of flavors), increase the bioavailability of nutritional components [134].
\nIn recent years, one of the most important applications of the AgNPs has been observed in catalysis of chemical reactions. Nanosilver catalysts’ with their unique reactivity and selectivity, stability, as well as recyclability in catalytic reactions with atom-economy and environmental benign nature, increases the interest in nanosilver-mediated organic synthesis in the last few years. Nanosilver of different shapes and sizes catalyzed many organic transformations such as cyclization, Michael addition, alkylation, alkynylation, oxidation, cross-coupling reaction, A3-coupling reaction, reduction, Friedal-crafts, Diel-Alder reaction, and many more [135]. Researchers are fascinated to silver nanoparticles, since it has enabled unprecedented or low selective transformations to highly reactive and chemoselective catalysis for various nanosilver-catalyzed reactions. For example, kinetically difficult reduction of p-nitrophenol is not possible even in presence of strong reducing agent NaBH4 and month long aging. But, by the addition of AgNPs in the same reaction mixture, it made the reaction possible by formation of the p-aminophenol [136]. Studies in this field, revealed the strong potential of nanosilver catalysis in the total synthesis of natural products and pharmaceutical molecules [137].
\nBioaerosols are airborne biological origins such as viruses, bacteria, fungi, which are capable of causing infectious, allergenic, or toxigenic diseases. Large quantities of these bioaerosols were accumulated on the filters of heating, ventilating, and air-conditioning (HVAC) systems [138]. It often resulted in the low quality of indoor air. The WHO estimated that 50% of the biological contamination present in indoor air comes from filter-medium after air filtration, which can add on microbial growth. These pathogens generate mycotoxins which are dangerous to human health. To reduce the microbial growth in air filters, Ag-deposited-activated carbon filters (ACF) were effectively used for the removal of bioaerosols. Antibacterial activity analysis of Ag-coated ACF filters was checked for
Studies supported that the silver nanoparticle (AgNP) can work as an excellent antiviral, antimicrobial, and disinfectant agents. The results obtained showed that silver nanoparticles in surface water, ground water, and brackish water are stable. However, in seawater conditions, AgNP tend to aggregate. The comparison of AgNP-impregnated ceramic water filters and ceramic filters impregnated with silver nitrate was made. The results showed that AgNP-impregnated ceramic water filters are more appropriate for this application due to the lesser amount of silver desorbed compared with silver nitrate-treated filters without disturbing the water chemistry conditions and performance of the filters. Quaternary ammonium functionalized silsesquioxanes-treated ceramic water filter desorbed less from the filters and achieved higher bacteria removal than the filters impregnated with AgNP. This indicates that the quaternary ammonium functionalized silsesquioxanes compound could be considered as a substitute for silver nanoparticles due to its lower price and higher performance [139].
\nNanosilver products such as beauty soap, hair shampoo and conditioner, body cleanser, tooth brush, sanitizer, facial masksheets, skin care line, makeupline, wetwipes, disinfectant spray, wash and laundry detergent, etc., have been influence our daily life at great extent [140]. Silver nanoparticles can also be incorporated in manufacturing of the toothpaste or oral care gels. Silver nanoparticles with particle size less than 15 nm and concentration of 0.004% w/w showed maximum efficiency to prevent the growth of bacteria that causes unpleasant oral smells and dental cavities [141].
\nThe nanoproduct can also be used in dyeing of cosmetic foundations, eye shadows, powders, lipsticks, inks, varnishes, or eyebrow pencils. According to Ha et al., the products with metal nanoparticles, unlike the conventionally used metallic pigments, are not harmful to human health, and may even have health benefits [142].
\nA soap with silver nanoparticles as one of the ingredients was prepared; and in 2013, the method for its preparation was patented [143]. Nia had used the silver nanoparticles to improve the plant growth of the plants (citrus fruits, grains, and oleaceae trees) [144]. Silver nanoparticles-treated structure of textile materials [145] were used for antimicrobal activities protected clothing. The authors reported that the silver nanoparticles coated nylon fibers used in making of floor coverings/carpets that helps to secure them against bad odors and the growth of pathogenic microorganisms [146].
\nThe commercial use of the engineered nanomaterials, with at least one-dimension of 100 nm or less, is increasing in the area of fillers, opacifiers, consumer/medical products (including plastics, soaps, pastes, food, cosmetics, medicine, drug carriers, and highly sensitive SERS application), catalysts, semiconductors, textile, waste water treatment, microelectronics, bioimaging, etc. Materials at nano-level may induce some specific physical or chemical interactions with their environment. As a result, they perform exceptional changes in the properties like conductivity, reactivity, and optical sensitivity, in comparison to their massive counterparts, which may enhance the processes such as dissolution, redox reactions, or the generation of reactive oxygen species (ROS). These processes may be accompanied by biological effects that would not be produced by larger particles of the same chemical composition. The nanomaterials are responsible for the possible undesirable interactions with biological systems and the environment which might generate toxicity. Therefore, there is an urgent requirement to establish the principles, procure the test procedures to ensure safe manufacture and commercial use of nanomaterials [147] to stop the uncontrolled release of nanoparticles to the environment through waste disposal, and to incorporate the nanowaste and nanotoxicology in the waste management. Thus, the bioaccumulation and toxicity of the nanoparticles may become important environmental issues. Although the amount of the nanoparticles in commercial products are lower than those present in soluble form but the toxicity resulting from their intrinsic nature (e.g., their size, shape, or density) may be significant. Moreover, the major challenge in the treatment of nanowaste is the current need of the time. Not only the proper understanding of its chemical, physical, and biological properties, but it also requires the apt number of studies on the impact (short- and long term effects) of these new materials on biological and environmental systems (acutely lacking area). It is necessary to have basic information from companies about the level and nature of nanomaterials produced or emitted and about the expectation of the life cycle time of nanoproducts as a basis to estimate the level of nanowaste in the future. Without the knowledge of how to use, store, facilitate the separation, and recovery of recyclable and non-recyclable nanomaterials, the development of the regulations in this field is difficult. Moreover, Ag metal has strong affinity toward the elements, i.e., O, Cl, S, and organic compounds (particularly, the thiol group containing compound) and oxidation capacity that shorten the lifetime of Ag-NPs in the environment. The kinetics of Ag-NPs corrosion increases with decreases in particle size. Sulfidation (significant amount of the sulfide ion present in polluted water) is the most probable corrosion process for metallic AgNPs undergo because of the very high stability of Ag2S. However, the mechanisms with the kinetics of the oxidation of Ag2S-NPs in to Ag2SO4, on contact with air or microbial transformation, is needed to be deal with as Ag2SO4 (Ksp = 1.2 × 10−5) is considerably more soluble than Ag2S (Ksp = 5.92 × 10−51). Furthermore, in comparison to the unsulfidized AgNPs and Ag ion, the toxicity of Ag2S-NPs has shown limited acute toxicity because sulfidation momentously decreases the solubility [148]. Recently, the plasmonic materials are in fashion because of their efficiency in optoelectronic materials; for example, in a recent report, the hot electron transfer from a plasmon-induced interfacial charge-transfer transition induced the quantum efficiency of the device up to 20% independent of incident photon energy [149]. In addition to above, a better understanding of the hot carrier generation, transport, emission and relaxation timescale, engineering of semiconductor-hot electron interface is still needed for better designing of the efficient hot carrier devices [150, 151, 152, 153]. Beside all the challenges, the future of silver nanoparticles is bright because of their potential use in biomedical applications as long lasting and enhanced antifungal, antibacterial, disinfection properties along with their utilization in drug delivery, diagnosis, bioimaging, biosensoring, etc. Moreover, their role as an effective molecular sieve, metallic sorbent, and catalyst for the removal of the environmental pollutions are commendable. There is great hope for the application of Ag-NPs in the versatile field of computers and informatics, cosmetics, textile, food, and medicine. Although a lot of work is done in this field, the full potential of silver nanoparticles is yet to come into lime light with better understanding of their mechanism and long lasting impact on environment and waste management.
