基体合金元素对SiC/Al界面结合影响的第一性原理及实验研究

doi:10.15541/jim20180540

摘要/Abstract

摘要：

采用基于密度泛函理论的第一性原理及实验相结合的方法, 探讨了Al基体中分别掺杂Mg、Si、Cu合金元素对SiC/Al界面结合的影响, 重点考察了合金元素在界面偏聚时的电子结构和成键情况。研究表明: 在未掺杂Al/SiC体系界面结构优化时, 以Si原子为终止面的Brigde结构是最稳定的结合方式; 当合金元素分别替换界面处的Al原子后, 界面处原子的分波态密度、Muliken电荷及成键原子集居数等电子结构参数均有不同程度的变化, 这不仅增加了界面处 Si与Al原子结合, 同时也增强了界面处和亚界面处的Al基体和SiC增强相原子之间的相互作用, 使体系更加稳定, 界面黏着功均有不同提升; 其中掺Mg提升效果最明显, 其次为掺Cu和掺Si; 利用第一性原理计算的掺杂Al/SiC体系黏着功和实验值较为接近且变化规律相同。

关键词: 合金元素, SiC/Al界面, 界面结合, 第一性原理

Abstract:

First-principle approach based on density functional theory and experimental method were used to study the interface bonding of SiC/Al substituted by alloy elements Mg, Si and Cu. The electronic structure and bonding of alloy elements at interface segregation were investigated. The results show that bridge-site model with bridge Si is the most stable combination way of SiC/Al interface after optimization of the interface structure of pure Al/SiC system. When Al atoms at the interface replaced by alloy elements separately, the electronic structural parameters such as partial density of states, Mulliken charge and bonding population, all vary in different degree, which not only increase the binding of Si and Al atoms at the interface, but also increase the interaction among alloy atoms, Al matrix and SiC reinforcement at the interface and sub-interface. It is conducive to enable the system more stable and the adhesion work of interface more differently. Among them, the increased adhesion work is the most obvious when Mg is doped, followed by Cu and Si. Furthermore, the adhesion work of Al/SiC systems doped alloy elements calculated by first-principle is close to the experimental values, and the law of change is the same.

Key words: alloy element, SiC/Al interface, interface bonding, first principle

中图分类号:

TB333

邹爱华, 周贤良, 康志兵, 饶有海, 吴开阳. 基体合金元素对SiC/Al界面结合影响的第一性原理及实验研究[J]. 无机材料学报, 2019, 34(11): 1167-1174.

ZOU Ai-Hua, ZHOU Xian-Liang, KANG Zhi-Bing, RAO You-Hai, WU Kai-Yang. Alloy Elements on SiC/Al Interface: a First-principle and Experimental Study[J]. Journal of Inorganic Materials, 2019, 34(11): 1167-1174.

图/表 12

表1 SiC基板的基本参数

Table 1 Basic parameters of SiC substrate

Size	Purity/wt%	Relative density/%	Roughness /nm
Φ20 mm×5 mm	>98.5	>97	19

表2 Al以及4H-SiC晶体表面的表面能

Table 2 Surface energy of Al and 4H-SiC crystal

Al_surf	(100)	(110)	(111)	(211)	SiC_surf	(001)	(011)	(111)	(211)
E^surf/(J·m^-2)	1.51	1.78	1.45	1.75	E^surf/(J·m^-2)	5.42	5.96	6.49	8.41

图1 以Si为终端的SiC(001)/Al(111)界面原子结构, A、B、C位分别记作桥位、顶位和空位

Fig. 1 Atomic structures of SiC (001) /Al (111) interfaces with Si-terminated, A, B and C sites as bridge, top and vacancy, respectively

图2 SiC(001)表面能随$\mu _{\text{Si}}^{\text{slab}}-\mu _{\text{Si}}^{\text{bulk}}$变化的关系图

Fig. 2 Surface energy curves of SiC(001) with different $\mu _{\text{Si}}^{\text{slab}}-\mu _{\text{Si}}^{\text{bulk}}$

图3 SiC(001)/Al(111)界面分离功与界面距离的关系曲线

Fig. 3 Adhesion work curves of SiC(001)/Al(111) with different interfacial distance (a) C-terminated, (b) Si-terminated

图4 (a)未掺杂、(b)1个、(c)2个、(d)4个Mg原子替换Al原子界面模型

Fig. 4 Interface model of SiC/Al doping Mg in Al matrix (a) 0; (b) 1; (c) 2; (d) 4

表3 合金原子(Mg、Si、Cu)掺杂前后SiC/Al界面粘着功的变化

Table 3 Adhesion work of SiC/Al interface before and after doping Mg, Si and Cu

Model	Add number	Total energy/eV	W_ad/(mJ·m^-2)
Al/SiC	0	-6573.7404	851
Al-Mg/SiC	1	-7491.2968	1140
	2	-8408.7099	1342
	4	-10243.2359	1015
Al-Si/SiC	1	-6624.1431	1024
	2	-6674.512	1242
	4	-6775.2566	936
Al-Cu/SiC	1	-7993.8884	1088
	2	-9413.8768	1254
	4	-12254.1254	642

