Physical Properties of the MAX Phases
I~
1. Introduction
The layered ternary carbides and nitrides with the
general formula MIl+IAX Il , where n= 1,2, or 3, M is
an early transition metal, A is an A-group element
(mostly IlIA or IVA), and X is either C or N, rep­
resent a new class of solids (Barsoum 2000, Barsoum
and EI-Raghy 200Ia). These phases are layered, with
M Il +1X Il layers interleaved with pure A-group el~­
ment layers) (Fig. I). The hexagonal MIl+IAX Il umt
cells~space group P63lmmc~have two formula
units per unit cell. There are roughly 50 ~2~X
phases (Nowotny 1970); three M 3AX 2: T1 3SIC 2
(Jeitschko and Nowotny 1967), Ti 3GeC 2 (Wolf­
sgruber et al. 1967), and Ti3 AIC 2 (Pietzka and Schus­
ter, 1996); and one M 4AX 3 , Ti 3AIN 4 (Barsoum et at.
1999, Rawn et al. 2000).
The M lI + 1AX lI phases combine an unusual, and
sometimes unique, set of properties (Barsoum 2000).
Like their corresponding binary carbides and ni­
trides, they are elastically stiff, good thermal and
electrical conductors, resistant to chemical attack and
have relatively low thermal expansion coefficients.
Mechanically, however, they cannot be more differ­
ent. They are relatively soft (1-5 GPa) and most
readily machinable, thermal shock resistant, and
damage tolerant (Barsoum and EI-Raghy 1996, Bar­
soum and Radovic 2004). Moreover, some are fa­
tigue- and creep- and oxidation-resistant. At higher
temperatures, they go through a ductile-to-brittle
transition. At room temperature, they can be com­
pressed to stresses as high as 1 GPa and fully recover
upon removal of the load, while dissipating 25% of
mechanical energy (Barsoum et al. 2003) (see Me­
chanical Properties of the MAX Phases (Barsoum and
Radovic 2004) for the mechanical properties of
MAX).
This article summarizes our current understanding
of the physical properties of bulk MIl+IAX Il phases. It
does not discuss recent MAX-based thin-film work
(Palmquist et al. 2002, Molina-Aldareguia et al. 2003,
Wilhelmsson et al. 2004), to list a few. This article is
divided into five sections and reviews their structure
and bonding (including theoretical) characteristics,
summarizes their elastic properties, and reviews their
electrical and thermal properties.
2. Structure and Bonding
The unit cells of the 211, 312, and 413 phases are
shown in Figs. l(a), l(b), and l(c), respectively. In
each case, almost close-packed M-Iayers are inter­
leaved with layers of pure group A-element, with the
X-atoms filling the octahedral sites between the
c c
I
~
a
A-layers M-layers
~
(a) (b) (c)
Figure 1
Schematic of (a) M 2AX, (b) M 3 AX 2 , and (c) M 4 AX 3
unit cells.
former. The M 6 X octahedra are identical to those
found in the rock salt structure of the corresponding
binary MX carbides. The A-group elements a~e lo­
cated at the centers of trigonal prisms that are slightly
larger, and thus better able to accommodate the
larger A-atoms, than the octahedral sites. In the
211's there are two layers of M separating the A­
layer~, in the 312's, three, and in the 413's there are
four.
The MIl+IAX Il phases known to date are listed in
Table I, together with their lattice parameters and
theoretical densities. The A-group elements are
mostly IlIA and IVA. All but four compounds are
211's, by far the most prevalent stru.cture: Al is the
most versatile A-group element With eight com­
pounds, including nitrides, 312's, and t?e sole 413
phase. Ga forms the most 211 phases, Wlt~ 9.. ..
Given the close chemical and structural slmIlanties
of the MAX and MX phases, much can be learned
about the former from what is known about the lat­
ter. Like the MX compounds (Cottrell 1995, Pierson
1996), it is useful to consider the ternaries to be in­
terstitial compounds in which the A- and X-atoms fill
the interstitial sites between the M-atoms. In such a
scheme, the c-parameter of the 211 phases, compris­
ing four M-Iayers per unit cell, should be :::::: 4 times
the a-parameter, for a cia ratio of::::::4, ~s ob~erv~d
(Table 1). Similar arguments. for the .312 s, With SIX
M-Iayers per unit cell, predict a ratIO. of : : : : 6, and
the 413's a ratio of ::::::8. The actual cia ratIOs are,
 Physical Properties of the MAX Phases