\nThe chapter started with a brief introduction of the nanomaterials along with their historical existence without in-depth knowledge. The importance of the silver NPs over other nanometals was established on the account of their properties such as surface-enhanced plasmonic character, cost, stability, and so on. The synthesis methods and advanced characterization tools were also discussed in keeping AgNPs in the mind. The applications of these competent nanoparticles along with their goodness and special qualities are also described in the chapter. In the end, the challenges and future prospective of this up-bringing area were discussed.
\nTitanium aluminide (TiAl) is a member of group material referred to as intermetallics, consisting of various metals resulting in ordered crystallographic structures formed when the concentration of the alloy exceeds the solubility limit [1]. Properties as low density, high strength and elevated temperature properties make TiAl replacement candidates for nickel-based superalloys used in the aerospace and automotive industries [2, 3, 4]. One such alloy tried and tested by General Electric [5] for commercial turbofan engines is Ti-48Al-2Cr-2Nb. Despite the attractive high-temperature properties attained in research to date, the inherent poor ductility of TiAl at ambient temperatures remains a concern [6]. Over the past 20 years and recently, much work has been devoted to material tailoring through compositional variations and alloying aimed at improving room temperature ductility [7, 8, 9, 10, 11].
Phase evolution in TiAl alloys governs the mechanical and physical properties to be obtained. Primarily, two ordered structures exist, namely, γ-TiAl (L10) and hexagonal α2-Ti3Al (D019), resulting from different thermo-mechanical treatments. Furthermore, the mechanical properties to be obtained are dependent on the microstructure. Three microstructures exist, namely, equiaxed single γ phase, fully or near (γ/α2) lamellar and duplex (consisting of colonies of lamellar γ/α2 and pure γ phase grains). The achieved microstructure is significant for its mechanical properties, especially in structural applications. Duplex microstructures with enhanced ductility measures such as fracture strength, yield strength and strain have been reported [12, 13, 14]. Fully lamellar structures, in particular, have shown the best creep performance as contrasted to other microstructural modifications [15, 16, 17].
For the intended application, considering the inherent brittle nature of TiAl alloys, material tailoring through microstructural evolution is often necessary. Additionally, the low ductility and brittleness of TiAl alloys at ambient temperatures make their processing using conventional methods difficult. To overcome problems associated with conventional processing, such as microstructural inconsistencies inherited from solidification and phase evolutions resulting in the scattering of mechanical properties, heat treatment cycles are often designed [18, 19, 20, 21]. Traditional methods requiring post-treatment are time-consuming, labour and capital intensive, waste a lot of start-up material, and require unnecessary production costs. Therefore, there is a need to manufacture TiAl alloy components without the above-mentioned technical deficiencies and limitations and satisfy industrial needs for component fabrication [22].
For the last decades of the 20th century [23], the Additive Manufacturing (AM) method has been employed to obtain objects by the subsequent material supply. AM mainly aims to complete a collection of traditional subtractive manufacturing practices while avoiding and limiting the need for post mechanical processing such as machining. Laser powder bed fusion (L-PBF) is an AM technique, historically referred to as Selective Laser Melting (SLM) developed by F&S Stereolithographietechnik GmbH with Fraunhofer ILT [24], where a component is manufactured by melting a powder bed in a layer-by-layer sequence employing laser beam irritation [25]. The L-PBF process is initiated by creating a 3D digital part model (usually scan data or a CAD file), followed by slicing the model into thin layers using special software. The powder bed is achieved by spreading powder onto the substrate surface. The powder bed is selectively melted through cross-sectional scanning generated from the 3D part model by applying a laser beam. After cross-section scanning, powder bed layering is achieved by sequentially adding layers one after the other repeatedly until the part is complete. Recent studies [25, 26, 27, 28, 29] have shown that L-PBF is an innovative and efficient process employed to manufacture TiAl alloys compared to historically employed traditional manufacturing processes such as casting [30, 31, 32], ingot metallurgy [33, 34, 35], or even solid-state powder sintering [36, 37, 38]. The benefits of L-PBF include short production cycles and cheaper production costs. Also, parts produced are of high quality and have been found to exhibit desirable performance [39].
Exploring AM technologies to improve on properties of TiAl and its alloys is essential. As such, mechanical properties like compressive and tensile ductility measures [40, 41, 42], wear resistance [43, 44], elevated temperature creep and oxidation resistance [45, 46, 47, 48] superior to those processed by conventional means have been reported. Operation temperatures in new-generation gas turbines have fast-tracked progress in material development in the aerospace industry.
The dual combination of high temperatures and contaminant-containing aircraft environments shifts focus to hot corrosion and oxidation. Hot corrosion and oxidation can lead to catastrophic failures through material consumption at an unpredictably rapid rate. Much work has been devoted to understanding the hot corrosion and oxidation of TiAl alloys already [49, 50, 51, 52, 53]. As such, this research paper serves as a summary of the laser additive manufacturing of TiAl alloys. Particular attention is also given to the mechanisms, kinetics, prevention control and recent developments in hot corrosion and oxidation of TiAl alloys.
The three main phases of the Ti-Al system consist of various TiAl compounds, namely, γ-TiAl, α2-Ti3Al and TiAl3 [1]. Of the three phases, only γ-TiAl and α2-Ti3Al have shown to be of engineering significance [54] with outstanding properties. They are lightweight and can be implemented for structural parts, automotive and elevated temperature aerospace applications. The γ-TiAl phase is a face-centred tetragonal ordered phase with an L10 structure. It consists of atomic layers at 90° to the c-axis [55] with lattice parameters a = 0.4005 nm, c = 0.4070 nm and a tetragonality ratio (
The α2-phase has high hydrogen and oxygen absorption rates and suffers from severe embrittlement, though it exhibits optimum high-temperature strength. The γ-phase has low gaseous absorption rates, outstanding oxidation resistance and poor room-temperature ductility. To maximise engineering benefits, dual-phase TiAl alloys consisting of γ + α2 phase are used. These alloys show excellent ductility [13, 58] at room temperatures due to the availability of refined lamellar colonies aiding γ-phase deformation [54, 59, 60]. The most known dual TiAl alloys with outstanding tensile properties are referred to as duplex alloys of the nominal (at.%) composition of Ti-(46–49) Al.
The four significant microstructures which may result in a Ti-Al system are namely, duplex (DP), near-gamma (NG), nearly lamellar (NL) and fully lamellar (FL). The obtained microstructures are greatly dependent on the processing route, Al compositional variations and thermo-mechanical treatments employed. Of the four, only fully lamellar and duplex have been considered necessary in engineering applications [54]. The evolutions (in Figure 1) of the microstructures mentioned above were be summarised in works by Cobbinah et al. [6] and Clemens et al. [61].
The central portion of the binary Ti-Al phase diagram together with microscopic optical (left) and backscattered scanning electron (right) images showing NG, DP, NL/NLγ and FL microstructures achieved via heat-treating within α and (α + γ) phase-field. The phases obtained are identified using contrast, where a light contrast is representative of α2-Ti3Al and γ-TiAl of a darker contrast [
NG microstructures are obtained via thermal treatments slightly above the eutectoid temperature (Teu), while DP microstructures are achieved between Teu and α-transus temperatures. The thermal treatment implemented significantly affects the volume fraction of lamellar grains present. As a result, NL microstructures are obtained at (Teu) and Tα relative temperatures, slightly under Tα. NL microstructures exhibiting a specified globular γ-grain volume fraction are shown as NLγ. FL microstructures are achieved by thermal treatments above Tα. Generally, the obtained properties compensate for other properties [22] as represented in Figure 1 and should be considered when the material is designed for structural applications. Furthermore, the microstructure-property relationship in TiAl alloys makes it easier to modify the material for the anticipated application.
