\r\n\t2) Human sexual disorders in males and females.
\r\n\t3) Psychological aspects of the human sexual response cycle and its disorders.
\r\n\t4) The therapeutic aspects.
\r\n\tThe human sexual response cycle and human sexual behavior are interrelated. How this inter-relationship and its association to normal sexual health need to be delineated. In a world torn between sex and sexually transmitted disease, clear-cut scientific information in the form of a monograph is required to educate.
\r\n\r\n\tHuman sexuality, gender identity, and sexuo-erotic orientation play great roles in human health and disease. Sex education is the need of the hour and a reflection will be timely.
",isbn:"978-1-80355-151-7",printIsbn:"978-1-80355-150-0",pdfIsbn:"978-1-80355-152-4",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,isSalesforceBook:!1,hash:"13af09c4cf93ae89789a3db597972cf6",bookSignature:"Dr. Dhastagir Sultan Sheriff",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/11267.jpg",keywords:"Master and Johnson's Cycle, Sex Education, Premature Ejaculation, Orgasmic Disorders, Sexual Aversion Disorders, Dyspareunia, Vaginismus, Sex Hormones, Sexually Transmitted Diseases, Impotence, Low Libido, Blood Analyses",numberOfDownloads:99,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"August 18th 2021",dateEndSecondStepPublish:"March 3rd 2022",dateEndThirdStepPublish:"May 2nd 2022",dateEndFourthStepPublish:"July 21st 2022",dateEndFifthStepPublish:"September 19th 2022",remainingDaysToSecondStep:"3 months",secondStepPassed:!0,currentStepOfPublishingProcess:4,editedByType:null,kuFlag:!1,biosketch:"Dr. Sheriff is a life counselor, sex educationist, and researcher with over 35 years of teaching experience, five authored books, and editorials written in the British Journal of Sexology and the Journal of Royal Society of Medicine. 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These materials, often referred to as blast and penetration resistant materials (BPRMs), require the ability to mitigate damage and dissipate energy and momentum. These materials are designed to stop fragments and/or projectiles while preventing behind armor debris or spall. Functionally graded ceramic particle reinforced metal-matrix composites (MMCs) are an emerging class of materials that show significant promise for applications in protective structures due to their improved damage mitigation response in addition to their superior strength, stiffness and wear resistance. The improved damage mitigation is attributed to the compositional/structural gradients introduced through the variation of the concentration of the reinforcing ceramic particles (SiC, Al2O3, etc.) in the matrix [Mortensen & Suresh, 1995; Suresh & Mortensen, 1997]. These functionally graded materials show promise to reduce the need for layered structures that are susceptible to delamination and the formation of axial cracks initiated at the interface of the ceramic and the more ductile backing material. The mechanisms responsible for plastic deformation and failure of these metal-matrix composites, however, are complex and are affected by multiple factors, such as the distribution and location/size of the reinforcing particles, grain size in the metal-matrix, the structural characteristics of the interface between the particles and matrix grains, and loading conditions [Li & Ramesh, 1998, Li et al., 2007]. The design and optimization of BPRM nanocomposite materials can be significantly accelerated by improvements in the understanding of the deformation and failure mechanisms under conditions of ballistic impact. An optimized design of these materials, therefore, requires a fundamental understanding of the links between the length scales (particle size/distribution, layer thickness) and properties (structure, chemistry, etc.) of these composites that enable enabling a combination of high strength and good ductility, and improved failure resistance in impact environments.
While there has been significant progress toward understanding the behavior of these materials, there are still major knowledge gaps to be filled with respect to the identification and characterization of the elementary processes responsible for plastic deformation and failure. These knowledge gaps are attributed to the inability to fully integrate theory, models, and experiments because of disparate time scales and the heterogeneous nature of these materials. The time scales of the processes in these experiments can range from picoseconds to micro-seconds and the length scales can range from nanometers to micrometers [Remington et al., 2004]. These small time scales of the processes make it difficult to identify and characterize the elementary processes responsible for plastic deformation and failure using experiments alone. The molecular dynamics (MD) simulation technique has the ability to provide the atomic level structural information on the relevant micromechanisms at the time-scales of the spall experiments and may be instrumental in physical interpretation of experimental observations [Dongare et al., 2010a]. The applicability of MD simulations as an analysis/predictive tool, however, relies on the accuracy of the interatomic potentials to model the interactions between atoms in the system. The complex heterogeneity arises from the multicomponent interactions that results in complex bonding characteristics at the metal-ceramic interfaces. This heterogeniety limits the applicability of the MD technique due to inavailability of interatomic potentials capable of providing an accurate description of the structural and energy characteristics of metal-ceramic interfaces at the atomic scale. A new class of interatomic potentials referred as the angular dependent Embedded Atom Method (A-EAM) [Dongare et al., 2009a; Dongare et al., 2009b] has been recently developed that extends the ability of MD simulations to MMCs by combining the potentials conventionally used for metals with those conventionally used for ceramics in one functional form.
This chapter provides an overview of the current availability of interatomic potentials to investigate deformation and failure behavior in metal-matrix composites at the atomic scales using MD simulations in Section 2. An in-depth discussion on the formulation of interatomic potentials for complex metal-ceramic interactions is provided in Section 3 and an example parameterization is provided in Section 4. The applicabilty the A-EAM is demonstrated by investigating the strengthening and failure behavior of Si-particle reinforced Al-matrix nanocrystalline composites at high strain rates in Section 5.
The MD simulations study the evolution of the system as a function of time using classical atomistic models defined as interatomic potentials [Allen & Tildesley (1987)]. The interatomic potentials,
The interatomic potentials typically are analytical functions that define the energy of an atom based on the coordinates of its neighboring atoms. The parameters of the analytical functions are chosen to describe properties of the material system as observed experimentally (crystal structure, cohesive energy, density, elastic constants, phase transformations, etc.) or as predicted using
The applicability of MD simulations to investigate deformation and failure micromechanisms in ceramic particle reinforced MMCs requires development of new computationally efficient interatomic potenials that are able to accurately reproduce the structural and energy characteristics of the metal matrix, the ceramic phase, as well as the metal-ceramic interface. An easier solution would be to design new alloy potentials by combining the well-established and thoroughly tested potentials developed for pure components within a unified approach. A number of studies have focused on the relationships between various potentials to justify this unified approach. For example, a potential for the Pt-C system was developed with an analytical form that reduces to the bond-order Brenner potential for C and an EAM-like potential for Pt [Albe et al., 2002]. Similar connections between the EAM formalisms and the bond-order scheme of the Tersoff potential [Brenner, 1989] and between the SW and MEAM potentials [Thijsse, 2002] have been discussed. These studies suggest that despite the apparent distinctions between the functional forms and underlying physical arguments used in the description of interatomic bonding in metallic and covalent systems, a unified approach is feasible.
This chapter discusses the idea of developing a unified interatomic potential for systems with mixed type of bonding is extended to combine the EAM potential for metals with the SW potential commonly used in simulations of Si [Dongare et al., 2009a] and the Tersoff potential for Si and C [Dongare et al., 2009b]. The combined Angular-dependent EAM (A-EAM) potential incorporates a description of the angular dependence of the interatomic interactions into the framework of the EAM potential to make it compatible with the SW/Tersoff potentials. The A-EAM potential retains all the properties of the pure components as predicted by the original SW/Tersoff and EAM potentials and therefore eliminates the need for extensive testing for pure systems. In addition, the scope of the potential parameterization is limited to cross-interaction between the components. An example of the parameterization of the cross-interaction in the A-EAM potential is given for the Al-Si system here to study the micromechanisms related to deformation and failure of functionally graded Si reinforced Al-matrix composites (A359 alloy). Experimentally, the as-cast Al-Si (A359) alloy consists of a dendritic microstructure containing fine Si particles (wt % ~ 9 % Si) [Li et al., 1998, 2007]. The EAM potential for Al in the form suggested in Ref. [Mishin et al., 1999] is chosen as it provides a good description of the unstable and stable stacking fault energies and the surface and grain boundary energies in Al. In addition, the advantage of this potential is in the simplicity of the functional form and the availability of parameterizations for many metals, allowing for an easy implementation for a broad range of alloy systems. For pure Si, the original parameterization of SW potential [Stillinger & Weber, 1985] is used as it has been found to provide a good description of the crystalline, liquid, and amorphous phases of Si. The choice of the EAM and SW potentials renders the A-EAM potential to be computationally efficient and also provides an accurate description of the pure systems. The functional formulation of the A-EAM potential and the parameterization for the Al/Si cross-interactions are described in Section 3 below.
A unified alloy potential based on a reformulation of the EAM and SW potentials in a compatible functional form is discussed in this section. A reformulation of the conventional EAM potential into a form that includes three-body terms in the expression for the total electron density function is presented first, followed by the description of an approach for incorporation of the angular dependence compatible with the SW potential.
In the EAM potentials [Daw & Baskes, 1984; Foiles, 1985; Johnson, 1988], the energy of an atom is expressed as
where
where
To make the connections to SW or Tersoff potentials and to allow for the introduction of the angular dependence of the interatomic interactions, the linear sum of partial electron density contributions in Eq. (2) can be expressed through the sum of products of partial electron densities,
The sum on the right hand side of the above equation includes two-body terms with identical pairs of atoms (
where in the first (two-body) term under the square root, the summation is over all atoms interacting with atom
This formulation can be used to design an angular-dependent EAM potential compatible with the Tersoff potential [Dongare et al., 2009b].
The energy of an atom in a system described by SW potential [Stillinger & Weber, 1985] is defined as
The potential consists of a two-body (
The three-body term is defined as
were
where the electron density and partial electron density contributions are defined as
where
The reformulation of the three-body term of the SW potential in the functional form of the EAM embedding function, Eq. (9) with the inclusion of the first (two-body) term under the square root in Eq. (4) can be used to wite a combined electron density as
Two parameters,
Here, the form of the two-body term of the SW potential, ij(rij) = U2(rij). As will be discussed in the next sections, the parameterization of the A-EAM potential for Al-Si interactions does not require an angular dependence of the electron density function for metal atoms. As a result, the computational efficiency of the evaluation of the A-EAM potential can be improved by rewriting the total electron density function in a form that does not involve the summation over triplets of neighboring atoms around a metal atom:
Similarly to Eq. (13), the parameters are set to δi = ci = 0 for metals (the triplet contribution to electron density is eliminated) and δi = 1 and ci = 2 for Si (the radial contribution to the electron density is eliminated). The additional parameter ni is equal to 1 for metals and 1/2 for Si. While in this work we use the formulation of the A-EAM potential given by Eq. (13a), the alternative formulation of Eq. (13) is useful when an angular dependence needs to be included in the electron density of metal atoms in order to provide an adequate representation of the interatomic interactions in metal-Si alloys.
The functional form and parameters of the embedding energy functions,
To test the ability of the combined A-EAM potential to reproduce the properties of systems with mixed metallic-covalent bonding, in this section we provide an example of parameterization of the potential fo Al-Si systems. The formulation of the A-EAM potential, given by Eq. (13a), implies that the presence of a Si atom contributes to the electron density of a neighboring metal atom only through the two-body term of the electron density function that does not have the angular dependence. On the other hand, the presence of a metal atom contributes to the electron density of a neighboring Si atom through the three-body (triplet interaction) term of the electron density function.