Table 1
Summary of all M"+lAX" phases, their lattice parameters and theoretical densities known to date.

lIB IlIA IVA VA VIA

Al Si P S
ThAIC, 4.11 (3.04, 13.60) ThSC, 4.62 (3.216.
11.22)
VzAIC, 4.82 (2.914, 13.19) VzPC, 5.38 ZrzSC, 6.20 (3.40,
(3.077, 10.91) 12.13)
CrzAIC, 5.24 (2.86, 12.8) Ti 3SiCz, 4.52 NbzPC, 7.09 NbzSCo.4 (3.27,11.4)
(3.0665, 17.671) (3.28. 11.5)
NbzAIC, 6.50 (3.10, 13.8) HfzSC (3.36, 11.99)
TazAIC, 11.82 (3.07. 13.8)
ThAIN, 4.31 (2.989. 13.614)
ThAIC z, 4.5 (3.075, 18.578)
Ti~IN3' 4.76 (2.988, 23.372)

Zn Ga Ge As
ThGaC, 5.53 (3.07. 13.52) ThGeC, 5.68
(3.07, 12.93)
VzGaC, 6.39 (2.93, 12.84) VzGeC, 6.49 (3.00, VzAsC, 6.63 (3.11, Se
12.25) 11.3)
CrzGaC, 6.81 (2.88, 12.61)
NbzGaC, 7.73 (3.13, 13.56)
MozGaC, 8.79 (3.01, 13.18) CrzGeC, 6.88
(2.95, 12.08)
TazGaC, 13.05 (3.10, 13.57) NbzAsC, 8.025
(3.31, 11.9)
TizGaN, 5.75 (3.00, 13.3) Ti 3GeC Z' 5.55
(3.087,17.76)
CrzGaN, 6.82 (2.875, 12.77)
VzGaN, 5.94 (3.00, 13.3)

Cd In Sn
SczInC TizSnC, 6.36
(3.163, 13.679)
TizCdC 9.71 TizInC, 6.2 (3.13. 14.06)
(3.1, 14.41)
ZrzInC, 7.1 (3.34, 14.91) ZrzSnC, 7.16 Sb Te
(3.3576, 14.57)
NbzInC, 8.3 (3.17,14.73) NbzSnC, 8.4
(3.241, 13.802)
HfzInC, 11.57 (3.30, 14.73) HfzSnC, 11.8
(3.320, 14.388)
TizInN, 6.54 (3.07, 13.97) HfzSnN, 7.72
(3.31, 14.3)
ZrzInN, 7.53 (3.27, 14.83)

TI Pb Bi
ThTIC, 8.63 (3.15, 13.98) TizPbC, 8.55
(3.20. 13.81)
Zrz TIC, 9.17 (3.36, 14.78) ZrzPbC, 9.2 (3.38,
14.66)
HfzTIC, 13.65 (3.32, 14.62) HfzPbC, 12.13
(3.55, 14.46)
ZrzTIN, 9.60 (3.3, 14.71)
The theoretical density (Mg m -3) is in bold letters. The a· and c·lattice parameters (A) are in brackets.

Adapted from Nowotny H 1970 Struktuchemie Einiger Verbindungen der Ubergangsmetalle mit den elementen C. Si. Ge. Sn. Prog. Solid State Chem.

2,27.

