New Solid Solution MAX Phases: (Ti_0.5, V_0.5)₃AlC₂, (Nb_0.5, V_0.5)₂AlC, (Nb_0.5, V_0.5)₄AlC₃ and (Nb_0.8, Zr_0.2)₂AlC

Figures & data

Table 1.  List of the 68 solid solutions known to date.

211	312
M element	M element
(Tix,V1−x)2AlC (x=0.25, 0.3, 0.4, 0.5, 0.6, 0.75, 0.8, 0.85) [9,10,11]	(Tix,V1−x)3AlC2 ()
(Tix,Cr1−x)2AlC (x=0.25, 0.75) [10]	(Tix,Cr1−x)3AlC2 (x=0.33) [25]
(Tix,Nb1−x)2AlC (x=0.5) [12]	(Crx,V1−x)3AlC2 (x=0.5) [26]
(Tix,Ta1−x)2AlC (x=0.4) [12]	A element
(Tix,Hf1−x)2InC (x=0.5) [13]	Ti3(Alx,Si1−x)C2 (x=0.1, 0.2, 0.4, 0.5,
(Tix,Hf1−x)2InC1.26 (x=0.47) [14]	0.75, 0.8, 0.85, 0.9, 0.95) [27,28,29,30]
(Tix,Zr1−x)2InC (x=0.5) [13]	Ti3(Alx,Sn1−x)C2 (x=0.8) [18]
(Crx,V1−x)2AlC (x=0.25, 0.3, 0.5, 0.7, 0.75, 0.9) [10,11,15]	Ti3(Al,Snx)C1.8 (x=0.2) [31]
(Crx,V1−x)2GeC (x=0.5) [16]	Ti3(Six,Ge1−x)C2 (x=0.43, 0.5, 0.75) [32,33]
(Vx,Ta1−x)2AlC (x=0.65) [12]	Ta3(Alx,Sn1−x)C2 (x=0.6) [34]
(Vx,Nb1−x)2AlC () [12]	X element
(Nbx,Zr1−x)2AlC (x=0.6, 0.8^a) [12]	Ti3Al(Cx,N1−x)2 (x=0.5) [35]
A element	413 and higher
Ti2(Alx,Sn1−x)C (x=0.18, 0.43, 0.68, 0.8) [17,18]	M element
Cr2(Alx,Ge1−x)C (x=0.25, 0.5, 0.75) [19]	(Tix,Cr1−x)4AlC3 (x=0.375) [25]
Cr2(Alx,Si1−x)C (x=0.96) [20]	(Crx,V1−x)4AlC3 (x=0.5) [26]
Cr2(Alx,Ga1−x)C (x=0.6) [21]	(Vx,Nb1−x)4AlC3 (
V2(Alx,Ga1−x)C (x=0.43, 0.56) [21]	(Tix,Nb1−x)5AlC4 (x=0.5) [36]
X element	(Crx, V1−x)5Al2C3 (x=0.5) [26]
Ti2Al(Cx,N1−x) (x=0.5) [22]
Ti2Al(Cx,Ny) (x=0.23, 0.45, 0.66; y=0.71, 0.45, 0.22) [23]
Ti2Al(Cx,N1−x)y (x=0.25, 0.5, 0.75; 0.7≤y≤1) [24]

^aThis work.

Table 2.  Source and characteristics of powders used.

Powder	Purity (wt%)	Particle size	Source
Titanium	99.5	−325 mesh	Alfa Aesar, Ward Hill, MA, USA
Vanadium	99.0	−325 mesh	Alfa Aesar, Ward Hill, MA, USA
Niobium	99.8	−325 mesh	Alfa Aesar, Ward Hill, MA, USA
Zirconium	99.5	50 mesh	Atlantic Equipment Engineers, Upper Saddle River, NJ, USA
Aluminum	99.5	−325 mesh	Alfa Aesar, Ward Hill, MA, USA
Graphite	99.0	−300 mesh	Alfa Aesar, Ward Hill, MA, USA

Table 3.  Summary for the starting composition, synthesis parameters and the resulted phases.