For Al-Si cross-interactions, the pair energy term is defined as:
where AC, BC, αC, βC, σC, RM, PC, and QC are fitting parameters. It should be noted that the partial electron density contributions
Since there are no stable AlSi alloys (in the solid phase) observed experimentally, the parameters for the electron density function and the pair energy function for Al-Si cross-interactions, given by Eqs. (14)-(15), are selected based on the results of DFT calculations performed for several representative Al-Si bulk alloy structures. Since the number of the energy and structural parameters evaluated in DFT calculations exceeds the number of the fitting parameters, the fitting procedure is not aimed at reproducing the exact values of the material properties predicted in the DFT calculations. Rather, the results of the DFT calculations and the experimental data on the enthalpy of mixing of liquid Al-Si solutions [Kanibolotsky et al., 2002] are considered together as a target in the optimization of the overall agreement. Although several sets of parameters were obtained that provided a good agreement (less than 10 % deviation) with DFT results, the prediction of the enthalpy of mixing of the liquid alloy was the true test to study material behavior in extreme environments (high temperatures, pressures, and strain rates). The final parameter set chosen was found to provide an overall satisfactory description of the DFT results in addition to excellent prediction of the mixing behavior of the liquid alloy.
The plots of the embedding energy, the pair energy, and the partial electron density for Si (red lines) and Al (green lines) are shown in Fig. 1.(a), (b), and (c) respectively. The plots of the the pair energy functions and the partial electron density functions and are shown by the dashed blue lines in Fig. 1.(b), and (c), respectively. Thus, according to Eq. (2) and the plots in Fig. 1., the presence of Al atoms in the neighborhood of a Si atom causes a reduction in the partial electron density at the location of a Si atom and a reduced pair energy and therefore results in the weakening of the strength of the Si-Si interactions. This weakening
Plots of the (a) embedding energy functions, (b) pair energy functions, and (c) partial electron density contributions for EAM Al (green line) and SW Si (red line) in the A-EAM formulation. The fitting of the cross-interactions is limited to the Al-Si pair energy and the Al-Si partial electron density contributions (dashed blue line) in (b) and (c), respectively. The enthalpy of mixing of liquid Al-Si alloy at 1870 K as predicted by the A-EAM potential (red line) is shown in (d) in comparison to experimental data [
increases the tolerance of the local configuration in Si to deviations from the perfect diamond lattice structure in the presence of Al atoms. This observation is consistent with the results of recent DFT calculations which show a weakening of the Si-Si bonds at Al/Si interface [Nakayama et al., 2006]. The prediction of the experimental dependence of the enthalpy of mixing for the liquid Al-Si alloy at 1870 K by the A-EAM potential is shown in Fig. 1.(d) in comparison to that obtained using experiments [Kanibolotsky et al., 2002]. The plot shows excellent agreement of the predication using the A-EAM potential that shows a minimum of -5.36 kJ/mol at a concentration of 49 at. % Si with experimental data exhibiting a minimum of -5.4 kJ/mol at a composition of 50 at. % Si. The accurate prediction of the mixing behavior across the composition range and the overall prediction of structural characteristics and energetics from DFT calculations enables the A-EAM to predict the relevant intermixing/melting behavior at Al/Si interfaces in extreme environments such as shock loading and radiation damage. More details of the fitting procedure and a quantitative analysis of the performance of the A-EAM potential in comparison to DFT calculations is provided elsewhere [Dongare et al., 2011].
MD simulations with the newly developed A-EAM Al/Si potential are used to investigate the strengthening and failure behavior of functionally graded Al/Si composites. Experimentally, the as-cast Al-Si (A359) alloy consists of a dendritic microstructure containing fine Si particles (wt % ~ 9 % Si) [Li et al., 2007]. While it is beyond the capabilities of MD simulations to model length scales that incorporate the gradation in composition as observed experimentally, the response of the material at local regions with different compositions can be investigated individually using MD simulations. Nanocrystalline Al/Si systems with varying volume fractions of Si grains are used as the first approximations of the local microstructure in the functionally graded Al/Si alloy. The initial Al/Si nanocrystalline systems with an average grain size of 6 nm and containing 43 grains are created using the Voronoi construction method [Derlet & Van Swygenhoven 2003]. The distribution of the Si grains is chosen at random with random grain orientations depending on the desired composition of the nanocomposites. To study the effect of volume fraction, five Al/Si nanocrystalline systems are created with volume fractions of ~ 5 %, ~ 16 %, ~ 28 %, ~ 35 %, and ~40% Si. The volume fraction is defined as the percentage of Si grains in the nanocrystalline Al/Si system. To facilitate easy comparison, the nanocrystalline composites of different compositions are created with the same grain morphologies and the same grain orientations. Periodic boundary conditions are used in all the three directions. The as-created systems are first relaxed to have zero pressure, and then equilibrated at 300 K for 100 ps. The elements of the atomic-level stress tensor are calculated as
where α and β label the Cartesian components, Ω0 is the atomic volume, Fij is the force on atom i due to atom j, Mi is the mass of atom i, and vi is the velocity of atom i. The strain (ε) calculated here is the engineering strain and the mean stress (
where
The common neighbor analysis (CNA) [Honneycutt & Andersen, 1987 in addition to coordination number (CN) is used to identify local deformations in the FCC and diamond-cubic lattice. The initial nanocrystalline Al/Si systems with an average grain size of 6 nm are shown in Fig. 2. with the atoms colored according to the CNA/CN values. The contour for the Al atoms colored according to the CNA/CN characterization is as follows: the green atoms represent bulk fcc stacking, the red colored atoms represent local hexagonal close-packed order (stacking faults), the yellow atoms represent a coordination greater than 12, the light blue atoms represent a coordination of 12 other than fcc, and the dark blue atoms represent a coordination less than 12. The contour for the Si atoms colored according to the CNA/CN characterization is as follows: the purple atomsrepresent the tetrahedral bonding in the diamond cubic lattice, the white atomsrepresent coordination greater than 4, and the dark blue atoms represent a coordination of less than 4. The time step for all of the MD simulation runs was chosen to be 4 fs. The temperature was allowed to evolve during the deformation process.
The initial configuration of nanocrystalline Al/Si systems with an average grain size of 6 nm and a total of 43 grains and each atom is colored according to the CNA/CN values. The compositions (volume fractions) are : (a) pure Al, (b) ~ 5 % Si, (c) ~ 16 % Si, (d) ~ 28 % Si, (e) ~ 35 % Si and (f) ~ 40 % Si.
At the macro scale, the strengths of materials are typically analyzed using the commonly used phenomenological yield criteria such as von Mises and Tresca [Hertzberg, 1996[29]. While, these criteria have been found to be appropriate to study deformation behavior in metals under quasi-static loading conditions, recent MD simulations suggest that several effects result in asymmetries in the tensile and compressive strengths and render these criteria to be inappropriate under dynamic loading conditions [Dongare et al., 2010a[30] ; Dongare et al., 2010b. As a result, the. MD simulations of uniaxial stress loading were carried out to compute the flow stress of the composite at high strain rates. Deformation simulations were carried out at constant strain rate by deforming the sample in the loading direction while maintaining zero stress conditions in the lateral directions. The scaling parameter in the loading directions is chosen so as to achieve a strain rate of 109 s-1. For each nanocrystalline system, three deformation simulations are carried out independently for loading in the X, Y, and Z directions to eliminate the effect of loading direction on the orientation of the Si grains in the composite.
The stress-strain curves obtained for the composite with a volume fraction of ~ 35 % Si are plotted in Fig. 3.(a) and (b) for loading in tension and compression, respectively. The curves are initially linear and lie on top of each other up to the yield point, after which they start to deviate from elastic behavior. The flow stress (σf) is defined as the peak value of the stress in the stress-strain curve [Dongare et al., 2010b; Dongare et al., 2010c]. It can be seen from Fig. 3. that the nanocrystalline composite is stronger in compression than in tension. The flow stress for the nanocrystalline Al/Si composite for various compositions are tabulated in Table 1 for conditions of uniaxial tensile stress and uniaxial compressive stress loading at a constant strain rate of 109 s-1.
Stress-strain curves for deformation of nanocrystalline Al/Si sample containing ~ 35 % Si grains under loading conditions of (a) uniaxial tensile stress, and (b) uniaxial compressive stress. The three curves represent the deformation in X, Y and Z directions. Here εx, εy, and εz are the engineering strains in the X, Y, and Z directions, respectively.
Calculated values of flow (peak) stress during uniaxial tensile/compressive deformation of nanocrystalline Al/Si composites with an average grain size of 6 nm and varying Si volume fraction at a constant strain rate of 109 s-1.
The snapshots for the nanocrystalline Al system at 10% strain are shown in Fig. 4.(a) for conditions of tensile loading and in Fig. 4.(b) for conditions of compressive loading at a strain of 10 %. Intermediate snapshots of composite containing ~ 35 % Si grains are shown in Fig. 4.(c) for conditions of tensile loading and in Fig. 4.(d) for conditions of compressive loading at a strain of 10 % with the atoms colored according to the CNA/CN characterization. The snapshots do not show significant dislocation activity in the nanocrystalline Al and the Al/Si composite due to the small grain size (6 nm) of the nanocrystalline systems. While no dislocations are observed in the Si grains, it can be seen that the presence of the reinforcing phase does not significantly alter the dislocation density of the Al grains. The higher strengths in the composite are therefore attributed to reduced grain boundary rotation/sliding at the Al/Si grain boundaries. The fraction of Al/Si grain boundaries increases with increasing fractions of Si grains and therefore results in higher strength of the nanocrystalline composite.
The average values of the flow stress in tension and compression are plotted in Fig. 5.(a) as a function of Si composition. While there are some deviations, the plot shows a general trend that the flow stress values increase with increasing Si fraction. The deviations in the trend are attributed to the small system size and the small number of grains. The asymmetry in the strength of the nanocomposites in tension and compression is plotted in Fig. 5.(b) for various Si compositions. The strength asymmetry for the pure nanocrystalline Al system is predicted to be very small (~ 1.6 %) and addition of Si results in an increase in the asymmetry as the Si composition in the nanocomposites increases. The higher asymmetry in the strength values at higher volume fractions results from the limited grain boundary rotation/sliding behavior of the Al/Si grain boundaries in compression as compared to tension as observed for pure nanocrystalline systems at higher strain rates [Dongare et al., 2010b; Dongare et al., 2010c]. These results are consistent with results from MD simulations using the MEAM potential which suggest that the inclusion of Si particles reduces the relative motion of the Al grains by suppressing both sliding/shearing along the grain boundaries and dislocation nucleation from the boundaries that results in enhanced strengths of the Al–Si nanocomposites [Ward et al., 2006].
Snapshots of the nanocrystalline Al system at a strain of 10 % in (a) tensile loading and (b) Compressive loading. The nanocrystalline Al/Si system with a volume fraction of ~40% Si at the same strain are shown in (c) for tensile loading, and in (d) for compressive loading. The atoms are colored according to the CNA/CN contour as indicated in
a) Calculated flow stress curves for deformation of nanocrystalline Al/Si sample for various volume fractions of Si. The red colored curve corresponds to tensile loading conditions and the black curve corresponds to compressive loading conditions.
