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",isbn:"978-1-83969-591-9",printIsbn:"978-1-83969-590-2",pdfIsbn:"978-1-83969-592-6",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!0,hash:"e39a567d9b6d2a45d0a1d927362c9005",bookSignature:"Dr. Umar Zakir Abdul Hamid and Associate Prof. Ahmad 'Athif Mohd Faudzi",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/10778.jpg",keywords:"Model-Based Control, Optimal Control, Industrial Automation, Linear Actuator, Nonlinear Actuator, System Identification, Soft Robotics, Service Robots, Unmanned Aerial Vehicle, Autonomous Vehicle, Process Engineering, Chemical Engineering",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"February 25th 2021",dateEndSecondStepPublish:"March 25th 2021",dateEndThirdStepPublish:"May 24th 2021",dateEndFourthStepPublish:"August 12th 2021",dateEndFifthStepPublish:"October 11th 2021",remainingDaysToSecondStep:"21 days",secondStepPassed:!1,currentStepOfPublishingProcess:2,editedByType:null,kuFlag:!1,biosketch:"Umar Zakir Abdul Hamid, Ph.D. is an autonomous vehicle expert, and with more than 30 scientific publications under his belt, Umar actively participates in global automotive standardization efforts and is a Secretary for a Society of Automotive Engineers (SAE) Committee.",coeditorOneBiosketch:"Associate Professor Dr. Ahmad 'Athif Mohd Faudzi has more than 100 scientific publications as of 2021 and is currently leading a team of 18 researchers in UTM doing research works on control, automation, and actuators.",coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"268173",title:"Dr.",name:"Umar Zakir Abdul",middleName:null,surname:"Hamid",slug:"umar-zakir-abdul-hamid",fullName:"Umar Zakir Abdul Hamid",profilePictureURL:"https://mts.intechopen.com/storage/users/268173/images/system/268173.jpg",biography:"Umar Zakir Abdul Hamid, PhD has been working in the autonomous vehicle field since 2014 with various teams in different countries (Malaysia, Singapore, Japan, Finland). He is now leading a team of 12 engineers working in the Autonomous Vehicle Software Product Development with Sensible 4, Finland. Umar is one of the recipients for the Finnish Engineering Award 2020 for his contributions to the development of all-weather autonomous driving solutions with the said firm. He is an aspiring automotive thought leader and often invited as a guest and keynote speaker to industrial and technical events. With more than 30 scientific and technical publications as author and editor under his belt, Umar actively participates in global automotive standardization efforts where he is a Secretary for a Society Automotive Engineers (SAE) Committee.",institutionString:"Sensible 4 Oy",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"1",institution:null}],coeditorOne:{id:"204176",title:"Associate Prof.",name:"Ahmad 'Athif Mohd",middleName:null,surname:"Faudzi",slug:"ahmad-'athif-mohd-faudzi",fullName:"Ahmad 'Athif Mohd Faudzi",profilePictureURL:"https://mts.intechopen.com/storage/users/204176/images/system/204176.png",biography:"Assoc. Prof. Ir. Dr. Ahmad `Athif Bin Mohd Faudzi received the B. Eng. in Computer Engineering, the M. Eng. in Mechatronics and Automatic Control from Universiti Teknologi Malaysia, Malaysia and the Dr. Eng. in System Integration from Okayama University, Japan in 2004, 2006, and 2010 respectively. He was a Visiting Research Fellow at the Tokyo Institute of Technology from 2015 to 2017. From March 2019 to date, he is the Director of the Centre for Artificial Intelligence and Robotics (CAIRO), Universiti Teknologi Malaysia, Malaysia. He is mainly engaged in the research fields of actuators (pneumatic, soft mechanism, hydraulic, and motorized actuators) concentrate his work in field robotics, bioinspired robotics and biomedical applications. He is a Professional Engineer (PEng), a Charted Engineer (CEng), a member of the IEEE Robotics and Automation Society (RAS) and a member of two Akademi Sains Malaysia Special Interest Group (ASM SIG) of Biodiversity and Robotics. He is also the recipient of Top Research Scientist Malaysia (TRSM) 2020 in the area of Robotics. As of 2021, he has more than 100 scientific publications and leads a team of 18 researchers in UTM doing research works on automation and actuators.",institutionString:"University of Technology Malaysia",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"University of Technology Malaysia",institutionURL:null,country:{name:"Malaysia"}}},coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"11",title:"Engineering",slug:"engineering"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"346794",firstName:"Mia",lastName:"Miskulin",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/346794/images/15795_n.png",email:"mia@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review, to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"4816",title:"Face Recognition",subtitle:null,isOpenForSubmission:!1,hash:"146063b5359146b7718ea86bad47c8eb",slug:"face_recognition",bookSignature:"Kresimir Delac and Mislav Grgic",coverURL:"https://cdn.intechopen.com/books/images_new/4816.jpg",editedByType:"Edited by",editors:[{id:"528",title:"Dr.",name:"Kresimir",surname:"Delac",slug:"kresimir-delac",fullName:"Kresimir Delac"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3621",title:"Silver Nanoparticles",subtitle:null,isOpenForSubmission:!1,hash:null,slug:"silver-nanoparticles",bookSignature:"David Pozo Perez",coverURL:"https://cdn.intechopen.com/books/images_new/3621.jpg",editedByType:"Edited by",editors:[{id:"6667",title:"Dr.",name:"David",surname:"Pozo",slug:"david-pozo",fullName:"David Pozo"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"51255",title:"Toughness Assessment and Fracture Mechanism of Brittle Thin Films Under Nano-Indentation",doi:"10.5772/64117",slug:"toughness-assessment-and-fracture-mechanism-of-brittle-thin-films-under-nano-indentation",body:'\nOver decades, hard thin film has been extensively utilized as protective layers to minimize detrimental influences of the environment. However, hard film usually has a brittle character, and hence fracture failure often occurs in hard thin film when it is subjected to high stress. In designing a high-performance film, it is of great importance to learn the fracture properties of the coating.