2
 Physical Properties of the MAX Phases

respectively, ~ 5.8 to 6 and 7.8, supporting the notion
of interstitial compounds.
With the exception of the Cr2AC phases, an excel­
lent correlation exists between the a-lattice parameters
of the MAX phases and the M-M distances in the
corresponding MX binaries (Barsoum 2000). Why the
three Cr-containing MAX phases do not fit the pattern
is unclear at this time, but may be related to the fact
that Cr is the only transition metal listed in Table 1
that does not crystallize in the rock salt structure.
In addition to the list shown in Table 1, the number
of possible solid-solution permutations and combi­
nations is obviously quite large; roughly a quarter of
the periodic table could, in principle, come into play.
It is possible to form solid solutions on the M -sites,
the A-sites, and the X-sites and combinations thereof.
A continuous series of solid solutions, Ti 2AIC o.8 _ x N",
where .\'=0 to ~0.8, occurs at 1490°C (Pietzka and
Schuster 1996). The ternaries Ti 3GeC 2 and Ti 3SiC 2
form a complete range of solid solutions (Ganguly
et al. 2004). Amongst the solid solutions that form on
the M-sites are: (Ti,VhSC (Nowotny et al. 1982);
(Nb,ZrhAIC, (Ti,VhAIC, (Ti,NbhAIC, (Ti,CrhAIC,
(Ti,TahAIC, (V,NbhAIC, (V,TahAIC, and (V,
CrhAIC (Schuster et al. 1980, Salama et al. 2002);
and (Ti, Hf)2InC (Barsoum et al. 2002a).
Lastly. it is important to note that currently there is
quite a bit of effort in theoretical modeling of the
MAX phases (Medvedeva et al. 1998, Sun and Zhou
1999, Holm et al. 2001, Hug and Frie 2002, Hug et al.,
Sun et al. 2004). The following conclusions of the the­
oretical work are noteworthy: (i) the M-X bonds are
comparable to those in the MX binaries (Medvedeva
et al. 1998), (ii) the density of states at the Fermi level,
N(EF}-as in some MX binaries but notably not TiC­
is substantial, (iii) there is strong overlap between the
p-orbitals of A- and the d-orbitals of the M-atoms, (iv)
the electronic states at the Fermi level are mostly d-d
M-orbitals (Medvedeva et al. 1998), and (v) there is a
net transfer of charge from the A-group element to the
X-atoms, at least in the M 2AIC phases (Hug et al.
2005). As discussed in the sections that follow, many of
these conclusions have been supported by experimental
results. Furthermore, recent ab initio work has been
quite successful in calculating the elastic properties of
some MAX phases (Sun et al. 2004) as well as the
Raman active vibrational modes (Spanier et al. 2005).
3. Elastic Properties
The MAX phases are elastically quite stiff (Table 2).
This is particularly true for the 312 and 413 phases.
Given that the densities of some of these solids are
relatively low, ~4.5 gcm- 3, their specific stiffnesses
are considerable. For example, the specific stiffness of
Ti 3SiC 2 is comparable to Si 3N 4 and roughly three
times that of Ti, a metal prized for that property. Po­
isson's ratios for all compounds hover around 0.2,
which is lower than that of Ti (0.3), and more in line
with stoichiometric TiC (~0.19). Not surprisingly,
given the larger fraction of M--X bonds in the 312's
and 413's as compared to the 211's, the latter are less
stiff. For example, at 161 GPa, the bulk modulus of
Ti 2AIN is significantly lower than the 216 GPa of
Ti 4 AIN 3. Increasing the atomic number of the A­
group element also results in lattice-softening. For ex­
ample, at 178 GPa, 216GPa, and 237GPa the Young's
moduli of Zr2SnC, Nb 2SnC, and Hf2SnC (EI-Raghy
et al. 2000), respectively, are all lower than any of the
AI-containing ternaries (Table 2).
In stark contrast to other layered solids such as
graphite, BN, and mica, and despite their huge plastic
anisotropies (Barsoum and Radovic 2004), the an­
isotropies in their elastic properties are quite mild.
For example, C33 and CII for Ti 3SiC 2 (Holm et al.

Table 2
Young's, E, shear, G, and bulk B. moduli of the select MAX phases and near-stoichimetric TiC. Also listed are the
theoretical densities.

Theo. density G E Jf' Bb N(E F )

Solid (gcm- 3) (GPa) (GPa) v (GPa) (GPa) 8D 8l; (l/eV unit cell)
Ti 2AIC 4.1 118 277 0.19 144 186c 732 672 d 4.9 d
V2AIC 4.81 116 235 0.20 152 20l c 696 625 d 7.5 d
Cr2AIC 5.24 102 245 0.20 138 166c 644 589 d 14.5d
Nb 2AIC 6.34 117 286 0.21 165 208 c 577 NA 5.1 e
Ti 3SiC2 4.52 139 339 0.2 190 206 715-780 715 h 5
Ti 3GeC 2 5.02 142 340 0.19 169 179 725 670 5A f
Ti 3AIC 2 4.2 124 297 0.2 165 226 758 764e 3.8 f
Ti~IN3 4.7 127 310 0.22 185 216 762 779 h 6.9 g
TiCo.96 4.93 205 ~500 0.19 272 940g 845 h 0.1--0.5 g
The Poisson ratio. v. 8 D calculated from Vm (column 8) and 8 D calculated from low-temperature heat capacity measurements (column 9) are listed. The

density of states at the Fermi level is listed in the last column.

a Calculated from E and G assuming elastic isotropy. bDirectiy measured in a diamond anvil celL c Manoun et al. (in press). d Drulis et al.