Additive manufacturing (AM) presents an opportunity to manufacture TiAl alloys with minimal processing difficulties compared to those experienced during conventional processing, such as near-net-shape forging or investment casting [62]. For tailoring TiAl alloys with optimum properties, laser powder bed fusion (L-PBF) and electron beam melting have been considered suitable [63, 64, 65, 66]. Recently, the production of TiAl alloys using L-PBF has gained special attention [29, 67, 68, 69, 70, 71] owing to the benefits offered. Some of these benefits [6] complex geometry formation, ease of part dimension control, production of highly defined parts with orifices, mass customisation and material flexibility. Furthermore, during local melting of the powders, high solidification rates are obtained. These result in more refined microstructures.
The component is manufactured (in Figure 2) by melting a powder bed in a layer-by-layer sequence employing laser beam irritation [25]. The process is initiated by creating a 3D digital part model (usually scan data or a CAD file), followed by slicing the model into thin layers using special software. The powder bed is achieved by spreading powder onto the substrate surface. In preparation for part manufacturing, powders are preheated below their melting temperatures to promote bonding and minimise distortion [6]. L-PBF part manufacturing is executed in an inert gas (preferably argon) sealed environment to prevent reactive powder oxidation.
Graphical representation of laser powder bed fusion method [
The need to replace previously used Ni-based superalloys in aerospace components has fast-tracked research and development of lightweight and cost-efficient TiAl alloys. To date, Ni-based alloys still outmatch TiAl alloys in fabrication costs and mechanical performance. This is mainly due to the poor room temperature ductility of TiAl alloys and the delay in engineering design practices for low ductility materials [54]. Additionally, the high part fabrication costs involved in producing TiAl alloys are related to the knowledge that low ductility fabrication processes, which also produce high melting point alloys, are unavailable. As such, there has been much investment in exploring complex part fabrication techniques, requiring minimal post-processing steps such as L-PBF.
The evidence of many research breakthroughs concerning the production of TiAl alloy parts using L-PBF does not make the processing technique immune to limitations. Efforts have been invested in overcoming processing limitations such as part cracking, micro-pore formation and uneven powder deposition through processing parameter optimisation [73]. Processing parameters can be varied to develop TiAl alloys with excellent mechanical properties in application. Some of these properties are beam size, laser power, scanning speed, scan hatch spacing and powder layer thickness [74].
Polozov et al. [75] confirmed that TiAl-based alloy crack-free samples could be built via L-PBF processing with a high-temperature platform preheating of 900°C. Fully densified samples (highest relative density of 99.9%) were attained at volume energy density 48 J/mm3. The refined microstructure consisted of equiaxed grains, lamellar α2/γ colonies and retained β-phase. As compared to conventionally produced TiAl alloys, high ultimate compressive strength and strain values were obtained.
Process parameters can be optimised to aid the fabrication of TiAl specimen, and unfortunately, the resultant part still shows pores, cracks and low densities. One needs to understand the crack and pore formation mechanisms and the defect-process parameter relationships in such a case. Shi and associates [70] investigated optimal L-PBF process window and the effect of substrate preheating. Moreover, the relationship between crack formation, pore formation, and the process parameters was studied and the crack propagation discrepancy with an increase in the number of deposition layers. It was concluded that crack formation was related to process parameters and the number of deposition layers. The cracks initiated in the 3rd layer are accounted for by residual stress accumulation and the deviations in the composition of Ti-47Al-2Cr-2Nb deposition layers. Furthermore, substrate (Ti-6Al-4 V) preheating at 200°C alleviated cracking. Finally, a good metallurgical bond between the substrate and Ti-47Al-2Cr-2Nb deposition layers was found.
The addition of yttrium (Y) to TiAl alloys (specifically class TNM) and process parameter optimisation dramatically affects the formability, and ultimately the cracking behaviour and control of L-PBF produced components. Gao et al. [76] fabricated TNM alloys with varying Y contents (0, 1, 2, 3, 4 wt.%) and investigated the mechanism of improved formability, cracking sensitivity, cracking behaviour and control mechanism by Y additions. Improvements in the formability of Y added-TNM alloys were assigned to lower melt viscosities and good laser energy absorption. The addition of 2, 3 and 4 wt.% Y to the TNM alloys coupled with a laser energy density greater than 7.00 J/mm2 formed crack-free samples. The obtained microstructure and phase constituents were reported to contribute to microcrack formation and control significantly. Lower Y additions resulted in coarse columnar grains, oxygen segregation at the grain boundaries with dominating brittle B2 phase with poor ductility. In contrast, higher Y additions (2–4 wt.%) refined equiaxed grains, enhanced the oxygen-scavenging effect (through the presence of Y2O3 particles), and decreased brittle B2 phase content at higher Y additions significantly improve the ductility.
Finally, adding Nb to γ-TiAl alloys was also reported to account for improved mechanical properties based. Ismaeel et al. [77] produced Ti-Al–Mn–Nb alloys on a TC4 substrate and studied the effects of different Nb contents on the microstructure and properties of the alloys. The phases obtained consisted of γ-TiAl and α2-Ti3Al and a consecutive microstructural change with increased Nb additions from near full dendrite to near lamellar. Also, adding 7 at.% of Nb resulted in improved alloy’s hardness, strength and plastic deformation. Moreover, the elevated temperature oxidation resistance and tribological properties were significantly improved.
Hot corrosion can be defined as a chemical degradation on the metallic surface of materials operating at high temperatures, enhanced by the presence of molten ash and gases containing elements such as sulphur (S), chlorine and sodium [78]. Such environmental elements during fuel combustion promote damage to the protective oxide film by forming contaminants such as V2O5 and Na2SO4 [79]. This degradation form was initially identified in the early 1950s on combustion engines and boilers [80] and has been explored in numerous research works [50, 81, 82, 83, 84, 85, 86, 87].
Hot corrosion exists as Type I (known as High-Temperature Hot Corrosion) or Type II (Low-Temperature Hot Corrosion), with the former occurring above 800–950°C and the latter at 600–750°C [88, 89]. The occurrence of either attack form is dependent on several parameters such as the composition of the alloy, contaminant, and gas. Furthermore, other vital parameters are temperature and temperature cycles, erosion processes and gaseous velocity [90, 91]. The main difference between high-temperature hot corrosion (HTHT) and low-temperature hot corrosion (LTHC) is the morphologies thereof. HTHC is distinguished by the occurrence of a non-porous protective scale, internal sulphidisation and chromium (Cr) depletion.
This form of attack, also referred to as molten salt-induced corrosion, comprises a liquid-phase salt mixture deposit observed at high temperatures at the start of deposition [92]. Traditionally, according to Nicholls and Simms [93], HTHC has been detected in a temperature array between the surface deposit melting point and vapour deposition dew point for the deposit. Above this suggested temperature band, instability of dew point deposit exists, resulting in evaporation. A series of chemical reactions occur, initially attacking the oxide film and progress to deplete Cr present in the substrate [94]. Oxidation of the base material is then accelerated by Cr depletion, promoting a porous oxide scale formation.
An example of this could be the formation of thermodynamically unstable liquid sodium sulfate (Na2SO4) deposits. The marine environment mainly sources such deposits in sea salt form, followed by atmospheric contaminants such as volcanic discharges and fuel. During combustion, the present Na2SO4 can combine with pollutants present in air or fuel (such as chlorides, V and Pb) to form a blend of low melting temperature salts, further broadening the temperature range attack [94]. In the presence of sodium chloride (NaCl), the following reaction after combustion can be observed:
HTHC can be classified into four stages from initiation up to failure [95]:
Stage I: Initial coating deterioration—roughening of the surface edges coupled with localised oxide layer disintegration and minor base metal layer depletion is observed. If the surface is left untreated, the condition will worsen. Surface recoating and stripping may be adequate to remedy this degree of damage.
Stage II: Oxide layer rapture—characterised by an acceleration and advancement in surface roughness compared to Stage 1 and the protective oxide layer’s failure. Although the mechanical integrity remains maintained, there is no way to salvage the component to its original state.