\nBecause of the size limitation, the fracture behavior of brittle thin films cannot be easily determined by the standard linear elastic fracture mechanics tension test or the three-point bending test. In this case, nano-indentation may be the only effective technique to quantitatively characterize the fracture toughness of the film. Anstis et al. [1] were the first to propose an indentation method to evaluate the fracture toughness of brittle materials by measuring the length of radial cracks. In their approach, the assumption was that radial cracks can develop well without any confinement during loading. This classical method has been successfully applied to some “thick” film/substrate systems where radial cracks are well propagated [2–5]. However, it is invalid for brittle thin films/substrate systems because the substrate effect is not negligible and has an effect on crack propagation. For brittle thin films, the energy method proposed by Li et al. [6] has been widely used in recent years for the measurement of fracture toughness although it suffers from some deficiencies that require further research. Subsequently, a number of studies [7–10] have proposed improvements to this energy method. An alternative approach for assessing the fracture toughness of brittle thin films is to use a stress-based model. The most important prerequisite for a stress-based model is understanding the stress distribution in brittle films. Finite element (FE) analysis [11–13] and simplified analytical solutions [14, 15] are two efficient ways to predict stress distribution under indentation. It is evident that stress distribution depends strongly on the indenter shape and the substrate. Different indenter shapes and substrates can result in various crack patterns. A number of indentation-induced crack patterns have been reported, such as radial cracks [16–18], ring cracks [7, 19, 20], picture-frame cracks [21, 22], spiral cracks [23, 24], and spalling [25, 26]. Understanding the mechanism of the above crack patterns by indentation would greatly support the development of a stress-based model.
\nThis chapter proposes a comprehensive and systematic view of fracture toughness assessment methods and fracture mechanisms for brittle thin films under nano-indentation. First, we present a review of the current indentation methods for characterizing the fracture toughness of brittle films, namely the classical method, energy method, numerical method, and stress-based method. The limits and application range of each method are discussed. Next, we review the observation of crack patterns in brittle thin films/substrates under nano-indentation. The various effects of indenter shape, substrate effects, and load levels on crack formation are discussed to gain an understanding of the fracture mechanism of cracking. The chapter concludes with a summary and a roadmap for future trends.
\nIt is agreed that a Vickers’ pyramid indenter may produce a median/radial crack pattern in brittle materials. Figure 1(a) shows a schematic representation of the median/radial crack pattern induced by a Vickers indenter. The average length of the radial cracks is cm, and a is the impression length. Lawn et al. [27] reported that the elastic/plastic field in material under indentation can be considered as a residual field in an unloaded solid and an ideal elastic field. Then the fracture toughness of materials can be obtained by measuring the length of the radial crack and the critical indentation load, P, as follows:
\nwhere χ is a factor relating to the indenter geometry and material properties of the tested specimen and is expressed in the form of
\nwhere E and H are the elastic moduli and hardness of the material, respectively. ξ is a constant depending on the indenter geometry and can be determined by linear fitting of the relation between P and
Schematic representation of the crack pattern induced by Vickers indenter: (a) the radial/median crack and (b) the Palmquist crack, based on [28].
The Palmquist crack is another commonly observed crack pattern in brittle materials caused by a Vickers indenter, as shown in Figure 1(b). To assess the fracture toughness of materials in which the Palmquist crack pattern is detected, Eq. (1) needs to be modified as
\nwhere ξv is a material constant and has the value of 0.015 reported in [29]. l is the average length of a Palmquist crack.
\nAlthough Eqs. (1) and (3) were initially derived from the stress distribution in material under a Vickers indenter, they can be extended to other types of pyramidal indenters, such as a Berkovich indenter and a cube-corner indenter. Comparison of the toughness results of various brittle materials obtained by a Berkovich indenter and a Vickers indenter in [29] showed that the Berkovich indenter could provide more accurate results at a low load range than those of the Vickers indenter, as the shape of the Berkovich indenter is sharper than that of the Vickers indenter. Furthermore, a cube-corner indenter is generally considered the sharpest indenter. It was reported by Pharr [30], therefore, that the cube-corner indenter can significantly reduce the cracking threshold, and is most suitable for toughness measurement of brittle materials at small load compared to other types of pyramidal indenter.
\nIt should be stated that the residual stress in materials has an effect on the elastic/plastic field, and thus on the results of the predicted toughness. If there is a considerable amount of residual stress in brittle materials, Eq. (1) should be changed as follows [31]:
\nwhere m denotes a dimensionless factor and σR denotes the residual stress in the materials.
\nEqs. (1)–(4) have been successfully utilized with “thick” film/substrate systems [2–5] where the radial cracks or Palmquist cracks could propagate well. However, the toughness measurement of a “thin” film can be affected by the substrate effect. As a rule of thumb, the substrate effect is negligible when the indentation depth is less than 10% of the film thickness for a soft film/hard substrate. If the film thickness is submicro, the maximum indentation depth should be lower than tens of nanometers in order to minimize the influence of the substrate. However, for most nano-indenters, it is nearly impossible to keep an ideal pyramidal shape on such a small scale. Furthermore, the “1/10 principle” is not adequate for a hard film/soft substrate, which results in an even lower peak depth in order to reduce the influence of the substrate. Therefore, other methods should be employed to evaluate the fracture toughness of brittle thin films.
\nTheoretically, using the energy method to characterize fracture toughness could minimize the substrate effect. Therefore, the energy method may be the most efficient method for the toughness measurement of brittle thin films. Li et al. [6] were the first to propose an energy method for assessing the fracture toughness of brittle thin films, and fracture toughness is given by
\nwhere Ef is the film modulus, ν is the Poisson’s ratio of the coating, lm is the crack length in the film plane, Ufr is the fracture energy, t’ is the effective film thickness, and has the form of
\nwhere t is film thickness and θ is the angle of the crack edge.
\nThe key point of the energy method is to identify the dissipated energy according to the indentation load-depth curve. First, the correspondence between the load-depth curve and crack formation needs to be determined. For a perfect “pop-in” as illustrated in Figure 2(a), there is a definite step in the loading curve suggesting where the crack initiates and ends. During the crack formation, a significant amount of energy is dissipated, which causes the discontinuity in the loading curve.
\nSchematic representation of (a) a perfect “pop-in” and (b) a “sliding pop-in” in load-depth curves [7].
