Insertion location conditions assigned to each phalanx.
\r\n\t
",isbn:"978-1-83881-111-2",printIsbn:"978-1-83880-992-8",pdfIsbn:"978-1-83881-112-9",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!0,isSalesforceBook:!1,isNomenclature:!1,hash:"acb2875b3bfc189c9881a9b44b6a5184",bookSignature:"Dr. Abdo Abou Jaoudé",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/11865.jpg",keywords:"Linear Operators, Normal Operators, Spectral Theorem, Applications, Differential Operators, Integral Operators, Functional Calculus, Complex Variables, Complex Analysis, Theory, Recent Advances, Latest Trends",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"April 13th 2022",dateEndSecondStepPublish:"June 21st 2022",dateEndThirdStepPublish:"August 20th 2022",dateEndFourthStepPublish:"November 8th 2022",dateEndFifthStepPublish:"January 7th 2023",dateConfirmationOfParticipation:null,remainingDaysToSecondStep:"2 months",secondStepPassed:!0,areRegistrationsClosed:!1,currentStepOfPublishingProcess:3,editedByType:null,kuFlag:!1,biosketch:"Abdo Abou Jaoudé is a pioneering Associate Professor of Mathematics and Statistics at Notre Dame University-Louaizé. He holds two PhDs in Mathematics and Prognostics from the Lebanese University and Aix-Marseille University. His research interests are in the field of mathematics.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"248271",title:"Dr.",name:"Abdo",middleName:null,surname:"Abou Jaoudé",slug:"abdo-abou-jaoude",fullName:"Abdo Abou Jaoudé",profilePictureURL:"https://mts.intechopen.com/storage/users/248271/images/system/248271.jpg",biography:"Abdo Abou Jaoudé has been teaching for many years and has a passion for researching and teaching mathematics. He is currently an Associate Professor of Mathematics and Statistics at Notre Dame University-Louaizé (NDU), Lebanon. He holds a BSc and an MSc in Computer Science from NDU, and three PhDs in Applied Mathematics, Computer Science, and Applied Statistics and Probability, all from Bircham International University through a distance learning program. He also holds two PhDs in Mathematics and Prognostics from the Lebanese University, Lebanon, and Aix-Marseille University, France. Dr. Abou Jaoudé's broad research interests are in the field of applied mathematics. He has published twenty-three international journal articles and six contributions to conference proceedings, in addition to seven books on prognostics, pure and applied mathematics, and computer science.",institutionString:"Notre Dame University - Louaize",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"4",totalChapterViews:"0",totalEditedBooks:"2",institution:{name:"Notre Dame University – Louaize",institutionURL:null,country:{name:"Lebanon"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"15",title:"Mathematics",slug:"mathematics"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"252211",firstName:"Sara",lastName:"Debeuc",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/252211/images/7239_n.png",email:"sara.d@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review, to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3092",title:"Anopheles mosquitoes",subtitle:"New insights into malaria vectors",isOpenForSubmission:!1,hash:"c9e622485316d5e296288bf24d2b0d64",slug:"anopheles-mosquitoes-new-insights-into-malaria-vectors",bookSignature:"Sylvie Manguin",coverURL:"https://cdn.intechopen.com/books/images_new/3092.jpg",editedByType:"Edited by",editors:[{id:"50017",title:"Prof.",name:"Sylvie",surname:"Manguin",slug:"sylvie-manguin",fullName:"Sylvie Manguin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"2270",title:"Fourier Transform",subtitle:"Materials Analysis",isOpenForSubmission:!1,hash:"5e094b066da527193e878e160b4772af",slug:"fourier-transform-materials-analysis",bookSignature:"Salih Mohammed Salih",coverURL:"https://cdn.intechopen.com/books/images_new/2270.jpg",editedByType:"Edited by",editors:[{id:"111691",title:"Dr.Ing.",name:"Salih",surname:"Salih",slug:"salih-salih",fullName:"Salih Salih"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"117",title:"Artificial Neural Networks",subtitle:"Methodological Advances and Biomedical Applications",isOpenForSubmission:!1,hash:null,slug:"artificial-neural-networks-methodological-advances-and-biomedical-applications",bookSignature:"Kenji Suzuki",coverURL:"https://cdn.intechopen.com/books/images_new/117.jpg",editedByType:"Edited by",editors:[{id:"3095",title:"Prof.",name:"Kenji",surname:"Suzuki",slug:"kenji-suzuki",fullName:"Kenji Suzuki"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3828",title:"Application of Nanotechnology in Drug Delivery",subtitle:null,isOpenForSubmission:!1,hash:"51a27e7adbfafcfedb6e9683f209cba4",slug:"application-of-nanotechnology-in-drug-delivery",bookSignature:"Ali Demir Sezer",coverURL:"https://cdn.intechopen.com/books/images_new/3828.jpg",editedByType:"Edited by",editors:[{id:"62389",title:"PhD.",name:"Ali Demir",surname:"Sezer",slug:"ali-demir-sezer",fullName:"Ali Demir Sezer"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"70363",title:"Diluted Magnetic Semiconductor ZnO: Magnetic Ordering with Transition Metal and Rare Earth Ions",doi:"10.5772/intechopen.90369",slug:"diluted-magnetic-semiconductor-zno-magnetic-ordering-with-transition-metal-and-rare-earth-ions",body:'Diluted magnetic semiconductors (DMSs) and oxides raised hopes of applications based on single elements combining the logic functionalities of semiconductors with the information storage capabilities of magnetic elements [1]. The research on DMSs is fascinating during the 1980s on II-VI semiconductors with little magnetic impurities that opened the optical and electronic phenomenon to introduce magnetic field effects [2]. The DMS required high Curie temperature, TC, for a material. Initially, II-VI semiconductors such as CdMnTe and ZnMnSe are widely investigated as DMSs for which the valence of the cation matches with the common magnetic ions, i.e., Mn [3]. Since the hole induced ferromagnetic order in p-type InMnAs and GaMnAs, a lot of research is carried out on III-V-based DMSs that unfortunately failed to give room temperature ferromagnetism (RTFM). After that, a lot of efforts are carried out to result RTFM in III-V-based DMS, i.e., GaN, GaSb, InAs, and oxide-based DMS, ZnO, TiO2, SnO2, In2O3, etc. These DMSs are attracting potential interest in spin-based information-processing applications. It needs high TC for such DMSs of GaN and ZnO that may relate for their wide-band gap [4]. However, the spintronic applications like spin-valve transistors, spin light-emitting diodes, nonvolatile memory, logic devices, etc. have remarkable interest of RTFM of DMSs [5]. Among DMSs, the Mn-doped GaAs is found to be ferromagnetic with TC ∼ 172 K is widely investigated [5].
Even though low transition temperatures, ferromagnetism in diluted magnetic semiconductors, DMSs is essential to explore new ideas to develop spintronic technology, which is actually the electrical manipulation of magnetism [6]. A small Mn percentage in III-V semiconductors of (In, Mn)As and (Ga, Mn)As replaces Ga or In atoms to stabilize the exchange interaction between charge carriers and localized spins. Due to low carrier concentration in these DMSs, it is possible to control a considerable portion of carriers by external electric fields using metal–insulator–semiconductor or p-n junction configuration (Figures 1a,b). It has a thin ferromagnetic semiconductor layer, to the extent that the field significantly alters the stability of the ferromagnetic phase and other magnetic properties. The value of TC is controlled in a ferromagnet with the application of an electric field which was observed for metal–insulator–semiconductor configuration of (In, Mn)As thin films [8]. Later, electrical manipulation of the coercive field (HC) is also possible for (In, Mn)As which means an applied electric field changes the magnetic anisotropy [9]. This is the exchange interaction which splits the carrier states according to the spin-orbit interaction [10].