Stage III: Detrimental sulphidisation—depicted by massive scale build-up on the component’s surface and indications of liquid Na2SO4 under the protective layer. The structural integrity of the part is significantly affected, attack by S contaminants proceeds.
Stage IV: Catastrophic attack—failure of the component occurs due to the observed significant blistered scale penetrating much into the base metal. Structural rigidity is lost.
This corrosion damage is characterised by a uniform attack, internal sulphide phases, depletion zone beneath a relatively smooth scale–metal interface [80, 96].
Type II corrosion has been reported [97, 98, 99, 100, 101, 102] as a liquid-phase deterioration by a blend of molten nickel (Ni) or cobalt (Co)-containing sulphates such as Na2SO4-CoSO4 or Na2SO4-NiSO4 accountable for corrosion initiation and propagation. The corrosion initiation is achieved through oxide layer fluxing, while propagation is accelerated by the mass movement of reactive elemental components through liquids present in the corrosion pits [80]. Studies [103, 104, 105, 106] have shown that conversion from CoO and NiO occurs when SO3 in the gas reacts with the sulphates, attributing to the extensive usage of mixed Na2SO4-NiSO4 in recent LTHC research studies.
LTHC can be found in coated or uncoated compressor and turbine parts. For instance, the sometimes turbine blade’s uncoated internal cooling systems operating at temperatures of about 650–750°C may be prone to this corrosion type [107]. The external rim of uncoated turbine blades reaches temperatures of 400–800°C [108]. LTHC is distinguished by the pit’s appearance and the absence of a sulphide zone at the corrosion front, consuming all the S [96].
Two HTHC mechanisms have been proposed, namely sulphide-oxidation and salt fluxing mechanisms [94]. Acidic and basic fluxing reactions, presented initially by Goebel and Pettit [109, 110], may be obtained and rely on the compositions of the alloy, oxide and underlying coating [93]. According to this model, fluxing occurs due to the decomposition of oxides into corresponding cations and O2− (known as acidic fluxing) or oxides with O2− forming anions (referred to as basic fluxing).
In acidic fluxing, oxide ions are donated to the deposit melt through dissolving the oxide scale [93]:
Acidic environments in molten deposits can be developed through two main processes, namely, alloy-induced and gas-phase acidic fluxing. Basic fluxing is achieved through the production of oxide ions in a Na2SO4 deposit. Such is obtained by removing S and oxygen from the residue through reactions with the alloy or underlying coating. Subsequently, the oxide scales (e.g., MO) produced can react with the oxide ions through reactions [93]:
A conventional model for LTHC was proposed by Luthra [111]. As suggested by the model, LTHC follows two stages, namely, formation of liquid-form sodium-cobalt sulphate and attack propagation through SO3 migration through the liquid salt. In nickel-based alloys, the mechanism suggested by Shih and associates [112] for LTHC is sulphidisation.
An alloy’s resistance to hot corrosion can mainly be determined using four standard tests: the electrochemical, crucible, accelerated oxidation, and burner-rig [94, 113]. The crucible tests remain the most highly ranked test for hot corrosion, simply consisting of either suspending, depositing, or completely immersing the testing sample in molten salts at elevated temperatures, as presented in Figure 3. As far as TiAl alloys are concerned, less work has been carried out to understand the hot corrosion behaviour of such alloys [114, 115, 116].
Configurations used in hot corrosion crucible testing [
Gas turbine environments can be precisely simulated by employing burner-rig tests [117, 118], shown in Figure 4. The salt is in aerosol or fog form and fuel oil/air is introduced into the testing chamber to generate the test environment [119]. Simmons et al. [120] indicated that hot corrosion is an electrochemical process since hot corrosion consists of electrochemical reactions in which the molten salt acts as the conductive media or electrolyte.
Burner rig hot corrosion test schematic representation where (a) is an illustrates the experimental setup for Na2SO4(g) exposure, (b) is an image of the specimen plate for Na2SO4(g) tests in a crucible with the salt container and (c) is an ex-situ salt hot corrosion schematic diagram setup for experimental studies [
Some of the approaches used to prevent hot corrosion include maintaining both fuel purity and composition, properly selecting structural alloys, employing coatings, cleaning hot parts and air filtering [94].
Initiation and propagation of hot corrosion are greatly affected by impurities such as vanadium (V), S, and various alkali earth metals [121]. This can be controlled by adding magnesium (Mg), Cr, barium and calcium to the combustion fuel to decrease corrosion rate. The presence of zinc (Zn) in the form of anodes in the combustion fuel or as part of the protective coating can significantly reduce the occurrence of LTHC. According to Hancock and associates [122], Zn drastically reacts with chloride ions (i.e., when excess NaCl is available) and transfers the chloride to the gas-salt interface to transform to chloride gas via sulphidisation.
The addition of Cr to superalloys has effectively reduced the occurrence of hot corrosion [123]. Historically [121, 124], Cr (15 wt.% for Ni-based and 25 wt.% for Co-based alloys) has been added to superalloys to reduce HTHC. Much related to TiAl alloys, Garip and Ozdemir [125] studied the effect of Cr, Mo and Mn on the cyclic hot corrosion behaviour, and subsequently reported the beneficial effects of Cr and Mn additions on the hot corrosion properties of the investigated samples. Cr’s effect on corrosion resistance is attributed to the ability of Cr to form Cr2O3, stabilising the chemistry melt, preventing reprecipitation of the protective oxide scale. Contrarily, increased Cr additions to superalloys can compromise the high-temperature strength and ductility [113] by forming TCP phases. The alloy and oxide film adhesion has been reported to be improved by the addition of zirconium, yttrium, scandium, cerium and lanthanum [113]. Silicon (Si), platinum (Pt), hafnium, Ti, Al, and Nb [126] were also found to increase resistance to hot corrosion.
Such as diffusion, overlay and thermal barrier (TBCs) coatings can be used on relatively resistant alloys to combat hot corrosion. An alloy’s surface enrichment by Al, Si or Cr achieves diffusion coatings. Various aluminide diffusion coatings (i.e., PWA70, MDC3V, PWA62, TEW LDC2, Elbar Elcoat 360 and Chromalloy RT22) have been developed and can be alloyed with Pt to improve cyclic oxidation at high temperatures [127]. Overlay coatings, commonly referred to as M (base metal)–Cr–Al–Y coatings, are designed for LTHC and HTHC surface protection. Overlay coatings with low Cr-high Al coatings are used for HTHC protection, while high Cr-low Al coatings are used for LTHC [94]. TBCs protects the substrate from gaseous flow caused by heat and consist of an external ceramic usually zirconia) and an oxidation-resistant bond-coat overlay. Other coatings include intelligent coatings like RT22 (Pt-aluminide) and Sermetal 1515 (a triple-cycle Si-aluminide treatment), have been reported [127].
Inexpensive alternatives include oxide-based glass and glass–ceramic coatings [128, 129]. Oxide-based glass and glass–ceramic coatings exhibit a remarkable combination of properties such as excellent chemical inertness, high-temperature stability and superior mechanical properties, which effectively can mitigate deterioration caused by hot corrosion. The introduction of halogens on the surface of the alloy encourages the preferential formation of aluminium halides at elevated temperatures. The aluminium halides are then converted to thin, continuous, and protective alumina oxides. Fluorine provides the best oxidation protection [130]. Further examples of surface modifications coating and methods studied on γ-TiAl alloys include magnetron sputtering [131], laser cladding [132], sol–gel [133], pack cementation [134], chemical vapour deposition [135], slurry [136], ion implantation [137].
Motoring washes can be flooded with plain water [121] to prevent hot corrosion using specified procedures in the maintenance manual for the specific engine model. Also, high-efficiency filters can be used to filter out air containing high sodium contents [138].