A more general case is a “sliding pop-in” in the load-depth curve when a high-resolution transducer is used in an experiment. In Figure 2(b), there is a clear starting point indicating the crack initiation. However, there is no end point in the load curve. Fu et al. [7] developed a method to define the end point of the “sliding pop-in” in a load-depth curve. They assumed that ∂P/∂h2 remains constant before and after a circumferential crack formation. Figure 3 shows ∂P/∂h2 as a function of h2. A quick drop of ∂P/∂h2 is observed, indicating the onset point of the “sliding pop-in” in the load-depth curve and also the initiation of the circumferential crack. After the crack is complete, the derivative ∂P/∂h2 becomes stable again and the value is similar to that before the crack initiation. Accordingly, the end point of the “sliding pop-in” is identified.
\nA method to define the end point of a “sliding pop-in” [7].
Schematic representation of a method to obtain the dissipated energy.
After the start point and end point of the crack in a loading curve have been obtained, the dissipated energy during crack formation may be calculated by different methods. For instance, a schematic of the load-depth curve in [6] is illustrated in Figure 4. The crack initiates at point A and ends at point B. If the crack does not occur, the loading curve follows the trend of the OA curve and reaches the point C. Hence, the enclosed area SABC is assumed to represent the dissipated energy during cracking [6]. This method is widely used to evaluate the fracture toughness of thin films, even though it ignores the change in elastic-plastic stress distribution of the film before and after crack propagation.
\nGiven the shortcomings of the method in [6], Chen et al. [8] developed another method to define the dissipated energy by using the curve of total work as a function of displacement. Figure 5 shows that a crack initiates at A and ends at D. The first work-displacement curve is extrapolated from A to C, and the second work-displacement curve is extrapolated from D to B. The work difference between CD and AB is considered to represent the dissipated energy during the crack formation. The negative or positive of AB relies on the film/substrate system. This method examines the work difference before and after cracking, and thus the energy caused by the change of elastic-plastic behavior is excluded. However, the accuracy of this method is still dependent on extrapolation of the imaginary work-displacement curves.
\nSchematic representation of a method to determine the dissipated energy CD-AB. Compared to CD, AB is positive in (a) or negative in (b), depending on the actual coated systems.
There are also a few studies focusing on estimating the bounds of the fracture energy. For instance, Toonder et al. [9] proposed an approach to evaluate the upper and lower limits of fracture energy by considering a material as pure elastic or perfect plastic. In Figure 6(a), if the film/substrate system behaves as an elastic material, all the deformation will recover after unloading as the dashed curve BO. If the film/substrate system displays perfect plastic behavior, there is no elastic recovery. The unloading curves before and after the crack will be AC and BD, respectively. In practice, the film/substrate system is an elastic-perfect plastic material, and therefore, the dissipated energy should be between the enclosed area of ABO and ABDC. Hence, the upper and lower limits of the dissipated energy during cracking are given by
\n(a) A method and (b) an improved method to define dissipated energy using load control and (c) displacement control.
Further, Chen et al. [10] enhanced the method in [9] by performing a more reliable analysis of the unloading curves, as shown in Figure 6(b). The bounds of the fracture toughness are expressed as
\nSimilarly, an approach to calculate the bounds of fracture energy of the film system under a displacement control is shown in Figure 6(c). The dissipated energy is given by [10]
\nThe energy method is efficient for obtaining the fracture toughness of brittle thin films because there is no need for information about crack propagation, such as crack size. However, the accuracy of the energy method depends highly on either the extrapolated imaginary load-depth curve or the imaginary total work-displacement curve. In experiments, it is impossible to know the accuracy of the imaginary extrapolated curve as the trend of the loading curve can be affected by many factors, such as roughness of the surface, defects in the films and the ratio of indentation depth to film thickness.
\nThe stress-based method is a straightforward approach for assessing the fracture toughness of brittle thin films. It is based on stress distribution in the brittle thin film under an indenter. To date, some analytical solutions have been derived for stress distribution in an incompressible elastic coating [32], compressible elastic coating/rigid substrate [33], and elastic film/elastic substrate [34, 35]. However, due to the complex elastic-plastic properties of film and substrate and the boundary condition of the indenter and film, it is not feasible to derive an analytical solution for evaluating the stress distribution in the brittle film/elastic-plastic substrate system. FE analysis is a useful tool for obtaining the fracture stress in film under indentation. Hence, stress distribution in a film is usually determined using FE analysis. For example, for a brittle film on a ductile substrate, the stress distribution under a conical indenter is obtained by FE analysis and is shown in Figure 7. A high tensile radial stress occurs at the surface of a film, which can open a crack.
\nRadial stress in film at the surface for various ratios of indentation depth h and film thickness t [7].
Stress applied to a crack during indentation: (a) constant stress and (b) linear stress [15].
When the stress distribution in a film has been obtained, the fracture toughness can be obtained by assuming the stress on pre-existing cracks as a uniformly distributed crack and a linearly distributed crack as shown in Figure 8(a) and (b). Based on the linear fracture mechanics, fracture toughness is expressed as
\nwhere s1 is a constant stress, s2 is the highest stress in a linear stress distribution, b is the crack length, and 1.12 and 0.439 are the geometric factors in Figure 8(a) and (b), respectively.
\nAn initial short crack may grow to a circumferential channel crack by self-adjusting to a curved shape when the energy release rate Gps by linear fracture mechanics is the same at each point, as reported by Steffensen et al. [11]. The energy release rate for the circumferential channel crack, Gss, is given by
\nGps is expressed as
\nThen the fracture toughness can be obtained by calculating the maximum of Gss as proposed by Madsen et al. [12],
\nAn alternative method for determining the fracture stress and thus the fracture toughness is to use a simplified stress-based model. The simplified model can give an explicit expression of fracture stress for a particular type of coated system. For example, Morasch and Bahr [14] developed a method to identify stress distribution of a brittle film/ductile substrate under an axisymmetric indenter. In their model, they believed that the ring crack was mainly induced by the film bending. Thus, the indentation load is assumed as a pressure with a radius of ac, and the plastic zone is considered as a uniform distributed pressure. The bending moment by these two types of pressure is given by
\nThen the bending stress can be obtained as
\nwhere z is the distance from the middle surface of the circular plate. It is clear that the maximum radial stresses occur on the surfaces z = ±t/2 of the plate. This coincides with observations from the literature [7] that circumferential cracks initiate from the top surface of the brittle film. When the radial stress on top of the film surface reaches the strength, circumferential cracks initiate and begin to propagate along the interface between the film and the substrate. Figure 9 shows the pressure distribution in the coated system with a modulus ratio of 14.0–69.8 under a spherical indenter and a conical indenter by FE analysis; however, it has been found that the pressure caused by the plastic zone is clearly not uniform.