The failure behavior of nanocomposites formed by adding Si particles to Al nanocrystalline materials has been investigated using molecular dynamics simulations with the MEAM potential [Ward et al., 2006]. These results suggest that failure initiates by the nucleation of a void at the interface between the Al/Si grains. Experimental studies of deformation and failure of the A359 alloy at high strain rates also suggest that the fracture propagates along the interdendritic network of Si [Li et al., 2007]. A valid test of the A-EAM potential, therefore, is to study the micromechanisms related to ductile failure in nanocrystalline Al/Si composites consisting of an embedded Si nanocrystal in a nanocrystalline Al matrix. Deformation is carried out under conditions of uniaxial expansion (εx = εy = 0, and εz = ε) at a constant strain rate of 109 s-1 to relate to experimental dynamic loading conditions of dynamic failure [Dongare et al., 2009c]. Three deformation simulations are carried out independently for loading in the X, Y, and Z directions to eliminate the effect of loading direction on the orientation of the Si grains in the composite.
The stresses averaged over the entire system in the X, Y, and Z direction and the are plotted in Fig. 6.(a) as a function of engineering strain (ε) for uniaxial tensile strain loading in the Z direction. The evolution of mean stress (σm) as a function of engineering strain (ε) in the loading direction is plotted in Fig. 6.(b) as obtained in the three simulation runs during uniaxial tensile strain loading independently in the X, Y, and Z directions. The stress-strain curves in Fig. 6 show three stages of deformation. The first stage corresponds to elastic deformation of the nanocrystalline system leading to a linear evolution of the curves for σx, σy, and σz up to the yield point. Continued deformation results in deviation from linearity due to GB sliding/rotation processes that are accommodated by the nucleation of dislocations [Dongare et al., 2009c]. Continued deformation results in an increase in the stress to a peak value after which, nucleation of voids results in the relaxation of stresses as indicated by a sharp drop in the stresses in the X, Y, and Z directions as shown in Fig. 6.(a).
The stress state transitions to an almost hydrostatic stress condition
a) Plots of stresses in X, Y, and Z direction as a function of strain (εz) during tensile deformation under conditions of uniaxial strain at a strain rate of 109 s-1. (b) Evolution of mean stress σm during uniaxial tensile strain loading independently in the X, Y, and Z directions at a strain rate of 109 s-1.
Continued deformation results in the stress state to transition back to that corresponding to uniaxial strain.
Intermediate snapshots of a section of the system are illustrated in Fig. 7. with the atoms colored according to CAN/CN contour. The snapshot in Fig. 7.(a) corresponds to a time just before the peak in the stress value (ε ~ 9.0 %). A single void is observed to nucleate at a grain boundary interface between the embedded Si nanocrystal and the neighboring Al grains in Fig. 7.(b). Also, there is relatively little dislocation activity at the GB interface between the Al/Si grains. This indicates that void nucleation cannot be attributed to a dislocation pile-up process, but rather results from the mechanical separation/sliding at the Al/Si grain boundary interface. The creation of the void is accommodated by the shearing of the nearby atoms leading to the formation of a disordered shell of atoms around the void as shown in Fig. 7.(c). Continued deformation increases the size of this shell of disordered atoms around the voids and the void shape changes to near spherical as shown in Fig. 7.(b)-(d). Although a few dislocations are observed to propagate into the grains surrounding the void, most of the material surrounding the void consists of disordered atoms and void growth is observed to occur by the shearing of the disordered regions. The creation of disordered atoms surrounding the void increases until a minima in stresses is reached in Fig. 6. This minima in stresses corresponds to the snapshot shown in Fig. 7.(e). A transition in the stress state back to that corresponding to uniaxial strain conditions results in a slower growth rate of the void that is accompanied by the recrystallization of the surrounding disordered regions. The recrystallization of the disordered region around the void is attributed to the increased temperature of the system due to nucleation and growth of the void [Dongare et al., 2009c]. The results from these MD simulations thus agree with those predicted by the MEAM potential [Ward et al., 2006] that the failure of the nanocomposite is initiated by the nucleation of the void at the Al/Si interface.
Snapshots of a section of the system at (a) 90 ps (εz ~ 0.09), (b) 100 ps (εz ~ 0.10), (c) 105 ps (εz ~ 0.105), (d) 110 ps (εz ~ 0.11), (e) 120 ps (εz ~ 0.12), and (d) 150 ps (εz ~ 0.15), showing the nucleation and growth of the void under conditions of uniaxial tensile strain at a constant strain rate of 109 s-1. The atoms are colored according to CNA/CN contour.
The value of the maximum mean tensile stress in Fig. 6.(b) can be compared to the peak spall pressure during spallation experiments. The plots suggest that the spall strength changes slightly for the nanocrystalline Al/Si composite with a change in loading direction. Intermediate snapshots of a section of the system at a strain of ε = 11 % during loading under conditions of uniaxial tensile strain in the X direction, the Y direction, and the Z direction are shown in Fig. 8.(a), (b), and (c), respectively at a constant strain rate of 109 s-1. The snapshots suggest that failure (nucleation of void) initiates along the Al/Si grain boundary interface. Thus, the embedding of a Si nanocrystal results in the initiation of failure at the Al/Si interface irrespective of the loading conditions. These results suggest that the failure resistance behavior of these metal-matrix composites is dependent on the characteristics of the metal-ceramic interfaces in the nanocomposites. More work is needed to be done to obtain the links between the length scales (particle size/distribution, layer thickness) and properties (structure, chemistry, etc.) of these composites for enabling high strength behavior and improved failure resistance so as to allow for an optimized microstructural design of the MMnCs for use in extreme environments.
Sectional snapshots of the nanocrystalline Al/Si system showing initiation of failure along the Al/Si grain boundary interface at a strain of ε = 11 % during loading under conditions of uniaxial tensile strain in (a) X direction (εz = εy = 0, and εx = ε), (c) Y direction (εx = εz = 0, and εy = ε), and (a) Z direction (εx = εy = 0, and εz= ε), at a constant strain rate of 109 s-1. The atoms are colored according to CNA/CN contour.
A new angular-dependent EAM interatomic potential is developed that allows for the study of metal-ceramic interfaces at the atomic scale. The A-EAM potential is obtained by combining the EAM potential for Al with the SW potential for Si. The A-EAM potential retains the original functional forms and parameters and therefore all the properties of the pure components as predicted by the original SW and EAM potentials. The formulation of the A-EAM potential limits the parameterization to only the cross-interaction between the Al-Si components. An example parameterization is demonstrated for the Al/Si system based on the on the results of DFT calculations performed for artificial bulk Al/Si alloys and the compositional dependence of the enthalpy of mixing in liquid Al-Si alloys at 1870 K. Large scale molecular dynamics simulations using the A-EAM potential are carried out to study the strengthening behavior of the ceramic (Si) particle reinforced nanocrystalline metal (Al) matrix composites for varying volume fractions of the ceramic phase. The results suggest that the strength of the nanocrystalline composite increases with an increase in the volume fraction of the ceramic phase. The nanocrystalline composite is observed to be stronger in compression loading as compared to tensile loading and this strength asymmetry is observed to increase with increasing volume fraction of the ceramic phase. The microscopic mechanisms related dynamic failure predicted using MD simulations suggest that failure initiates at the metal-ceramic interface. These results suggest that the performance of the nanocomposites in extreme environments can be improved by a tailored design of a metal-ceramic interfaces in the nanocomposite. Future work will therefore focus on a fundamental understanding of the effect of the structure, size and distribution of the reinforcing ceramic phase that will enable high strengths of the nanocomposite in extreme environments.
This work has been done during AMD’s tenure as a National Research Council (NRC) Research Associate funded by the US Army Research Office.
We are living in a world of many challenges such as climate changes, polluted environment, resource depletion, and increasing demand for fuel. The use of oil reserves to fulfill our need of fuel has caused many drastic challenges from energy security to change in temperature. Rapid industrialization has increased the demand of petroleum products and consequently has raised the monopoly of few countries, which can manipulate petroleum price and create instability. This may also create environmental problems by emission of greenhouse gases and subsequently effect on climate change. The most important source of energy is petroleum that is largely used in transportation and industries; therefore, viability of liquid fuel is enhanced. As the environmental issues are growing, more research is being conducted to address the problems. The search for alternative source of petrol that is less costly with minimal environmental effects has become the center of attention. For instance, biomass is considered as a sustainable resource that can be utilized in large-scale production of biofuel that can be utilized as an alternative source of fuel and may present solution to environmental problems. Furthermore, relying on fossil fuel could be detrimental as it has been predicted of its depletion by 2050. The total annual primary production of biomass is over 100 billion tonnes of carbon per year, and the energy reserve per metric tonne of biomass is between 1.5E3 and 3E3 kW hours that is sufficient to cater the needs of the world energy requirements [1].
\nBioenergy products like bioethanol, biohydrogen, and biodiesel can be obtained from lignocellulose biomass which is considerably large renewable bioresource and obtained from plants. The term “lignocellulosic biomass” is defined as lignin, cellulose, and hemicellulose that constitute the plant cell wall. Strong cross-linking associations are present between these components that cause hindrance in the breakdown of plant cell wall. Polysaccharides and lignin are cross-linked via ester and ether linkages [2, 3, 4]. Microfibrils that are formed by cellulose, hemicellulose, and lignin help in the stability of plant cell wall structure [5, 6].
\nLignocellulose was first produced from food crop such as corn, oilseed, and sugarcane. But the use of edible feedstock for bioenergy products formation is being discouraged to prevent the rise in food competition. Thus, second-generation biofuels are obtained from plants wastes to avoid competition of land and water resources between energy crops and food crops. Currently, lignocellulose is being produced from wood residues, agricultural residues, food industry residue, grasses, domestic wastes, municipal solid wastes, and nonfood seeds [7, 8, 9]. The lignocellulose wastes (LCW) are largest renewable bioresource reservoir on earth that is being wasted as pre and postharvest agricultural wastes. Thus, many steps need to be adopted for use of these renewable resources for the production of bioenergy products. Recovery of many products like enzymes, methane, activated carbon, lipids, resins, methane, carbohydrates, surfactants, resins, organic acids, ethanol, amino acids, degradable plastic composites, biosorbents, biopesticides, and biopromoters can be achieved by utilizing LCW. The added benefits of using LCW besides recovery of different products are the removal of LCW waste from the environment. Also, utilization of LCW eliminates the use of food for bioethanol production. The US government has planned the production of 21 billion gallon of biofuels by 2022 [2, 5]. Biofuel production from lignocellulosic biomass reduces the emission of greenhouse gases.
\nPretreatment brings physical, biological, and chemical changes to biomass structure; therefore, it is very important to consider the type of pretreatment. In order to break down the hindrance caused by strong association within the cell wall, pretreatment is an important step which can increase the availability of lignocellulosic biomass for cellulase enzymes, their digestibility, and product yield. Before subjection to enzymatic hydrolysis, pretreatment of biomass can increase the rate of hydrolysis by 3–10-fold. Pretreatment of LCW is not an easy step as it seems after the installation of power generator; pretreatment is the second most costly process at industrial level. In crystalline cellulose, the disruption of hydrogen bonds, cross-linked matrix disruption, and increase in porosity as well as surface area of cellulose are the three tasks that are performed via a suitable pretreatment methods. The outcome of pretreatment also differs due to the difference in the ratio of cell wall components [10, 11]. The option to use dilute acid pretreatment method is more effective against poplar tree bark or corn as compared to the same method used for sweet gum bark or cornstalks. Few requirements of an effective, efficient, and economically suitable pretreatment process that including use of cheap chemicals, very less consumption of chemicals, prevention of hemicellulose and cellulose from denaturation, minimal energy requirement and consumption, cost-effective size reduction process, and reactive cellulosic fiber production are the factors that need to be considered for pretreatment. There are several methods of pretreatment that can be divided into four categories, namely, chemical, physical, biological, and physiochemical pretreatment [12, 13, 14, 15].
