Uncover the mystery of interfacial interactions in immiscible composites by spectroscopic microscopy: A case study with W-Cu

doi:10.1016/j.jmst.2022.03.014

Abstract

Abstract:

Characterizing immiscible metallic composites with electron microscopy and X-ray spectroscopy is the classic way of obtaining their structural and physical details. Nevertheless, such a combination lacks ability to tell the interfacial interactions at grain boundaries. Here we demonstrate a novel strategy to uncover the mystery of interfacial interactions in such systems by spectroscopic microscopy. The morphological and spectral data of samples were simultaneously recorded and analyzed, which reveals critical information regarding interfacial electronic modes. Taking W-Cu as a model, we experimentally quantified its connectivity and unambiguously identified conditional bonding between W and Cu. Further, we chemically reconstructed the specific W-Cu boundary that possessed the strongest interactions and investigated its atomic structure. The mechanism of W-Cu bonding was proposed and verified by first-principle calculations. The above methodology holds great promise to serve as a universal approach in achieving in-depth understanding of immiscible composites.

Key words: Metal-matrix composites, Interface, Physical properties, Spectroscopic microscopy, Interfacial bonding

Zhi Zhao, Fawei Tang, Chao Hou, Xintao Huang, Xiaoyan Song. Uncover the mystery of interfacial interactions in immiscible composites by spectroscopic microscopy: A case study with W-Cu[J]. J. Mater. Sci. Technol., 2022, 126: 106-115.

Figures/Tables 7

Fig. 1. Optical images of various samples. (a) Scheme of the spectroscopic microscopy. (b) Representative bright field image of W powders (1-5 µm in diameter). (c) Dark field image of the same sample in (b). (d) Representative bright field image of Cu powders (500 nm in diameter). (e) Dark field image of the same sample in (d). (f) Representative bright field image of a W-Cu composite. (g) Dark field image of the same sample in (f). (h) A comparison between the optical and SEM images of a W-Cu sample. Scale bars: 2 µm.

Fig. 2. Spectral characterizations of W and Cu powders. (a) BF spectra of W powders of various diameters. (b) DF spectra of W powders of various diameters. (c) BF spectra of Cu powders of various diameters. (d) DF spectra of Cu powders of various diameters. The dashed lines indicate the peak position of each band in the spectra. The grey zones in the plots represent the range of WI and CuI bands.

Fig. 3. Experimental and simulated spectra of W-Cu composites. (a) Scheme of three potential situations at W-Cu interfaces. (b) BF of a W-Cu sample. (c) DF spectrum of a W-Cu sample. (d) The calculated RN value as a function of experimental W and Cu BF spectra for sample 1. The minimum RN value is marked by the red circle. (e) The calculated RN value as a function of experimental W and Cu DF spectra for sample 1. The minimum RN value is marked by the red circle. (f) The experimental and simulated W-Cu BF spectrum with the minimum RN. (g) The experimental and simulated W-Cu DF spectrum with the minimum RN.

Table 1. Critical parameters of a few W-Cu samples from experiments and spectral fittings.

Sample	W diameter (Optical)	W diameter (SEM)	Cu diameter (optical)	Cu diameter (SEM)	W(Actual)	W(Fitted)	Conductivity(% IACS)
S1	25 µm	170 nm	1 µm	<170 nm	58 at.%	58 at.%	31%
S2	25 µm	800 nm	1 µm	<800 nm	58 at.%	59 at.%	33%
S3	46 µm	2.4 µm	1 µm	<2 µm	58 at.%	57 at.%	32%
S4	25 µm	200 nm	74 µm	<200 nm	45 at.%	46 at.%	43%

Fig. 4. Spectral evidence of interactions between W and Cu. (a) Experimental and simulated DF/BF spectra of W-Cu samples. (b) Time lapse vis-NIR spectra of Cu solution incubated with W powder. (c) DF image of W powders after incubation with Cu(II) solution. (d) Magnified BF images of representative regions containing copper crystals. Scale bars: 10 µm. (e) DF/BF spectra of regions containing copper crystals. The red dashed line is at 527 nm.