\nPressure distribution in the interface under a conical indenter with a half-included angle α of (a) 56.3°, (b) 60.0°, and (c) 70.3°, and a spherical indenter with a radius R of (d) 100 nm, (e) 500 nm, and (f) 1000 nm [15].
Schematic representation of a stress-based (a) model I and (b) model II.
In view of that, Fu et al. [15] proposed two stress-based models, as shown in Figure 10. The film is modeled as a circular elastic plate clamped at its edge. The radius of the circular plate, a, equals that of the plastic zone of the substrate beneath an axisymmetric indenter. A plastic zone of the ductile substrate beneath the film is considered as distributed pressure. Then the bending moments in films for model I and model II are given by
\nwhere P is the indentation load and r is the radial distance from the center. Subscripts 1 and 2 indicate models I and II, respectively.
\nThe radial stress can be predicted by substituting the bending moment into Eq. (15). The normalized stresses (predicted radial stress divided by the maximum radial stress) predicted by models I and II are shown in Figure 11. It is clear that there is a high tensile stress outside the contact radius. Moreover, the highest compressive stress occurs at the center, which causes the radial crack. The stress obtained by the proposed models is comparable to the FE results and experimental observations [15].
\nAfter the stress distribution has been obtained, fracture toughness is obtained using linear fracture mechanics and a crack channeling criterion according to Eqs. (10)–(13) and Eq. (15).
\nIt should be worth noting that the stress-based model is valid for a particular coated system only, that is, the brittle film/ductile substrate. In the next section, we introduce the mechanism of cracking in a brittle film on a ductile substrate to support the stress-based model.
\nNormalized stress as a function of rr/rp (ring crack radius/plastic zone radius) predicted by the model I and model II (Poisson’s ratio is assumed to be 0.21).
Toughness measurement using a stress-based method depends strongly on the fracture mechanism of cracking. Understanding the mechanism of the crack pattern in brittle thin films could provide guidance in developing a more accurate stress-based model for toughness assessment of the film. In this section, the fracture mechanisms of various crack patterns under indentation are discussed in detail.
\nA number of types of crack pattern induced by an indentation in brittle thin film have been reported, such as radial cracks [16–18], ring cracks [7, 19, 20], picture-frame cracks [21, 22], spiral cracks [23, 24], and spalling [25, 26]. The crack patterns are dependent on the substrate effect, indenter shape, and the indentation load level. Regarding the substrate effect, the coated system can be divided into two types, namely the brittle film/hard substrate system and the brittle film/ductile substrate system, depending on the effects of the substrate on cracking. Accordingly, we discuss the fracture mechanisms in these two types of coated system under different types of indenter.
\nIn a brittle film on a hard substrate, it has been found that cracks often occur at the contact edge of the indenter due to the stress concentration. For example, three radial cracks were detected in a diamond-like carbon (DLC) film/silicon substrate with a film thickness of 115 nm under a Berkovich indenter, as shown in Figure 12(a). The radial cracks were mainly caused by the stress concentration at the contact edge. Also, a significant pileup was found around the impression. Due to the confinement of the substrate and the pileup, the radial cracks did not propagate along the edge. Therefore, it would be invalid to use a classical method to characterize the fracture toughness of the film. For a ZnO film on an architectural glass substrate, picture-frame cracks were detected inside the impression, as shown in Figure 12(b). Meanwhile, radial cracks along the indenter edge were also detected. Bull [36] argued that the picture-frame cracks were caused by the high contact stress. In addition, the FE result in Figure 18(a) shows that a high stress occurs around the edge of the indenter, which supports the argument of Bull [36].
\n(a) Radial cracks and (b) picture-frame cracks [21] in a brittle film/hard substrate.
With an increase in the peak indentation load, the film on a hard substrate usually ends up with a failure of spalling, as reported in [25]. In their work, ring-like cracks together with spalling failure were observed in a DLC film caused by a conical indenter. The film outside the ring-like cracks was detached from the silicon substrate. Also, the crack pattern in a DLC film/silicon substrate caused by a cube-corner indenter was also shown in [25]. It is evident that radial cracks, ring-like cracks, and spalling occur in the films. Around the impression, the film is not detached from the substrate because of the high compressive contact stress. The spalling occurs outside the impression. It is shown that spalling occurs with a relatively higher load, regardless of the type of indenter.
\nSchematic representation of various stages of indentation-induced cracking in a brittle film/hard substrate system.
The spalling that usually occurs in a brittle film/hard substrate follows three stages, as illustrated in Figure 13. First, a ring-like crack initiates and propagates toward the interface due to the high contact stress. In the second stage, delamination occurs owing to the weak bonding between film and substrate. Then the film begins to buckle because of the delamination caused by the extrusion of the indenter. In the last stage, the buckled film results in a high tensile stress. When the tensile stress reaches the film strength, the film begins to break, and spalling forms. During the formation of spalling, a significant energy release occurs, which leads to a perfect “pop-in” in the load-depth curve. Then we could measure the released energy according to the “pop-in” in the load-depth curve as described in Section 2.2.