(a, b) Electric control of ferromagnetism (schematic representation). (c) a spin-polarized current changes the magnetization direction, i.e., (GaMn)As (adapted from [
For low-power-consumption computer memory devices, the DMSs influencing the magnetization direction to achieve magnetic data-storage and memory devices of hard disks directs with the direction of magnetization [7]. In a hard disk, the data is stored on a disk-shaped magnet in local magnetization form; to write information, a pulse of current is applied to a small electromagnet that scans the disk. In this process, an energy is wasted due to a magnetic field exists between the current and the manipulated magnetization. However, a spin-polarized current is applied directly to the magnet instead of using current to generate the magnetic field is an alternative way as schematized in Figure 1c. Such a current would exert torque on the magnetization by exchanging spin-angular momentum with it as it passes through the magnet. Exploitation of this phenomenon, called spin torque, is expected to allow the development of compact magnetic memory devices that can run on low-power consumption. In Figure 1c, the metal–insulator–semiconductor device involving a semiconductor—a (GaMn)As film—that has ferro magnetic properties at low temperatures [7]. The device includes a ‘gate’ electrode isolated electrically from the (GaMn)As film. When a negative voltage is applied to the gate electrode, carriers in the film that have positive charge (electron “holes”) are attracted toward the electrode and vice versa. This property allows the density of the electron holes, and thus the magnetic anisotropy in the (GaMn)As film beneath the electrode, to be controlled electrically, resulting in a change in the magnetization direction.
The researcher has initially found high TC in doped III-V DMS, which for a long time was stuck at 110 K [1]. After that, several groups stressed out the defects—mainly Mn atoms that form interstitials rather than substituting for Ga—responsible for this limit, and TC was raised up to 150 K. Dietl [1] proposed a Zener model to perform so many experiments on (Ga, Mn)As, which create problem with higher concentration of Mn due to the interplay between the disorder and localization, and electron–electron correlations have a very influential effect on carrier-mediated ferromagnetism at and above room temperature [11]. For example, for the Co-doped ZnO, the Co occupies the Zn sites as Co is paramagnetic and there is no ferromagnetism associated with Co, even when lots of carriers are added by Al co-doping and the temperature is very low (5 K) [12]. Moreover, the solubility of Co in ZnO is high, making it is easy to substitute Co for Zn throughout the crystal. However, by considering defect-mediated ferromagnetism, an intrinsic form of high-TC ferromagnetism in dilute magnetic oxides with lots of defects is observed. This is because electrons associated with defects couple antiparallel to dopant spins within the orbital volume of the defect. With high TC, the defect coupling is strong. But, it is difficult to control defects for practical applicability. To realize high-temperature ferromagnetism in DMSs, a wide-band gap ZnO is undoubtedly a major development if the ferromagnetism is unambiguously established to be intrinsic (carrier induced) [13]. Coey et al. [14] proposed that the ferromagnetic exchange is mediated by shallow donor electrons to form bound magnetic polarons that overlap to create a spin-split impurity band. It is reported that the oxygen vacancies might change the band structure of host oxides to induce ferromagnetism [15]. The formation of BMP, which includes electrons locally trapped via oxygen vacancies, with the trapped electron occupying an orbital overlapping with the d shells of transition metal (TM) neighbors, might explain the room temperature ferromagnetism (RTFM) in DMS. Within the BMP model, the greater density of oxygen vacancy yields a greater overall volume occupied by BMP, thus increasing their probability of overlapping more TM ions into the ferromagnetic domains to enhance ferromagnetism. Zhen et al. [16] used first principle calculations on Co-doped ZnO and observed the exchange coupling mechanism that accounts magnetism with oxygen vacancies.
DMS ZnO has the hexagonal wurtzite structure (direct wide-band gap, Eg ∼ 3.3 eV at 300 K) due to its stability at room temperature and normal atmospheric pressure. The atomic arrangement of the wurtzite structure is comprised of four zinc ions (Zn2+) occupying the corner of a tetrahedral coordinate with one oxygen ion (O2−) located at the center and vice versa (Figure 2a) [20]. The particle size, doping, and co-doping are used to induce the band gap of ZnO [17]. Dietl et al. [1] reported RTFM for DMS for which 3d ions substituted ZnO. However, the nanocrystals of pure ZnO also produce RTFM [21]. Gao et al. [22] suggested oxygen vacancies locating at the surface of ZnO nanoparticles are responsible for RTFM. It is also found that the ZnO nanoparticles had absorbed certain organic molecules to modify the electronic structure to give RTFM without any magnetic impurity ions [21].
(a) Hexagonal wurtzite ZnO unit cell. Density of states (schematic) of Zn1-
From the survey of many theoretical studies, it has been found that a slight doping of TM metal ions is likely ∼5%, induce ferromagnetic ordering that observed at room temperature [21]. Venkatesan et al. [18] postulated on the basis of spin-split donor impurity-band model to observe RTFM in DMS ZnO with 5% of Sc, Ti, V, Fe, Co, or Ni, but not Cr, Mn, or Cu ions. For Cr, Mn, Cu, or Zn, no moment appreciably greater than the experimental uncertainty (<0.1 μB) is observed at room temperature. The basic action in a spintronic device is that the electrons are traveling from a ferromagnetic metal, through a normal metal, to a second ferromagnetic metal. When the magnetizations of the two ferromagnetic metals are in an aligned state, the resistance is low, whereas the resistance is high in the antialigned state. For the light 3d elements, the 3d↑ states lie high in the 2
Wang et al. [19] reported that the Cr, Fe, Co, and Ni dopants in ZnO occupy the Zn sites and couple antiferromagnetically, while Mn exhibits no site preference and distributes uniformly in ZnO lattice. For hexagonal ZnO, the lattice constants are
In rare earth (RE) elements, magnetization appears due to unfilled 4f orbitals leading to higher magnetic moment per atom, though 4f electrons interacted with 5d or 6 s electrons [24], but exhibits weak exchange interaction with other RE ions, which is contrast to TM ions 3d electrons are directly interacted. The RE ion-doped ZnO has ferromagnetism that is induced by p-f hybridization via defect carriers [27]. Compared with 3d TMs, 4f RE ions have larger magnetic moments. The intrinsic defects such as oxygen vacancies play an important role on the magnetic properties of RE/ZnO. However, the exchange interaction by simultaneous doping from TM and RE ions in ZnO is 4f-5d-3d, which is antiferromagnetic when the 5d band is less than half full and the 3d band is more than half full. The first principle calculations revealed that the superexchange interaction between two magnetic Nd ions is mediated by the nonmagnetic O ions responsible for higher magnetic moment of ZnO [28]. This approach of doping RE elements with intrinsic strong magnetic anisotropy and tailoring the coupling between dopants and defects should be a general approach toward stable ferromagnetic order in ZnO nanomaterials. Among RE ions, Sm3+ with five 4f electrons offers a unique possibility to induce the bifunctional properties for RTFM as well as visible luminescence in ZnO, making suitable material in spin transport properties and spin-LEDs [29].
The DMS ZnO materials are synthesized by different methods such as thermal evaporation method [30], chemical vapor deposition [31], sol-gel spin-coating technique [32], spray pyrolysis [33], hydrothermal synthesis [34], solid state reaction [29], coprecipitation method [35], etc.
Recently, a lot of research work has been reported on RE ion-based DMS ZnO [36]. Sun et al. [37] reported La-doped ZnO quantum dots in which luminescent behavior is greatly enhanced by introducing defects and oxygen vacancies (VO). This is due to larger ionic size of La3+ in ZnO lattice that induces stress. However, Bantounas et al. [38] suggested the weak magnetic coupling in Gd/ZnO and the material remain paramagnetic at room temperature. Aravindh et al. [39] gives origin of ferromagnetism in Gd/ZnO in which oxygen vacancies play an important role. Using DFT calculation, it is analyzed that the RE Ce atoms replaced those Zn sites in the wurtzite structure, which is the nearest neighbor to TM/Fe or Co atoms [40]. The 4f electrons in Ce are tightly bound around the nucleus and shielded by 5s2p6d16s2 electrons, leading to strong local spin. For Ce-doped TM/ZnO, the larger ratio of dopant cation to cation radius structure causes more defects, leading to a larger concentration of electrons and holes.