(submitted). e Lofland et al. (2004). fFinkel et al. (2004). g Finkel (2003). h Ho et al. (1999).

3
 Physical Properties of the MAX Phases

2001) and some M 2 AIC phases (Sun et al. 2004) are 400
almost equal. Similarly, the compressibilities along a­ Cr2AIC Ti,Si
and c-directions are comparable for most MAX Young's moduli o .,
350
phases measured to date (Onodera et af. 1999, Ma­ Ti 4 A1N?
~
Ti 2AIC .
noun et al. 2004a, 2004b, 2005). 0.. V2AIC~g o
300
Another important measure of the stiffness of a S o Ti 3GeC 2
solid is its Debye temperature, (}D, which can be es­ "3 Nb 2AIC
timated assuming "6
250
0

( h) (3~bNAV)
.~
1/3 Vi 200
- V2AIC
eD = -
kB 4rrMw
I'm (I) "
;)
"@ 150
.~
0)
where b, ~, and M w are the density. number of atoms ...0
100 Bulk moduli
per formula unit, and its molecular weight, respec­ O.l

tively. ]1m is the mean velocity of sound in the solids ~

defined as 50

I'm = 3(1',1'1)
3] 1/3 o "-'--'-'--'--'--'--'-'--'-~L.L.>..-'-'-"""""-L..L..L.L.J.-'--'-""""""-'--'-""""""'L.L.>..""""'W
(2) o 50 100 150 200 250 300 350 400
[
21'31 + 1',3
Experimental elastic moduli (GPa)

where VI and I's are the longitudinal and shear veloc­
ities, respectively. Column 8 in Table 2 lists (}D values
calculated from Eqn. (l). In general, the Debye tem­
peratures are quite high and more in line with stiff
light ceramics such as Ab03 and Si3N 4 than with
metals. The values are also in good agreement with
those calculated from low-temperature heat-capacity
measurements (column 9, Table 2). Table 2 also lists
the elastic properties of near-stoichiometric TiC for
companson.
The AI-containing MAX phases and ThSiC 2 have
another useful attribute: their stiffnesses are not a
strong function of temperature. For example, at
1273 K the shear modulus of Ti 3AIC 2 is ~ 88% of its
room temperature value (Finkel et af. 2000). In that
respect, their resemblance to the MX binaries is no­
table.
Figure 2 compares the measured shear and
Young's moduli of select MAX phases to those pre­
dicted from ab initio calculations. With a few excep­
tions, like Cr2AlC and Ta2AlC, the agreement has to
be considered quite good, considering that the calcu­
lations are 0 K calculations and assume perfect crys­
tals (Holm et al. 2001, Sun et af. 2004); in reality
neither condition is met.
Another clue to the nature of the bonding is Raman
spectroscopy. The Raman modes for these compounds
have been deciphered (Spanier et al. 2005) and they
show that there are essentially two types of vibrations:
low-energy (for the most part <300cm- l ) shear
modes (along the a-direction) involving the A- and
M-atoms, and higher-energy modes involving vibra­
tions along the c-axis. The low-energy shear modes are
not unlike the ones observed in graphite and other
layered solids, that have been labeled rigid-layer modes
(Zallen et al. 1971, Zallen and Slade 1974). These
modes are a manifestation of the weakness of the M-A
bonds in shear relative to the M-X bonds. That said, it
Figure 2
Summary of experimentally determined and
theoretically calculated bulk (red squares) and Young's
moduli (blue circles) of select MAX phases.
is incorrect to conclude from this statement that any of
the bonds in the MAX phases are weak.
4. Electronic Transport
One of the characteristics of the MAX is their metal­
like resistivity, P, that increases linearly with increas­
ing temperature. Figure 3(a) plots the temperature
dependence of P-Po, where Po is the residual resis­
tivity at 0 K. (The curves are shifted slightly in the y­
direction for clarity). Table 3 lists the actual room
temperature resistivities, PRT.
Both theoretical and experimental results strongly
suggest that the electronic properties of the MAX
phases are dominated by the d-d M-orbitals (Med­
vedeva et af. 1998, Lofland et al. 2004, Hug et al.
2005) and that these properties are, in turn, compa­
rable to those of their respective transition metals.
Before discussing the former, it is useful to briefly
summarize what is known about the latter. The re­
sistivities of transition metals are proportional to the
density of states at the Fermi level, N(EF ) (Mott and
Jones 1936, Ashcroft and Mermin 1976). Accord­
ingly, the electron mobilities at 0 K, flo, should be
inversely proportional to N(EF ). The quality of the
crystal as measured by the residual resistivity ratio,
RRR (PRT/ Po), is also important. Thus, a correlation
between flo and (RRR - l)/N(Ep ) should exist and is
indeed experimentally verified (Fig. 3(b». Similarly,
dp/dT should also scale with N(E F ) and the electron/
phonon coupling factor (Hettinger et af. 2005). That

