Al0.88Cu0.94Fe0.18

Liu, Y.; Liu, H.; Wen, B.; Fan, C.

doi:10.1107/S2414314623008702

inorganic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 10| October 2023| x230870

https://doi.org/10.1107/S2414314623008702

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Al_0.88Cu_0.94Fe_0.18

Yibo Liu,^a Huizi Liu,^a Bin Wen ^a and Changzeng Fan ^a,^b ^*

^aState Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, People's Republic of China, and ^bHebei Key Lab for Optimizing Metal Product Technology and Performance, Yanshan University, Qinhuangdao, Hebei 066004, People's Republic of China
^*Correspondence e-mail: chzfan@ysu.edu.cn

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 11 September 2023; accepted 4 October 2023; online 12 October 2023)

The intermetallic phase with composition Al_0.88Cu_0.94Fe_0.18 was synthesized by high-temperature sintering of a mixture with initial chemical composition Al₇₈Cu₄₈Fe₁₃. Al_0.88Cu_0.94Fe_0.18 adopts the CsCl structure type in space-group Pm $[\overline{3}]$ m. The structure analysis revealed that one site is co-occupied by Al and Cu with a ratio of 0.88 (5):0.12 (5) and the other is co-occupied by Fe and Cu with a ratio of 0.2 (4):0.8 (4). The Al/Cu⋯Fe/Cu separation is 2.5465 (13) Å.

Keywords: crystal structure; high-temperature sintering; β phase; Al–Cu–Fe system.

CCDC reference: 2299144

Structure description

Phases in the ternary Al–Cu–Fe alloy system often have complex crystal structures as well as quasicrystals (QC). For example, an aperiodic diffraction pattern was observed for the alloy with composition Al₆₃Cu₂₄Fe₁₃, exhibiting tenfold rotation symmetry and characterized as a quasi-crystalline phase, as revealed by the first natural quasicrystal (Bindi et al., 2011 ). The present phase Al_0.88Cu_0.94Fe_0.18 belongs to the β-phase in the Al–Cu–Fe system, which is similar to that of the B2-FeAl phase (Rosas & Perez,1998 ). Meyer et al. (2007 ) suggested that the β-phase has a b.c.c. crystal structure, and the lattice parameter of β-Al₅₀Cu₂₀Fe₃₀ was a = 2.925 Å as determined by X-ray diffraction. Kalmykov et al. (2009 ) studied the Al–Cu–Fe phase diagram at 853 K, and considered that the lattice parameter of the β-AlCuFe phase increased with the increase of Cu content. The lowest copper content of the β-phase is 7.3 at.% corresponding to a lattice parameter of a = 2.9171 Å, while the β-phase with the highest copper content of 45.5 at.% has a = 2.9390 Å. Shalaeva & Prekul (2011 ) studied two kinds of β-phases with nominal composition of Al₅₀Cu₃₃Fe₁₇, namely the β₁- and β₂-phases. The lattice parameters of the two phases were found to be 2.939 and 2.969 Å, respectively, by X-ray diffraction, and the average compositions of the two phases were Al_51.5Fe₁₉Cu_29.5 and Al_48.5Fe₁₃Cu_38.5, respectively, by the electron-probe method. It should be noted that only the lattice parameters of the β-phase have been given in the aforementioned studies while an exact crystal structural model has not been provided. According to the Springer Materials database, there are several crystal-structure models for the β-phase in previous studies; however, such a given structure model only represents a possibility inferred from the composition rather than a refined one.

In the present study, the crystal structure model for the β-phase in the Al–Cu–Fe system has been refined on basis of single-crystal X-ray diffraction data. This phase has similar lattice parameters to the previously reported β-phase. Its chemical composition was refined to be Al_0.88Cu_0.94Fe_0.18, in accordance with the complementary EDX results (see Table S1 of the supporting information).