The Zn0.94Fe0.03Ce0.03O (ZFCeO) and Zn0.94Co0.03Ce0.03O (ZCCeO) nanoparticles were synthesized by a sol-gel process [40]. Figure 3a shows the X-ray diffraction (XRD) results for ZFCeO and ZCCeO nanoparticles using Rietveld refinement (space group
(a) XRD pattern of Zn0.94Fe0.03Ce0.03O (ZFCeO) and Zn0.94Co0.03Ce0.03O (ZCCeO) nanoparticles. (b, d) Raman and UV-visible absorption (for energy band calculation) spectra of Zn0.95Ni0.05O (ZNiO), Zn0.91Ni0.05Ce0.04O (ZNiO/Ce), Zn0.95Cu0.05O (ZCuO), and Zn0.91Cu0.05Ce0.04O (ZCuO/Ce) nanoparticles. (c) Photoluminescence spectra for ZnO with Co, Mn, and Fe nanoparticles (adapted from [
where
where
where u is a positional parameter. The volume per unit cell for the hexagonal system is calculated using.
The calculated values of the lattice parameters are
The Zn0.95Ni0.05O (ZNiO), Zn0.91Ni0.05Ce0.04O (ZNiO/Ce), Zn0.95Cu0.05O (ZCuO), and Zn0.91Cu0.05Ce0.04O (ZCuO/Ce) nanoparticles were synthesized by sol-gel process [27]. XRD pattern found wurtzite structure with lattice distortion to perform lattice defects. The average particles size is D = 27, 81, 57 and 159 nm, respectively, measured for ZNiO, ZNiO/Ce, ZCuO, and ZCuO/Ce. The Raman modes observed at room temperature for these pure Ni-, Cu-, and Ce-doped ZnO are shown in Figure 3b. The presence of E2 mode in all samples indicates that the doping does not change the wurtzite phase. It is observed that Ni and Cu doping on ZnO gradually decreases the intensity of E2(high) mode as compared with pure ZnO [22]. But, it is again strengthen with Ce co-doping. This type of change in E2(high) mode with dopant ions might induce structural defects and local lattice distortions of wurtzite lattice [32]. The E2(high)-E2(low) modes indicate oxygen defects or vacancy formation. The peak position of E2(high) mode also changes with Ni, Cu, and Ce doping that is ascribed with the change in the level of oxygen vacancies [33]. The magnetic results also reported low temperature ZFC/FC magnetic measurement that show AF-FM ordering and the doping of Ce ions results to high Tc. At 300 K, the values of Ms(emu g−1) = 0.073, 0.085, 0.053, and 0.132, and at 10 K Ms(emu g−1) = 0.096, 0.198, 0.136, and 0.251, respectively, for ZNiO, ZNiO/Ce, ZCuO, and ZCuO/Ce. The enhancement in the oxygen vacancies and ferromagnetism with Ce doping might depend on mixed valence state Ce3+/Ce4+ ions.
The photoluminescence spectra for Fe (0.15%)-, Co (0.20%)-, and Mn (0.20%)-doped ZnO nanoparticles are given in Figure 3c [41]. Pure ZnO nanoparticles show emission maxima at 385 nm along with blue (424 nm, 468 nm) and green (521 nm) luminescence. Transitions from Zn interstitials to valence band are attributed with blue emission (424 nm). Oxygen vacancies are related with blue (468 nm) and green emission (521 nm). The green emission is understood to be due to the recombination of electrons in singly occupied oxygen vacancies with photoexcited holes in the valence band. The blue emission is caused by two defect levels, either transition from Zni to the valance band or transition from bottom of the conduction band to the interstitial O(Oi).
Figure 3d′ shows UV-visible absorption spectra measured at room temperature for Ni-, Cu-, and Ce-substituted ZnO nanoparticles. The absorption peaks are observed corresponding to violet emission, i.e., ZNiO (409 and 426 nm), ZNiO/Ce (433 nm), ZCuO (407 and 427 nm), and ZCuO/Ce (401 and 429 nm). In order to evaluate the effect of dopant on Ni, Cu, Ce, on ZnO, the energy band gap, Eg, is calculated using the Tauc relation [27] used for a direct transition using:
The ZnO nanowires were synthesized by a thermal evaporation method with 1 atom % Mn doping [44]. Figure 4a is a SEM image of Mn/ZnO nanowires of several micrometer lengths and 70 nm diameters. The reported work given TC to be 437 K from SQUID measurements. The difference of ΔMR is up to 2.5% as the gate voltage changes from −40 to +40 V at T = 1.9 K, which suggests the electric field control of ferromagnetism for realizing spin logic devices.
(a) Scanning electron microscopy (SEM) pattern for ZnO/Mn nanowires. (b) HRTEM for Zn0.92Fe0.05La0.03O nanoparticles. (c) TEM pattern for Zn0.91Ni0.05Ce0.04O nanoparticles. (d) AFM pattern for pure ZnO (adapted from [
DMSs Zn0.92Fe0.05La0.03O (ZFLaO53) nanoparticles were synthesized by sol-gel process [21]. The value of nanoparticles size is 99 nm. The lattice spacing is calculated from high-resolution transmission electron microscopy (HRTEM) images (Figure 4b), which show that the distorted lattice has an enhanced interplanar spacing
The magnetic properties of Zn1-
(a1–a4) partial spin DOS of TM 3d and O 2p in Zn24TM4O28 supercell. (b) DOS of Zn46O48Gd2 and Zn46O47Gd2 supercell. (c, c′) Total and projected DOS of Zn51VZnO54Nd2 nanowire. Fermi level spin-density isosurface (green dotted), Zn(blue), O(red), and Nd(green spheres) (adapted from [
Figure 5b shows the first-principle calculation for Zn46O48Gd2 and Zn46O47Gd2 nanowires with and without oxygen vacancies, VO [39]. The spin-up and spin-down DOSs of doped nanowire are significantly different from that of the pristine nanowire. The majority Gd f states (spin-up) that are located well below the valence band maximum are fully occupied. However, the minority unoccupied Gd f states are localized in the vicinity of the Fermi level. The Gd d states in the conduction band overlap with the Gd f states. The hybridization of Gd f states with the states of the host material occurs at the Fermi level. By introducing oxygen vacancies, the Gd f state near the Fermi energy becomes partially occupied by donor electrons. Consequently, the carrier concentration around VO is increased, which mediates the interaction between the s (mostly from Zn) and f electrons. This is evident from the DOS, as the s-f coupling is more prominent than p-f and f-f couplings. For such case, the carrier involved long-range ferromagnetic order to determine the exchange interactions in DMS ZnO. Moreover for these Gd-doped ZnO, oxygen vacancies donate two electrons to the system, mediating the ferromagnetic exchange, and hence, the s-f coupling is more prominent than other mechanisms.
In Figure 5c, the origin of the giant magnetic moment and anisotropy at atomic level is performed by spin-polarized DFT calculations on Zn52O54Nd2 nanowire model using spin density (Δρ = ρ↑ − ρ↓) and the projection of DOS onto the O-2p and Nd-4f orbitals [28]. The total magnetic moment is high as 6 μB calculated from supercell and 3 μB per unit cell, and the two Nd atoms are ferromagnetically coupled. It is found that the magnetism mainly comes from the 4f electrons of Nd ions with the local spin moment of ∼3 μB, and both Zn and O atoms have nearly zero spin contribution. Moreover, significant hybridization is observed between Nd 4f and O 2p orbitals, which leads to the superexchange interaction between two magnetic Nd ions mediated by the nonmagnetic O ions. Both O and Zn vacancies are considered, and it is found that VZn can enhance the magnetism of about 1 μB as compared with defect-free system. This enhanced magnetism mainly comes from the unsaturated 2p orbitals of the surrounding O atoms.