4
 Physical Properties of the MAX Phases

0.7 that their Hall and Seebeck coefficients are quite

small-in some cases vanishingly small-and are a
weak function of temperature (Barsoum et af. 2000d,
0.6
Y 00 et al. 2000, Finkel et al. 2003, Finkel et al. 2004,
Hettinger et al. 2005). Furthermore, the magnetore­
0.5 sistance (l1p/ p = [p(H) - p(H = 0)/ p(H = 0)]), where
/""0
H is the applied magnetic field intensity, is positive,
E parabolic, and nonsaturating.
0.4
c: These results are of crucial importance because
3 they imply that the MAX phases are compensated
0

Q..

I 0.3 conductors and a two-band conduction model is op­

Q..
erative. In the low-field limit of the two-band model,
0.2 the following applies:
I
(j = - = e(nJ1n + PJ1 p ) (3)
0.1 p

I1p = cJ.Ji2 = J1nJ1p np(Pn + pp)2 B2 (4)

0
0 50 100 150 200 250 300 Po (J1 n n+ppp)2
(a) Temperature (K)
(p;p - J1~n)
0.06 RH = 0 (5)
e(ppp + Pnn)­
0.05 where B is the magnetic field. There are thus four
/""0

I
unknowns: the concentration of electrons and holes,
I '" Ti 2 AIC 11, p, and their mobilities Iln and J1p, respectively.
>­
N
0.04 • Given the small RH and Seebeck coefficient values. it
§ is reasonable to assume that n ~ p in most cases.
With that assumption, it is possible to solve for the
~ 0.Q3 four unknowns; the results are listed in Table 3.
:0 2
R > 0.95 Based on these results and those shown in Fig. 3,
0
S the following points pertaining to all MAX phases,
I::
0 0.02 except Ti4 AlN 3 , are salient:
b
()
<U (i) Most of the room temperature resistivities of
~ the MAX phases fall in the relatively narrow range of
0.01
0.2--0. 7l!Q m. This is also true of other MAX phases
. - - Ti 4AIN 3 not listed in Table 3 (Barsoum 2000). The resistivities
O ...... L...L-L...L-J--L-J--L-.l.....L......................L..J....L..J....l--L-.L-L..L-L.............lo....I...J
of solid solution compositions, however, can be sig­
o 0.5 1 1.5 nificantly higher.
(b) (RRR - I)/N(EF ) (ii) For the most part, n ~ p and Iln ~ Ill'" The
densities of electronic carriers fall in the relatively
Figure 3 narrow range of I to 3 X 10 27 m 3 . Note nand pare
(a) Temperature dependence of p - Po for select MAX not related to N(E p ).
phases. (b) functional dependence of electronic charge (iii) At 4 K, the less defective samples, as measured
mobilities at 4 K on RRR and the density of states at the by the RRR, have higher mobilities. The 4 K mob­
Fermi level. N(EF ) (Hettinger et al. 2005). ilities are also inversely proportional to N(E p ).
(iv) dp/dT is proportional to N(E p ).
The ternary Ti 4 AlN 3 is somewhat unique in that its
it does can be seen by comparing the slopes of the resistivity is more in line with semimetals than metals.
lines shown in Fig. 3(a) with the N(EF ) values listed in The reason for this state of affairs is not clear at this
Table 3. time, but is most probably related to the fact that the
To fully understand electronic transport in a solid, sample tested was not stoichiometric, but closer to
the density of charge carriers as well as their mob­ Ti4 AlN2 .9 . The high defect concentration leads to a
ilities should be known. Typically, Hall coefficient, significantly reduced mobility (Table 3).
R H , measurements are used to measure the concen­ Solid solutions also result in reduced mobilities,
trations and sign of the majority charge carriers. but not equally. Substitutions on the A-sites appear
With that information, the mobility is determined to have little effect on resistivity (Finkel et al.
from the conductivity values. The MAX phases, 2004); substitutions on the M-sites, however, have a
however. are unlike most other metallic conductors in much more dramatic effect (Barsoum et al. 2002b).