Fig. 5. Crystallographic characterizations of W-Cu interactions. (a) TEM image of W particles coated by a thin layer of copper. Inset: A low magnification image of connected W particles. (b) HR-TEM image of a W-Cu boundary in (a). (c) Selected area diffraction pattern of the W side in (b). (d) EDS elemental mapping at the W-Cu boundary. The yellow and purple color represent W and Cu, respectively. (e) TEM image of a copper crystal found in optical microscope. (f) Selected area diffraction pattern of the green-circled region in (e). (g) Selected area diffraction pattern of the yellow-circled region in (e). (h) HR-TEM image of W-Cu boundary in (e). (i, j) HR-TEM image of the representative crystallographic morphology of W that supports Cu crystal growth. (k) HR-TEM image of a W-W-Cu triple junction.

Fig. 6. First-principle study on W-Cu bonding. (a) The boundary structure of W(110)/Cu(200) before and after relaxation. (b) The boundary structure of W(110)-d/Cu(200) before and after relaxation. (c) The LCD plot of the yellow-boxed region in (a). (d) The LCDD plot of the yellow-boxed region in (a) and LCDD of selected regions. (e) The LCD plot of the yellow-boxed region in (b). (f) The LCDD plot of the yellow-boxed region in (b). (g) LDOS of the yellow boxed regions in (a) and (b). The purple dashed line indicates the Fermi energy level.