\nIn a brittle film on a ductile substrate, the crack pattern and fracture mechanism are quite different from those in a brittle film/hard substrate system. For example, Figure 14(a) and (b) shows the crack patterns in a DLC film/polyether ether ketone (PEEK) substrate under a conical indenter and a Berkovich indenter, respectively. In Figure 14(a), a few radial cracks and a ring cracks are observed. The radial cracks do not reach the ring crack, which indicates that the two types of crack are independent of each other. Examination of the stress distribution in the films in Figure 15 shows that there is a high tensile stress on the surface of the film, and a plastic zone occurs in the substrate underneath the indenter. In the FE analysis, we found that the position of the ring crack was between the contact radius and the plastic zone, as shown in Figure 16. The stiffness difference between plastic zones caused the film to bend. As a result, a high tensile radial stress, which caused the ring crack formation, occurred on the surface of the indenter. It should be noted that the radial tensile stress consisted mainly of a bending stress, as well as a stretching stress in the thin film due to the contact load. If the modulus ratio of film and substrate, Ef/Es, was significantly high, the stretching stress was negligible. In other words, the ring crack was caused mainly by film bending, which made the position of the ring crack move toward the plastic zone side. On the other hand, if Ef/Es was low, the ring crack ran to the indenter edge. These conclusions confirmed the feasibility of the present stress-based model in Section 2.
\n(a) Ring crack and (b) picture-frame crack [22] in a DLC film/PEEK substrate.
FE results of (a) maximum in-plane principal stress and (b) equivalent plastic strain distribution [7].
Fracture mechanism of a brittle film on a ductile substrate by indentation [15].
(a) Energy release rate of the plane strain crack Gps propagating through the film and energy release rate of the channel front Gss for indentation depth, and (b) illustration of a channel crack propagating through the film.
The FE analysis gives the stress distribution of film under an axisymmetric indenter, which can provide information about crack initiation. To fully understand the formation process of a ring crack, more detail is necessary. Prior to the indentation, it is highly improbable that a circular defect exists in the film. The crack channeling criterion may be the best explanation for the formation of a ring crack. Figure 17(a) shows the energy release rate by a linear fracture mechanics and a crack channeling energy release rate. In the first stage, a pre-existing short crack exists as shown in Figure 17(b). As the stress in the film increases, the crack begins to propagate toward the interface when the energy release rate by linear fracture mechanics reaches the fracture toughness. With the increase in crack length, the energy release rate by the linear fracture mechanics decreases. When it reaches the critical energy release rate for a channeling crack, the channeling ring crack initiates. The short crack adjusts its own curvature to form a ring crack because the Gps at each point around the circle is the same. After that, the ring crack propagates and stops at the interface. Hence, we could obtain the fracture toughness of the brittle film on a ductile substrate if a ring crack is observed using Eq. (13).
\nIn Figure 14(b), three radial cracks were detected and two picture-frame cracks were observed outside the contact region. Also, no delamination occurred. The FE results in Figure 18 show that the radial crack is induced by the high compressive stress due to the contact stress, which is the same as the observation in a brittle film/hard substrate. However, a high tensile stress occurs outside the contact region. With an increase in Ef/Es, the high stress in a film surface moves outward to the contact area. The film bending by a Berkovich indenter is also controlled by the plastic zone below. After the critical stress is reached, the crack may propagate to the interface or parallel to the edge of the indenter, depending on the value of the energy release rate using the channeling crack criterion or linear fracture mechanics.
\nMaximum principal stress distribution in a brittle film on a ductile substrate (dashed lines indicate projected contact edges) with a modulus ratio of (a) Ef/Es = 2.3, (b) Ef/Es = 14.0, and (c) Ef/Es = 41.9 [22].
If we keep increasing the indentation load in a brittle film/ductile substrate system, multiple ring cracks sometimes appear on the surface. Figure 19 shows multiple ring cracks in a DLC film/PEEK substrate. The film thickness is 140, 400, and 1300 nm, respectively in Figure 19(a–c). The peak indentation load is 10 mN. It is evident that, in all the films, there are a few radial cracks in the middle and a few ring cracks outside the radial crack. When the thickness increases to 400 nm, we can also observe a similar radial crack and ring crack pattern. In a brittle film with a high thickness, however, the crack pattern changes to a combination of both ring crack and spalling in Figure 19(c). In other words, ratio of indentation depth and film thickness also affects the crack patterns. In a thin film, the ring crack is controlled by the plastic zone in the substrate under the indenter. The contribution of the plastic zone is less when a thick film is tested because the critical depth is much smaller than the film thickness. The substrate effect might not be dominant in crack formation, and the fracture mechanism is similar to that in the bulk brittle material.
\nMultiple ring cracks in a DLC film/PEEK substrate with film thickness of (a) 140 nm, (b) 400 nm, and (c) 1300 nm.
Given the mechanism of ring crack formation, FE analysis integrated with cohesive elements can be used to simulate the formation of a ring crack. We ignore the channel crack formation here. The simulation steps are as follows:
\nStep 1. | \nAn FE analysis is performed without using cohesive elements. When the tensile stress in a surface reaches the tensile strength, the analysis stops, and the position of the peak tensile stress is recorded. | \n
Step 2. | \nCohesive elements are inserted into the FE model at the recorded position along the thickness. | \n
Step 3. | \nThe FE analysis is rerun, and when the tensile stress in the film surface equals the strength, a ring crack (represented by the cohesive elements) begins to initiate and propagates toward the interface. When the stress outside the first ring crack reaches the tensile strength, the position of the peak tensile stress is recorded again. | \n
Step 4. | \nRepeat Step 2 to insert another group of cohesive elements for the second ring crack formation. | \n
It is seen that the FE results agree well with the experimental observations in Figure 20. However, it is noted that the drawback of this FE model is that it cannot simulate the propagation of a channeling crack.
\nAnother specimen is a 100 nm Al2O3 film on a PEEK substrate. After indentation, there was still a multiple ring crack pattern under a conical indenter as shown in Figure 21(a). We recorded the critical load and the ring crack diameter. We found the linear relation between the critical load and the diameter of the ring crack shown in Figure 22. In a bi-layer film, a much more complex crack pattern, a flower-shaped crack, was induced. For instance, we found that the crack pattern became a flower-shaped crack in the surface of a TiO2/Al2O3 film/PEEK substrate system, as illustrated in Figure 21(b). That crack is induced by the combination of substrate effect and the interaction of the two brittle films. For instance, the confinement of TiO2 film causes uncertainty of channeling crack formation.
\nFocused ion beam observation of multiple ring crack and (b) simulation results of maximum principal stress, modified from [37].
Crack pattern in (a) an Al2O3 film/PEEK substrate, and (b) a TiO2/Al2O3/PEEK substrate.
