Research Papers

First-Principles Investigation of Intergranular Fracture in Copper by Grain Boundary Segregation of Sulfur

[+] Author and Article Information
Xudong Wang

Université de Versailles
45 Avenue des Etats-Unis,
Versailles 78035, France
e-mail: xudong.wang2@uvsq.fr

Lahouari Benabou

Université de Versailles
45 Avenue des Etats-Unis,
Versailles 78035, France
e-mail: lahouari.benabou@uvsq.fr

1Corresponding author.

Contributed by the Materials Division of ASME for publication in the JOURNAL OF ENGINEERING MATERIALS AND TECHNOLOGY. Manuscript received March 2, 2017; final manuscript received June 21, 2017; published online August 9, 2017. Assoc. Editor: Peter W. Chung.

J. Eng. Mater. Technol 140(1), 011008 (Aug 09, 2017) (5 pages) Paper No: MATS-17-1064; doi: 10.1115/1.4037274 History: Received March 02, 2017; Revised June 21, 2017

Grain boundary (GB) embrittlement by sulfur in fcc CuΣ5(012)[100] symmetrical tilt grain boundary (STGB) is simulated by first-principles calculations. The surface and grain boundary segregation energies are estimated by progressively placing solute atoms in the potential segregation sites in the boundaries. Based on the calculated segregation energies, the cohesive energy of the grain boundary is evaluated as a function of the sulfur atoms concentration. It is found that, when a two atomic layers’ concentration is attained, the cohesive energy is reduced by one order of magnitude compared to its value for the clean grain boundary.