Fig. 1 shows the distribution of the atoms in the unit cell of Al_0.88Cu_0.94Fe_0.18. The environments of the Al1/Cu1 and Cu2/Fe1 sites are shown in Figs. 2 and 3, respectively. The Al1/Cu1 atom at (0, 0, 0) is centered at a dodecahedron, which is surrounded by six Al1/Cu1 atoms and eight Cu2/Fe1 atoms; conversely, the Cu2/Fe1 site at (1/2, 1/2, 1/2) is surrounded by eight Al1/Cu1 atoms and six Cu2/Fe1 atoms. The shortest Al1/Cu1 to Cu2/Fe1 separation is 2.5465 (13) Å and the shortest Al1/Cu1 to Al1/Cu1 contact is 2.9405 (15) Å.

Figure 1
The crystal structure of Al_0.88Cu_0.94Fe_0.18.

Figure 2
(a) The dodecahedron formed around the Al1/Cu1 atom at the 1a site; (b) the environment of the Al1/Cu1 atom with displacement ellipsoids given at the 99% probability level. [Symmetry codes: (i) x − 1, y − 1, z − 1; (ii) x − 1, y, z; (iii) x, y − 1, z; (iv) x − 1, y − 1, z; (v) x, y, z − 1; (vi) x − 1, y, z − 1; (vii) x, y − 1, z − 1; (viii) x, y, z + 1; (ix) x, y + 1, z.]

Figure 3
(a) The dodecahedron formed around the Cu2/Fe1 atom at the 1b site; (b) the environment of the Cu2/Fe atom with displacement ellipsoids given at the 99% probability level. [Symmetry codes: (ii) x − 1, y, z; (iii) x, y − 1, z; (v) x, y, z − 1; (viii) x, y, z + 1.]

Synthesis and crystallization

The high-purity elements Al (indicated purity 99.95%; 0.7163 g), Cu (indicated purity 99.99%; 1.0372 g) and Fe (indicated purity 99.9%; 0.2485 g) were mixed in the molar ratio 78:48:13 and ground in an agate mortar. The blended powders were placed into a cemented carbide grinding mound of 9.6 mm diameter and pressed at 4 MPa for about 3 min. The obtained cylindrical block was put into a silica glass tube and vacuum-sealed by a home-made sealing machine. The resulting ampoule then was placed in a furnace (SG-XQL1200) and heated up to 1373 K for 2 h with with a heating rate of 10 K min⁻¹. The temperature was then reduced to 1073 K for 10 h. Finally, the sample was slowly cooled to room temperature by turning off the furnace power. Suitable pieces of single-crystal grains were broken and selected from the product for single-crystal X-ray diffraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All atoms in the unit cell co-occupied the Wykoff positions. Different choices of refinement are listed in Table S2 of the supporting information. The maximum and minimum residual electron densities in the final difference map are located 0.0 Å and 1.01 Å from the atoms Cu1.

Table 1
Experimental details

Crystal data
Chemical formula	Al_0.88Cu_0.94Fe_0.18
M_r	93.42
Crystal system, space group	Cubic, Pm $[\overline{3}]$ m
Temperature (K)	299
a (Å)	2.9405 (15)
V (Å³)	25.43 (4)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	22.36
Crystal size (mm)	0.14 × 0.12 × 0.12

Data collection
Diffractometer	Bruker D8 Venture Photon 100 CMOS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.439, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	385, 14, 14
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.636

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.013, 0.031, 1.44
No. of reflections	14
No. of parameters	5
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.48
Computer programs: APEX3 and SAINT (Bruker, 2015 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2017/1 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2017 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2299144

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314623008702/hb4450sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623008702/hb4450Isup2.hkl

ESI. DOI: https://doi.org/10.1107/S2414314623008702/hb4450sup3.docx

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: APEX3 (Bruker, 2015); data reduction: APEX3 and SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2017); software used to prepare material for publication: publCIF (Westrip, 2010).