	Soaking parameters
Starting composition			Resulted phases, wt% from
(atomic ratio)	Temperature (°C)	Time (λ)	Rietveld refinement of XRD
Ti:V:Al:C 1.5:1.5:1.3:2.0	1,450	2	90.60(3)%
			9.40(8)% TiC
V:Nb:Al:C 1.0:1.0:1.3:1.0	1,550	2	71.8 3(2)%
			16.39(2)%
			11.78(2)%
Nb:Zr:Al:C 1.5:0.5:1.1:1	1,600	4	90.31(2)%
			1.1(2)% Zr5Al3
			8.59(4)% ZrC

Figure 1. Powder XRD patterns of sample with (Ti_0.5, V_0.5)₃AlC₂ starting composition: (a) observed pattern (black crosses), Rietveld generated pattern (red lines) and difference between the two (blue lines). The black and blue ticks below the pattern represent the peak positions of the 312 phase and TiC phase, respectively; (b) shown in center. The two other patterns were generated by Materials Studio assuming LPs listed in Table 4 for Ti₃AlC₂ [46] and V₃AlC₂.[47]

Table 4.  Summary of the LPs and z-coordinates of the solid solutions obtained herein by Rietveld analysis of the XRD data, and those previously reported for their end members.

MAX phase	a-LP (Å)	c-LP (Å)	Atom (Wyckoff)	z-Coordinate	Ref.
	2.99941(6)	18.1494(7)	Ti/V (4f)	0.1294(2)	This work
			C (4f)	0.0701(7)
	3.075	18.578	Ti (4f)	0.128	[46]
			C (4f)	0.064
	2.908^a	17.778^a	V (4f)	0.1298	[47]
			C (4f)	0.0693
		17.904			[48]
	3.0098(1)	13.488(1)	Nb/V (4f)	0.0903(2)	This work
	3.04	13.5			[12]
	3.106	13.888			[37]
	2.917	13.21			[49]
	3.0961(2)	23.821(2)	Nb/V (4e)	0.1585(3)	This work
			Nb/V (4f)	0.0554(3)
			C (4f)	0.110(2)
	3.13	24.121	Nb (4e)	0.1574	[50]
			Nb (4f)	0.0553
			C (4f)	0.1086
	2.931	22.719	V (4e)	0.1548	[51]
			V (4f)	0.0544
			C (4f)	0.108
	3.13468(8)	14.0003(7)	Nb/Zr (4f)	0.0914(1)	This work
	3.19	14.3			[44]
	3.106	13.888			[37]
	3.255^a	14.570^a			[44]

Note: When reported, numbers in parentheses represent one standard deviation of the last significant digit.

^aEstimated from theoretical calculations, not experimental.

Figure 2. HRTEM images of (a) (Ti_0.5, V_0.5)₃AlC₂, (c) (Nb_0.5, V_0.5)₂AlC and (e) (Nb_0.5, V_0.5)₄AlC₃ in the [112¯0] direction. Diffraction patterns are shown in (b), (d) and (f), respectively.

Figure 3. XRD pattern of (Nb_0.5, V_0.5)₂AlC sample: (a) observed (black crosses), Rietveld generated (red lines) and difference between the two (blue lines). The black, blue and red ticks below the pattern represent the peak positions of the 211 phase, 413 phase and Al₃Nb phase, respectively; (b) shown in center. The two other patterns were generated by Materials Studio assuming LPs listed in Table 4 for Nb₂AlC [37] and V₂AlC.[49]

Figure 4. XRD pattern of (Nb_0.8, Zr_0.2)₂AlC sample: (a) observed (black crosses), Rietveld generated (red lines) and difference between the two (blue lines). The black, blue and red ticks below the pattern represent the peak positions of the 211 phase, Zr₅Al phase and ZrC phase, respectively; (b) shown in center. The two other patterns were generated by Materials Studio assuming LPs listed in Table 4 for Nb₂AlC [37] and Zr₂AlC.[44]

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