References 42

[1]	A.K. Bhalla, J.D. Williams, Powder Metall, 19 (1976), pp. 31-37.
[2]	B. Curzadd, A. Von Müller, R. Neu, U. Von Toussaint, Nucl. Fusion, 59 (2019), Article 086003.
[3]	R.M. German, K.F. Hens, J.L. Johnson, Int. J. Powder Met., 30 (1994), pp. 205-215.
[4]	L.L. Dong, M. Ahangarkani, W.G. Chen, Y.S. Zhang, Int. J. Refract. Hard Met., 75 (2018), pp. 30-42.
[5]	M.P. Echlin, A. Mottura, M. Wang, P.J. Mignone, D.P. Riley, G.V. Franks, T.M. Pollock, Acta Mater, 64 (2014), pp. 307-315.
[6]	C. Hou, L. Cao, Y. Li, Tang F, X. Song, Nanotechnology, 31 (2019), Article 084003.
[7]	O. El-Atwani, J.A. Hinks, G. Greaves, S. Gonderman, T. Qiu, M. Efe, J.P. Allain, Sci. Rep., 4 (2014), pp. 1-7.
[8]	H.D. Espinosa, R.A. Bernal, T. Filleter, Small, 8 (2012), pp. 3233-3252.
[9]	W. Wu, C. Hou, L. Cao, X. Liu, H. Wang, H. Lu, X. Song, Nanotechnology, 31 (2020), Article 135704.
[10]	Y. Li, C. Hou, H. Lu, S. Liang, X. Song, Int. J. Refract. Hard Met., 79 (2019), pp. 154-157.
[11]	C. Hou, X. Song, F. Tang, Y. Li, L. Cao, J. Wang, Z. Nie, NPG Asia Mater, 11 (2019), pp. 1-20.
[12]	H. Zhang, W.C. Cao, C.Y. Bu, K. He, K.C. Chou, G.H. Zhang, Int. J. Refract. Hard Met., 88 (2020), Article 105194.
[13]	S. Liang, L. Chen, Z. Yuan, Y. Li, J. Zou, P. Xiao, L. Zhuo, Mater. Charact., 110 (2015), pp. 33-38.
[14]	Y. Zhang, L. Zhuo, Z. Zhao, Q. Zhang, J. Zhang, S. Liang, B. Luo, Q. Chen, H. Wang, J. Alloys Compd., 823 (2020), Article 153761.
[15]	Q. Zhang, S. Liang, B. Hou, L. Zhuo, Int. J. Refract. Hard Met., 59 (2016), pp. 87-92.
[16]	K. Zhou, W.G. Chen, J.J. Wang, G.Y. Yan, Y.Q. Fu, Int. J. Refract. Hard Met., 82 (2019), pp. 91-99.
[17]	J.L. Johnson, J.J. Brezovsky, R.M. German, Metall. Mater. Trans. A, 36 (2005), pp. 1557-1565.
[18]	J.L. Johnson, J.J. Brezovsky, R.M. German, Metall. Mater. Trans. A, 36 (2005), pp. 2807-2814.
[19]	W. Chen, L. Dong, H. Zhang, J. Song, N. Deng, J. Wang, Mater. Lett., 205 (2017), pp. 198-201.
[20]	P. Zhao, S. Guo, G. Liu, Y. Chen, J. Li, J. Alloys. Compd., 601 (2014), pp. 289-292.
[21]	J. Zhang, Y. Huang, Y. Liu, Z. Wang, Mater. Des., 137 (2018), pp. 473-480.
[22]	P. Villain, P. Goudeau, P.O. Renault, K.F. Badawi, Appl. Phys. Lett., 81 (2002), pp. 4365-4367.
[23]	P. Goudeau, P. Villain, T. Girardeau, P.O. Renault, K.F. Badawi, Scr. Mater., 50 (2004), pp. 723-727.
[24]	Y. Gai, F. Tang, C. Hou, H. Lu, X. Song, Acta. Metall. Sin., 56 (2020), pp. 1036-1046.
[25]	M.D. Segall, P.J.D. Lindan, M.J. Probert, C.J. Pickard, P.J. Hasnip, S.J. Clark, M.C. Payne, J. Phys-Condens. Ma., 14 (2002), pp. 2717-2744.
[26]	M.Y. Wang, W. Wang, M. Ji, X.L. Cheng, Appl. Surf. Sci., 439 (2018), pp. 350-363.
[27]	P. Basumatary, D. Konwar, Y.S. Yoon, Appl. Catal. B-Environ., 267 (2020), Article 118724.
[28]	X.B. Wu, Y.W. You, X.S. Kong, J.L. Chen, G.N. Luo, G.H. Lu, C.S. Liu, Z.G. Wang, Acta Mater, 120 (2016), pp. 315-326.
[29]	B. Ohler, S. Prada, G. Pacchioni, W. Langel, J. Phys. Chem. C, 117 (2013), pp. 358-367.
[30]	M. Minissale, C. Pardanaud, R. Bisson, L. Gallais, J. Phys. D Appl. Phys., 50 (2017), Article 455601.
[31]	P.F. Robusto, R. Braunstein, Phys. Status Solidi. B, 107 (1981), pp. 443-449.
[32]	D.B. Pedersen, S. Wang, J. Phys. Chem. C, 111 (2007), pp. 17493-17499.
[33]	T. Svensson, E. Adolfsson, M. Lewander, C.T. Xu, S. Svanberg, Phys. Rev. Lett., 107 (2011), Article 143901.
[34]	A. Penttilä, K. Lumme, J. Quant. Spectrosc. Radiat. Transfer., 110 (2009), pp. 1993-2001.
[35]	J.L. McHale, Molecular spectroscopy CRC Press, Boca Raton (2017).
[36]	V. Amendola, R. Pilot, M. Frasconi, O.M. Maragò, M.A. Iatì, J. Phys. Condens. Matter., 29 (2017), Article 203002.
[37]	Z. Zhao, Y. Cao, Y. Cai, J. Yang, X. He, P. Nordlander, P.S. Cremer, ACS Nano, 11 (2017), pp. 6594-6604.
[38]	J. Singleton, Band theory and electronic properties of solids Oxford University Press, Oxford (2001).
[39]	J.G. Speight, Lange's handbook of chemistry McGraw-Hill Education, New York (2017).
[40]	L. Wang, L. Xu, C. Srinivasakannan, S. Koppala, Z. Han, H. Xia, J. Alloys. Compd., 764 (2018), pp. 177-185.
[41]	Y.S. Kim, D.L. Bae, H. Yang, H.S. Shin, G.W. Wang, J.J. Senkevich, T.M. Lu, J. Electrochem. Soc., 152 (2005), p. C89.
[42]	R.S. Mulliken, I. J. Chem. Phys., 23 (1955), pp. 1833-1840.