Although much work has been devoted to understanding the hot corrosion kinetics of Ni-based and Co-based superalloys, TiAl alloys emerged to have sparked much interest in recent years [1, 56, 57, 139]. Historically, reported works utilised alloys produced using conventional methods; however, more attention has recently shifted to AM routes [70, 73, 140, 141, 142, 143, 144, 145, 146]. Despite much devotion to improving structure–property relations of TiAls, little work has been reported on the hot corrosion of additively manufactured TiAl.
Garip and Ozdemir [147] produced an alloy to the nominal at.% composition of Ti-48Al-10Cr using electric current activated sintering and studied the hot corrosion kinetics of the alloys in Na2SO4 salt for 180 h at 700–900°C. A severe hot corrosion attack was observed at 900°C (refer to Figure 5), with a porous and loose layer consisting of Na2Ti3O7, TiO2, Al2O3 traces of TiS phase.
Cross-sectional SEM images showing oxide scale microstructures with EDS analysis points represented in at.%, after hot corrosion exposure at (a) 800°C and (b) 900°C for 180 h [
In a study led by Xiong et al. [67], bare alloys TiAl, TiAlNb, and Ti3AlNb, were severely damaged after exposure at 750°C in (Na, K)2SO4 + NaCl melts as compared to those coated with enamel or TiAlCr. The corrosion mechanism was described to be much related to self-catalysis of sulphidisation and chlorination of metallic components. The initial mass loss observed is due to chloride volatility via metallic component chlorination. Of the alloys investigated, TiAlNb exhibited the best corrosion resistance due to adhesive Al2O3 enriched scale formation. Lastly, the degradation acceleration of sputtered TiAlCr coating was reported to be due to the chlorination of Cr and Al.
Additions of Nb and Si to traditional TiAl coatings were found to improve the hot corrosion resistance of a Ti-6Al-4 V alloy. In the stated work, Dai et al. [148] investigated the corrosion mechanisms on a mass loss basis following exposure at 800°C in a 75 wt.% Na2SO4 + NaCl salt mixture. Increasing single Nb additions deteriorated the hot corrosion resistance of the coating. Comparatively, increasing single Si additions continued to improve hot corrosion resistance. However, additions of both Nb and Si simultaneously showed better resistance to corrosion than single element additions. The corrosion protection of both Nb and Si (as seen in Figure 6) was related to SiO2 and Al2O3 formation in the initial stages of hot corrosion. Secondly, Si additions were reported to promote the formation of a Na2O-Al2O3-TiO2-SiO2 enamel, hindering contact between the corrosive media and the oxide scales.
Representative hot corrosion model of TiAl-xNbySi coating where (a) illustrates TiO2 and Al2O3 formation and (b) shows an acidic dissolution of TiO2 to form sodium titanates including NaTiO2 and Na2TiO3 [
Tang et al. [149] studied the effect of enamel coatings on γ-TiAl against hot corrosion at 900°C. The enamel coating remained stable in the (Na,K)2SO4 melts, thus effectively protecting it against hot corrosion attack. Silicon-based coatings have also been shown to protect TiAl alloys. Rubacha et al. [150] evaluated the hot corrosion resistance of silicon-rich coated Ti-46Al-8Ta (at.%) alloy in NaCl, Na2SO4 and a mixture of the two salts. The formation of an amorphous SiO2 layer with TiO2 (rutile) and α cristobalite crystals enhanced the hot corrosion resistance of the TiAl alloy. Furthermore, Wu and colleagues [151] studied the hot corrosion resistance of a SiO2 coated TiAl alloy in 75 wt.% Na2SO4 + 25 wt.% NaCl salt mixture at 700°C. The enhanced hot corrosion resistance of the TiAl alloy was attributed to the formation of a compact and adherent amorphous SiO2 embedded with Na2Si4O9 and cristobalite. The incorporation of Si in aluminide coatings has also provided long-term oxidation protection of γ-TiAl alloys at temperatures of 950°C by forming a continuous and uniform α-alumina oxide scale [152].
When metallic materials are exposed to elevated temperatures in air, oxidation occurs, resulting in the formation of oxide scales. The crystal structure of the individual metals significantly affects the oxidation rate of high-temperature applicative parts [153, 154].
The following reactions may occur when TiAl alloys are subject to an oxidising environment:
The ultimate oxidation resistance of alloyed TiAls is achieved by forming protective Al2O3, Cr2O3 and SiO2 scales due to their outstanding thermal stabilities. In contrast, the unfavourable formation of porous TiO2 with a high crack tendency is often observed [153]. Cobbinah et al. [155] found that 4 and 8 at.% Ta additions to Ti-46.5Al alloy promoted the significant formation of a consistent, non-porous Al2O3 layer at the metal-oxide boundary. Additionally, the layer operated as a diffusion barrier and preceded to outstanding oxidation resistance of the TiAl alloys.
In a study by Pan et al. [156], a comprehensive understanding is provided of the role of alloying on the oxidation resistance of TiAl alloys. Protection was related much to the formation of Ti3Sn layer diminishing oxygen diffusion inwardly, promoted by Sn additions. Moreover, spallation resistance was enhanced by the Al2O3 oxide pegs providing a mechanical locking. The effect of cathodically electrodepositing a SiO2 film on the oxidation resistance of a TiAl alloy was studied [157]. After 900°C exposure in air, the resultant alumina- and silicon-enriched glass-like oxide scale (in Figure 7) was reported, preventing oxygen diffusion leading to remarkably decreased alloy oxidation rates.
Representation of a γ-TiAl alloy coated with E-SiO2 film (a) and after thermal oxidation test (b) [
Surface modification of TiAl alloys via anodising has sparked interest in many high-temperature oxidation studies [158, 159, 160, 161]. For instance, the oxidation behaviour and protection mechanisms of a TiAl alloy were studied by anodising in a methanol/NaF solution and produced an aluminium (Al)-and fluorine-enriched anodic film [162]. After 100 h exposure at 850°C, no evidence of cracking and spallation was displayed on the surface. The enhanced high-temperature oxidation resistance is mainly attributed to the halogen effect, generation of Al2O3 and oxidised Al–F species inhibiting external oxygen diffusion. Much effort has been devoted to developing coatings for γ-TiAl alloys, summarised in an evaluation by Pflumm et al. [130]. Amongst many available coating methods, Si-modified aluminide coatings produced via pack cementation have gained popularity. One such study [81] demonstrated that a continuous α-Al2O3 scale remained adherent after exposure to a temperature of 950°C for 3000 h.
When a metal operating at elevated temperatures is exposed to air, an oxide scale forms. As oxide scale formation proceeds, the metal’s weight change can be plotted against time. Several laws such as linear, parabolic, logarithmic or cubic can be observed when studying oxidation kinetics [163]. In as far as TiAl alloys are concerned, either linear or parabolic oxidation kinetics prevail. While the former offers no protection against high-temperature oxidation, the latter promotes diffusion-controlled oxide scale formation, improving much on the oxidation resistance of the base material. Parabolic oxidation follows and obeys the following law:
where
The optimum oxidation protection governed by the parabolic law often results in a thick and continuous TiO2 and Al2O3 scale. As such, Swadźba et al. [48] investigated the short-term oxidation behaviour of a TiAl 48–2-2 alloy produced by AM at a temperature range of 750–900°C in air. At 900°C, a non-porous scale consisting of TiO2, Al2O3 and nitrates, exhibiting parabolic oxidation (in Figure 8), was observed.
Mass change against time plots for (a) oxidation rate constant of the AM produced TiAl 48–2-2 alloy and (b)–(c) the power-law constant – n extrapolation [
Garip [164] likewise studied the oxidation kinetics at 900°C in air for 200 h for TiAl alloys produced via pressureless and resistance sintering. Both alloys exhibited a nearly parabolic oxidation response, with oxidation rate constants of the pressureless sintered alloy of 0.6391 mgn cm−2n h−1, 1.8 times higher than that of the alloy compacted using resistance sintering. Multi-layered oxide scales consisting of TiO2 and Al2O3 were obtained.