Critical load Psc versus the diameter of ring-like crack dr (solid lines indicate the trend) [38].
A spiral crack after unloading.
The spiral crack is another crack pattern induced by indentation. In Figure 23, a spiral crack is shown in a DLC film on a PEEK substrate. Under a conical indenter, a high equivalent stress arises near the interface owing to the film bending. Then a small defect grows to a spiral crack in the film. Once the indenter begins to withdraw, the increasing equi-biaxial stress field provides the driving force for a spiral crack extension due to the film bending curvature effect as reported in [23].
\nIn this chapter, several methods for the measurement of fracture toughness of brittle film/substrate systems were presented and detailed. Fracture mechanisms for some particular crack patterns were introduced to give a better understanding of the stress-based model. The conclusions are as follows:
\nThe classic method was a widely used method for toughness measurement in “thick” films where a radial crack was well developed. The energy method was an efficient method for determining the toughness of thin films and depends on obtaining the dissipated energy during cracking. The stress method was a straightforward method based on stress distribution and the fracture mechanism in brittle films under indentation. In particular, the fracture mechanism in brittle films depends on the substrate effect, indenter shape, and load level, which can result in different crack patterns. The FE method may be the most efficient tool to characterize the evolution of stress under indentation.
\nTo date, there is still no generally accepted method for the measurement of brittle thin films using nano-indentation. Each method mentioned above has its limitations. In future, with a better understanding of each crack pattern, it is expected that a general stress-based solution for the toughness measurement of thin film will be developed.
\nIn the meantime, a more detailed numerical model is needed to investigate the complex experimental observation. An example might be an FE model that can simulate the indentation process considering the combination of a channeling crack and delamination.
\nYouhong Tang is grateful for the research support of the Premier’s Research and Industry Fund (PRIF) with a Catalyst Research Grant (Grant No.: CRG 65) for the research work. Li Chang is grateful for the funding from the Faculty of Engineering and Information Technologies, the University of Sydney, under the Faculty Research Cluster Program. The authors greatly acknowledge Ahmadzada for the samples of Al2O3 film/PEEK substrate and TiO2/Al2O3/PEEK substrate.
\nIn the most recent the environmental provident and threatening conduct of arsenic has increased the consideration of the world due to its pollution and hazardous effects throughout the world [1, 2]. Arsenic contamination is serious issue throughout the world and is substantial risk factor in most of countries including China, U.S.A, India, Pakistan, Bangladesh, Mexico and Argentina. Human revelation to arsenic is through oral route involving food and water or through inhalation of agricultural pesticides [3, 4, 5]. According to World Health Organization fact sheet, arsenic contamination is major public issue requires emergency amendments [6]. As the arsenic contamination of ground water is most serious issue for human health in China, India, Pakistan, inner-Mongolia and Bangladesh [7]. Arsenic is present round the earth in environment and is extremely toxic for life. It is metalloid occurring 20th in earth crust, 14th in sea water and 12th in human body [8]. Toxic effects of arsenic on health is wide spread in both humans and animals [9], as epidemiological substantiation proved that chronic arsenic exposure is associated with increased risk of liver, bladder and skin cancer, cardiovascular diseases, diabetes mellitus neuropathies, and ocular diseases [10, 11, 12]. Arsenic ingestion leads to accumulation in liver, kidney and lungs and small amount in gastrointestinal tract, muscle nervous system and spleen because these organs are rich in oxidative enzymes [13]. The toxic effects of arsenic mostly occur from chronic exposure to humans and animals. Epidemiological studies have revealed that chronic arsenic exposure is associated with elevated risk of liver, lung, kidney, and skin cancer in addition to other ailments such as vascular, diabetic, reproductive and neurologic [14, 15]. On the contrary arsenic has been considered as an effective chemotherapeutic agent in the treatment of human cancer [16]. Various experimental models have been developed to understand the diseases caused by arsenic exposure. However reproductive and developmental toxicity have been poorly understood. Numerous studies documented elevated spontaneous abortion and stillbirth and decreased birth weight by utero arsenic exposure [17]. Arsenic as a risk factor for developing fetus has primarily been studied through murine studies, signifying the reproductive toxicity of arsenic. In animal’s studies on arsenic toxicities revealed that arsenic is associated with spermatotoxicity [18] inhibition of testicular steroidogenesis and reduction of weight of testes and accessory organs [19]. In the current review, we try to summarize the existing information on arsenic toxicity from the available literature. We initiate by describing how and when the arsenic contamination took place by considering the course through current literature lens. We present an overview of how human and animals have been affected in the light of colors of various exposure sources by considering the relationship between arsenic toxicity and environment influenced by human activities. Furthermore, we conclude with a preview of future directions and challenges for this field.
Endocrine Disruption.
The gene regulation of mineralocorticoid, glucocorticoids, and androgen and progesterone receptors is disrupted by arsenic [20]. The mechanistic effect of arsenic on these four steroid hormones is studies on glucocorticoids receptors. Arsenic altered receptor of transcription regulation of DNA dependent glucocorticoids, signifying that transcriptional machinery is required for glucocorticoids regulation [21]. Comprehensive mutational investigation of glucocorticoids revealed that only receptor is not the causal target for arsenic effect, as studies that entire C-terminal and N-terminal domains can be removed from glucocorticoids receptors without altered arsenic effects, which indicate the primary mediator of the response of central DNA binding domain. However mutation of almost all the predicted sites of DNA binding domains did not eliminate function and also did not ablate the arsenic effects [21] Abnormalities of male reproductive system such as hypospadias, prostate, testicular cancer and cryptorchidism, may instigate through endocrine disruption [19].