\nPore size and surface area of lignocellulosic biomass can be increased, whereas crystallinity and degree of polymerization of cellulose can be decreased with the application of physical methods. Physical pretreatments include milling, sonication, mechanical extrusion, ozonolysis, and pyrolysis.
\nOn the inherent ultrastructure of cellulose and degree of crystallinity, milling can be performed to render lignocelluloses more amenable to cellulases. Cellulases are enzyme that catalyze cellulose, but for the catalysis and best results, the substrate availability needs to be enhanced for optimized functioning of the enzymes. Before the subjection of the LCW to enzymatic hydrolysis, milling and size reduction of the lignocellulosic matter should be performed. Milling process has several types like ball milling, colloid milling, vibro-energy milling, hammer milling, and two-roll milling. For wet material, colloid mill, dissolver, and fibrillator are suitable, whereas for dry materials hammer mill, extruder, cryogenic mill, and roller mill are used. For both wet and dry material, ball milling can be used. For waster paper, hammer milling is the most suitable pretreatment option. Enzymatic degradation can be improved by milling as it reduces the degree of crystallinity and material size. Up to 0.2 mm reduction in particle size can be seen by milling and grinding. Reduction in particle size of biomass can be achieved up to a certain limit; beyond that limit reduction in particle size does not effect in the pretreatment procedure. Corn stover with small particle size, i.e., from 53 to 75 μm, is more productive as compared to large particle size corn stover ranging from 475 to 710 μm. The difference in particle size shows that productivity can significantly affect the pretreatment process. Ball milling causes a massive drop in crystallinity index from 4.9 to 74.2% which makes this process more suitable for saccharification of straw at mild hydrolytic conditions with more production of fermentable sugars [12, 16, 17, 18]. For better results of hydrolysis, milling can be used in combination with enzymatic hydrolysis. Mechanical action, mass transfer, and enzymatic hydrolysis can be achieved at the same time when two methods are combined. A number of ball beads in bill mill reactor play a crucial role in the α-cellulose hydrolysis, as less enzyme loading is required, and 100% rate of hydrolysis can be achieved in comparison to pretreatment of biomass that is carried without the use of milling procedure. Highest hydrolysis rate with high yield of reducing sugar was obtained when rice straw was put into fluidized bed opposed jet mill for fine grinding after cutting, steam explosion, and pulverization. For pretreatment of biomass, ball milling is an expensive option in terms of energy consumption, which is a huge disadvantage at industrial scale. Also, incapability of milling for removing lignin makes it a less suitable option as enzyme accessibility to the substrate is reduced in the presence of lignin. Reduction in crystallinity, degree of polymerization, and increase in surface area can be effected by the type of biomass, type of milling used for pretreatment, and duration of the milling process [19, 20, 21].
\nFor improving digestibility and reducing crystallinity, vibratory ball milling is very effective. Low energy consumption has an important advantage of using wet disk milling which produces fibers that improve hydrolysis of cellulose, whereas hammer milling produces finer bundles. Due to this reason milling is not preferred when wet disk milling is available [22, 23]. Other study results of conventional ball and disk milling are compared. With the use of conventional ball milling, maximum yields of xylose and glucose were obtained, i.e., 54.3 and 89.4%, respectively [24]. Wet milling produces less yield, but it has the advantage of not producing inhibitors and very low energy consuming capability. An increase of 110% in enzymatic hydrolysis was achieved when wet milling was combined with alkaline pretreatment. Optimum parameters for wet milling pretreatment of corn stover were 10 mm diameter 20 steel balls, 1:10 solid-to-liquid ratio, 350 rpm/min speed, and 0.5 mm particle size [25] (Figures 1 and 2).
\nColloid milling (
Hammer milling (
Commonly used method for plant biomass pretreatment is microwave irradiation. This pretreatment method has several advantages that include ease of pretreatment, increased heating capacity, short processing time, minimal generation of inhibitors, and less energy requirement. Microwave irradiation in closed container was first reported in 1984 by team of researchers from Kyoto University, Japan. They treated sugarcane bagasse, rice straw, and rice hulls with microwaves in the presence of water. The conditions used for microwave treatment include glass vessels of 50 mL, 2450 MHz energy, and 2.4 kW microwave irradiation [26]. Classical pretreatment methods were carried out at high pressure and temperatures. Chemical interactions between lignocellulosic material break as a result of high temperature, thus increasing substrate availability to the enzymes. Under high-pressure steam injection or indirect heat injection, high temperature between 160 and 250°C is provided to lignocellulosic material in conventional heating methods. However, in order to prevent temperature gradients, crushing of lignocellulosic material into small particles is needed. To avoid large temperature gradients, microwave is a good choice as it uniformly distributes heat which also avoids degradation of lignocellulosic material into humic acid and furfural. For effective degradation, microwave irradiation is combined with mild alkali treatment. Sugar yield of 70–90% from switch grass was obtained from alkali and irradiation combined pretreatment [27]. As microwave irradiation is performed at high temperature, therefore, closed containers are required to achieve high temperature. Three properties, namely, penetration, reflection, and absorbance are exhibited by microwave. Microwave passes through glass and plastic, absorbed by water and biomass, whereas microwaves are reflected by metals. Based on these properties, microwave reactors can be divided into two types, one that allows the passage of microwaves, whereas the other kind reflects the microwaves. Glass or plastic is the building material of the first type of microwave reactors, whereas the second types of reactors are composed of steel. Through quartz windows, microwaves can enter into the reactor as these are placed in the reactor. Closed, sealable, pressure-resistant glass tube container having gasket made up of Teflon can be used for the high temperature, i.e., 200°C, for microwave irradiation pretreatment. Sensors are used to control and ensure temperature inside the microwave. Teflon-coated sensors are a good choice because of the thermostability, corrosion-free nature, and zero absorbance properties. In a microwave oven, Teflon vessels are used by some scientists due to its advantageous properties [28, 29]. Normally vessel sizes vary from 100 mL to several hundred milliliters. A 650 mL vessel with 318 mm length, connected nitrogen bottle, gauges, and thermometers are installed on the top of the microwave that was designed by Chen and Cheng [30]. Besides the glass vessels and stainless steel tanks with temperature and pressure sensors, automatic controlling system for microwave input and mechanical stirrer are also used (Figure 3).
\nMicrowave irradiation (
When materials that can pass through a defined cross section die, it appears out with the fixed definite profile. This is the extrusion process which is known for sugar recovery from biomass. Adaptability to modifications, no degradation products, controllable environment, and high throughput are few advantages related to mechanical extrusion pretreatment process. Single screw extruder and twin screw extruder are two types of extruders.
\nSingle screw extruder is based on three screw elements, forward, kneading, and reverse. With the minimum shearing and mixing, bulk material of varying pitches and lengths can be transported by forward screw element. Prominent mixing and shearing effect is produced by kneading screw elements with weak forward conveying effect, whereas the use of immense mixing and shearing involves material that is pushed back by reverse screw elements. A screw configuration is defined by the arrangement of different stagger angels, lengths spacing, pitches, and positions. Twin screw extruder can accomplish multiple tasks at the same time like mixing, shearing, grinding, reaction, drying, and separation. High enzymatic hydrolysis rates are achieved by the use of single and twin screw extruders. Different parameters like speed of screw, temperature of barrel, and compression ratio can significantly affect recovery of sugars. Short-time extruders provide fast heat transfer, proper mixing, and increased shear. When material passed through the extruder barrel, structure of biomass is disturbed, exposing more surface for enzymatic hydrolysis [31, 32, 33]. During extrusion process, lignocellulosic material can be treated with alkali or acid in order to increase sugar recovery. Acidic treatment is less preferred than alkali because of the corrosion caused by acid to the extruder material. Corrosion problem can be solved by the use of AL6XN alloy for barrel fabrication and screws of extruder. With less carbohydrate degradation and role in the delignification, alkali treatment is suitable for lignocellulosic material. Sodium hydroxide is most commonly used to break ester linkages and solubilization of lignins and hemicelluloses. Alkali treatment can be applied by addition of alkali using volumetric pump into the extruder or by soaking the lignocellulosic material in alkali at room temperature [31, 34, 35] (Figure 4).
\nTwin screw extruder (
For the production of bio oil from biomass, process of pyrolysis is used. Pyrolysis is a thermal degradation of lignocellulosic biomass at very high temperature without the presence of oxidizing agent. At temperature ranging between 500 and 800°C, pyrolysis was performed. Rapid decomposition of cellulose resulted in the formation of products like pyrolysis oil and charcoal [36]. Based on temperature, pyrolysis pretreatment process is divided into fast and low pyrolysis. Certain factors affect the end products like biomass characteristics, reaction parameters, and type of pyrolysis. Due to high-value energy-rich product formation, easy transport management retrofitting, combustion, storage, and flexibility in utilization and marketing, thermal industries are adapting to the process of pyrolysis. Presence of oxygen and less temperature increase the efficiency of this process. A study on the bond cleavage rate of cellulose was carried out in the presence of nitrogen and oxygen. During the process of pyrolysis, breakage of 7.8 × 109 bonds/min/g cellulose in the presence of oxygen and breakdown of 1.7 × 108 bonds/min/g cellulose in the presence of nitrogen at 25°C were observed. In order to obtain more efficiency and results, microwave-assisted pyrolysis is preferred due to the microwave dielectric heating [37]. Thermochemical conversion of biomass into biofuels can be performed via three technologies, gasification, pyrolysis, and direct combustion [38]. Different yields of products from pyrolysis are due to different modes of pyrolysis. Bio oil is a mixture of polar organics and water. Pyrolysis is used where bio oil production is required. Fast pyrolysis in a controlled environment leads to the formation of liquid products (fuels). Torrefaction is an emerging technique which is also known as mild pyrolysis. It differs from pyrolysis with reference to thermochemical process that is carried out at temperature range between 200 and 300°C. Partial decomposition of biomass occurs in this process, and ultimate product obtained is terrified biomass. Whereas, in the process of pyrolysis, plant biomass is decomposed into vapor, aerosols, and char. Torrefaction has been categorized into two categories based on dry and wet torrefaction.
\nDry torrefaction needs an inert environment and completely dry biomass and normal atmospheric pressure. Biochar is the major product in this type of biomass pretreatment. Hydrothermal carbonization and hydrothermal torrefaction are other terminologies used for wet torrefaction. Unlike dry torrefaction, pressurized vessel of water is used to carry out the pretreatment. Biomass used for wet torrefaction contains moisture content, but after torrefaction, a drying process is necessary in this type of torrefaction. A pressure between 1 and 250 MPa is required to carry out wet torrefaction. Biomass used during wet torrefaction pretreatment produces hydro-char as a main product [39].