Oxidation protection offered by forming a continuous Al2O3 scale followed by a multilayer of TiO2 + Al2O3 is limited, unfortunately, to the maximum service temperature of ~830°C. Above this temperature, the protection potential presented by the oxide scales formed severely deteriorates, limiting the high-temperature application potential for structural components [165]. The current trend in research is to improve the oxidation resistance of TiAl through alloy modifications.
Nb is one element used in many research works [86, 87, 88, 89, 90] to improve the oxidation resistance of TiAl alloys. Al activities are promoted by Nb additions and accelerate protective Al2O3 oxide film formation, limiting oxygen diffusion into the alloy [166]. Also, the α2 phase present in TiAl alloys is significantly decreased by Nb additions, decreasing its oxygen solubility [54]. Although Nb was primarily used for improving oxidation resistance [167], other high-temperature properties such as strength and creep resistance have been enhanced by the presence of Nb.
The creep resistance and the oxidation resistance of TiAl and its alloys can be enhanced by adding Si. The oxidation improvement is said to be achieved through the refinement of TiO2 particles, inducing refined and compact TiO2 scales on the surface [165]. Moreover, Si promotes Al diffusion into the oxide scale, stabilises Ti, reduces Ti4+ ions and impedes external Ti4+ ions diffusion [168].
The effect of adding molybdenum (Mo) alone to TiAls to improve on high-temperature oxidation is minimal. The protection of Mo-containing TiAl alloys is through the formation of inner oxide layers of TiO2 and Ti2AlMo near the substrate surface [165]. Unfortunately, Mo additions cannot alter the external oxide film formed (i.e., comprises of loose and porous TiO2 scales) and its characteristics. It is recommended in practice that the improvement of high-temperature oxidation cannot be derived from adding Mo alone; instead, the combination of Mo with other alloys can have a beneficial effect on the alloys’ resistance to oxidation [169].
Cr additions promote the formation of Cr2O3 oxides, which act as mass ion transport barriers [170], enhancing oxidation resistance. In addition, the Al content existing in the alloys can be significantly suppressed by Cr additions, promoting the formation of Al2O3 scales. Oxygen diffusion at elevated temperatures can be accelerated by Cr3+ ion doping in titanium oxide, improving oxygen vacancy concentration. Contrarily, the doping effect may impair the TiAl alloy’s oxidation by making Ti4+ interstitially occupying TiO2 sites, improving the potential energy with a noticeable decrease in diffusion activation energy, encouraging the diffusion of Ti4+ in TiO2 [171].
Zirconium (Zr) additions can also enhance oxidation properties by altering the characteristics of the oxide formed during the primary stages of oxidation and promote oxide grain nucleation [172]. As a result, the refinement of the oxide particles occurs, which can hinder oxygen diffusion. Rare earth metals have been reported to enhance the oxidation resistance of TiAl alloys. As discussed in detail in a research paper by Dai et al. [165], the protection mechanism is contributed by grain refinement, substrate purification, oxide adherence improvement and promotion of Al selective oxidation.
The need for materials to give excellent mechanical properties under high temperatures and extreme conditions such as TiAl is in demand. The use of such alloys would mean a reduction in pollution and noise levels for aero-based engines due to improved thermal efficiencies. There are challenges in producing such alloys using the conventional arc and induction melt casting techniques due to the extremely high melting temperatures of the alloys. The AM route, particularly L-PBF, presents an opportunity to produce such alloys. What is critical in such trials is the operating parameters during processing. This has a direct influence on the performance and mechanical properties of the alloys so produced. Hot corrosion and oxidation of TiAl alloys are of great concern in gas turbine engines. Hot corrosion can be classified into HTHC and LTHC, with particular reference to mechanisms and characteristics. Protection control methods may result in fewer catastrophic failures. The hot corrosion process must be either totally prevented or detected early to avoid catastrophic failure. A sound understanding of oxidation mechanisms and kinetics of TiAl alloys makes it easier to tailor oxidation-resistant alloys by alloy modifications.
This research work is based on the research supported wholly/in part by the National Research Foundation of South Africa (Grant number 130004).
The authors declare no conflict of interest.
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Several genes have been indicated as putative to coat color modification, altering the basic color by dilution, redistribution, or lacking of pigments.",book:{id:"5405",slug:"trends-and-advances-in-veterinary-genetics",title:"Trends and Advances in Veterinary Genetics",fullTitle:"Trends and Advances in Veterinary Genetics"},signatures:"Adriana Pires Neves, Eduardo Brum Schwengber, Fabiola Freire\nAlbrecht, José Victor Isola and Liana de Salles van der Linden",authors:[{id:"188768",title:"Associate Prof.",name:"Adriana",middleName:null,surname:"Pires Neves",slug:"adriana-pires-neves",fullName:"Adriana Pires Neves"},{id:"188993",title:"Dr.",name:"Eduardo",middleName:null,surname:"Brun Schwengber",slug:"eduardo-brun-schwengber",fullName:"Eduardo Brun Schwengber"},{id:"188994",title:"Mrs.",name:"Fabiola",middleName:null,surname:"Freire Albrecht",slug:"fabiola-freire-albrecht",fullName:"Fabiola Freire Albrecht"},{id:"188996",title:"Ph.D. Student",name:"Liana",middleName:null,surname:"de Salles van der Linden",slug:"liana-de-salles-van-der-linden",fullName:"Liana de Salles van der Linden"},{id:"188997",title:"Mr.",name:"José Victor",middleName:null,surname:"Vieira Isola",slug:"jose-victor-vieira-isola",fullName:"José Victor Vieira Isola"}]},{id:"59305",doi:"10.5772/intechopen.74008",title:"Avian Coccidiosis, New Strategies of Treatment",slug:"avian-coccidiosis-new-strategies-of-treatment",totalDownloads:3686,totalCrossrefCites:2,totalDimensionsCites:4,abstract:"The control of avian coccidiosis since the 1940s has been associated with the use of ionophores and chemical drugs. Recently, a significant interest in natural sources has developed due to the pressure to poultry industry to produce drug-free birds. Consequently, the search of products derived from plants and other natural sources has increased in the last years. Today, many commercial products containing essential oils, extracts, and other compounds are available. The use of these compounds of natural origin is related to an increased immune response, a body weight gain, destruction of oocyst, among other benefits. The main inconvenience of these products is the act on some species of Eimeria, but not all. This genetic variability found in the parasite makes the use of products difficult to control and treat coccidiosis. In this chapter, several proposals of treatment are presented based on the use of natural products, considering the new strategies of treatment with minimal consequences to birds.",book:{id:"5543",slug:"farm-animals-diseases-recent-omic-trends-and-new-strategies-of-treatment",title:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment",fullTitle:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment"},signatures:"Rosa Estela Quiroz-Castañeda",authors:[{id:"187735",title:"Dr.",name:"Rosa Estela",middleName:null,surname:"Quiroz Castañeda",slug:"rosa-estela-quiroz-castaneda",fullName:"Rosa Estela Quiroz Castañeda"}]},{id:"58461",doi:"10.5772/intechopen.72638",title:"Natural Compounds as an Alternative to Control Farm Diseases: Avian Coccidiosis",slug:"natural-compounds-as-an-alternative-to-control-farm-diseases-avian-coccidiosis",totalDownloads:2078,totalCrossrefCites:1,totalDimensionsCites:3,abstract:"Coccidiosis is one of the most aggressive and expensive parasite diseases in poultry industry worldwide. Currently, the most used control techniques are chemoprophylaxis and anticoccidial feed additives. Although there is a great variety of commercial anticoccidial drugs and vaccines in the market, there is also a significant resistance to use them in animals with human as final consumer. To date, none available product offers effective protection toward coccidiosis; however, the search for novel strategies to control this disease continues, and natural products have arisen as a potential way to cope with avian coccidiosis. In this chapter, we highlight recent advances in natural compounds, their anticoccidial properties, and mechanisms.",book:{id:"5543",slug:"farm-animals-diseases-recent-omic-trends-and-new-strategies-of-treatment",title:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment",fullTitle:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment"},signatures:"Mayra E. Cobaxin-Cárdenas",authors:[{id:"223051",title:"Dr.",name:"Mayra E.",middleName:null,surname:"Cobaxin-Cárdenas",slug:"mayra-e.