5
 Physical Properties of the MAX Phases

Table 3
Summary of room temperature resistivity results, mobilities of electronic carriers, and their densitites.

300K mobilities (m 2 y- 1s-l) Carrier density (1027 m -3)

Compound P (].lOrn) Pn Pp 11 P References

Ti 3SiC2 0.22 0.005 0.006 2.5 2.5
Ti3Sio.5Geo.5C2 0.27 :::::0.005 :::::0.005 2 2 Finkel et al. (2004)
Ti 3GeC 2 0.26 0.009 0.008 1.5 1.5

Ti 3AIC 2 0.39 0.0046--0.0042 0.0054---().003 1.5-1.6 1.5-2

Ti~IN3 2.61 0.00034 7 Finkel et al. (2003)

Ti 2AIC 0.36 0.0090 0.0082 1.0 1.0

Y2 AIC 0.26 0.0046 0.0039 2.7 2.7 Hettinger et al. (2005)
Cr2AIC 0.74 0.0034 0.0036 1.2 1.2
Nb 2AIC 0.39 0.0038 0.0031 2.7 2.7

TiCo.95 1-1.6 0.0012-0.0017 0.24---() .4 Barsoum et at. (2000d)

Substitutions on the X-sites have an effect that is only (ii) For the non AI-containing MAX phases,
observed if the concentration of defects, presumably Kph« K e (Table 4).
vacancies and displaced atoms, in the end-members (iii) The AI-containing MAX phases are decent
are low. phonon conductors (Fig. 4(b)). The best phonon
conductors at room temperature are Ti 3AIC 2 and
5. Thermal Properties Y2AIC; the worst is Nb 2AIC.
(iv) MAX-phase solid solutions totally suppress
5.1 Thermal Conductivities Kph. This is true of substitutions on the A-sites (Fig.

Before discussing the thermal conductivities of the
MAX phases, it is instructive to briefly review the
theory of thermal conductivity in solids. The thermal
conductivity, Kth, is given as
Kth = K e + Kph (6)
where h'e and Kph are, respectively, the electronic and
phonon contributions to Kth. K e can be estimated
from the Wiedemann-Franz law, that is,
LoT
Ke = - (7)
P more detail elsewhere (Barsoum 2000), this result
where L g is the classic Lorenz number,
2.45 x \0- W Q K 2. Using the electrical reslstlVlty
values (Table 3) and their temperature-dependencies
(not shown), it is straightforward to calculate K e from
Eqn. (7) and, Kph from Eqn. (6).
The temperature dependencies of the MAX phase
K'S are plotted in Fig. 4(a); the corresponding phonon
contributions are shown in Fig. 4(b). The room tem­
perature results are listed in Table 4, together with
the corresponding parameters for near-stoichiometric
TiC", TiN", and NbC" for comparison. From these
results, it is reasonable to conclude the following:
(i) All MAX phases are essentially good ther­
mal conductors because they are good electrical
conductors.
4(b)). Along the same lines, at all temperatures, and
similar to their MX counterparts (Williams 1971), the
more Kph is suppressed, the more defective the sam­
ples. For example, in the M 2AIC phases, a correlation
exists between the quality of the crystal, as measured
by RRR, and Kph (Hettinger et al. 2005).
Stiff, lightweight solids with high Debye temper­
atures are typically good phonon conductors. Given
the rigidity of some of MAX phases, for example,
ThSiC 2 , the fact that phonon conductivity is sup­
pressed is somewhat surprising. As discussed in
can be attributed to the scattering efficiency of the
A-group atoms that tend to play the role of a "rat­
tier" in these structures. Rattlers are atoms that
vibrate about their equilibrium position more than
other atoms (Keppens et al. 1998, Sales et al. 1999).
Analysis of high-temperature (up to 1200°C) neu­
tron diffraction spectra has shown that Si is indeed a
rattler in Ti 3SiC 2 (Barsoum et al. 1999b, Barsoum
2000).
The situation for Al is more ambiguous. The re­
sults for Ti 4 AIN 3, over the same temperature range,
have shown that while the vibrational amplitudes
of the Al atoms are greater than those of Ti or N
(Barsoum et al. 2000e), the differences are not as
large as in the case of Si. It thus appears that Al is

6
 Physical Properties of the MAX Phases

50 that the Ti 3 SiC 2 sample tested had less defects than

Ti 3 AIC:> And yet at room temperature, Kph for the
former is ~ 5 times smaller than for the latter (Fig.
4(b». Given the similarities of their elastic properties,
,.~ 40 and almost identical molecular weights and Debye
~
E temperatures (Table 2), it is obvious that Si is a much
more potent phonon scatterer than AI.
~
In general, beyond AI, increasing the atomic
f' 30