The Zn0.94Cr0.06O nanorods were synthesized by a radio frequency magnetron sputtering deposition technique at different substrate temperatures [46]. The Cr K-edge X-ray absorption near-edge structure and X-ray photoelectron spectroscopy (XPS) results revealed that the Cr3+ ions are located at the substitutional Zn sites. The magnetization versus the magnetic field (M-H) loops of Zn0.94Cr0.06O nanorods measured at room temperature is shown in Figure 6a. The moment per Cr atom increases with the increasing substrate temperature. The sample prepared at room temperature has a net moment of 0.76 μB/Cr. With increasing substrate temperature to 650°C, the value of magnetic moment shows a remarkable increase to 1.16 μB/Cr. The coercive field, Hc, of Zn0.94Cr0.06O nanorod grown at room temperatures, 300, 500, and 650°C, are around 104, 42, 53, and 82 Oe, respectively.
(a) M-H hysteresis of Zn0.94Cr0.06O nanorods. SQUID measurements: Magnetic moment (b) with temperature (c) with applied field, for ZnO/Mn nanowires. (d) M-H plots for ZnO/(Mn, Dy) nanoparticles (adapted from [
The Mn(1 atom%)-doped ZnO nanowires were synthesized by a gas phase surface diffusion process using MBE system [44]. Figure 6c shows the M-H hysteresis loops measured at T = 10, 100, 200, 300, and 350 K for an assembly of Mn-doped ZnO nanowires. The extracted Ms is 2.2 μB/Mn ion at 10 K and reduces to 1.4 μB/Mn ion at 300 K. Both values are smaller than the theoretical value of 5 μB/Mn ion of Mn2+ state [1]. The temperature-dependent magnetization (Figure 6b) via ZFC and FC at H = 100 Oe shows a typical FM behavior while no intersection is observed in the temperature region of 10–400 K, which reaffirms that Tc is higher than 400 K. However, these FC/ZFC curves show the blocking temperature at Tb = 90 K. The existence of the blocking temperature may result from intrinsic defects, such as oxygen vacancies [47], which contribute weak intrinsic ferromagnetism. The bifurcation begins to increase as the temperature goes below 100 K, and the effect of the external magnetic field starts to overcome the thermal fluctuation and dominate the overall magnetization when the temperature is lower than 100 K.
Figure 6d shows the magnetic results at room temperature with simultaneous doping of Mn and Dy in ZnO nanoparticles prepared by sol–gel process (Mn = 0 and 2% and Dy = 0, 2, 4, and 6%) [24]. The M-H results show that as doping concentration of Dy is increased, magnetic behavior changes from weak ferromagnetic/superparamagnetic to ferromagnetic states. The observed magnetic behavior is linked with oxygen vacancies as determined with EXAFS and PL measurements. The oxygen vacancy-mediated exchange interaction between the Dy3+ ions is due to the formation of BMPs.
The RTFM is enhanced with Sm doping into ZnO is given by M-H hysteresis at room temperature (Figure 7a) [29]. It infers that ferromagnetism is intrinsic and formed due to the percolation of BMPs. These BMPs are made up with magnetic cations and defect carrier. A very weak ferromagnetism is observed in pristine ZnO, which is the effect of Zni and/or oxygen vacancy defects rather Zn vacancies (VZn). Because the formation energy of VZn is too high, it is not preferably formed in ZnO [48].
(a) M-H hysteresis for ZnO/Sm nanoparticles. (b) M-H hysteresis for ZnO/Nd. (c) SQUID M(T) behavior for ZnO/Gd (adopted from [
The pure and Nd-doped ZnO nanoparticles were synthesized by the coprecipitation method, and the magnetic results are shown by M-H hysteresis (Figure 7b) [42]. All the M-H hysteresis exhibited weak ferromagnetism at room temperature. However, the magnetization increases with increasing Nd3+ concentration. The value of saturation magnetization, MS, is (emu g−1) = 0.041, 0.051, and 0.069, respectively, for Zn0.97Nd0.03O, Zn0.94Nd0.06O, and Zn0.91Nd0.09O. The concentration of oxygen vacancies has a major role in mediating FM exchange interaction among Nd3+ ions. It is revealed that O vacancies and Zn interstitials are generated with an increase in Nd3+ doping to induce long-range ferromagnetism consistent with the BMP model. Moreover, the s-f coupling between the RE ions (f) and the ZnO host(s) states contributed ferromagnetism of DMSs [14]. The coercivity is also increased with Nd3+ concentration.
Ney et al. [43] reported that for small doping concentrations (1.3% Gd), a large fraction of the Gd atoms is substitutional on Zn lattice sites within wurtzite structure. The magnetic behavior is purely paramagnetic with magnetic moment 7 μB
The Zn1-
(a) M-H hysteresis at room temperature for Zn1-
Figure 8b shows Fe 2p XPS spectra in a binding energy 707–728 eV of Zn0.94Fe0.03Ce0.03O (ZFCeO) nanoparticles to find their contribution into ferromagnetism [40]. The Fe2+ and Fe3+ 2p3/2 peaks always show satellite peaks at 6 and 8 eV above the principal peaks at 709.5 and 711.2 eV, respectively. The satellite peak is found in energy region of 6–8 eV above 2p3/2 principal peak, which indicates that ZFCeO DMS has Fe coexisting in both Fe2+ and Fe3+ states. For this, a multiple fitting of Fe 2p peaks with satellites show peaks corresponding to Fe2+ (709.60 and 722.51 eV) and Fe3+ (710.82 and 723.97 eV). It indicates that the Fe ions have mixed valences of +2 and + 3. The peaks related with 2p3/2 709.89 eV and 2p1/2 723.35 eV are also observed. Therefore, it is found that the Fe exists in mixed Fe2+ and Fe3+ oxidation states to give RTFM due to Fe2+-Fe3+ transitions via oxygen vacancies.
The magnetic results for Zn0.95Fe0.05O (ZFO5) and Zn0.92Fe0.05La0.03O (ZFLaO53) with Ms(emu g−1) = 0.328 and 0.044 and Mr(emu g−1) = 0.0083 and 0.0064 with Hc(Oe) = 12 and 144, respectively, are reported. The origin of observed magnetism at room temperature for La-doped ZFO5 is described via ZFC and FC magnetization SQUID measurement. Figure 8c shows temperature-dependent ZFC and FC measurement with H = 500 Oe. The superimposition of ZFC/FC plots between 150 and 300 K, as well as their clear separation at low temperature with blocking temperature, TB is observed. The observed TB might correspond with Néel temperature, TN (∼42 K) of AF [52]. For more detail, M-H hysteresis is also measured at 200, 100, 50, and 10 K (Figure 8c′). The values Ms and Mr are enhanced with temperature when going from 300 to 10 K. This is due to the exchange interaction from AF to FM states. It is also shown that for 200–50 K, Hc varies so slowly, but at 10 K, it abruptly increased to 117 Oe, which is smaller than 144 Oe that is observed at room temperature. It means after AF transition, there is some possibility of FM clustered growth in ZFLaO sample [53]. The localization of electrons in magnetic clusters leads to develop high-spin and low-spin intersite electronic transitions. These magnetic clusters may also result from magnetic polarons [54].
