Calculations of stability of alloyed cementite from valance electron structure

Abstract

Based on the empirical electronic theory of solids and molecules (EET), the actual model for unit cell of cementite (θ-Fe₃C) was built and the valence electron structures (VES) of cementite with specified site and a number of Fe atoms substituted by alloying atoms of M ( M=Cr, V, W, Mo, Mn ) were computed by statistical method. By defining P as the stability factor, the stability of alloyed cementite with different numbers and sites of Fe atoms substituted by M was calculated. Calculation results show that the density of lattice electrons, the symmetry of distribution of covalent electron pairs and bond energy have huge influence on the stability of alloyed cementite. It is more stable as M substitutes for Fe² than for Fe¹. The alloyed cementite is the most stable when Cr, Mo, W and V substitute for 2 atoms of Fe² at the sites of Nos. 2 and 3 (or No. 6 and No. 7). The stability of alloyed cementite decreases gradually as being substitutional doped by W, Cr, V, Mo and Mn.

Keywords

valence electron structure / alloyed cementite / stability / density of lattice electrons / symmetry of bonds / bond energy

References

[1] WongJ N, ChulM B, SeiJ O, KwonS J. Effect of interlamellar spacing on cementite dissolution during wire drawing of pearlitic steel wires [J]. Scripta Materialia, 2000, 42(5): 457-463

[2] HonoK, OhnumaM, MueayamaM, NishdaS, YoshieA, TakahashiT. Cementite decomposition in heavily drawn pearlite steel wire [J]. Scripta Materialia, 2001, 44(6): 977-983

[3] ChaeJ Y, JangJ H, ZhangG H, KimK H, LeeJ S, BhadeshiaH K D H, SuhD W. Dilatometric analysis of cementite dissolution in hypereutectoid steels containing Cr [J]. Scripta Materialia, 2011, 65(3): 245-248

[4] LanguillaumeJ, KapelskiG, BaudeletB. Cementite dissolution in heavily cold drawn pearlitic steel wires [J]. Acta Materialia, 1997, 45(3): 1201-1212

[5] DanoixF, JulienD, SauvageX, CopreauxJ. Direct evidence of cementite dissolution in drawn pearlitic steels observed by tomographic atom probe [J]. Materials Science and Engineering A, 1998, 250(1): 8-13

[6] ZhouC T, XiaoB, FengJ, XingJ D, XieX J, ChenY H, ZhouR. First principles study on the elastic properties and electronic structures of (Fe, Cr)3C [J]. Computational Materials Science, 2009, 45(4): 986-992

[7] LiZ-l, LiuZ-l, LiuW-dong. Valence electron structure of cementite phase and its interface and the tempering phenomenon [J]. Science in China Series E: Technological Sciences, 2002, 45(3): 282-289

[8] WunC C J, EmilyA C. Structure and stability of Fe3C-cementite surfaces from first principles [J]. Surface Science, 2003, 530(1): 88-100

[9] ZhangR-linThe empirical electron theory of solids and molecules [M], 1993ChangchunJilin Science and Technology Press287-290

[10] YuR-h, ZhangR-l, ZhengW-t, HuA-guang. Valence structure and properity of cementite [J]. Chinese Science Bulletin, 1993, 38(7): 665-667

[11] YeY-f, FanT-x, ShangY-x, ChenZ-min. The different coefficient of bonding force between intrastratal and interlamination of M3C type cementite [J]. Science in China Series E: Technological Sciences, 1997, 27(4): 300-303

[12] HuangL, GaoK-y, WenS-p, Huangh, WangW, NieZ-ren. Valance electron structure analysis of equilibrium and metastable phases of Al₃M(M=Ti, Zr, Hf) [J]. Acta Metallurgica Sinica, 2012, 48(4): 492-501

[13] XuW-d, ZhangR-l, YuR-huang. The bonding energy caculation of transition metal compound [J]. Science in China Series A: Mathematics, 1988, 3: 323-330

[14] LiuZ-l, LiZ-l, LiuW-dong. Calculation of the valence electron structures of alloying cementite and its biphase interface [J]. Science in China Series E: Technological Sciences, 2001, 44(5): 542-552

[15] MinX-g, SunY-s, XueF, DuW-w, WuD-yun. Analysis of valence electron structures (VES) of intermetallic compounds containing calcium in Mg–Al-based alloys [J]. Materials Chemistry and Physics, 2003, 78(1): 88-93