"0
­ >
u
=
<=
number of the A-group element results in significant
phonon scattering (e.g., compare ThInC with Ti 2AIC
in Table 4).
o
u 20
(;j
E
v 5.2 Thermal Expansion
.....c::
10 The thermal expansion coefficients, TECs, of the
MAX phases fall in the narrow range of 8 to
lOx 10- 6 K- 1 (Table 5). A correlation exists be­
tween the TECs of the ternaries and the correspond­
50 100 150 200 250 300 ing MX binaries (Barsoum 2000, EI-Raghy et al.
(a) Temperature (K) 2000). For example, the TECs of the Hf-containing
MAX phases are lower than those containing Ti,
35 which in turn are lower than Cr2AIC. For compar­
ison, the TECs of HfC. TiC, and CrlC~ are
6.6 x 10- 6 K- 1, 7.4 X 10- 6 K -I, and 10.5 x 10- 6 K -I,
30 respectively (Pierson 1996). Somewhat surprisingly,
,.

~
given their plastic anisotropy, the anisotropies in
their thermal expansions (Barsoum 2000) and com­
E 25
pressibilities (Onodera et al. 1999, Manoun et al.
~ 2004a, 2004b, 2005) are relatively mild.
C
:§ 20
u
=
"0 5.3 Thermal Stability
<= 15
0
u
<= The MIl+1AX Il ternaries do not melt but decompose
0
<=
0
peritectically according to the following reaction:
..c:: 10
c..
(8)
5
The decomposition temperatures vary over a wide
range; from ~ 850°C for Cr2GaN (Farber and Bar­
0 soum 1999) to above 2300 cC for Ti 3 SiC 2 (Du et al.
0 50 100 150 200 250 300
2000). The decomposition temperatures of the Sn­
(b) Temperature (K) containing ternaries range from 1200 °C to 1400 °C
Figure 4 (EI-Raghy et al. 2000). It is important to note that the
Temperature dependence of thermal conductivities of decomposition temperature is a function of many
select MAX phases: (a) total thermal conductivity and variables, the most important of which is oxygen
(b) phonon contribution to total thermal conductivities. contamination and/or other impurities (Tzenov et al.
The data points and their corresponding MAX phase 2000).
are color coded to match each other.
5.4 Chemical Reactivit.v and Oxidation Resistance
better bound, and thus less of a rattler, in the The Mn+IXIl layers are chemically quite stable. By
MIl+1AIC, ternaries, which partially explains why Kph comparison, the A-group layers are relatively weakly
is not negligible in these compounds. Probably, the bound and are thus the most reactive species. For
most convincing evidence for this hypothesis is to example, heating Ti 3 SiC 2 in a C-rich atmosphere
compare Kph for the isostructural compounds, results in the loss of Si and the formation of TiC,
Ti 3 SiC 2 and Ti 3AIC 2. Based on the RRR values that (EI-Raghy and Barsoum 1998). When the same com­
are higher for Ti 3 SiC 2, and the peak heights of the pound is placed in molten cryolite (Barsoum et al.
curves shown in Fig. 4(b), it is reasonable to conclude 1999a) or molten Al (EI-Raghy et at. 2001) essentially

7
 Physical Properties of the MAX Phases

Table 4

Summary of room temperature thermal conductivity (WmK-- 1) results for a number of ternary carbides, near­

stoichiometric TiC" and NbC x '

Compound Kth Ke References

Ti 3SiC 2 34 33 (97%) ~ 1 (3%) Barsoum et al. (1999)

40 Finkel et al. (2004)
TbGeC 2 38 38 (100%) Finkel et al. (2004)
Ti 3AIC 2 40 21 (52%) 19 (42%) Finkel et al. unpublished
Ti,AIN 2.9 12 2.8 (23%) 9.2 (77%) Barsoum et al. (2000c)
ThAIC 33 20.5 (62%) 12.5 (38%) Hettinger et al. (2005)
46 20 (43%) 26 (57%) Barsoum et al. (2000a)
V 2AIC 48 29 (61 %) 19 (39%) Hettinger et al. (2005)
Cr2AIC 23 9 (39%) 14 (61 %)
Nb 2AIC 29 19 (66%) 10 (34%)
23 23 (100%) Barsoum et at. (2002b)
TiNbAlC 16.6 9.4 (56%) 7.2 (43%)
Nb 2SnC 17.5 17.5 (100%) Barsoum et al. (2000b)
Ti 2InC ~26.5 26.5 (100%) Barsoum et at. (2002a)
TiHfInC ~20 20 (100%)
Hf2InC ~26.5 26.5 (100%)
TiC 33.5 12 (36%) 21.5 (64%) Taylor (1961)
TiC o.96 14.4 7.35 (50%) 7.05 (50%) Lengauer et al. (1995)
NbC, 14c 21 a Pierson (1996)
a L o <2.45 x 1O- 8 WQK c.