-cobaxin-cardenas",fullName:"Mayra E. Cobaxin-Cárdenas"}]},{id:"58679",doi:"10.5772/intechopen.72636",title:"Genome-Based Vaccinology Applied to Bovine Babesiosis",slug:"genome-based-vaccinology-applied-to-bovine-babesiosis",totalDownloads:1161,totalCrossrefCites:1,totalDimensionsCites:3,abstract:"Genomics approaches in veterinary research have been a very useful tool to identify candidates with potential to be used in prevention of animal diseases. In Babesia, genome information analysis has elucidated a wide variety of protein families and some members are described in this chapter. Here, we present some of the most recent studies about B. bovis and B. bigemina genomes where some proteins have been identified with potential to prevent infections by these parasites.",book:{id:"5543",slug:"farm-animals-diseases-recent-omic-trends-and-new-strategies-of-treatment",title:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment",fullTitle:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment"},signatures:"Juan Mosqueda, Diego Josimar Hernández-Silva and Mario\nHidalgo-Ruiz",authors:[{id:"220191",title:"Dr.",name:"Juan",middleName:null,surname:"Mosqueda",slug:"juan-mosqueda",fullName:"Juan Mosqueda"}]}],mostDownloadedChaptersLast30Days:[{id:"59305",title:"Avian Coccidiosis, New Strategies of Treatment",slug:"avian-coccidiosis-new-strategies-of-treatment",totalDownloads:3686,totalCrossrefCites:2,totalDimensionsCites:4,abstract:"The control of avian coccidiosis since the 1940s has been associated with the use of ionophores and chemical drugs. Recently, a significant interest in natural sources has developed due to the pressure to poultry industry to produce drug-free birds. Consequently, the search of products derived from plants and other natural sources has increased in the last years. Today, many commercial products containing essential oils, extracts, and other compounds are available. The use of these compounds of natural origin is related to an increased immune response, a body weight gain, destruction of oocyst, among other benefits. The main inconvenience of these products is the act on some species of Eimeria, but not all. This genetic variability found in the parasite makes the use of products difficult to control and treat coccidiosis. In this chapter, several proposals of treatment are presented based on the use of natural products, considering the new strategies of treatment with minimal consequences to birds.",book:{id:"5543",slug:"farm-animals-diseases-recent-omic-trends-and-new-strategies-of-treatment",title:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment",fullTitle:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment"},signatures:"Rosa Estela Quiroz-Castañeda",authors:[{id:"187735",title:"Dr.",name:"Rosa Estela",middleName:null,surname:"Quiroz Castañeda",slug:"rosa-estela-quiroz-castaneda",fullName:"Rosa Estela Quiroz Castañeda"}]},{id:"58604",title:"Genomics of Apicomplexa",slug:"genomics-of-apicomplexa",totalDownloads:1181,totalCrossrefCites:2,totalDimensionsCites:2,abstract:"Apicomplexa is a eukaryotic phylum of intracellular parasites with more than 6000 species. Some of these single-celled parasites are important pathogens of livestock. At present, 128 genomes of phylum Apicomplexa have been reported in the GenBank database, of which 17 genomes belong to five genera that are pathogens of farm animals: Babesia, Theileria, Eimeria, Neospora and Sarcocystis. These 17 genomes are Babesia bigemina (five chromosomes), Babesia divergens (514 contigs) and Babesia bovis (four chromosomes and one apicoplast); Theileria parva (four chromosomes and one apicoplast), Theileria annulata (four chromosomes), Theileria orientalis (four chromosomes and one apicoplast) and Theileria equi (four chromosomes and one apicoplast); Eimeria brunetti (24,647 contigs), Eimeria necatrix (4667 contigs), Eimeria tenella (12,727 contigs), Eimeria acervulina (4947 contigs), Eimeria maxima (4570 contigs), Eimeria mitis (65,610 contigs) and Eimeria praecox (53,359 contigs); Neospora caninum (14 chromosomes); and Sarcocystis neurona strains SN1 (2862 contigs) and SN3 (3191 contigs). The study of these genomes allows us to understand their mechanisms of pathogenicity and identify genes that encode proteins as a possible vaccine antigen.",book:{id:"5543",slug:"farm-animals-diseases-recent-omic-trends-and-new-strategies-of-treatment",title:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment",fullTitle:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment"},signatures:"Fernando Martínez-Ocampo",authors:[{id:"195818",title:"Dr.",name:"Fernando",middleName:null,surname:"Martinez",slug:"fernando-martinez",fullName:"Fernando Martinez"}]},{id:"59436",title:"Pathogenomics and Molecular Advances in Pathogen Identification",slug:"pathogenomics-and-molecular-advances-in-pathogen-identification",totalDownloads:1642,totalCrossrefCites:2,totalDimensionsCites:2,abstract:"Today exists a spread spectrum of tools to be used in pathogen identification. Traditional staining and microscopic methods as well as modern molecular methods are presented in this chapter. Pathogen identification is only the beginning to obtain information related to pathogenicity of the microorganism in the near future. Once the pathogen is identified, genome-sequencing methods will provide a significant amount of information that can be elucidated only through bioinformatics methods. In this point, pathogenomics is a powerful tool to identify potential virulence factors, pathogenicity islands, and many other genes that could be used as therapeutic targets or in vaccine development. In this chapter, we present an update of the molecular advances used to identify pathogens and to obtain information of their diversity. We also review the most recent studies on pathogenomics with a special attention on pathogens of veterinary importance.",book:{id:"5543",slug:"farm-animals-diseases-recent-omic-trends-and-new-strategies-of-treatment",title:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment",fullTitle:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment"},signatures:"Rosa Estela Quiroz-Castañeda",authors:[{id:"187735",title:"Dr.",name:"Rosa Estela",middleName:null,surname:"Quiroz Castañeda",slug:"rosa-estela-quiroz-castaneda",fullName:"Rosa Estela Quiroz Castañeda"}]},{id:"61222",title:"The Use of Genetically Modified Organisms for Repopulation of Species of Commercial Importance in Aquatic Environment: Effects on Genetic Pool, Risks to Protected Areas and Policies for Their Proper Management",slug:"the-use-of-genetically-modified-organisms-for-repopulation-of-species-of-commercial-importance-in-aq",totalDownloads:1073,totalCrossrefCites:1,totalDimensionsCites:1,abstract:"In recent years, the reproduction of organisms through genetic engineering has been presented as an option for the repopulation of fish stocks of species that are at the limit or have passed their maximum sustainable exploitation. However, are the potential