Aluminium copper iron top

Crystal data top

Al_0.88Cu_0.94Fe_0.18	Mo Kα radiation, λ = 0.71073 Å
M_r = 93.42	Cell parameters from 367 reflections
Cubic, Pm3m	θ = 6.9–26.9°
a = 2.9405 (15) Å	µ = 22.36 mm⁻¹
V = 25.43 (4) Å³	T = 299 K
Z = 1	Lump, drak gray
F(000) = 43	0.14 × 0.12 × 0.12 mm
D_x = 6.101 Mg m⁻³

Data collection top

Bruker D8 Venture Photon 100 CMOS diffractometer	14 reflections with I > 2σ(I)
phi and ω scans	R_int = 0.021
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 26.9°, θ_min = 6.9°
T_min = 0.439, T_max = 0.746	h = −3→3
385 measured reflections	k = −3→3
14 independent reflections	l = −3→3

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Primary atom site location: isomorphous structure methods
R[F² > 2σ(F²)] = 0.013	w = 1/[σ²(F_o²) + (0.0246P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.031	(Δ/σ)_max < 0.001
S = 1.44	Δρ_max = 0.32 e Å⁻³
14 reflections	Δρ_min = −0.48 e Å⁻³
5 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Al1	0.000000	0.000000	0.000000	0.0113 (13)	0.88 (5)
Cu1	0.000000	0.000000	0.000000	0.0113 (13)	0.12 (5)
Fe1	0.500000	0.500000	0.500000	0.0105 (6)	0.2 (4)
Cu2	0.500000	0.500000	0.500000	0.0105 (6)	0.8 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Al1	0.0113 (13)	0.0113 (13)	0.0113 (13)	0.000	0.000	0.000
Cu1	0.0113 (13)	0.0113 (13)	0.0113 (13)	0.000	0.000	0.000
Fe1	0.0105 (6)	0.0105 (6)	0.0105 (6)	0.000	0.000	0.000
Cu2	0.0105 (6)	0.0105 (6)	0.0105 (6)	0.000	0.000	0.000

Geometric parameters (Å, º) top

Al1—Fe1ⁱ	2.5465 (13)	Al1—Al1^v	2.9405 (15)
Al1—Fe1	2.5465 (13)	Al1—Al1^viii	2.9405 (15)
Al1—Fe1ⁱⁱ	2.5465 (13)	Al1—Al1^ix	2.9405 (15)
Al1—Fe1ⁱⁱⁱ	2.5465 (13)	Cu1—Cu2	2.5465 (13)
Al1—Fe1^iv	2.5465 (13)	Fe1—Fe1^viii	2.9405 (15)
Al1—Fe1^v	2.5465 (13)	Fe1—Fe1^v	2.9405 (15)
Al1—Fe1^vi	2.5465 (13)	Fe1—Fe1ⁱⁱⁱ	2.9405 (15)
Al1—Fe1^vii	2.5465 (13)	Fe1—Fe1ⁱⁱ	2.9405 (15)
Al1—Al1ⁱⁱⁱ	2.9405 (15)