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Korzhavyi, P. A. , Abrikosov, I. A. , and Johansson, B. , 1999, “ Theoretical Investigation of Sulfur Solubility in Pure Copper and Dilute Copper-Based Alloys,” Acta Mater., 47(5), pp. 1417–1424. [CrossRef]
Moya, F. , Moya-Gontier, G. E. , and Cabané-Brouty, F. , 1970, “ Sulfur Diffusion in Copper: Small Penetration Curves,” Phys. Status Solidi A, 2(1), pp. 101–108. [CrossRef]
Moya-Gontier, G. E. , and Moya, F. , 1973, “ Influence de la Ségregation aux Joints sur la Diffusion Intergranulaire du Soufre Dans le Cuivre,” Acta Metall., 21(5), pp. 701–708. [CrossRef]
Sun, Z. , Laitem, C. , and Vincent, A. , 2008, “ Dynamic Embrittlement at Intermediate Temperature in a Cu–Ni–Si Alloy,” Mater. Sci. Eng. A, 477(1–2), pp. 145–152. [CrossRef]
McMahon, C. J. , 2004, “ Brittle Fracture at Grain Boundaries,” Interface Sci., 12(2–3), pp. 141–146. [CrossRef]
McMahon, C. J. , Pfaendtner, J. A. , and Muthiah, R. C. , 1995, “ Quasi-Static Intergranular Brittle Fracture: Dynamic Embrittlement,” Czech. J. Phys., 45(11), pp. 965–978. [CrossRef]
Benabou, L. , and Sun, Z. , 2014, “ Homogenization Scheme for Brittle Intergranular Decohesion in Polycrystalline Aggregates,” Mech. Res. Commun., 55, pp. 114–119. [CrossRef]
Benabou, L. , and Sun, Z. , 2015, “ Analytical Homogenization Modeling and Computational Simulation of Intergranular Fracture in Polycrystals,” Int. J. Fract., 193(1), pp. 59–75. [CrossRef]
Sofronis, P. , Liang, Y. , and Aravas, N. , 2001, “ Hydrogen Induced Shear Localization of the Plastic Flow in Metals and Alloys,” Eur. J. Mech. A, 20(6), pp. 857–872. [CrossRef]
Sun, Z. , Benabou, L. , and Xue, H. , 2016, “ Numerical Modelling and Simulation of Intergranular Fracture Due to Dynamic Embrittlement for a Cu–Ni–Si Alloy,” Mech. Res. Commun., 75, pp. 81–88. [CrossRef]
Yamaguchi, M. , Shiga, M. , and Kaburaki, H. , 2006, “ Grain Boundary Decohesion by Sulfur Segregation in Ferromagnetic Iron and Nickel—A First-Principles Study,” Mater. Trans., 47(11), pp. 2682–2689. [CrossRef]
Tschopp, M. A. , Coleman, S. P. , and McDowell, D. L. , 2015, “ Symmetric and Asymmetric Tilt Grain Boundary Structure and Energy in Cu and Al (and Transferability to Other fcc Metals),” Integr. Mater. Manuf. Innov., 4(11), pp. 1–14.
Mishin, Y. , Mehl, M. J. , Papaconstantopoulos, D. A. , Voter, A. F. , and Kress, J. D. , 2001, “ Structural Stability and Lattice Defects in Copper: Ab-Initio, Tight-Binding, and Embedded-Atom Calculations,” Phys. Rev. B, 63(22), p. 224106. [CrossRef]
Sellers, S. , Schultz, A. J. , Basaran, C. , and Kofke, D. A. , 2010, “ Atomistic Modeling of β-Sn Surface Energies and Adatom Diffusivity,” Appl. Surf. Sci., 256(13), pp. 4402–4407. [CrossRef]
Rice, J. R. , and Wang, J. S. , 1989, “ Embrittlement of Interfaces by Solute Segregation,” Mater. Sci. Eng. A: Struct., 107, pp. 23–40. [CrossRef]
Kresse, G. , and Furthmüller, J. , 1996, “ Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set,” Phys. Rev. B, 54(16), p. 11169. [CrossRef]
Perdew, J. P. , Burke, K. , and Ernzerhof, M. , 1996, “ Generalized Gradient Approximation Made Simple,” Phys. Rev. Lett., 77(18), p. 3865. [CrossRef] [PubMed]
Kresse, G. , and Joubert, D. , 1999, “ From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method,” Phys. Rev. B, 59(3), p. 1758. [CrossRef]
Yamaguchi, M. , Shiga, M. , and Kaburaki, H. , 2005, “ Grain Boundary Decohesion by Impurity Segregation in a Nickel-Sulfur System,” Science, 307(5708), pp. 393–397. [CrossRef] [PubMed]
McLean, D. , 1957, Grain Boundaries in Metals, Oxford University Press, London.
Serebrinsky, S. , Carter, E. A. , and Ortiz, M. , 2004, “ A Quantum-Mechanically Informed Continuum Model of Hydrogen Embrittlement,” J. Mech. Phys. Solids, 52(10), pp. 2403–2430. [CrossRef]
Rimoli, J. J. , and Ortiz, M. , 2010, “ A Three-Dimensional Multiscale Model of Intergranular Hydrogen-Assisted Cracking,” Philos. Mag., 90(21), pp. 2939–2963. [CrossRef]


Grahic Jump Location
Fig. 1

(a) Structure of Cu Σ5(012)[100] STGB, and (b) GB energy with respect to misorientation angle for [100] and [110] STGBs in Cu (Reprinted with permission from Tschopp et al. [12]. Copyright 2015 by Springer.)

Grahic Jump Location
Fig. 2

(a) GB unit cell of fcc Cu Σ5(012)[100] STGB containing 68 Cu atoms (yellow balls indicate S atoms when inserted in the GB vacancies at sites 0). The c-axis of the cell is 2.34 nm. (b) Top view of the fractured surface at the GB. The area of the GB plane, A, is 0.584 nm2.

Grahic Jump Location
Fig. 3

Segregation energy for one S atom at various segregation sites in the unit cell of Cu. Sites 0, 1, 2 are GB sites, and sites 9 and 10 are surface sites (inner bulk sites, which are less favorable, are not shown).

Grahic Jump Location
Fig. 4

McLean’s equation Cgb=Cbulk exp (−ΔEseg/RT)/[1+Cbulk exp (−ΔEseg/RT)] plotted at 200 °C for bulk solute concentration varying from 1 to 10,000 at ppm

Grahic Jump Location
Fig. 5

Total and average segregation energy for the (a) GB and (b) free surface of Cu. The total segregation energy is normalized by the area of the GB.

Grahic Jump Location
Fig. 6

Calculated cohesive energy of Cu Σ5 GB with respect to the amount of solute atoms segregating at the GB (comparison with data on Ni Σ5 GB)



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