\nIn this method, pores are created in the cell membrane due to which cellulose exposes to such agents that cause its breakdown by entering into the cell. High voltage ranging between 5.0 and 20.0 kV/cm is applied in a sudden burst to biomass for nano- to milliseconds. Sample was placed between two parallel plate electrodes, and the strength of electric field is given as
Pulse electric field (
In this pretreatment, acids are used to pretreat lignocellulosic biomass. The generation of inhibitory products in the acid pretreatment renders it less attractive for pretreatment option. Furfurals, aldehydes, 5-hydroxymethylfurfural, and phenolic acids are the inhibitory compounds that are generated in huge amount in acid pretreatment. There are two types of acid treatments based on the type of end application. One treatment type is of short duration, i.e., 1–5 min, but high temperature > 180°C is used, and the second treatment type is of long duration, i.e., 30–90 min, and low temperature < 120°C is utilized. Due to hydrolysis by acid treatment, separate step of hydrolysis of biomass can be skipped, but to remove acid, washing is required before the fermentation of sugars [43, 47]. For acid pretreatment, such reactors are required that show resistance to corrosive, hazardous, and toxic acids; therefore, acid pretreatment is very expensive. Flow through, percolation, shrinking-bed, counter current rector, batch, plug flow are different types of rectors that have been developed. For enhancing economic feasibility of acid pretreatment, recovery of concentrated acid at the end of the treatment is an important step.
\nTo treat lignocellulosic biomass, concentrated acids are also used. Most commonly used acids are sulfuric acid or hydrochloric acid. In order to improve the process of hydrolysis for releasing fermentable sugars from lignocellulosic biomass, acid pretreatment can be given. For poplar, switch grass, spruce, and corn stover, sulfuric acid pretreatment is commonly used. Reducing sugars of 19.71 and 22.93% were produced as a result of the acid pretreatment of Bermuda grass and rye, respectively. In percolation reactor, pretreatment of rice straw was carried out in two stages using aqueous ammonia and dilute sulfuric acid. When ammonia is used, 96.9% reducing sugar yield was obtained, while 90.8% yield was obtained in case of utilization of dilute acid.
Besides sulfuric acid and hydrochloric acid, other acids like oxalic acid and maleic acid are also used for the pretreatment of lignocellulosic biomass. Oxalic and maleic acids have high pKa value and solution pH as compared to sulfuric acid. Because of having two pKa values, dicarboxylic acids hydrolyze biomass more efficiently than sulfuric acid and hydrochloric acid. Other advantages include less toxicity to yeast, no odor, more range of pH and temperature for hydrolysis, and no hampering of glycolysis. Maleic acid has khyd/kdeg, due to which hydrolysis of cellulose to glucose is preferred over glucose breakdown. Effects of oxalic, sulfuric, and maleic acid pretreatment on biomass at the same combined severity factor (CSF) were determined [53]. The use of maleic acid produces high concentration of xylose and glucose as compared to oxalic acid.
\nApart from acids, few bases are also used for pretreatment of biomass. Lignin contents greatly affected the result of alkaline treatment. As compared to other pretreatment methods, alkali treatment requires less pressure and temperature and ambient condition, but alkali pretreatment needs time in days and hours. Degradation of sugar in alkali treatment is less than that by acid treatment, and also the removal and recovery of caustic salt are possible and easy in case of alkali treatment. Ammonium, sodium, calcium, and potassium hydroxides are used for alkaline pretreatment, but among these sodium hydroxide is the most commonly used alkaline pretreatment agent, whereas calcium hydroxide is the cheapest yet effective among all other alkali agents for pretreatment. By neutralizing calcium with carbon dioxide, calcium can be recovered easily in form of insoluble calcium carbonate. Using lime kiln technology, calcium hydroxide can be regenerated. Apparatus required for alkali pretreatment is basically temperature controller, a tank, CO2 scrubber, water jacket, manifold for water and air, pump, tray, frame, temperature sensor, and heating element. The first step of pretreatment consists of making lime slurry with water. The next step is spraying of this slurried lime on biomass; after spray, store the biomass for hours or, in some case, days. Contact time can be reduced by increasing temperature [54, 55, 56, 57]. Crystallinity index increases in lime pretreatment because of the removal of lignin and hemicellulose. Structural features resulting from lime pretreatment affect the hydrolysis of pretreated biomass. Correlation of three structural factors, viz., lignin, acetyl content and crystallinity, and enzymatic digestibility, was reported by Chang and Holtzapple [58]. He concluded that (1) regardless of crystallinity and acetyl content, in order to obtain high digestibility, extensive delignification is enough. (2) Parallel barriers to hydrolysis are removed by delignification and deacetylation. (3) Crystallinity does not affect ultimate sugar yield; however, it plays some role in initial hydrolysis. It is evident from these points that lignin content should be reduced to 10% and all acetyl groups should be removed by an effective pretreatment process. Thus in exposing cellulose to enzymes, alkaline pretreatment plays an important role. By increasing enzyme access to cellulose and hemicellulose and eliminating nonproductive adsorption sites, lignin removal can play its role in increasing effectiveness of enzyme.
\nAqueous organic solvents like methanol, acetone, ethanol, and ethylene glycol are used in this method with specific conditions of temperature and pressure. Organosolv pretreatment is usually performed in the presence of salt catalyst, acid, and base. The biomass type and catalyst involved decide the temperature of pretreatment, and it can go up to 200°C. Lignin is a valuable product, and to extract lignin this process is used mainly. Cellulose fibers are exposed when lignin is removed, which leads to more hydrolysis. During organosolv pretreatment, fractions and syrup of cellulose and hemicellulose, respectively, are also produced. There are certain variable factors like catalyst type, temperature, and concentration of solvent and reaction time which affects the characteristics of pretreated biomass like crystallinity, fiber length, and degree of polymerization. Inhibitor formation is triggered by long reaction, high temperature, and acid concentrations [59, 60]. In a study by Park et al. [61], effect of different catalyst was checked for the production of ethanol and among sulfuric acid, sodium hydroxide, and magnesium sulfate, and sulfuric acid was found to be most effective in ethanol production, but for enhancing digestibility the use of sodium hydroxide is proven to be effective. Sulfuric acid is a good catalyst, but its toxicity and inhibitory nature make it less favorite. Organosolv is not a cost-effective pretreatment process because of the high cost of catalysts, but it can be made cost-effective by recovering and recycling of solvents. Solvent removal is important because its presence effects fermentation, microorganism growth, and enzymatic hydrolysis. There is added risk of handling such harsh organic solvents. Acid helps in hydrolysis and depolymerization of lignin. Upon cooling lignin is dissolved in phenol, and in the aqueous phase, sugars are present. Formasolv involving formic acid, H2O, and hydrochloric acid is a type of organosolv in which lignin is soluble and at low temperature process can be carried out. For pretreatment with ethanosolv cellulose, hemicellulose and pure lignin can be recovered, but high pressure and temperatures are required when ethanosolv is used, and less toxic nature of ethanol as compared to other organosolv makes it favorite for pretreatment. Ethanosolv when used in pretreatment effects the enzymatic hydrolysis, so to prevent this low ethanol, water is used [62]. Recovery of ethanol and water reduces the overall cost of the pretreatment. For sugarcane bagasse Mesa et al. [63] used ethanosolv at 195°C for 60 min, and results showed formation of 29.1% sugars from 30% ethanol. Alcohol-based organosolv pretreatment is combined with ball milling by Hideno et al. [24] to pretreat Japanese cypress and observed a synergistic effect on digestibility. 50.1, 41.7, and 48.1% yield of organosolv pulping was obtained from ethylene glycol-water, acetic acid-water, and ethanol-water in a study done by Ichwan and Son [64]. Poplar wood chips were first treated with stream and then with organosolv to separate cellulose, lignin, and hemicellulose. About 88% hydrolysis of cellulose to glucose, 98% recovery of cellulose, and 66% increase in lignin extraction were reported by Panagiotopoulos et al. [65].
\nFor the pretreatment of lignocellulose, scientist took a great interest in using ionic liquids, for decades. Ionic liquids containing cations or anions are a new class of solvents with high thermal stability and polarity, less melting point, and negligible vapor pressure [66, 67]. Normally large organic cations and small inorganic anions compose ionic liquids. Factors like degree of anion charge delocalization and cation structure significantly effect physical, biological, and chemical ionic liquid properties. Interactions between ionic liquids and biomass get affected by temperature, cations and anions, and time of pretreatment.
\nIonic liquids actually compete for hydrogen bonding with lignocellulosic components, and in this competition disruption of network occurs. 1-Ethyl-3-methylimidazolium diethyl phosphate-acetate, 1-butyl-3-methylimidazolium-acetate, cholinium amino acids, cholinium acetate, 1-ethyl-3-methylimidazolium diethyl phosphate-acetate, 1-allyl-3-methylimidazolium chloride, and chloride are ionic liquids used for the treatment of rice husk, water hyacinth, rice straw, kenaf powder, poplar wood, wheat straw, and pine. Among other ionic liquids are imidazolium salts which are most commonly used [42]. 1-Butyl-3-methylimidazolium chloride is used for pretreatment by Dadi et al. [68] who observed a twofold increase in yield and rate of hydrolysis. For the pretreatment of rice straw, Liu and Chen [69] used 1-butyl-3-methylimidazolium chloride also known as (Bmim-Cl) and observed significant enhancement in the process of hydrolysis due to modifications in the structure of wheat straw by Bmim-Cl. Bmim-Cl played role in the reduction of polymerization and crystallinity. A twofold increase in hydrolysis yield from sugarcane bagasse was observed in a study by Kuo and Lee [70] as compared to untreated bagasse. 1-Ethyl-3-methylimidazolium-acetate is used in a study by Li et al. [71] for the pretreatment of switch grass in order to remove lignin at a temperature of 160°C for 3 hours. Results showed 62.9% lignin removal enhanced enzymatic digestibility, and reduced cellulose crystallinity was reported by Tan et al. [72] on palm tree pretreatment with 1-butyl-3-methylimidazolium chloride. Slight changes in composition of biomass occurred after ionic liquid pretreatments although significant changes were observed in the structure of biomass. Ionic liquid pretreatment is less preferred over other techniques because of high thermal and chemical stability, less dangerous conditions for processing, low vapor pressure of solvents, and retaining liquid state at wide range of temperature. Ionic liquids can be recycled easily and are non-derivatizing. Disadvantage of using ionic liquid pretreatment is that noncompatibility of cellulase and ionic liquids results in the unfolding and inactivation of cellulase. At less viscosity cellulose solubilizes at low temperature; that’s why while using ionic liquids, viscosity is an important factor to be considered regarding the energy consumption of the whole process. High temperatures trigger more side reactions and negative side effects like reducing ionic liquid stability [73].