Fe1ⁱ—Al1—Fe1	180.0	Al1^x—Fe1—Al1	180.0
Fe1ⁱ—Al1—Fe1ⁱⁱ	109.5	Al1^x—Fe1—Al1^xi	109.5
Fe1—Al1—Fe1ⁱⁱ	70.529 (1)	Al1—Fe1—Al1^xi	70.529 (1)
Fe1ⁱ—Al1—Fe1ⁱⁱⁱ	109.5	Al1^x—Fe1—Al1^ix	109.5
Fe1—Al1—Fe1ⁱⁱⁱ	70.5	Al1—Fe1—Al1^ix	70.5
Fe1ⁱⁱ—Al1—Fe1ⁱⁱⁱ	109.5	Al1^xi—Fe1—Al1^ix	109.5
Fe1ⁱ—Al1—Fe1^iv	70.529 (1)	Al1^x—Fe1—Al1^xii	70.529 (1)
Fe1—Al1—Fe1^iv	109.5	Al1—Fe1—Al1^xii	109.5
Fe1ⁱⁱ—Al1—Fe1^iv	70.5	Al1^xi—Fe1—Al1^xii	70.5
Fe1ⁱⁱⁱ—Al1—Fe1^iv	70.5	Al1^ix—Fe1—Al1^xii	70.5
Fe1ⁱ—Al1—Fe1^v	109.5	Al1^x—Fe1—Al1^viii	109.5
Fe1—Al1—Fe1^v	70.529 (1)	Al1—Fe1—Al1^viii	70.529 (1)
Fe1ⁱⁱ—Al1—Fe1^v	109.5	Al1^xi—Fe1—Al1^viii	109.5
Fe1ⁱⁱⁱ—Al1—Fe1^v	109.5	Al1^ix—Fe1—Al1^viii	109.5
Fe1^iv—Al1—Fe1^v	180.0	Al1^xii—Fe1—Al1^viii	180.0
Fe1ⁱ—Al1—Fe1^vi	70.5	Al1^x—Fe1—Al1^xiii	70.5
Fe1—Al1—Fe1^vi	109.5	Al1—Fe1—Al1^xiii	109.5
Fe1ⁱⁱ—Al1—Fe1^vi	70.5	Al1^xi—Fe1—Al1^xiii	70.5
Fe1ⁱⁱⁱ—Al1—Fe1^vi	180.0	Al1^ix—Fe1—Al1^xiii	180.0
Fe1^iv—Al1—Fe1^vi	109.5	Al1^xii—Fe1—Al1^xiii	109.5
Fe1^v—Al1—Fe1^vi	70.5	Al1^viii—Fe1—Al1^xiii	70.5
Fe1ⁱ—Al1—Fe1^vii	70.529 (1)	Al1^x—Fe1—Al1^xiv	70.529 (1)
Fe1—Al1—Fe1^vii	109.5	Al1—Fe1—Al1^xiv	109.5
Fe1ⁱⁱ—Al1—Fe1^vii	180.0	Al1^xi—Fe1—Al1^xiv	180.0
Fe1ⁱⁱⁱ—Al1—Fe1^vii	70.5	Al1^ix—Fe1—Al1^xiv	70.5
Fe1^iv—Al1—Fe1^vii	109.5	Al1^xii—Fe1—Al1^xiv	109.5
Fe1^v—Al1—Fe1^vii	70.5	Al1^viii—Fe1—Al1^xiv	70.5
Fe1^vi—Al1—Fe1^vii	109.5	Al1^xiii—Fe1—Al1^xiv	109.5
Fe1ⁱ—Al1—Al1ⁱⁱⁱ	54.7	Al1^x—Fe1—Fe1^viii	54.7
Fe1—Al1—Al1ⁱⁱⁱ	125.3	Al1—Fe1—Fe1^viii	125.3
Fe1ⁱⁱ—Al1—Al1ⁱⁱⁱ	125.3	Al1^xi—Fe1—Fe1^viii	125.3
Fe1ⁱⁱⁱ—Al1—Al1ⁱⁱⁱ	54.7	Al1^ix—Fe1—Fe1^viii	125.3
Fe1^iv—Al1—Al1ⁱⁱⁱ	54.7	Al1^xii—Fe1—Fe1^viii	125.3
Fe1^v—Al1—Al1ⁱⁱⁱ	125.3	Al1^viii—Fe1—Fe1^viii	54.7
Fe1^vi—Al1—Al1ⁱⁱⁱ	125.3	Al1^xiii—Fe1—Fe1^viii	54.7
Fe1^vii—Al1—Al1ⁱⁱⁱ	54.7	Al1^xiv—Fe1—Fe1^viii	54.7
Fe1ⁱ—Al1—Al1^v	54.7	Al1^x—Fe1—Fe1^v	125.3
Fe1—Al1—Al1^v	125.3	Al1—Fe1—Fe1^v	54.7
Fe1ⁱⁱ—Al1—Al1^v	125.3	Al1^xi—Fe1—Fe1^v	54.7
Fe1ⁱⁱⁱ—Al1—Al1^v	125.3	Al1^ix—Fe1—Fe1^v	54.7