[16] LvZ Q, FuW T, SunS H, BaiX H, GaoY, WangZ H. First-principles study on the electronic structure, magnetic properties and phase stability of alloyed cementite with Cr or Mn [J]. Journal of Magnetism and Magnetic Materials, 2011, 33: 915-919

[17] GaoY, LvZ Q, SunS H, QuM G, ShiZ P, ZhangR H, FuW T. First principles study on surface structure and stability of alloyed cementite doped with Cr [J]. Materials Letters, 2013, 100: 170-172

[18] WangC X, LvZ Q, FuW T, LiY, SunS H, WangB. Electronic properties, magnetic properties and phase stability of alloyed cementite (Fe,M)3C (M=Co,Ni) from density-functional theory calculations [J]. Solid State Sciences, 2011, 13: 1658-1663

[19] GaoY, WangB, GuoM W, LvZ Q, SunS H, ZhangR H, FuW T. First-principles study on surface structural, magnetic and electronic properties of alloyed cementite with Co or Ni [J]. Computational Materials Science, 2014, 85: 154-158

[20] WangB W, XieY P, ZhaoS J, LiJ, HuL J. Density functional theory study of the influence of Ti and V partitioning to cementite in ferritic steels [J]. Physica Status Solidi B: Basic Solid State Physics, 2014, 251: 950-957

[21] UmemotoM, LiuZ G, MasuyamaK, TsuchiyaK. Influence of alloy additions on production and properties of bulk cementite [J]. Scripta Materialia, 2001, 45(3): 391-397

[22] LiuQ-d, ChuY-l, WangZ-m, LiuW-q, ZhouB-xing. 3D atom probe characterization of alloying elements partitioning cementite of Nb-V Microalloying steel [J]. Acta Metallurgica Sinica, 2008, 44(11): 1281-1285

[23] DunlopG L, CarlssonC J, FrimodigG. Precipitation of VC in ferrite and pearlite during direct transformation of a medium carbon microalloyed steel [J]. Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science, 1978, 9(2): 261-266

[24] SheinI R, MedvedevaN I, IvanovskiiA L. Electronic structure and magnetic properties of Fe3C with 3d and 4d impurities [J]. Physica Status Solidi B: Basic Solid State Physics, 2007, 244(6): 1971-1981

[25] LiuZ-l, LinCheng. Statistics of alloy electronic structure parameter and calculation of mechanics performance [M]. Beijing: Metallurgical Industry Press., 200820-22

[26] LiJ-p, MengS-h, HanJ-c, ZhangX-h, LuoX-guang. Valence electron structure and properties of the ZrC_1-xN_x solid solution [J]. Rare Metal Materials and Engineering, 2008, 37(6): 980-983

[27] PengK, YiM-z, RanL-p, GeY-cheng. Valence electron structure and properties of (Mo_1-x,W_x)Si₂ solid solutions [J]. Rare Metal Materials and Engineering, 2010, 39(3): 414-416

[28] JiangS-y, LiS-chun. Valence electron structures and properties of Al-Ce compounds [J]. Rare Metal Materials and Engineering, 2013, 42(S2): 397-400

[29] JiangS-y, LiS-chun. Effect of valance electron structure of La-Al compounds on aluminum alloy properties [J]. Transactions of Materials and Heat Treatment, 2013, 34(7): 31-35

[30] SuJ-h, JiangT, RenF-zhang. Effect of Cr on electron structure and properties of copper [J]. Transactions of Materials and Heat Treatment, 2012, 33(4): 152-155

[31] LuoX-g, LiJ-p, HuP, DongS-liang. Empirical electron theory model for calculating hardness of Covalent crystals [J]. Chinese Science Bulletin, 2010, 55(19): 1957-1962

[32] ChaitanyaK A, MarcelH F S. First-principles prediction of partitioning of alloying elements between cementite and ferrite [J]. Acta Materialia, 2010, 58(19): 6276-6281

[33] UmemotoM, LiuZ G, MasuyamaK, TsuchiyaK. Influence of alloy additions on production and properties of bulk cementite [J]. Scripta Materialia, 2001, 45(4): 391-397

[34] UmemotoM, TodakaY, TakahashiT, LiP, TokumiyaR, TsuchiyaK. Characterization of bulk cementite produced by mechanical alloying and spark plasma sintering [J]. Journal of Metastable and Nanocrystalline Materials, 2003, 15: 607-614