Male reproductive system is directly affected by arsenic exposure, as it targets particular reproductive organs and neuroendocrine system and it also disrupt sertoli cells during fetal development. Sertoli cells propagate during prepubertal, fetal, neonatal period and these stages are chiefly susceptible to adverse effects of arsenic (Figure 1) [22]. The interruption of spermatogenesis at cell differentiation stage can decline the overall sperm count, and cause sperm DNA damage [23]. Arsenic accumulation in seminal vesicles, prostate and epididymis reduces the progressive sperm motility [24]. Beyond this arsenic also cause hormonal disturbance through affecting endocrine system, disturbing the secretion of androgen from leyding cells, it has significant association between arsenic exposure and sperm motility in arsenic exposed patients [24]. Environmental epidemiological evidences show that in general environmental conditions there is association between arsenic exposure and sperm quality in male [25]. The total arsenic concentration and sperm concentration are strongly correlated in the in the seminal plasma of heavily exposed human population [26]. The quality of semen of arsenic exposed population is decreased and there was a strong association between sperm percentage of the group exposed by arsenic, as the sperm concentration was lower in arsenic exposed group than non-exposed group [27].
Reproductive toxicity of arsenic.
The interference in spermatogenesis at cell differentiation stage can reduce the overall sperm count, increased anomalous sperms, and impaired constancy of sperm [28]. As accumulation of arsenic in seminal vesicles, seminal fluid, prostate, and epididymis may impair the sperm progressive motility [29]. In addition arsenic causes hormonal disproportion affecting neuroendocrine system and androgens, as there is strong evidence that oxidative stress vulnerably affect the spermatozoa due to extreme production of reactive oxygen species resulting in the peroxidation of poly unsaturated fatty acids in the plasma membrane [30]. Arsenic increase the reactive oxygen species production and decrease the glutathione, and other antioxidant level which lead to lipid per oxidation of cell membrane causing apoptosis leads to oxidative DNA damage [31, 32]. Damage of sperm membrane reduces sperm motility and ability to fuse with oocyte, whereas the sperm DNA damage compromise parental genomic involvement to the embryo [33] and increase the risk of infertility, and serious disease in offspring [34].
In addition to affecting sperm quality, some epidemiological studies documented that arsenic exposure in the environment is increasing the sterility risks in populations which result in decrease androgen hormones level in body, sexual dysfunction and chromosomal aberration (Figure 2) [35]. As level of hormones and arsenic concentration is measured in the blood of infertile males which indicated that the concentration of arsenic and blood luteinizing hormones are strongly negatively correlated. LH can stimulate testosterone production in interstitial cell, the dysfunction or absence of testosterone lead to male infertility [36]. Epidemiological studies revealed that in Taiwan due to drinking of arsenic contaminated water the risk of prostate cancer is 6 times more than other population [37]. In many studies it is documented that risk of arsenic exposure affect genetic integrity in chromosome repeat region and it has certain effect on Y chromosome [37]. A group reported that arsenic exposure may increase erectile dysfunction; the experimental showed that the risk of erectile dysfunction was 3.4 fold higher in arsenic exposed population [38].
Genotoxicity of arsenic adapted from [39].
Recent data has summarized toxicological effects on female reproductive system in humans and animals implicating impaired fertility effects [40]. Infertility has been predicted as substantial public health hazard and becoming medical challenge round the globe [41], as it ahead of any uncertainty that lifestyle and quality of ambient environment can play fundamental role in reproductive success in both human and animal population [42]. It is demonstrated that exposure to toxic metals such as arsenic, lead and cadmium may be extremely involved in impaired fertility [43]. Arsenic is highly toxic and hazardous for pregnant humans and animals because it can disrupt the neuroendocrine system as it may inhibit estrogen binding receptors and un-regulate the progesterone receptors and it is potential source of estrogen dependent diseases such as breast cancer, endometritis and spontaneous abortions in human population [44]. Elevated endometrial cancer risk is associated with intake of arsenic [45]. Arsenic exposure may also affect angiogenesis in endometrium during pregnancy which is the most important for embryogenesis. These ailments lead to endometrial dysfunction, premature birth, subfertility, sterility and spontaneous abortions [17].
Arsenic is well recognized for its reproductive toxicity, as in case of male reproductive system it is accounted that to hinder activities of spermatogenetic enzymes and impede spermatogenesis [28]. Arsenic may act on brain or pituitary or and on germ line cells and affect the female reproductive system such as it reduce ovarian steroidogenesis, prolong diestrus, degenerate ovarian follicles and decrease the plasma level of estradiol and progesterone [46]. Furthermore reduced plasma gonadotrophin level may decline activities of ovarian 3β- HSD (Hydroxysteroid dehydrogenase) and 17β- HSD (Hydroxysteroid dehydrogenase), which are essential regulatory enzymes for steroidogenesis [47]. As it is observed that low plasma level of estradiol may be the cause of diestrus. Furthermore, arsenic exposure in human causes reproductive toxicity, including elevated incidence of miscarriages, still birth and low birth weight in offspring [17]. Similarly, it also effect on viability in the conceptus, dam mortality and weight gain of fetus [48]. Arsenic plays a potential role in disruption of female hormonal function, such as interfering hormone synthesis and hormone normal function. All hormones are differing in their structure and function and have various routes of synthesis with numerous steps. Arsenic exposure through pesticides and other products may disrupt the chain of hormone synthesis such as inhibition of estrogen biosynthesis [49], by preventing the conversion of androgen into estrogen [50]. Methylated arsenic may interfere in dopamine beta hydroxylase activity resulting in reduced conversion of dopamine into nor-epinephrine [19] which may lead to hindrance of hypothalamic catecholamine activity involved in generation of pro-estrus surge in LH, which stimulates ovulation [51]. It also inhibits various other enzymes which are involved in progesterone synthesis [52]. Disruption in LH timing surge could alter the viability and quality of oocytes [51] and inhibition of progesterone secretion may lead to poor conception (Figure 1) [48]. The distorted estrogen signaling may cause over expression of estrogen receptors through promoter region hypo-methylation and cause epigenetic change to produce estrogen like effect by direct or indirect stimulation of estrogen receptors.