Fe1^iv—Al1—Al1^v	125.3	Al1^xii—Fe1—Fe1^v	54.7
Fe1^v—Al1—Al1^v	54.7	Al1^viii—Fe1—Fe1^v	125.3
Fe1^vi—Al1—Al1^v	54.7	Al1^xiii—Fe1—Fe1^v	125.3
Fe1^vii—Al1—Al1^v	54.7	Al1^xiv—Fe1—Fe1^v	125.3
Al1ⁱⁱⁱ—Al1—Al1^v	90.0	Fe1^viii—Fe1—Fe1^v	180.0
Fe1ⁱ—Al1—Al1^viii	125.3	Al1^x—Fe1—Fe1ⁱⁱⁱ	125.3
Fe1—Al1—Al1^viii	54.7	Al1—Fe1—Fe1ⁱⁱⁱ	54.7
Fe1ⁱⁱ—Al1—Al1^viii	54.7	Al1^xi—Fe1—Fe1ⁱⁱⁱ	54.7
Fe1ⁱⁱⁱ—Al1—Al1^viii	54.7	Al1^ix—Fe1—Fe1ⁱⁱⁱ	125.3
Fe1^iv—Al1—Al1^viii	54.7	Al1^xii—Fe1—Fe1ⁱⁱⁱ	125.3
Fe1^v—Al1—Al1^viii	125.3	Al1^viii—Fe1—Fe1ⁱⁱⁱ	54.7
Fe1^vi—Al1—Al1^viii	125.3	Al1^xiii—Fe1—Fe1ⁱⁱⁱ	54.7
Fe1^vii—Al1—Al1^viii	125.3	Al1^xiv—Fe1—Fe1ⁱⁱⁱ	125.3
Al1ⁱⁱⁱ—Al1—Al1^viii	90.0	Fe1^viii—Fe1—Fe1ⁱⁱⁱ	90.0
Al1^v—Al1—Al1^viii	180.0	Fe1^v—Fe1—Fe1ⁱⁱⁱ	90.0
Fe1ⁱ—Al1—Al1^ix	125.3	Al1^x—Fe1—Fe1ⁱⁱ	125.3
Fe1—Al1—Al1^ix	54.7	Al1—Fe1—Fe1ⁱⁱ	54.7
Fe1ⁱⁱ—Al1—Al1^ix	54.7	Al1^xi—Fe1—Fe1ⁱⁱ	125.3
Fe1ⁱⁱⁱ—Al1—Al1^ix	125.3	Al1^ix—Fe1—Fe1ⁱⁱ	54.7
Fe1^iv—Al1—Al1^ix	125.3	Al1^xii—Fe1—Fe1ⁱⁱ	125.3
Fe1^v—Al1—Al1^ix	54.7	Al1^viii—Fe1—Fe1ⁱⁱ	54.7
Fe1^vi—Al1—Al1^ix	54.7	Al1^xiii—Fe1—Fe1ⁱⁱ	125.3
Fe1^vii—Al1—Al1^ix	125.3	Al1^xiv—Fe1—Fe1ⁱⁱ	54.7
Al1ⁱⁱⁱ—Al1—Al1^ix	180.0	Fe1^viii—Fe1—Fe1ⁱⁱ	90.0
Al1^v—Al1—Al1^ix	90.0	Fe1^v—Fe1—Fe1ⁱⁱ	90.0
Al1^viii—Al1—Al1^ix	90.0	Fe1ⁱⁱⁱ—Fe1—Fe1ⁱⁱ	90.0

Symmetry codes: (i) x−1, y−1, z−1; (ii) x−1, y, z; (iii) x, y−1, z; (iv) x−1, y−1, z; (v) x, y, z−1; (vi) x−1, y, z−1; (vii) x, y−1, z−1; (viii) x, y, z+1; (ix) x, y+1, z; (x) x+1, y+1, z+1; (xi) x+1, y, z; (xii) x+1, y+1, z; (xiii) x+1, y, z+1; (xiv) x, y+1, z+1.

Funding information

Funding for this research was provided by: The National Natural Science Foundation of China (grant Nos. 52173231 and 51925105); Research Foundation of Education Bureau of Hebei Province (grant No. E2022203182); The Innovation Ability Promotion Project of Hebei supported by Hebei Key Lab for Optimizing Metal Product Technology and Performance (No. 22567609H).

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