Table 5
Summary of dilatometric thermal expansion values for select MAX phases ( x 106 K -1).

Compound TCE Compound TCE Compound TCE

Ti 2AlC 8.8 Ti 2AlN 8.2 Ti2AINo.5Co.s 8
Ti 3SiC 2 9.1 Ti 3AlC 2 9.0 Ti 4 AlN 2.9 9.7
Ti 3Al(C,Nh 7.0 Ti3(Sios,Geo.s)C2 9.3 Cr2AlC 12.0
Ti 2SnC 10 Zr2SnC 8.3 Nb 2SnC 7.8
Hf2SnC 8.1 Zr2PbC 8.2 HfzPbC 8.3
NbzAlC 7.5 (Nbos,Tio.shAlC 8.5
TizInC 9.5 (Tio.s,Hfo.shlnC 8.6 Hf2InC 7.6
The uncertainity for most values is ±O.2.

the same reaction occurs: the Si escapes and TiC x
forms. In some cases, for example, Ti 2 InC, vacuum at
elevated temperatures is sufficient to result in the loss
of the A-group element and the formation of TiC,
(Barsoum et al. 2002a).
Given their excellent high-temperature mechanical
properties (Barsoum and Radovic 2004), some of the
MAX phases are being considered candidates for a
number of high-temperature applications, both struc­
tural and nonstructural. Since air is to be used, how­
ever, their oxidation resistance is of paramount
importance. Early reports on Ti 3SiC 3 suggested it
was oxidation-resistant to temperatures as high as
1400 °C (Barsoum et at. 1997). At this time, however,
it appears that the highest temperature at which
ThSiC 3 can be used continuously in air is ~ 900°C
(Barsoum et al. 2003).
The most promising MAX phase to date, however,
with superb oxidation resistance is Ti 2AIC (Sundberg
et al. 2004). After 10 000 cycles from 1350 °C to room
temperature, a thin, adherent protective 15 /-lm Ab03
layer was found. The formation of Al 2 0 3 is the key to
high-temperature oxidation protection. It is worth
noting that the formation of Ab03 is another exam­
ple of the reactivity of the A-group element vis-a-vis
the Mn+lX" blocks. Note that alumina forms despite
the fact that the Al concentration is half that of Ti,
another reactive metal. Wang and Zhou (2003) also
reported the formation of alumina layers in Ti 3AIC 2,
where the Al concentration is one third that of Ti.

8

In general, the oxidation of the MAX phases oc­
curs according to the following reaction:
Mll+lAXn + b02 = (n + 1)MO x / n + 1 + AO,. + nX02h - x - y
For example, the oxidation of Ti 3SiC2 results in the
formation of an outer pure rutile, Ti0 2, layer and an
inner rutile and Si02 layer. Even in the case of
Ti ll+ 1 AIC, the formation of a continuous alumina
layer is a function of the purity of the samples. Im­
pure samples or those with high contents of TiC tend
to form Ah03 and rutile, rather than a pure layer of
Ah03 (Barsoum 2001, Barsoum et al. 2001), Ti 2InC
forms Ti02 and In203, the Sn-containing ternaries,
Sn02, etc. (Chakraborty et al. 2003).
6. Concluding Remarks
Some of the physical properties of the MAX phases,
such as thermal expansion, elastic properties, and
thermal conductivity, have much in common with
their respective MX binaries. Their electronic struc­
ture and transport, however, are more akin to those
of the transition metals themselves.
The unique combination of properties possessed by
the MAX phases---ease of machinability, low fric­
tion, thermal and structural stability, good thermal
and electrical conductivities-render them attractive
for many applications such as rotating electrical con­
tacts and bearings, heating elements, nozzles, heat
exchangers, tools for die pressing, among many oth­
ers. Many of these applications are currently being
field-tested and are at various stages of development.
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10
 Physical Properties of the MAX Phases

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