\nOzone pretreatment is a great option for lignin content reduction in lignocellulosic biomass. In vitro digestibility of biomass is enhanced by the application of ozone pretreatment. Inhibitors are not formed in this pretreatment which is a great advantage because other chemical pretreatments produce toxic residues. In ozone pretreatment, ozone acts as an oxidant in order to break down lignin. Ozone gas is soluble in water and being a powerful oxidant, by breaking down lignin, releases less molecular weight, soluble compounds. Wheat straw, bagasse, cotton straw, green hay, poplar sawdust, peanut, and pine can be pretreated with ozone in order to degrade lignin and hemicellulose; however, only slight changes occur in hemicellulose, whereas almost no changes occur in cellulose. Ozonolysis apparatus consists of ozone catalytic destroyer, iodine trap used for testing efficiency of catalyst, oxygen cylinder, ozone generator, three-way valve, ozone UV spectrophotometer, pressure regulation valve, process gas humidifier, vent, and automatic gas flow control valve [40, 41, 74, 75, 76]. Moisture content hugely effects oxidization of lignin via ozone pretreatment as lignin oxidation decreases with increase in the moisture content of biomass. Ozone mass transfer is limited at less water concentration, which ultimately effects its reactivity with biomass. Longer residence time of ozone is caused by the blockage of pores by water film [77]. During ozonolysis, pH of water decreases because of the formation of organic acids. Alkaline media trigger delignification because it removes lignins that are bonded to carbohydrates [78, 79].
\nBiomass delignification is associated with the production of inhibitory compounds. Certain aromatic and polyaromatic compounds are produced as a result of delignification [80]. Structural changes in lignin are observed by Bule et al. [81] in a study; different lignin subunits showed aromatic opening and degradation of β-O-4 moieties in NMR analysis. How do aromatic structures of control- and ozone-pretreated samples differ? A spectrum showed a decrease in aromatic carbon signal concentration. Changes were observed in methoxy groups that suggest the breakdown of ester-linked structure. Different reactor designs are used for the ozone pretreatment of biomass, for example, batch reactor, Drechsel trap reactor, fixed bed reactor, rotatory bed reactor, and multilayer fixed bed reactor. Plug flow reactors are used by most researchers [82]. Heiske et al. [83] compared the characteristics of single layered and multiple layered bed reactors in order to improve the wheat straw conversion to methane. Straw with 16.2% lignin concentration was obtained from single layered reactor, whereas in multiple layered reactor, lignin concentration decreased up to 7.2% at the bottom layer. Due to wax degradation in ozone-pretreated wheat straw, production of fatty acid compounds is observed by Kádár et al. [84]. About 49% lignin degradation was observed when corn stover was pretreated with ozonolysis in a study by Williams [85].
\nAFEX technique belongs to the category of physicochemical pretreatment methods. In this low temperature process, concentrated ammonia (0.3–2 kg ammonia/kg of dry weight) is used as a catalyst. Ammonia is added to biomass in a reactor of high pressure; after 5–45 min of cooking, pressure is released rapidly. Normally temperature around 90°C is used in this process. Ammonia can be recovered and reused because of its volatility. The principle of AFEX is similar to steam explosion. Apparatus for AFEX includes reactor, thermocouple well, pressure gauge, pressure relief valve, needle valve, sample cylinder, temperature monitor, and vent. Rate of fermentation is seen to be improved by AFEX pretreatment of various grasses and herbaceous crops. For treatment of alfalfa, wheat chaff and wheat straw AFEX technology is used. Hemicellulose and lignin cannot be removed by using AFEX technology; hence, small amount of material is solubilized only. Degradation of hemicellulose into oligomeric sugars and deacetylation occur during AFEX pretreatment which is the reason of hemicellulose insolubility. After AFEX pretreatment of Bermuda grass and bagasse, 90% hydrolysis of cellulose and hemicellulose was achieved. Effectiveness of AFEX pretreatment decreases with increase in the lignin content of biomass, for example, newspaper, woods, nutshells, and aspen chips. In case of AFEX pretreatment for newspaper and aspen chips, maximum hydrolysis yield was 40% and 50%, respectively. So for the treatment of biomass with high lignin content, AFEX pretreatment is not a suitable choice.
\nAmmonia recycle percolation (ARP) is another method that uses ammonia. Aqueous ammonia (10–15 wt %) is used in this method. With a fluid velocity of 1 cm/min and temperature of 150–170°C and residence time of 14 minutes, aqueous ammonia passes through biomass in this pretreatment, and ammonia is recovered afterwards. Under these conditions, ammonia reacts with lignin and causes the breakdown of lignin breakdown linkages. Liquid ammonia is used in AFEX technique whereas in ammonia recycle percolation method/technique, aqueous ammonia is used.
\nIn this method, high-pressure saturated steam is used to treat lignocellulosic biomass, and then suddenly pressure is reduced, due to which lignocellulosic biomass undergoes explosive decompression. Initiation temperature of steam explosion 160–260°C and 0.69–4.83 MPa pressure is provided for few seconds to minutes, and then lignocellulosic biomass is exposed and retained at atmospheric pressure for a period of time; this triggers hydrolysis of hemicellulose and at the end explosive decompression, terminated the whole process. Cellulose hydrolysis potential increases due to the cellulose degradation and lignin transformation caused by high temperature. During the steam explosion pretreatment, acid and other acids formed, which played their role in the hydrolysis of hemicellulose. Fragmentation of lignocellulosic material occurs due to turbulent material flow and rapid flashing of material to atmospheric pressure [86, 87, 88]. In steam explosion pretreatment, the use of sulfuric acid or carbon dioxide decreases time, temperature, and formation of inhibitory products and increases hydrolysis efficiency that ultimately leads to complete removal of hemicellulose. Steam explosion pretreatment is not that effective for pretreating soft woods; however, acid catalyst addition during the process is a prerequisite to make the substrate accessible to hydrolytic enzymes. By using steam, targeted temperature can be achieved to process the biomass without the need of excessive dilution. Sudden release of pressure quenches the whole process at the end and also lowers the temperature. Particulate structure of biomass gets opened by rapid thermal expansion which is used to terminate the reaction. Steam explosion gets affected by certain factors like moisture content, residence time, chip size, and temperature. By two ways optimal hydrolysis and solubilization of hemicellulose can be achieved; either use high temperature and short residence time or low temperature and high residence time. Low energy requirement is a great advantage of steam explosion pretreatment, whereas in mechanical pretreatment 70% more energy is required as compared to steam explosion pretreatment in order to obtain the same, reduced particle size. So far steam explosion pretreatment with addition of a catalyst is tested and came closest to scaling up at commercial level due to its cost-effectiveness. In Canada, at Iogen demonstration plant, steam explosion pretreatment is used at a pilot scale. For hardwood and agriculture residues, steam explosion pretreatment is a very effective pretreatment process.
\nSupercritical carbon dioxide explosion treatment falls in the category of physiochemical pretreatment. Scientists had tried to develop a process cheaper than ammonia fiber explosion and a process which would operate at temperature lower than stream explosion temperature. In this process, supercritical carbon dioxide is used that behaves like a solvent. Supercritical fluids are compressed at room temperature above its critical point. When carbon dioxide is dissolved in water, carbonic acid is formed which causes less corrosiveness due to its special features. During the process, carbon dioxide molecules enter into small pores of lignocellulosic biomass due to its small size. Carbon dioxide pretreatment is operated at low temperature which helped in prevention of sugar decomposition by acid. Cellulosic structure is disrupted when carbon dioxide pressure is released which ultimately increased the accessibility of the substrate to the cellulolytic enzymes for the process of hydrolysis [11, 40, 41, 43]. Dale and Moreira [89] used carbon dioxide pretreatment for alfalfa and observed 75% theoretical release of glucose. Zheng et al. [90] performed experiments to show comparison among ammonia explosion, steam pretreatment, and carbon dioxide pretreatment of recycled paper and sugarcane bagasse. The results showed that carbon dioxide explosion pretreatment is cost-effective than AFEX.
\nHot compressed water is another terminology used for this method of treatment. High temperature (160–220°C) and pressure (up to 5 MPa) are used in this type of pretreatment in order to maintain the liquid state of water. However, chemicals and catalysts are not used in liquid hot water pretreatment method [42]. In this method, water in liquid form remains in contact with lignocellulosic biomass for about 15 min. In this treatment pressure is used to prevent its evaporation, and sudden decompression or expansion in this pretreatment process is not needed. This method has proved to be very effective on sugarcane bagasse, wheat and rye straw, corncobs, and corn stover. Different terms like solvolysis, aqueous fractionation, aquasolv, and hydrothermolysis are used by different researchers to describe this pretreatment method [42, 60, 91]. Based on biomass flow direction and water flow direction into reactor, liquid hot water pretreatment can be performed in three different ways. The first method is co-current pretreatment, which is carried out by heating biomass slurry and water at high temperature, holding it for a controlled residence time at pretreatment conditions, and finally applying cool environment. The second method involves the countercurrent pretreatment that engages pumping of hot water against biomass at controlled conditions. The third method is the flow-through pretreatment, which can be carried out by the flow of hot water through lignocellulosic biomass which acts like a stationary bed.
\nTo investigate the effect of liquid hot water pretreatment, a study was conducted by Abdullah et al. [92] that determined the different hydrolysis rates of cellulose and hemicellulose. Two steps of optimization of various conditions were considered. The first step was performed at less severity for hydrolyzing hemicellulose, whereas the second step was performed at high severity for cellulose depolymerization. Disadvantage of liquid hot water pretreatment is high energy consumption requirement for downstream process because of the involvement of large amount of water. However, the advantage of this process is that chemicals and catalysts are not required and no inhibitor is formed [60].
\nIn this pretreatment method, oxygen/air and water or hydrogen peroxide is used to treat biomass at high temperatures (>120°C) for half an hour at 0.5–2 MPa pressure [11, 93]. This pretreatment method is also used for the treatment of waste water and soil remediation. This method has proven to be very effective for pretreatment of lignin enriched biomass. Certain factors like reaction time, oxygen pressure, and temperature effect the efficiency of wet oxidation pretreatment process. Water acts like acid at high temperature, so it induces hydrolysis reaction as hydrogen ion concentration increases with increase in temperature which ultimately decreases the pH value. Pentose monomers are formed as a result of hemicellulose breakdown in wet oxidation pretreatment, and oxidation of lignin occurs, but cellulose remains least affected. There are certain reports on the addition of alkaline peroxide or sodium carbonate. The addition of these chemical agents help in bringing down temperature reaction and reduce the formation of inhibitory compounds. Efforts to improve the degradation of hemicellulose at high temperature lead to the formation of inhibitory compounds like furfural and furfuraldehydes. However, amount of the production of inhibitors in wet oxidation pretreatment is certainly less than that of liquid hot water pretreatment or steam explosion method. There is extremely less possibility of using this process at industrial scale because of two reasons. One is the combustible nature of oxygen, and the other is the high cost of hydrogen peroxide used in the process [94].
\nSPORL stands for sulfite pretreatment to overcome recalcitrance of lignocellulose, and this technique is used for pretreatment of lignocellulosic biomass [95]. SPORL is performed in two steps. The first step involves treatment of biomass with magnesium or calcium sulfite for the removal of lignin and hemicellulose fractions. The second step involves the reduction in size of pretreated biomass via mechanical disk miler. Effect of SPORL pretreatment was studied by Zhu et al. [22, 23] on spruce chips by employing conditions like temperature 180°C, half an hour time duration, 8–10% bisulfite, and 1.8–3.7% sulfuric acid. By employing these conditions, more than 90% substrate was converted to cellulose when cellulase of 14.6 FPU and 22.5 CBU β-glucosidase was used in hydrolysis. Low-yield inhibitors like hydroxymethyl furfural (HMF) (0.5%) and furfural (0.1%) were produced during this process. These percentages are far less as compared to acid-catalyzed steam pretreatment of spruce. In another study, SPORL-pretreated Popular NE222, beetle-killed lodgepole pine, and Douglas fir were purified. Low contents of sulfur and molecular mass were obtained with high phenolic derivative production [96].