Figure 9a shows the M-H hysteresis for Zn0.95Co0.05O (ZCO5), Zn0.92Co0.05La0.03O (ZCLO53), and Zn0.92Co0.05Gd0.03O (ZCGO53) nanostructure, measured at room temperature [36]. The pure ZCO5 shows weak ferromagnetism of Ms(emu g−1) = 0.354 and Mr(emu g−1) = 0.0276 with Hc(Oe) = 40 Oe. However, the La- and Gd-doped ZCO5 result into paramagnetic-type behavior. The weak ferromagnetism in ZCO5 exists due to antiferromagnetic, AF interactions among Co2+ ions [41, 55]. The AF coupling between Co impurities is favored when Co atoms are separated by more than a ZnO unit. While the ferromagnetic coupling is stable if AF interaction in neighboring Co–Co ions falling into contour of BMPs. However, the observed paramagnetism in La- and Gd-doped ZCO5 is related with AF interaction establishment following 4f-5d-3d transition in Co and RE ions, suggested by Singh et al. [56].
(a) M-H hysteresis for Co-, La-, and Gd-doped ZnO nanoparticles, measured at room temperature. (b) M(T) and M(H) (inset) for Zn0.996Co0.004O (ZCO04) nanoparticles. (b′ and b′′) XPS spectra for Co 2p and O 1 s. (c) Temperature-dependent
The Zn0.996Co0.004O (ZCO04) nanoparticles synthesized with sol–gel process for which free-charge carriers and oxygen vacancies might induce long-range ferromagnetic ordering [15]. The XRD pattern results into wurtzite structure of ZCO04. The ZCO04 crystalline product has nanorod formation with D(nm) = 23 ± 3 and L(nm) = 57 ± 5. Figure 9b (inset) showed the RTFM of Ms (emu g−1) 0.0062 and Mr (emu g−1) = 0.0038 with Hc = 54 Oe. However, the pure ZnO nanorods are diamagnetic [50]. Xu et al. [57] reported RTFM with higher surface-to-volume ratio of nanostructure, which contribute large amount of surface oxygen vacancies defects. It is expected that the RTFM is attributed via exchange interactions among unpaired electron spins arising from either vacancies or surface defects, which is explained on the basis of donor impurity band exchange model form BMPs [58]. It is theoretically investigated that the oxygen vacancies have remarkable change in band structure of host oxides to induce ferromagnetism [59]. For this case of BMPs, the electrons are locally trapped by oxygen vacancies, with the trapped electron occupying an orbital overlapping with the
To evaluate the origin of RTFM of ZCO04 nanoparticles, the temperature-dependent magnetization is given in Figure 9b via ZFC and FC at H = 500 Oe. The separation between ZFC and FC starts increasing with reducing temperature from 300 to 5 K which indicates antiferromagnetic interactions converted to ferromagnetic state. The absence of blocking temperature in ZFC might indicate long-range antiferromagnetism without any cluster growth. The exchange interactions between neighboring magnetic ions mediated by an F-center form a BMP contributing long-range ferromagnetism. At 10 K, the magnetic hysteresis is also shown in the inset of Figure 9b with Ms(emu g−1) = 0.0154 and Mr(emu g−1) = 0.002 with Hc(Oe) = 93.
Figures 9b′,b′′ shows the XPS spectra for Co 2p and O 1 s of Zn0.996Co0.004O (ZCO04) nanoparticles. For Co 2p, the doublet is the spin-orbit coupling (2p3/2 and 2p1/2) given in Figure 9b′. The values of binding energy, Co 2p3/2 ∼ 780.019 eV, 2p1/2 ∼ 795.51 eV, and ΔE ∼ 15.51 eV, and satellite peak (S) ∼ 785.48 eV are observed. The binding energies of Co 2p3/2 and 2p1/2 indicate that the Co ions exist either in +3 or + 2 valence states [60]. The difference ΔE of binding energy among Co 2p3/2 and 2p1/2 levels corresponds well with Co2+ that is homogeneously surrounded by oxygen in tetrahedral coordination [61]. However, the peak S is found in the energy region of 6–8 eV above the principle peak Co 2p3/2 and the value of S ∼ 6 eV. It indicates the formation of multiple coordinations, i.e., tetrahedral or octahedral Co2+ ions. For more clarification, Co 2p peaks shown by octahedral Co2+ (
To find defects/vacancies in ZCO04, the O 1 s spectra is shown in Figure 9b′′, which deconvoluted into three peaks (Oa, Ob, Oc) [15]. The peak located on low-binding energy side, Oa ∼ 528.79 eV, is attributed with O2− ions in wurtzite structure. This Oa of O 1 s is associated with Zn-O bonds. The Ob peak at 531.19 eV is associated with O2− ions in the oxygen-deficient regions within the ZnO matrix, which indicate defect formation. The Oc peak at 532.16 eV is attributed to chemisorbed oxygen on the surface of the ZnO.
The temperature-dependent real, χ′(T), and imaginary, χ′′(T), components of the AC magnetic susceptibility of Ce-doped ZFO nanoparticles at frequencies 100, 300, 500, and 1000 Hz are shown in Figure 9c [40]. The frequency-independent peak maxima of χ′ correspond to magnetic phase transition into an AF state with TN = 56 K is observed. A slight dispersion in the χ′(T) after the peak maxima is also observed. It indicates the existence of certain spin glass, ferromagnetic clusters and cluster glass magnetic type states [62]. However, the peak of χ′′(T) increases with decreasing frequency. This is qualitatively different from the behavior of most spin glasses in which we expect an increase of the peak magnitude with increasing frequency. Thus, the obtained AC magnetization data supports the formation of the AF DMS materials with a certain cluster glass formation.
The spintronic materials are the ferromagnetic oxide semiconductors for which both charge and spin degrees of freedom exist, but with weak ferromagnetism and small coercivity, there is a limitation in practical applications. Thus, these DMSs are widely characterized for the development of semiconductor devices, which create a new dimensionality to control and achieve high TC ferromagnetism. The first principle calculation revealed that the Cr, Fe, Co, and Ni dopants in ZnO prefer to occupy surface sites instead of bulk sites, while Mn exhibits no site preference and distributes uniformly in ZnO. In addition, the TM ions in ZnO are intrinsically AF because their substitution at Zn sites does not introduce any extra carriers. The interaction among localized spins on the TM ions and delocalized carrier electrons originating from the O vacancies is responsible for the required magnetic transition. The doping RE ions with intrinsic strong magnetic anisotropy and tailoring the coupling between dopants and defects should have a general approach toward a stable ferromagnetic order in DMS ZnO. The observed magnetism of DMS ZnO for both TM and RE ions might result with BMPs in oxygen vacancies.
This research work is financially supported by CSIR India, for giving a Senior Research Associate fellowship (Pool Scientist; letter No. B-12287).
In general, traditional mechanics and robotics have been the fundamental foundation for artificial hand/manipulator design. As a result, robotic and electro-mechanical manipulators lack the dexterity and anthropomorphism that comes from considering the physiological and biological aspects inherent in the human hand. This chapter looks at three key biomechanical inspired principles that directly influence artificial hand function and dexterity. These are:
Joint stabilization
Tendon structures
Tendon excursion
Figure 1 below gives an example of one potential anthropomorphic manipulator employing the above-mentioned principles.
Anthropomorphic approach toward artificial hand design.
The very nature of human anatomy presents a unique challenge in the replication of the human hand. Mechanical engineering approaches rely on the expectation that the artificial hand design approach is quantifiable. The following reasons provided by [1] providing insight as to why mimicking the human body is not a straight forward process.
The boundaries of ligaments, tendons, and muscles are not easily definable.
Ligament, tendon, and muscle insertions differ from person to person.
Some tendons and ligaments possess non-linear characteristics that make measurement inaccurate.
Some human tissues have no measurable resting position.
For these reasons quantifiable methods are hard to realize. In reality, working in the space of anthropomorphic manipulator design becomes subject to engineer/designer best practice or previously knowledge. This reality often lends to this chapter, will express the value of a paradigm shift by exploring the biomechanical and physiological design principles that contribute to anthropomorphic manipulator design. The chapter concludes with a set of defined grasps that are a direct result of the design paradigm shift.