Inorganic arsenic affect the nervous system causing behavioral changes and peripheral neuropathies [53], as chronic exposure of arsenic during pregnancy may affect fetal brain development as a result mutilation of behavioral skills, including cognitive abilities and social competency. It is further conformed that exposure of chronic arsenic increase the risk of spontaneous abortions and stillbirths [54]. Significant association of arsenic exposure was found during pregnancy causing spontaneous abortions and stillbirth [3, 55]. It was reported that the elevated the risk of still birth and neonatal mortality amongst 200 married women in Bengal [55, 56]. All pregnant women were provided proper care in arsenic exposed area, showed significant association between arsenic concentration and birth defects. In the recent study spontaneous abortions and still births were observed between exposed and unexposed women, which included 240, women living in arsenic exposed area in West Bengal of India with high concentrated arsenic drinking water [55, 57] as well as [58] documented the most common arsenic exposed regions in West Bengal, and miscarriage was observed due to arsenic contaminated water. However spontaneous abortions and still births were observed in almost all the arsenic exposed areas throughout the world [55]. Furthermore, a hospital based study was conducted in Texas community with low level of arsenic exposure through inhalation primarily arsenic based agricultural products reported spontaneous abortions and stillbirths [59].
According to WHO documentation more than 10% of women are at the risk of infertility through the exposure of heavy metals such as arsenic which are the major environmental contaminant which may cause reproductive disorders [60]. WHO surveyed that the problem of infertility was pre dominantly greater in female than in males. Ovulation disturbances account for common cause of sub fertility in women [61, 62], as ovulation disturbances are present in uneven or lacking menstrual periods and can overcome through reproductive hormones. The risk of infertility increased in women due to hormonal disturbance, delay ovulation, chromosomal aberration in oocytes by higher exposure level of toxicity. Hormonal imbalance is an important cause of infertility in females due to endocrine disruption by arsenic toxicity which is the major cause of infertility in females (Figure 2) [40]. It may also cause cycle abnormality, such as decline in estrus cycle number and elevated duration of diestrus [63]. Ovulation issues, endocrine interference with estrogenic properties may inhibit ovulation and the mid cycle LH surge from pituitary gland in females which may lead to female fertility problems [40, 64]. However, most studies revealed that the arsenic exposure through pesticides and insecticides is the major cause of infertility in females, as these decrease the number of mature follicles and elevate the number of atretic follicles and this indicates potential reduction in fertility [65]. Increased exposure to methylated arsenic may lead to decrease in uterus weight which may affect implantation and increase pre-implantation embryonic loss which leads to infertility in females [66]. A recent study revealed that the women exposed to pesticides have longer menstrual cycle and increased probability of missed periods, as studied in USA; infertile women were observed have three times more exposure to pesticides, in which whole chain of gametogenesis is affected [67].
Several studies have documented the elevated inter individual variability in receptiveness of arsenic toxicity underlying genetic factor as a cause of variability. The genotoxicity of arsenic cause deoxyribonucleic acid modification such as chromosomal aberrations, mutation, micronuclei formation, deletion, sister chromatid exchange [68]. Numerous studies have been done to explain the genotoxic effect of arsenic, over and above stimulation of oxidative stress and distorted DNA repair [69]. For the purpose of understanding several studies confirmed the manipulation of genetic polymorphism in gene coding enzymes involved in mechanism of arsenic metabolism and detoxification [70]. It has been demonstrated that arsenic does not affect DNA directly and is considered a poor mutagen, as regardless of its low mutagenicity it affects the mutagenicity of other carcinogens. For illustration, an elevated increase in mutagenicity of arsenic with ultraviolet light has been observed in mammalian cells [71]. Progression of experimentation proposed that arsenic genotoxicity is associated with the generation of reactive oxygen species during its biotransformation [68]. The generation of reactive oxygen species is able to break DNA strands, cross links and chromosomal aberration [72]. One of the mechanisms of arsenic destroys to DNA is base adjustment in particular 8-oxoguanine is one of the most frequently formed DNA nuclease modifications which are a mutagenic miscoding lesion that lead to G: C to T: A transverse [73].
Moreover arsenic can induce DNA strand breaks even at low concentration [70], as single strand breaks are caused by reactive oxygen species on DNA base directly or indirectly during base excision repair mechanism [74]. As it was observed that human fibroblast cells demonstrate single strand break and chromatid substitute interfering with polyadenosinediphosphate ribose polymerase activity which is a protein important for single strand DNA break and double strand DNA break repair process (Figure 2) [75]. Recent studies revealed that chronic arsenic exposure induces oxidative DNA damage, reduced thymic functions and subsequent immunosuppression in childhood [76]. Arsenic is well known inducer of chromosomal aberration which involves both clastogenic and a euploidogenic [77]. Recent studies documented cytogenetic monitoring by using chromosomal aberration and micronuclei assay in order to observe genotoxic effects of arsenic in human and animal population [78]. Inhibition of DNA repair is considered one of the most important effects of genotoxicity of arsenic. Nucleotide excision repair and base excision repair are the two process of DNA repair which are inhibited by reactive oxygen species of arsenic [79]. Earlier studies revealed that arsenic exposure may hinder the nucleotide excision repair mechanism of DNA repair but in recent studies it is observed that it also inhibit the base excision repair mechanism (Figure 2) [80]. Changes in DNA repair mechanisms have been confirmed in human exposed population, as arsenic exposure was linked with reduced expression of excision repair to at low dose. They have found that arsenic metabolites can affect several processes in the cell [81, 82, 83]. Particularly cellular activity of human 8-oxoguanine DNA glycosylase was the most sensitively affected by dimethylmonoarsenic acid [80]. Recently, epidemiological studies revealed that arsenic may affect single nucleotide polymorphism in genes of DNA repair pathways [84]. Arsenic causes DNA damage and changes cellular capacity for DNA repair. Consequently alterations in DNA repair capacity is associated to the presence of polymorphisms in DNA repair genes which are related to risk of developing disturbance induced by arsenic [85].
One of the most important revelations is the effect of toxic metals on reproductive system in mammals. In the preceding section we attempted to provide a recent and clear glimpse in all aspects regarding arsenic toxicity on reproduction in mammals. It is the most important concern that should be explored for better understanding and seeking preventive measures to get rid of this striking issue. Arsenic is an important environmental toxicant that affects the reproductive system of mammals. These toxic effects are influenced by variant sources and routes as well as doses and periods of exposure. Integration of novel information on the formation of fate and actions of arsenic toxicity in human and animal population and other species will reduce the uncertainties in the risk assessment for arsenic. This effort would help to protect the public health against the toxic and carcinogenic effects associated with arsenic exposure.
Authors are thankful to anonymous reviewers for their valuable comments in critical review of the manuscript.
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