\nSPORL pretreatment on switch grass with temperature ranging between 163 and 197°C, 3–37 min time duration, 0.8–4.2% sulfuric acid dose, and 0.6–7.4% sodium sulfite dose was performed by Zhang et al. [97]. The results with enhanced digestibility by the removal of hemicellulose due to sulfonation and decreased hydrophobicity of lignin were obtained. SPORL yielded 77.3% substrate as compared to 68.1% for dilute acid treatment and 66.6% through alkali pretreatment. When sodium sulfite, sodium hydroxide, and sodium sulfide were used in SPORL pretreatment of switch grass, an improved digestibility of switch grass was achieved. When SPORL treatment was applied with optimized conditions, 97% lignin and 93% hemicellulose were removed from water hyacinth, and 90% hemicellulose and 75% lignin were achieved for rice husk [98].
\nConventional methods for chemical and physical pretreatments require expensive reagents, equipment, and high energy. On the other hand, biological pretreatment requires live microorganisms for the treatment of lignocellulosic material, and this method is more environment friendly and consumes less energy. There are certain microorganism present in nature that exhibit cellulolytic and hemicellulolytic abilities. White-rot, soft-rot, and brown fungi are known for lignin and hemicellulose removal with a very little effect on cellulose. White rot is able to degrade lignin due to the presence of lignin degrading enzymes like peroxidases and laccases. Carbon and nitrogen sources are involved in the regulation of these degrading enzymes [41]. Cellulose is commonly attacked by brown rot, whereas white and soft rot target both lignin and cellulose contents of plant biomass. Commonly used white-rot fungi species are
Pretreatment of wheat straw was studied by Hatakka [100]. The results showed 13% conversion of wheat straw into sugars by
The Internet has irrevocably changed the dynamics of scholarly communication and publishing. Consequently, we find it necessary to indicate, unambiguously, our definition of what we consider to be a published scientific work.
",metaTitle:"Prior Publication Policy",metaDescription:"Prior Publication Policy",metaKeywords:null,canonicalURL:"/page/prior-publication-policy",contentRaw:'[{"type":"htmlEditorComponent","content":"A significant number of working papers, early drafts, and similar work in progress are openly shared online between members of the scientific community. It has become common to announce one’s own research on a personal website or a blog to gather comments and suggestions from other researchers. Such works and online postings are, indeed, published in the sense that they are made publicly available. However, this does not mean that if submitted for publication by IntechOpen they are not original works. We differentiate between reviewed and non-reviewed works when determining whether a work is original and has been published in a scholarly sense or not.
\\n\\nThe significance of Peer Review cannot be overstated when it comes to defining, in our terms, what constitutes a published scientific work. Peer Review is widely considered to be the cornerstone of modern publishing processes and the key value-adding contribution to a scholarly manuscript that a publisher can make.
\\n\\nOther than the issue of originality, research misconduct is another major issue that all publishers have to address. IntechOpen’s Retraction & Correction Policy and various publication ethics guidelines identify both redundant publication and (self)plagiarism to fall within the definition of research misconduct, thus constituting grounds for rejection or the issue of a Retraction if the work has already been published.
\\n\\nIn order to facilitate the tracking of a manuscript’s publishing history and its development from its earliest draft to the manuscript submitted, we encourage Authors to disclose any instances of a manuscript’s prior publication, whether it be through a conference presentation, a newspaper article, a working paper publicly available in a repository or a blog post.
\\n\\nA note to the Academic Editor containing detailed information about a submitted manuscript’s previous public availability is the preferred means of reporting prior publication. This helps us determine if there are any earlier versions of a manuscript that should be disclosed to our readers or if any of those earlier versions should be cited and listed in a manuscript’s references.
\\n\\nSome basic information about the editorial treatment of different varieties of prior publication is laid out below:
\\n\\n1. CONFERENCE PAPERS & PRESENTATIONS
\\n\\nGiven that conference papers and presentations generally pass through some sort of peer or editorial review, we consider them to be published in the accepted scholarly sense, particularly if they are published as a part of conference proceedings.
\\n\\nAll submitted manuscripts originating from a previously published conference paper must contain at least 50% of new original content to be accepted for review and considered for publication.
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\\n\\n2. NEWSPAPER & MAGAZINE ARTICLES
\\n\\nNewspaper and magazine articles usually do not pass through any extensive peer or editorial review and we do not consider them to be published in the scholarly sense. Articles appearing in newspapers and magazines rarely possess the depth and structure characteristic of scholarly articles.
\\n\\nSubmitted manuscripts stemming from a previous newspaper or magazine article will be accepted for review and considered for publication. However, Authors are strongly advised to report any such publication in an accompanying note to the External Editor.
\\n\\nAs with the conference papers and presentations, Authors should obtain any necessary permissions from the newspaper or magazine that published the work, and indicate that they have done so in a note to the External Editor.
\\n\\n3. GREY LITERATURE
\\n\\nWhite papers, working papers, technical reports and all other forms of papers which fall within the scope of the ‘Luxembourg definition’ of grey literature do not pass through any extensive peer or editorial review and we do not consider them to be published in the scholarly sense.
\\n\\nAlthough such papers are regularly made publicly available via personal websites and institutional repositories, their general purpose is to gather comments and feedback from Authors’ colleagues in order to further improve a manuscript intended for future publication.
\\n\\nWhen submitting their work, Authors are required to disclose the existence of any publicly available earlier drafts in a note to the Academic Editor. In cases where earlier drafts of the submitted version of the manuscript are publicly available, any overlap between the versions will generally not be considered an instance of self-plagiarism.
\\n\\n4. SOCIAL MEDIA, BLOG & MESSAGE BOARD POSTINGS
\\n\\nWe feel that social media, blogs and message boards are generally used with the same intention as grey literature, to formulate ideas for a manuscript and gather early feedback from like-minded researchers in order to improve a particular piece of work before submitting it for publication. Therefore, we do not consider such internet postings to be publication in the scholarly sense.
\\n\\nNevertheless, Authors are encouraged to disclose the existence of any internet postings in which they outline and describe their research or posted passages of their manuscripts in a note to the Academic Editor. Please note that we will not strictly enforce this request in the same way that we would instructions we consider to be part of our conditions of acceptance for publication. We understand that it may be difficult to keep track of all one’s internet postings in which the researcher´s current work might be mentioned.
\\n\\nIn cases where there is any overlap between the Author´s submitted manuscript and related internet postings, we will generally not consider it to be an instance of self-plagiarism. This also holds true for any co-Author as well.
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\\n"}]'},components:[{type:"htmlEditorComponent",content:'A significant number of working papers, early drafts, and similar work in progress are openly shared online between members of the scientific community. It has become common to announce one’s own research on a personal website or a blog to gather comments and suggestions from other researchers. Such works and online postings are, indeed, published in the sense that they are made publicly available. However, this does not mean that if submitted for publication by IntechOpen they are not original works. We differentiate between reviewed and non-reviewed works when determining whether a work is original and has been published in a scholarly sense or not.
\n\nThe significance of Peer Review cannot be overstated when it comes to defining, in our terms, what constitutes a published scientific work. Peer Review is widely considered to be the cornerstone of modern publishing processes and the key value-adding contribution to a scholarly manuscript that a publisher can make.
\n\nOther than the issue of originality, research misconduct is another major issue that all publishers have to address. IntechOpen’s Retraction & Correction Policy and various publication ethics guidelines identify both redundant publication and (self)plagiarism to fall within the definition of research misconduct, thus constituting grounds for rejection or the issue of a Retraction if the work has already been published.
\n\nIn order to facilitate the tracking of a manuscript’s publishing history and its development from its earliest draft to the manuscript submitted, we encourage Authors to disclose any instances of a manuscript’s prior publication, whether it be through a conference presentation, a newspaper article, a working paper publicly available in a repository or a blog post.
\n\nA note to the Academic Editor containing detailed information about a submitted manuscript’s previous public availability is the preferred means of reporting prior publication. This helps us determine if there are any earlier versions of a manuscript that should be disclosed to our readers or if any of those earlier versions should be cited and listed in a manuscript’s references.
\n\nSome basic information about the editorial treatment of different varieties of prior publication is laid out below:
\n\n1. CONFERENCE PAPERS & PRESENTATIONS
\n\nGiven that conference papers and presentations generally pass through some sort of peer or editorial review, we consider them to be published in the accepted scholarly sense, particularly if they are published as a part of conference proceedings.
\n\nAll submitted manuscripts originating from a previously published conference paper must contain at least 50% of new original content to be accepted for review and considered for publication.
\n\nAuthors are required to report any links their manuscript might have with their earlier conference papers and presentations in a note to the Academic Editor, as well as in the manuscript itself. Additionally, Authors should obtain any necessary permissions from the publisher of their conference paper if copyright transfer occurred during the publishing process. Failure to do so may prevent Us from publishing an otherwise worthy work.
\n\n2. NEWSPAPER & MAGAZINE ARTICLES
\n\nNewspaper and magazine articles usually do not pass through any extensive peer or editorial review and we do not consider them to be published in the scholarly sense. Articles appearing in newspapers and magazines rarely possess the depth and structure characteristic of scholarly articles.
\n\nSubmitted manuscripts stemming from a previous newspaper or magazine article will be accepted for review and considered for publication. However, Authors are strongly advised to report any such publication in an accompanying note to the External Editor.
\n\nAs with the conference papers and presentations, Authors should obtain any necessary permissions from the newspaper or magazine that published the work, and indicate that they have done so in a note to the External Editor.
\n\n3. GREY LITERATURE
\n\nWhite papers, working papers, technical reports and all other forms of papers which fall within the scope of the ‘Luxembourg definition’ of grey literature do not pass through any extensive peer or editorial review and we do not consider them to be published in the scholarly sense.
\n\nAlthough such papers are regularly made publicly available via personal websites and institutional repositories, their general purpose is to gather comments and feedback from Authors’ colleagues in order to further improve a manuscript intended for future publication.
\n\nWhen submitting their work, Authors are required to disclose the existence of any publicly available earlier drafts in a note to the Academic Editor. In cases where earlier drafts of the submitted version of the manuscript are publicly available, any overlap between the versions will generally not be considered an instance of self-plagiarism.
\n\n4. SOCIAL MEDIA, BLOG & MESSAGE BOARD POSTINGS
\n\nWe feel that social media, blogs and message boards are generally used with the same intention as grey literature, to formulate ideas for a manuscript and gather early feedback from like-minded researchers in order to improve a particular piece of work before submitting it for publication. Therefore, we do not consider such internet postings to be publication in the scholarly sense.
\n\nNevertheless, Authors are encouraged to disclose the existence of any internet postings in which they outline and describe their research or posted passages of their manuscripts in a note to the Academic Editor. Please note that we will not strictly enforce this request in the same way that we would instructions we consider to be part of our conditions of acceptance for publication. We understand that it may be difficult to keep track of all one’s internet postings in which the researcher´s current work might be mentioned.
\n\nIn cases where there is any overlap between the Author´s submitted manuscript and related internet postings, we will generally not consider it to be an instance of self-plagiarism. This also holds true for any co-Author as well.