图5 Mg原子掺杂前后界面处Al和Si原子的PDOS图

Fig. 5 PDOS of Al and Si at the interface before and after doping Mg

表4 合金原子(Mg、Si、Cu)掺杂前后SiC/Al界面处原子Millken电荷

Table 4 Millken charge of atom at SiC/Al interface before and after doping Mg, Si and Cu

Atom number	Model	Charge population
Atom number	Model	s(Mg,Si,Cu)	p(Mg,Si,Cu)	d(Si, Cu)	Total(Mg, Si, Cu)
Al(1)	Without Mg,Si,Cu	1.11,1.11,1.11	1.76,1.76,1.76	0, 0	2.87, 2.87, 2.87
Al(1)	With Mg,Si,Cu	1.15,1.14,1.14	1.84,1.74,1.75	0, 0	2.99, 2.88, 2.89
Al(2)/(Mg,Si,Cu)	Without Mg,Si,Cu	1.11,1.11,1.11	1.76,1.76,1.76	0, 0	2.87, 2.87, 2.87
Al(2)/(Mg,Si,Cu)	With Mg,Si,Cu	0.52,1.58,0.68	6.54, 2.5, 0.84	0, 9.76	7.07, 4.08, 9.76
Al(4)	Without Mg,Si,Cu	1.11,1.11,1.11	1.76,1.76,1.76	0, 0	2.87, 2.87, 2.87
Al(4)	With Mg,Si,Cu	1.14,1.12,1.11	1.85,1.8,1.83	0, 0	2.99, 2.92, 2.94
Si(2)	Without Mg,Si,Cu	1.39,1.39,1.39	2.5, 2.5, 2.5	0, 0	3.98, 3.98, 3.98
Si(2)	With Mg,Si,Cu	1.5,1.42,1.45	2.54, 2.56, 2.54	0, 0	4.04, 3.98, 3.99
Si(4)	Without Mg,Si,Cu	1.39,1.39,1.39	2.5, 2.5, 2.5	0, 0	3.89, 3.89, 3.89
Si(4)	With Mg,Si,Cu	1.4,1.4,1.39	2.55, 2.5, 2.53	0, 0	3.95, 3.9, 3.92

表5 合金原子(Mg、Si、Cu)掺杂前后SiC/Al界面及附近成键原子集居数

Table 5 Populations of atoms at and near SiC/Al interface before and after doping Mg, Si and Cu

Bond type	Population
Bond type	Without Mg	With Mg	Without Si	With Si	Without Cu	With Cu
Al(1)-Si(1)	0.36	0.4	0.36	0.37	0.36	0.38
Al(2)/(Mg,Si,Cu)-Si(2)	0.36	0.35	0.36	0.28	0.36	0.31
Al(3)-Si(3)	0.36	0.39	0.36	0.34	0.36	0.37
Al(4)-Si(4)	0.36	0.4	0.36	0.36	0.36	0.37
Al(4)-Al(5)	0.24	0.25	0.24	0.23	0.24	0.25
Si(4)-C(4)	0.24	0.25	0.23	0.23	0.24	0.26

图6 900 ℃时纯Al及其合金(Al-Mg、Si、Cu)在α-SiC基板上接触角随时间的变化

Fig. 6 Contact angle of pure Al and its alloy (Al-Mg, Si, Cu) on α-SiC substrate at 900 ℃ varies with time

表6 不同体系界面黏着功

Table 6 Adhesion work of different interface systems

Model	This experiment/ (mJ·m^-2)	First principles/ (mJ·m^-2)
SiC/Al	839	851
SiC/Al-Mg	1246	1140
SiC/Al-Si	1167	1024
SiC/Al-Cu	1220	1088

