Fabrication of graphene/copper nanocomposites via in-situ delamination of graphite in copper by accumulative roll-compositing
Introduction
Graphene has been extensively applied in various fields owing to its unique properties, such as superior strength (~130 GPa) and Young's modulus (~1.0 TPa) [1], high electrical and thermal conductivities [2,3]. The superb properties of graphene make it a promising reinforcement for producing nanocomposites with unique structural-functional properties [[4], [5], [6], [7], [8], [9], [10], [11], [12]]. The application and performances of graphene-reinforced composites can be benefited from the easy fabrication of graphene sheets and uniform incorporation of them in the matrix. For fabrication of graphene as raw materials, various methods have been developed, such as mechanical exfoliation of graphite [[13], [14], [15]], liquid exfoliation of graphite [[16], [17], [18]], epitaxial growth [19,20], chemical vapor deposition [[21], [22], [23]] and chemical oxidation and reduction [24,25]. Production of graphene by non-complicated processes is highly desired for versatile applications. Since the famous trial to exfoliate graphene from graphite mechanically [13], applicable methods based on mechanical milling have been reported to have the potential to directly exfoliate graphite into graphene [14,15]. Nevertheless, more effective methods for the mechanical exfoliation of graphite into graphene are of great interests.
On the other hand, a great challenge for developing graphene-reinforced composites has been the easy-stacking and agglomeration of graphene nanosheets in the matrix, which can limit utilizing the extraordinary properties of 2D graphene [26]. Using graphene as reinforcement has been expected to overcome the contradictory between mechanical and physical properties as found in Cu alloys and Cu matrix composites reinforced by ceramic particles [[27], [28], [29], [30]]. Various efforts have been applied to fabricate high performance graphene-reinforced copper matrix (Gr/Cu) composites by facilitating the incorporation of graphene into Cu matrix. By using molecular level mixing and self-assembly, Gr/Cu composites with nacre-like structure were fabricated, and the composites have a high tensile strength of 748 MPa, an electrical conductivity of 62.86% IACS (International Annealed Copper Standard) and a limited tensile elongation of 1.45% [31]. Multi-layer Gr/Cu composites fabricated by ball milling and high-ratio differential speed rolling exhibit a tensile strength of 425.5 MPa and a total elongation of 16.4% [32]. Yang et al. [33] reported a novel configuration design of nanocarbon-reinforced Cu matrix via unzipping carbon nanotubes into graphene nanoribbons. The electrical conductivity was retained at 92.6% IACS but the tensile strength was only 295 MPa. In most of the studies, graphene was ex-situ introduced into Cu matrix. Gr/Cu composites produced with in-situ grown graphene exhibit a tensile strength, total elongation and electrical conductivity of 378 MPa, 32.3% and 93.8% IACS, respectively [34]. To summarize, most of the Gr/Cu composites produced up to now exhibit only moderate enhancement efficiency in the mechanical and electrical properties as compared to the expected contributions of graphene. Meanwhile, literature data for the strength and electrical conductivity of Gr/copper composites are quite diverse and lower than the theoretical ones. A recent study [26] demonstrated that the three-dimensional continuous graphene network architecture has the advantage in achieving high performance Gr/Cu composites over the homogeneous structure with random distribution of graphene in the matrix.
Fabrication of Gr/Cu composites with excellent comprehensive properties such as high strength, good ductility and good electrical conductivity is still a great challenge. It is interesting to figure out the potential to achieve high-performance Gr/Cu composites by improving the dispersion of graphene in matrix. Moreover, a facile method for the fabrication of Gr/Cu composites by using cheap raw materials such as commercial graphite is of great interest to industrial applications. In this study, we presented a plastic-deformation-based method that simultaneously enables the in-situ formation of graphene nanosheets by exfoliating graphite and the uniform dispersion of them in Cu matrix. Our results showed that the shear-induced delamination of graphite can be functioned by applying accumulative roll-compositing (ARC) to the initial Cu/graphite/Cu sandwiches. The roll-bonding of copper layers accompanied with the in-situ delamination of graphite facilitates the uniform dispersion of graphene nanosheets in the continuous Cu matrix. The as-produced Gr/Cu composites exhibit an excellent combination of high tensile strength, ductility and electrical conductivity. We showed therefore the high effectiveness of exfoliating graphite into graphene nanosheets and the great benefit of achieving homogenous dispersion of graphene in Cu matrix by the simple plastic-deformation-based method.
Section snippets
Raw materials
Commercial graphite foils (99.9%, Beijing Crystal Special Carbon Technology Co., Ltd) with 0.2 mm in thickness were cut into strips with dimensions of 40 mml × 20 mmw × 0.2 mmt. The graphite foils were cleaned several times with acetone and deionized water and dried at room temperature. Pure copper (99.97%, Luoyang Copper Co., Ltd) sheets with 1 mm in thickness were used. The as-received Cu sheets were annealed in an Ar atmosphere at 600 ○C for 2 h and cut into strips with dimensions of 100 mml
Delamination of graphite during ARC
The original graphite foil consists of multiple layers of graphite sheets that are parallel to the rolling surface, as shown in Fig. 1a. The XRD pattern of the raw graphite foils (Fig. 1b) shows two main peaks at 2θ = 26.5° and 54.7°, corresponding to (002) and (004) crystal planes of hexagonal graphite, respectively, indicating a highly directional orientation of the graphite crystals. During the ARC process (Fig. 1d–g), most of the (002) basal planes of graphite are parallel to the
Mechanism of ARC-induced delamination of graphite
The substantial exfoliating of graphite into few-layer or even monolayer graphene sheets by the present ARC process can be accounted for several reasons. First, due to the highly oriented graphitic structure of the raw graphite foils, lamellar graphitic basal planes can be arranged to be parallel to the rolling plane. This facilitates the interplanar slip and peeling of graphitic layers during rolling process. Second, rolling deformation gives rise to highly directional shear stress that is
Conclusion
In situ Gr/Cu composites were prepared based on plastic deformation processing that enables the simultaneous exfoliation of graphite into graphene sheets and uniform incorporation of them in Cu matrix. Commercial graphite foils can be directly delaminated into few-layer or monolayer graphene sheets by applying ARC process to ultrahigh rolling cycles without any additives or chemical treatments. The ARC-induced delamination mechanism of graphite was mediated by the shear-induced slipping and
Credit authorship contribution statement
F. Chen: Investigation, Methodology, Data Curation, Formal analysis, Writing-Original draft preparation. Q.S. Mei: Conceptualization, Supervision, Writing - Review & Editing. J.Y. Li: Conceptualization, Writing - Review & Editing, Formal analysis. C.L. Li: Writing - Review & Editing, Formal analysis. L. Wan: Writing - Review & Editing, Formal analysis. G.D. Zhang: Writing - Review & Editing. X.M. Mei: Investigation. Z.H. Chen: Investigation. T. Xu: Investigation. Y.C. Wang: Investigation.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
Financial supports from the National Natural Science Foundation of China (Grant 51371128) and the Fundamental Research Funds for the Central Universities of China (Grants 2042017KF0190, 2042019kf0036) were gratefully acknowledged. We thank Center for Electron Microscopy of Wuhan University for TEM observations.
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