effects on genetic diversity known? The possible mutations? The risks to protected ecosystems? or Are there adequate policies and regulations for its management? This chapter aims to review the biological and population effects of the use of these organisms and the potential impacts they can cause to natural protected areas, as well as if there are adequate regulations or policies for their use. Finally, the authors give indicators for the sustainable integrated management of genetically modified organisms.",book:{id:"6647",slug:"animal-genetics-approaches-and-limitations",title:"Animal Genetics",fullTitle:"Animal Genetics - Approaches and Limitations"},signatures:"Maurilio Lara-Flores and Evelia Rivera-Arriaga",authors:null},{id:"58730",title:"Metagenomics and Diagnosis of Zoonotic Diseases",slug:"metagenomics-and-diagnosis-of-zoonotic-diseases",totalDownloads:1800,totalCrossrefCites:0,totalDimensionsCites:0,abstract:"Zoonotic diseases represent a public health problem worldwide, since approximately 60% of human pathogens have a zoonotic origin. A variety of methodologies have been developed to diagnose zoonosis, including culture-dependent and immunological-based methods, which allow the identification of a huge range of pathogens. However, some of them are not detected easily with these approaches. Additionally, molecular tests have been developed, and they are designed to identify a single pathogen or mixtures of them. In this context, metagenomics comes as an alternative to get genome sequences of different microorganisms, which comprise a microbial community. Metagenomics have been used to characterize microbiomes and viromes, which are not cultivable under laboratory conditions. This methodology could be a powerful tool in the diagnosis of zoonotic diseases because it allows not only identification of genus and species, but also detection of some proteins in specific conditions on specific tissues, through structural and functional metagenomics, respectively.",book:{id:"5543",slug:"farm-animals-diseases-recent-omic-trends-and-new-strategies-of-treatment",title:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment",fullTitle:"Farm Animals Diseases, Recent Omic Trends and New Strategies of Treatment"},signatures:"Laura Inés Cuervo-Soto, Silvio Alejandro López-Pazos and Ramón\nAlberto Batista-García",authors:[{id:"201362",title:"Dr.",name:"Ramón Alberto",middleName:null,surname:"Batista-García",slug:"ramon-alberto-batista-garcia",fullName:"Ramón Alberto Batista-García"}]}],onlineFirstChaptersFilter:{topicId:"303",limit:6,offset:0},onlineFirstChaptersCollection:[],onlineFirstChaptersTotal:0},preDownload:{success:null,errors:{}},subscriptionForm:{success:null,errors:{}},aboutIntechopen:{},privacyPolicy:{},peerReviewing:{},howOpenAccessPublishingWithIntechopenWorks:{},sponsorshipBooks:{sponsorshipBooks:[],offset:0,limit:8,total:null},allSeries:{pteSeriesList:[{id:"14",title:"Artificial Intelligence",numberOfPublishedBooks:9,numberOfPublishedChapters:89,numberOfOpenTopics:6,numberOfUpcomingTopics:0,issn:"2633-1403",doi:"10.5772/intechopen.79920",isOpenForSubmission:!0},{id:"7",title:"Biomedical Engineering",numberOfPublishedBooks:12,numberOfPublishedChapters:104,numberOfOpenTopics:3,numberOfUpcomingTopics:0,issn:"2631-5343",doi:"10.5772/intechopen.71985",isOpenForSubmission:!0}],lsSeriesList:[{id:"11",title:"Biochemistry",numberOfPublishedBooks:32,numberOfPublishedChapters:318,numberOfOpenTopics:4,numberOfUpcomingTopics:0,issn:"2632-0983",doi:"10.5772/intechopen.72877",isOpenForSubmission:!0},{id:"25",title:"Environmental Sciences",numberOfPublishedBooks:1,numberOfPublishedChapters:12,numberOfOpenTopics:4,numberOfUpcomingTopics:0,issn:"2754-6713",doi:"10.5772/intechopen.100362",isOpenForSubmission:!0},{id:"10",title:"Physiology",numberOfPublishedBooks:11,numberOfPublishedChapters:141,numberOfOpenTopics:4,numberOfUpcomingTopics:0,issn:"2631-8261",doi:"10.5772/intechopen.72796",isOpenForSubmission:!0}],hsSeriesList:[{id:"3",title:"Dentistry",numberOfPublishedBooks:8,numberOfPublishedChapters:129,numberOfOpenTopics:2,numberOfUpcomingTopics:0,issn:"2631-6218",doi:"10.5772/intechopen.71199",isOpenForSubmission:!0},{id:"6",title:"Infectious Diseases",numberOfPublishedBooks:13,numberOfPublishedChapters:113,numberOfOpenTopics:3,numberOfUpcomingTopics:1,issn:"2631-6188",doi:"10.5772/intechopen.71852",isOpenForSubmission:!0},{id:"13",title:"Veterinary Medicine and Science",numberOfPublishedBooks:11,numberOfPublishedChapters:105,numberOfOpenTopics:3,numberOfUpcomingTopics:0,issn:"2632-0517",doi:"10.5772/intechopen.73681",isOpenForSubmission:!0}],sshSeriesList:[{id:"22",title:"Business, Management and Economics",numberOfPublishedBooks:1,numberOfPublishedChapters:19,numberOfOpenTopics:2,numberOfUpcomingTopics:1,issn:"2753-894X",doi:"10.5772/intechopen.100359",isOpenForSubmission:!0},{id:"23",title:"Education and Human Development",numberOfPublishedBooks:0,numberOfPublishedChapters:5,numberOfOpenTopics:1,numberOfUpcomingTopics:1,issn:null,doi:"10.5772/intechopen.100360",isOpenForSubmission:!0},{id:"24",title:"Sustainable Development",numberOfPublishedBooks:0,numberOfPublishedChapters:15,numberOfOpenTopics:5,numberOfUpcomingTopics:0,issn:null,doi:"10.5772/intechopen.100361",isOpenForSubmission:!0}],testimonialsList:[{id:"13",text:"The collaboration with and support of the technical staff of IntechOpen is fantastic. 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She has over 160 Scientific Publications in International Journals and Conferences and she is the author of 5 books on Innovation and Decision Making in Industrial Applications and Engineering.",institutionString:null,institution:{name:"Parthenope University of Naples",institutionURL:null,country:{name:"Italy"}}},editorTwo:null,editorThree:null,series:{id:"24",title:"Sustainable Development",doi:"10.5772/intechopen.100361",issn:null},editorialBoard:[{id:"179628",title:"Prof.",name:"Dima",middleName:null,surname:"Jamali",slug:"dima-jamali",fullName:"Dima Jamali",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bSAIlQAO/Profile_Picture_2022-03-07T08:52:23.jpg",institutionString:null,institution:{name:"University of Sharjah",institutionURL:null,country:{name:"United Arab Emirates"}}},{id:"170206",title:"Prof.",name:"Dr. Orhan",middleName:null,surname:"Özçatalbaş",slug:"dr.-orhan-ozcatalbas",fullName:"Dr. Orhan Özçatalbaş",profilePictureURL:"https://mts.intechopen.com/storage/users/170206/images/system/170206.png",institutionString:null,institution:{name:"Akdeniz University",institutionURL:null,country:{name:"Turkey"}}},{id:"250347",title:"Associate Prof.",name:"Isaac",middleName:null,surname:"Oluwatayo",slug:"isaac-oluwatayo",fullName:"Isaac Oluwatayo",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bRVIVQA4/Profile_Picture_2022-03-17T13:25:32.jpg",institutionString:null,institution:{name:"University of Venda",institutionURL:null,country:{name:"South Africa"}}},{id:"141386",title:"Prof.",name:"Jesús",middleName:null,surname:"López-Rodríguez",slug:"jesus-lopez-rodriguez",fullName:"Jesús López-Rodríguez",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bRBNIQA4/Profile_Picture_2022-03-21T08:24:16.jpg",institutionString:null,institution:{name:"University of A Coruña",institutionURL:null,country:{name:"Spain"}}},{id:"208657",title:"Dr.",name:"Mara",middleName:null,surname:"Del Baldo",slug:"mara-del-baldo",fullName:"Mara Del Baldo",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bRLMUQA4/Profile_Picture_2022-05-18T08:19:24.png",institutionString:"University of Urbino Carlo Bo",institution:null}]},onlineFirstChapters:{},publishedBooks:{paginationCount:6,paginationItems:[{type:"book",id:"9493",title:"Periodontology",subtitle:"Fundamentals and Clinical Features",coverURL:"https://cdn.intechopen.com/books/images_new/9493.jpg",slug:"periodontology-fundamentals-and-clinical-features",publishedDate:"February 16th 2022",editedByType:"Edited by",bookSignature:"Petra Surlin",hash:"dfe986c764d6c82ae820c2df5843a866",volumeInSeries:8,fullTitle:"Periodontology - 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