To this point in time, the human hand has been the “golden standard” of function, versatility and dexterity in grasping tasks as proven by the ongoing attempts to artificially recreate it [2]. Mimicking the qualities and properties of the human hand has always been a lofty and hard to realize goal, however, due to the current technological advancements of our age we are closer to achieve it than ever before. For these reasons this research is progressive, of great value and exciting. The ability of an artificial hand to function in an unmodified human environment directly relates to its capacity to function like the human hand. Traditional approaches to artificial hand design have been susceptible to ignore and/or omit the organic biological features of the human anatomy that are essential to hand function. Recent trends are tending toward artificial hand design that includes multidisciplinary viewpoints that consider more than just traditional mechanical principles.
In artificial hand design it is important to consider the Degrees of Freedom (DoF) the hand possesses. The DoF of a system is the number of independent parameters that define its configuration. The reviews [3, 4] describe some of the available electromechanical hands currently on the market [5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16]. Each review supports the general view that as the DoF of an artificial hand increases so does its anthropomorphism and function. Research into modeling the human hand claims that 24 DoF accurately represents the posture and movement of the human hand (including the wrist) [17]. There is consensus around this point with most literature agreeing that the human hand has between 21 and 26 DoF depending on whether you include or exclude the wrist [18]. The difference in DoF between studies can also be attributed to the DoF associated with the carpal bones of the hand and whether or not they are included.
Latter attempts at hand design employ the idea of bio-mimicry or an approach that is human inspired. The focus of these types of hands are on the tendinous structures actuating the hand and their synergies with ligaments, joints and actuators [4] approaches artificial hand design by mimicking the human bones and joints of the hand. Naturally, this makes for an esthetically pleasing design. In contrast to this approach a bulky unnatural looking wrist was implemented in the design and was recognized as required improvement [19] builds upon the idea of biomimicry by developing artificial tendinous structures that mimic the human hand and by improving the design of artificial thumbs. Their approach was esthetically pleasing and functioned well. Within their approach there was a new idea to incorporate joint capsules at each joint. Further studies [1] in the same year presented work on mimicking the mechanics and material properties possessed by the human hand and incorporating them into working artificial prototypes. The work presented herein emphasis the synergistic tendon networks, bone configuration, bone orientation, and joint development that are required in artificial hand design. It is expected that these types of approaches will increase in popularity and improve as the research climate and time allows.
The following section addresses the connection that exists between hand function and artificial ligament design. Firstly, it is important to understand how the bones of the human hand lay a foundation for the ligaments to layer on. The bones on which hand ligaments are inserted provide ligament pathways on which joint stabilization relies. Incorrect placement of ligaments severely effects the way a bone moves, transfers force and thus can drastically reduce the function of a hand. The bones of the human hand are essential to hand function, however, without the stabilizing ligaments and tendons they are of little use. Each joint of the hand has a series of ligaments that limit undesirable movement and protect the hand against excessive force. Hence, joint stabilization by virtue of the biological layers present in the human hand are integral to hand function.
Joint stabilization is integral to hand function; therefore, it is important to unpack the role and location of the ligaments responsible for finger joint stabilization and movement. In particular, the following section describes and defines the collateral ligament, the volar plate, and the annular ligament. Each ligament is then put in context by applying them to the design shown in Figure 1. We begin by explaining the collateral ligament and follow that by exploring both the volar plate and annular ligament.
This section describes the artificial collateral ligament by defining suitable insertion locations of the ligament for each phalanx of the hand that optimizes the movement between adjacent bones. The collateral ligament acts as the primary stabilizer of phalanx joints and is responsible for connecting bones. Taking the index finger as an example we name and orient the bones of the finger in Figure 2.
Index finger bone configuration and orientation.
Determining the insertion positions of the collateral ligament on the artificial proximal phalanx (Figure 3) is defined by two features. These features are: The phalanx length, LP, and the centroid, c. the phalanx length, LP is the summation of LBC and LHC while the centroid is found through the CAD software SOLIDWORKS using the mass property evaluation.
Collateral ligament insertion points.
The coordinate system is established on the centroid of the phalanx. The phalanx length and the location of the centroid determine the ligament insertion locations IH and IB. LB and LH define the limits that bound the insertion locations. The coordination of the head insertion IH and base insertion IB are given by
and
Where
Condition (1) is expressed by
Condition (2) is expressed by
Condition (3) is expressed by
For ease of application Table 1 below outlines the conditions applicable to both the head and base of each phalanx.
Metacarpal | Proximal | Intermediate | Distal | |||||
---|---|---|---|---|---|---|---|---|
Head | Base | Head | Base | Head | Base | Head | Base | |
Condition 1 | x | x | ||||||
Condition 2 | x | |||||||
Condition 3 | x | x | x |
Insertion location conditions assigned to each phalanx.
Any major variance from the values and conditions listed in this table are detrimental to the joints range of motion and its stabilization. Through this method collateral ligament insertion is generalized for all artificial hand design. The geometry of the bones in the hand compliment the collateral ligaments at each bone-ligament interface. Collateral ligament placement determines joint function and therefore hand function. Bone surfaces are congruent and possess depressions or protuberances that give clues to ligament insertion locations. The bone surfaces also permit human like range of motion at each joint. Figure 4 shows the resulting range of motion,
MCP and PIP joints including their ranges of motion.
The resulting range of motion of the artificial MCP and PIP joints sit within two degrees measurement of their natural human counterparts, meaning digit function and dexterity are maximized. The collateral ligaments are vitally important to hand function, however, as recognized at the beginning of this section there are three main ligaments responsible for joint stabilization. The next section will look at the remaining ligaments which are the volar plate and the annular ligament.
The collateral ligament represents one of the three stabilizing ligaments of the joints of the fingers. This section will describe the role and placement of the volar plate and the annular ligaments with respect to the previously described artificial collateral ligament. The combination of these three ligaments make up the joints of the finger and work in harmony to provide the function and dexterity of the hand. The collateral ligament provides lateral stability and is represented in the black box Figure 5. The insertions are achieved via an extruded cut through the proximal phalanx and abide by the conditions stated in Table 1.
The stabilizing ligaments of the MCP joint.
In synergy with the collateral ligament is the volar plate. The volar plate functions to protect the fingers against hyperextension with its insertion points highlighted in the red boxes of Figure 5. These insertions are found on the palmar side of the metacarpal head and the palmar side proximal base. A properly function volar plate limits rotation about the joint and absorbs excessive force placed on the joint in unwanted directions. It can most easily be thought of as a limiter of unwanted movement.
An artificial sagittal band is incorporated into the design of the artificial hand (yellow box of Figure 5). Although the sagittal band and the collateral ligament share insertion locations their functions are very different. The sagittal band creates a pathway for the extensor tendon responsible for force transferral and finger extension. It also eliminates transverse tendon slippage. In addition to the sagittal band the hand incorporates annular ligaments. These ligaments share insertions with the volar plate. These ligaments are light in color but outlined by blue boxes in Figure 5. The combination of these ligaments allows abduction/adduction and flexion/extension at the MCP joint. The lateral movement in the MCP joint is limited through the placement and angle of the collateral ligaments while rotation is limited by the volar plate. If designed correctly the congruence provided by the geometry of the bones allows smooth movement through the flexion and extension movements of the joint. The concave/convex relationship between the bones also allows abduction and adduction.
The PIP joint (Figure 6) connects the intermediate and proximal phalanges. The PIP joint on its own is a planar manipulator capable of only flexion and extension and just like the MCP is stabilized by the collateral ligament (black box Figure 6).
The stabilizing ligaments of the PIP joint.