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Methods of analysis, deduction and induction and comparative method were used in this paper. The paper reviews and analyzes statistical data of international trade with China as well as of Chinese outbound tourism and provides an estimate of what share Slovenia and Montenegro received. Starting off with the research question ‘Are the revenue from the export of China and revenue from Chinese inbound tourism (‘invisible export’) in gross domestic product (GDP) growing?’ we have concluded that China is becoming a more important partner for both countries. There is a strong positive correlation between exports in China and the number of overnights of Chinese tourists both in Slovenia and Montenegro and that expenditure of Chinese tourists visiting these two countries increases every year as well. Expenditure and share of expenditure of Chinese tourists visiting Slovenia and Montenegro in Chinese exports increase every year. Share of expenditure of Chinese tourists and export in Chinese GDP increase every year.",book:{id:"5492",slug:"international-trade-on-the-brink-of-change",title:"International Trade",fullTitle:"International Trade - On the Brink of Change"},signatures:"Andrej Raspor, Ana Stranjančević, Iva Bulatović and Darko\nLacmanović",authors:[{id:"193991",title:"Dr.",name:"Andrej",middleName:null,surname:"Raspor",slug:"andrej-raspor",fullName:"Andrej Raspor"},{id:"194137",title:"Dr.",name:"Ana",middleName:null,surname:"Stranjančević",slug:"ana-stranjancevic",fullName:"Ana Stranjančević"},{id:"194138",title:"Dr.",name:"Iva",middleName:null,surname:"Bulatović",slug:"iva-bulatovic",fullName:"Iva Bulatović"},{id:"194139",title:"Dr.",name:"Darko",middleName:null,surname:"Lacmanović",slug:"darko-lacmanovic",fullName:"Darko Lacmanović"}]}],mostDownloadedChaptersLast30Days:[{id:"58969",title:"Corruption, Causes and Consequences",slug:"corruption-causes-and-consequences",totalDownloads:27405,totalCrossrefCites:11,totalDimensionsCites:13,abstract:"Corruption is a constant in the society and occurs in all civilizations; however, it has only been in the past 20 years that this phenomenon has begun being seriously explored. It has many different shapes as well as many various effects, both on the economy and the society at large. Among the most common causes of corruption are the political and economic environment, professional ethics and morality and, of course, habits, customs, tradition and demography. Its effects on the economy (and also on the wider society) are well researched, yet still not completely. Corruption thus inhibits economic growth and affects business operations, employment and investments. It also reduces tax revenue and the effectiveness of various financial assistance programs. The wider society is influenced by a high degree of corruption in terms of lowering of trust in the law and the rule of law, education and consequently the quality of life (access to infrastructure, health care). There also does not exist an unambiguous answer as to how to deal with corruption. Something that works in one country or in one region will not necessarily be successful in another. 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The theoretical propositions reveal that while trade openness leads to a greater economic efficiency, market imperfections, differences in technology and endowments may lead to adverse effect of trade liberalisation on individual countries. In this chapter, we re-examine the empirical evidence pointing to the benefits of trade liberalisation and bring theoretical issues on possible adverse effect of openness to the fore. It has been argued that ‘passive’ trade liberalisation may not necessarily lead to positive economic outcomes, particularly in less advanced transition economies. Considering the empirical work on the matter, a lot of controversies are related to measurement issues. We find that openness measured by trade intensity indicators may lead to misleading conclusions about the trade growth nexus. 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More specifically, I explored the consequences of the dynamics detected by the models on monetary policy implementation for 10 OECD countries. This study indicates that factors that may cause a rise in short-term interest rates with respect to the USA can lead to volatility in exchange rates and thus macroeconomic instability. It is also implied that sustaining macroeconomic growth and decreasing inflation can result in increased export performance, which in turn provides the amount of US dollars to curb volatility in US dollar quotations. Accordingly, this study reveals that high importance should be given to both monetary and non-monetary factors in the open-economy framework to detect the possible impacts on trade and capital flows by dynamic stochastic general equilibrium (DSGE) models. Due to their exchange rate risk of economic agents, I also suggest that the economic policy makers of these countries had better create a theoretical framework including financial frictions, economic agents’ preferences and different shocks to smooth the variations in exchange rates and minimise the negative outcomes of Brexit.",book:{id:"6487",slug:"trade-and-global-market",title:"Trade and Global Market",fullTitle:"Trade and Global Market"},signatures:"Oguzhan Ozcelebi",authors:[{id:"226325",title:"Prof.",name:"Oguzhan",middleName:null,surname:"Ozcelebi",slug:"oguzhan-ozcelebi",fullName:"Oguzhan Ozcelebi"}]},{id:"53827",title:"Malaysia and China: The Trade Balances, Foreign Exchanges and Crises Impacts",slug:"malaysia-and-china-the-trade-balances-foreign-exchanges-and-crises-impacts",totalDownloads:2046,totalCrossrefCites:0,totalDimensionsCites:0,abstract:"China appears as the biggest trading partner for ASEAN economies, but it is inconclusive whether the complementarities between China and regional economies offset China’s competitive threat. This study tries to assess if real exchange fluctuations and the demand-supply channels determine the Malaysia-China trade balances in the global crises era, 1997–2010. The finding generally supports the complementary role of China in the Malaysia-China bilateral trading. However, despite the long-run effect of real exchange on trade balances, the Keynesian demand channel was not uphold during and after the global financial crisis—due to the contractionary effect on Malaysian output. The Chinese inflation impact is also not evident following the foreign exchange shocks. Meanwhile, currency devaluation for exports gains is insufficient to sustain Malaysia output expansion against China. Further productivity growth in real and tradable sectors is essentially needed.",book:{id:"5492",slug:"international-trade-on-the-brink-of-change",title:"International Trade",fullTitle:"International Trade - On the Brink of Change"},signatures:"Tze-Haw Chan",authors:[{id:"191390",title:"Dr.",name:"Chan",middleName:null,surname:"Tze-Haw",slug:"chan-tze-haw",fullName:"Chan Tze-Haw"}]},{id:"53059",title:"Brazil in the Twenty-First-Century International Trade: Challenges and Opportunities",slug:"brazil-in-the-twenty-first-century-international-trade-challenges-and-opportunities",totalDownloads:1731,totalCrossrefCites:3,totalDimensionsCites:3,abstract:"This chapter discusses the impacts of globalization on international trade patterns and the required shifts in trade policies. Highlighting the effects of production fragmentation, geographic dispersion and the expansion of global value chains (GVCs), the chapter outlines the Brazilian experience to illustrate the difficulties that various countries face in acknowledging this economic reality and providing appropriate policy responses. It draws on the global value chains literature to analyze Brazil’s foreign trade policies implemented during the recent ruling of the Labor Party (PT) presidents Lula da Silva and Dilma Rousseff (2003 to 2015), discussing the Brazilian strategy (or the lack of one) to integrate into global value chains. Results of this exercise have led to the conclusion that a non–GVC-oriented trade policy has allowed Brazil to integrate only superficially into globalized international production and commercial flows. The chapter concludes providing an outlook on the policy shifts required for increasing Brazil’s insertion into global value chains and boosting a more prominent role in international trade.",book:{id:"5492",slug:"international-trade-on-the-brink-of-change",title:"International Trade",fullTitle:"International Trade - On the Brink of Change"},signatures:"Susan Elizabeth Martins Cesar de Oliveira",authors:[{id:"191481",title:"Dr.",name:"Susan",middleName:"Elizabeth Martins Cesar De",surname:"Oliveira",slug:"susan-oliveira",fullName:"Susan Oliveira"}]}],onlineFirstChaptersFilter:{topicId:"463",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:87,numberOfOpenTopics:6,numberOfUpcomingTopics:0,issn:"2633-1403",doi:"10.5772/intechopen.79920",isOpenForSubmission:!0},{id:"7",title:"Biomedical Engineering",numberOfPublishedBooks:12,numberOfPublishedChapters:98,numberOfOpenTopics:3,numberOfUpcomingTopics:0,issn:"2631-5343",doi:"10.5772/intechopen.71985",isOpenForSubmission:!0}],lsSeriesList:[{id:"11",title:"Biochemistry",numberOfPublishedBooks:27,numberOfPublishedChapters:287,numberOfOpenTopics:4,numberOfUpcomingTopics:0,issn:"2632-0983",doi:"10.5772/intechopen.72877",isOpenForSubmission:!0},{id:"25",title:"Environmental Sciences",numberOfPublishedBooks:1,numberOfPublishedChapters:9,numberOfOpenTopics:4,numberOfUpcomingTopics:0,issn:"2754-6713",doi:"10.5772/intechopen.100362",isOpenForSubmission:!0},{id:"10",title:"Physiology",numberOfPublishedBooks:11,numberOfPublishedChapters:139,numberOfOpenTopics:4,numberOfUpcomingTopics:0,issn:"2631-8261",doi:"10.5772/intechopen.72796",isOpenForSubmission:!0}],hsSeriesList:[{id:"3",title:"Dentistry",numberOfPublishedBooks:8,numberOfPublishedChapters:129,numberOfOpenTopics:0,numberOfUpcomingTopics:2,issn:"2631-6218",doi:"10.5772/intechopen.71199",isOpenForSubmission:!1},{id:"6",title:"Infectious Diseases",numberOfPublishedBooks:13,numberOfPublishedChapters:107,numberOfOpenTopics:3,numberOfUpcomingTopics:1,issn:"2631-6188",doi:"10.5772/intechopen.71852",isOpenForSubmission:!0},{id:"13",title:"Veterinary Medicine and Science",numberOfPublishedBooks:10,numberOfPublishedChapters:103,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:12,numberOfOpenTopics:2,numberOfUpcomingTopics:1,issn:null,doi:"10.5772/intechopen.100359",isOpenForSubmission:!0},{id:"23",title:"Education and Human Development",numberOfPublishedBooks:0,numberOfPublishedChapters:0,numberOfOpenTopics:2,numberOfUpcomingTopics:0,issn:null,doi:"10.5772/intechopen.100360",isOpenForSubmission:!1},{id:"24",title:"Sustainable Development",numberOfPublishedBooks:0,numberOfPublishedChapters:10,numberOfOpenTopics:4,numberOfUpcomingTopics:1,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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He completed a one-year Post-Doctoral Fellowship awarded by the DFAIT (Foreign Affairs and International Trade Canada) at the Institute of Biomedical Engineering of the University of New Brunswick (Canada) in 2010. Currently, he is Professor in the Faculty of Electrical Engineering (UFU). He has authored and co-authored more than 200 peer-reviewed publications in Biomedical Engineering. He has been a researcher of The National Council for Scientific and Technological Development (CNPq-Brazil) since 2009. He has served as an ad-hoc consultant for CNPq, CAPES (Coordination for the Improvement of Higher Education Personnel), FINEP (Brazilian Innovation Agency), and other funding bodies on several occasions. He was the Secretary of the Brazilian Society of Biomedical Engineering (SBEB) from 2015 to 2016, President of SBEB (2017-2018) and Vice-President of SBEB (2019-2020). 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His fields of interest are anterior segment disease, keratoconus, glaucoma, corneal dystrophies, and cataracts. His research topics include\nintraocular lens power calculation, eye modification induced by refractive surgery, glaucoma progression, and validation of new diagnostic devices in ophthalmology. \nHe has published more than 100 papers in international and Italian scientific journals, more than 60 in journals with impact factors, and chapters in international and Italian books. 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