参考文献 27

[1]	SONG M, HE Y H . Effects of die-pressing pressure andextrusion on the microstructures and mechanical properties of SiC reinforced pure aluminium composites. Mater. Design, 2010,31(2):985-989.
[2]	FOX R T, NEWMAN R A, PYZIK A J , et al. Al₂O₃-B₄C-Al composite material system via pressure less infiltration methods. Int. J. Appl. Ceram. Technol., 2010,7(6):837-845.
[3]	LEE H S, JEON K Y, KIM H Y , et al. Fabrication process and thermal properties of SiCp/Al metal matrix composites for electronic packaging applications. J. Mater. Sci., 2000,35(24):6231-6236.
[4]	LI C Y, HU Y K, ZHENG X J , et al. Study of microstructure of SiCp/ZL101A composites by vacuum hot-pressing sintering processing. Rare Metal Mater. Eng., 2014,41(2):413-416.
[5]	HE P, HUANG S Y, WANG H C , et al. Electroless nickel -phosphorus plating on silicon carbide particles for metal matrix composites. Ceram. Int., 2014,40(10):16653-16664.
[6]	BHUSHAN R K, KUMAR S, DAS S . Optimisation of porosity of 7075 Al alloy 10% SiC composite produced by stir casting process through Taguchi method. Int. J. Mater. Eng. Innov., 2009,1(1):116-129.
[7]	MANDALl D, VISWANATHAN S . Effect of re-melting on particles distribution and interface formation in SiC reinforced 2124Al matric composite. Mater. Charact., 2013,86:21-27.
[8]	RATNAPARKHI P L, HOWE J M . Characterization of a diffusion- bonded Al-Mg alloy/SiC interface by high resolution and analytical electron microscopy. Metall. Mater. Trans. A, 1994,25(3):617-627.
[9]	LUO Z P . Crystallography of SiC/MgAl₂O₄/Al interfaces in a pre-oxidizied SiC reinforced SiC/Al composite. Acta Mater., 2006,54(1):47-58.
[10]	MANDALl D, VISWANATHAN S . Effect of heat treatment on microstructure and interface of SiC particle reinforced 2124 Al matrix composite. Mater. Charact., 2013,85:73-81.
[11]	AGUILAR-MARTÍNEZ J A, PECH-CANUL M I, RODRÍGUEZ- REYES M , et al. Effect of Mg and SiC type on the processing of two-layer Al/SiCp composites by pressureless infiltration. J. Mater. Sci., 2004,39(3):1025-1028.
[12]	EUSTATHOPOULOS N, LAURENT V, RADO C . Wetting kinetics and bonding of Al and Al alloys on α-SiC. Mater. Sci. Eng. A, 1996,205(1/2):1-8.
[13]	KOBASHI M, CHOH T . The wettability and the reaction for SiC particlce/Al alloy system. J. Mater. Sci., 1993,28(3):684-690.
[14]	FERRO A C, DERBY B . Wetting behavior in the Al-Si/SiC system: interface reactions and solubility effects. Acta Mater., 1995,43(8):3061-3073.
[15]	MA X C, WU J B . An investigation on wettability and interfacial phenomena of Al-SiC system. J. Mater. Sci. Eng., 1994,12(1):37-41.
[16]	ZHANG Q, JIA L T, WU G H . Fabrication of oxidized SiC particles reinforced aluminum matrix composite by pressureless infiltration technique. J. Inorg. Mater., 2012,27(4):353-357.
[17]	LIU J Y, LIU Y C, LIU G Q , et al. Oxidation behavior of silicon carbide particales and their interfacial characterization in aluminum matrix composites. Chin. J. Nonferrous Met., 2002,12(5):961-966.
[18]	ZHANG D, SHEN P, SHI L X . Wetting and evaporation behaviors of molten Mg on partially oxidized SiC substrates. Appl. Surf. Sci., 2010,256(23):7043-7047.
[19]	JONES R O, GUNNARSSON O . Density-functional formalism: sources of error in local-density applications. Phys. Rev. Lett., 1989,61(3):689-746.
[20]	HONG T, SIMTH J R, SROLOVITZ D J . Theory of meta-ceramic adhesion. Acta Metall. Mater., 1995,43(7):2721-2730.
[21]	HAYES R L, ORTIZ M, CARTER E A . Universal binding-energy relation for crystals that accounts for surface relaxation. Phys. Rev. B, 2004,69(17):1324-1332.
[22]	SHI L X, SHEN P, ZHANG D, JIANG Q C . Wetting and evaporation behaviors of molten Mg-Al alloy drops on partially oxidized α-SiC substrates. Mater Z. Chem. Phys., 2011,130(3):1125-1133.
[23]	SAIZ E, CANNON R M, TOMSIA A P . Reactive spreading in ceramic/metal systems. Oil Gas Sci. Technol., 2001,56(1):89-96.
[24]	HOEKSTRA J, KOHYAMA M . Ab initio calculations of the β-SiC(001)/Al interface. Phys. Rev. B, 1998,57(4):2334-2341.
[25]	WINKLER B, PICKARD C J, SEGALL M D , et al. Density- functional study of charge disordering in Cs₂Au(I)Au(Ⅲ)Cl₆ under pressure. Phys. Rev. B, 2001,63(21):214103-214106.
[26]	LIU Y M, SHI J Y, LU Q Q , et al. Research progress of solid surface energy calculation based on Young's equation. Mater. Rev., 2013,23(11):123-129.
[27]	CANDAN E, ATKINSON H V, TUREN Y , et al. Wettability of aluminum-magnesium alloys on silicon carbide substrates. J. Am. Ceram. Soc., 2011,94(3):867-874.