The palmar side of the PIP joint houses the volar ligament. The insertion points of this ligament are outlined in Figure 6 by red boxes. This ligament functions to protect the joint from hyperextension and shares an insertion with the annular pulleys. The PIP joint provides simple planar movement that allows the hand to grasp and manipulate objects with precision and force. Bone geometry and size naturally limits the unwanted motion inherent in the joint, allowing a natural moving and anthropomorphic esthetic.
The final joint of the finger is the distal interphalangeal (DIP) joint. This joint connects the intermediate and distal phalanges. The DIP joint is a copy of the PIP joint described above.
The thumb has traditionally been an incredibly hard appendage to mimic and replicate artificially. On its own the thumb is the single largest contributor to hand function and dexterity. It is what sets humans apart from the rest of the animal kingdom. With these sentiments in mind it is important to consider the biomechanical makeup of the thumb and incorporate it within the design process.
The Carpometacarpal (CMC) joint of the thumb provides the hand with complex multi-axial movement. The reason for this is the complex geometry of the trapezium bone and its relationship with the metacarpal of the thumb. Artificial ligaments provide stabilization for the CMC joint of the thumb on the artificial hand. The five artificial ligaments are based on the human counterparts and are described below.
The Anterior Oblique ligament (Figure 7) is the first of the stabilizing ligaments of the thumb. T1 represents the trapezium bone while M1 indicates the metacarpal bone of the thumb. The anterior oblique ligament functions to limit unwanted movement that would cause the CMC dislocation. The ligament connects the metacarpal bone and trapezium bones. The insertion points are highlighted in red.
The anterior oblique ligament of the CMC joint. (palmar view).
In addition to the anterior oblique ligament there is the second stabilizing ligament shown in Figure 8. This ligaments function is to stabilize the joint and to limit the movement between the thumb and the palm. As shown, this ligament is inserted near the base of the index metacarpal and the thumb metacarpal (insertions are highlighted in red).
CMC joint and its artificial ligaments (dorsal view).
Ligaments three, four and five are artificial replications of the dorsal deltoid shaped ligaments. These are also stabilizing ligaments and are named the dorsal radial ligament, the dorsal central ligament and the posterior oblique ligament. These ligaments share an insertion on the trapezium bone and are connected the surface of the metacarpal bone of the thumb. Each ligament inserts at different points along the metacarpal surface to provide the thumb with a considerable range of motion. All three ligaments contribute to allowing and restricting of movement within their respective three-dimensional spaces. These three ligaments are shown Figure 9 and are highlighted in red.
The CMC joint and its artificial dorsal deltoid shaped ligaments (palmar/lateral view).
The previously mentioned ligaments work in synergy to stabilize the thumb joint and create the base on which the CMC joint relies for function. Along with the complex geometry of the bones at the CMC join these ligaments are responsible for the complex multi-axial movement of the thumb.
This and previous sections have conveyed one possible approach to joint stabilization in artificial anthropomorphic manipulators. The following section will now move into the actuation of these joints by tendons.
Movement of the human skeleton originates from the transferral of forces between it and its associated tendon/muscle. This is especially important for understanding hand movement as each minute movement can be attributed to the actuation of a muscle or tendon. This section approaches the biomimicry of this process by separating the complex movement of the hand into two. Firstly, the tendons that control the fingers and secondly, the tendons that control the thumb.
The finger has two primary movements and two minor movements. The primary movements are flexion and extension. The extensor tendon straightens the finger while the flexor tendons bend the finger. The minor movements of the finger are called adduction and abduction. These movements are induced by the contraction and elongation of the palmar interossei muscles. In order to understand the movements of these tendons and how they transfer force into the bones we need to look at their insertion points. We start by outlining the insertions of the extensor tendon. The first insertion is on the distal phalanx and the second is on the intermediate phalanx. These positions are highlighted in the red boxes in Figure 10. After its insertion on the intermediate phalanx the extensor tendon splits. This split helps to engage the finger in abduction and adduction. Artificial sagittal bands control the extensor tendon pathway as shown in Figure 10 (white boxes) and prevent transverse slipping of the tendon. The flexion of the fingers in the hand are actuated by the Flexor Digitorum Profundus (FDP) tendon.
The pathway and insertion points of the extensor tendon. (Dorsal view).
These FDP tendons traverse the palmar side of the hand and insert at the distal phalanx of each finger. The following section will outline the tendons of the thumb responsible for the thumb function, movement and anthropomorphism.
The thumb is a masterpiece of mechanical complexity and is capable of producing complex multi-axial movement. It is essential to understand its basic anatomy and function. Four main tendons are responsible for this movement.
The Abductor Pollicis Longus (APL).
The Flexor Pollicis Longus (FPL).
The Extensor Pollicis Brevis (EPB).
The Extensor Pollicis Longus (EPL).
The design and function of these tendons are described in the next section.
The artificial FPL shown in Figure 11 (left-hand side) is channeled through the carpal tunnel and directed toward the base of the thumbs distal phalanx where it is inserted. The APL also shown in Figure 11 (right-hand side) inserts into the thumbs metacarpal on the radial side and provides the thumb with abduction at the CMC joint.
The artificial FPL and APL insertions of the thumb. (Palmar view).
Figure 12 (red boxes) below shows the insertion points of the EPB and the EPL. The EPB inserts into the thumbs proximal phalanx. This tendon is responsible for extension and abduction of the thumb at the CMC joint. The EPL is channeled through the rear of thumb and inserts at the tip distal phalanx. The EPL allows complete thumb extension whereas the PB can only provide partial extension.
The artificial EPL and EPB insertions of the thumb.
It is through a complex synergy that the above-mentioned tendons provide the complex multi axial movement including flexion, extension, and circumduction.
Tendon excursion is often thought of as a limiting factor in electromechanical hand design. Tendon excursion is the displacement an artificial tendon experiences when the associated muscle/actuator contracts and induces tensile forces on it. Tendon excursion is can effect hand movement negatively.
For example, wrist movement induces tendon excursion on all the FDP tendons of the fingers. This can be seen in the natural flexion of the fingers during wrist extension and their natural extension during wrist flexion (Figure 13).
Tendon excursion in the FDP of each finger induced by wrist movement.
The angles
Where,
The effect of tendon excursion can be quantified by measuring the elongation/displacement flexor tendons while the wrist is moving. After measuring the artificial FDP displacement each finger was displaced by over 10 mm. A 10 mm displacement represents more than 50 percent of the fingers total motion, thus, tendon excursion cannot be ignored. In a similar manner the effect of tendon excursion on the thumb is too large to ignore, therefore we look to the following section as one solution to manage the unwanted effects of tendon excursion.
The source of displacement for each artificial tendon stems from its actuator, therefore, solutions can be found by adjusting the tendons actuator to account for the unwanted tendon excursion. Let us assume an anthropomorphic manipulator we have a series of four servomotors actuating four artificial FDP tendons. A servomotor correction factor can be implemented within the control scheme which considers the wrist angle. The correction factor allows the wrist induced excursion to meet equilibrium with the individual finger servomotors during wrist movement using:
Where,
The excursion correction angles displayed in Figure 14 shows how servomotor angles change with respect to wrist position.
Servomotor correction angles for wrist movement induced tendon excursion in the fingers.
Including these types of correction tables into the control schemes of all electromechanical anthropomorphic hands is trivial but important for hand function and control.
Artificial tendons provide movement in the hand. These tendons induce rotations about the joints of the digits. Assignments are shown in Table 2.
Digit | Tendon label | Digit movement |
---|---|---|
Thumb | 1 and 6 | Tendon 1 is for flexion and extension |
Index finger | 2 | Tendon 6 is for opposition and reposition |
Middle finger | 3 | Flexion and extension |
Ring finger | 4 | Flexion and extension |
Little finger | 5 | Flexion and extension |
Tendon arrangement for finger actuation.
Figure 15 shows the joint angles of each phalanx with respect to each previous joint. Using the relationship between tendon displacement and joint angles we can define a grasp type.
Artificial hand finger tendon network and the associated joint angles.
For simple tendon networks composed of 3 pulleys in a digit, the tendon extension,
Where,
The extensions shown above can be used to determine grasp strength. Each tendon tendons is connected to individual servomotors to actuate digit movement. The artificial hand has six servomotors, one for each finger and two for the thumb. A grasp type in this context is defined as
Where,
when
A physical representation of Eq. (9) is shown in the working principle of finger actuation displayed below in Figure 16.
Digit extension and flexion due to the servo motor angle.
In continuation of the rule established above Figure 17 below demonstrates the four common grasp types and their definitions. The grasps shown are:
Palmar pinch.
Tripod grasp.
Power grasp sphere (3 finger).
Power grasp.
Grasp types performed by the artificial hand and their definitions.
In the case of objects where one of its dimensions are much larger than the other a tip pinch grasp or a power grasp is appropriate (Figure 18).
Tip pinch and power grasp examples and definitions.
This chapter has outlined artificial anthropomorphic manipulator design by providing potential solutions to the challenges of mimicking the biomechanics of the human hand. Our current reality is that mechanical design considerations have been prioritized over bio-mimicry, this chapter approaches this challenge with a perspective that is refreshing and valuable. The biomechanical concepts explored in this chapter are vital in the design of artificial anthropomorphic manipulators. These biomechanical concepts contribute to the function, esthetics and performance of the manipulator and should not be ignored. It is expected that as joint stabilization, tendon structures and tendon excursion become prioritized that we will reach a level of anthropomorphism not realized in any other period in the history of artificial hand design.
MCP | Metacarpophalangeal |
PIP | Proximal Interphalangeal |
DoF | Degrees of Freedom |
DIP | Distal Interphalangeal |
CMC | Carpometacarpal |
FDP | Flexor Digitorum Profundus |
APL | Abductor Policis Longus |
FPL | Flexor Policis Longus |
EPL | Extensor Policis Longus |
EPB | Extensor Policis Brevis |
Lp | Phalanx length |
IH | Head insertion |
IB | Base insertion |
LHC | Head to centroid length |
LBC | Base to centroid length |
LB | Base Length |
LH | Head Length |
LBI | Percentage of phalanx length |
LHI | Percentage of phalanx length |
ei | Tendon extension |
ωf | Wrist flexion |
ωe | Wrist extension |
ωfmax | Maximum wrist flexion |
ωemax | Maximum wrist extension |
φi | Servo horn angle |
φimax | Maximum servo horn angle |
rij | radius of pulley |
R | servo horn radius |
T1 | Trapezium bone |
M1 | metacarpal bone |
e | tendon displacement |
c | centroid/force-form closure |
d | displacement |
i | Index finger |
m | Middle finger |
r | Ring finger |
l | Little finger |
S1–S4 | Servo motors |
IntechOpen - where academia and industry create content with global impact
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\n\nSara Uhac, COO
\n\nSara Uhac was appointed Managing Director of IntechOpen at the beginning of 2014. She directs and controls the company’s operations. Sara joined IntechOpen in 2010 as Head of Journal Publishing, a new strategically underdeveloped department at that time. After obtaining a Master's degree in Media Management, she completed her Ph.D. at the University of Lugano, Switzerland. She holds a BA in Financial Market Management from the Bocconi University in Milan, Italy, where she started her career in the American publishing house Condé Nast and further collaborated with the UK-based publishing company Time Out. Sara was awarded a professional degree in Publishing from Yale University (2012). She is a member of the professional branch association of "Publishers, Designers and Graphic Artists" at the Croatian Chamber of Commerce.
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\n\nAdrian Assad De Marco joined the company as a Director in 2017. With his extensive experience in management, acquired while working for regional and global leaders, he took over direction and control of all the company's publishing processes. Adrian holds a degree in Economy and Management from the University of Zagreb, School of Economics, Croatia. A former sportsman, he continually strives to develop his skills through professional courses and specializations such as NLP (Neuro-linguistic programming).
\n\nDr Alex Lazinica
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He is a member of the Turkish Biochemical Society, American Chemical Society, and German Genetics society. Dr. Ekinci published around ninety scientific papers, reviews and book chapters, and presented several conferences to scientists. He has received numerous publication awards from several scientific councils. 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He worked on the structure-function relationships of glycoconjugates and his main project was the investigations on the biological roles of the de-N-glycosylation enzymes (Endo-N-acetyl-β-D-glucosaminidase and peptide-N4-(N-acetyl-β-glucosaminyl) asparagine amidase). From 2002 he contributes to the understanding of the Blood-brain barrier functioning using proteomics approaches. He has published more than 70 papers. 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Since then, he has been working as an Adjunct Professor in the same Department at the University of Pavia. His research activity during the first years was primarily focused on the purification and structural characterization of enzymes from animal and plant sources. During this period, Prof. Iadarola familiarized himself with the conventional techniques used in column chromatography, spectrophotometry, manual Edman degradation, and electrophoresis). Since 1995, he has been working on: i) the determination in biological fluids (serum, urine, bronchoalveolar lavage, sputum) of proteolytic activities involved in the degradation processes of connective tissue matrix, and ii) on the identification of biological markers of lung diseases. In this context, he has developed and validated new methodologies (e.g., Capillary Electrophoresis coupled to Laser-Induced Fluorescence, CE-LIF) whose application enabled him to determine both the amounts of biochemical markers (Desmosines) in urine/serum of patients affected by Chronic Obstructive Pulmonary Disease (COPD) and the activity of proteolytic enzymes (Human Neutrophil Elastase, Cathepsin G, Pseudomonas aeruginosa elastase) in sputa of these patients. More recently, Prof. Iadarola was involved in developing techniques such as two-dimensional electrophoresis coupled to liquid chromatography/mass spectrometry (2DE-LC/MS) for the proteomic analysis of biological fluids aimed at the identification of potential biomarkers of different lung diseases. He is the author of about 150 publications (According to Scopus: H-Index: 23; Total citations: 1568- According to WOS: H-Index: 20; Total Citations: 1296) of peer-reviewed international journals. 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She gained considerable experience in developing and validating new methodologies whose applications allowed her to determine both the amount of biomarkers (Desmosine and Isodesmosine) in the urine of patients affected by COPD, and the activity of proteolytic enzymes (HNE, Cathepsin G, Pseudomonas aeruginosa elastase) in the sputa of these patients. Simona Viglio was also involved in research dealing with the supplementation of amino acids in patients with brain injury and chronic heart failure. She is presently engaged in the development of 2-DE and LC-MS techniques for the study of proteomics in biological fluids. The aim of this research is the identification of potential biomarkers of lung diseases. 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She is also the Global Harmonization Initiative (GHI)",institutionString:"Australian College of Business & Technology",institution:{name:"Kobe College",institutionURL:null,country:{name:"Japan"}}}]},{type:"book",id:"6820",title:"Keratin",subtitle:null,coverURL:"https://cdn.intechopen.com/books/images_new/6820.jpg",slug:"keratin",publishedDate:"December 19th 2018",editedByType:"Edited by",bookSignature:"Miroslav Blumenberg",hash:"6def75cd4b6b5324a02b6dc0359896d0",volumeInSeries:2,fullTitle:"Keratin",editors:[{id:"31610",title:"Dr.",name:"Miroslav",middleName:null,surname:"Blumenberg",slug:"miroslav-blumenberg",fullName:"Miroslav Blumenberg",profilePictureURL:"https://mts.intechopen.com/storage/users/31610/images/system/31610.jpg",biography:"Miroslav Blumenberg, Ph.D., was born in Subotica and received his BSc in Belgrade, Yugoslavia. He completed his Ph.D. at MIT in Organic Chemistry; he followed up his Ph.D. with two postdoctoral study periods at Stanford University. 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