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Characterization of Ti4AlN3

Article in Metallurgical and Materials Transactions A · April 2012

DOI: 10.1007/s11661-000-0268-y

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Characterization of Ti4AIN3
A.T. PROCOPIO, M.W. BARSOUM, and T. EL-RAGHY

Bulk samples of Ti4AIN3 were fabricated by reactive hot isostatic pressing (hipping) of TiH2, AlN,
and TiN powders at 1275 8C for 24 hours under 70 MPa. Further annealing at 1325 8C for 168 hours
under Ar resulted in dense, predominantly single-phase samples, with ,1 vol pct of TiN as a secondary
phase. This ternary nitride, with a grain size of '20 mm on average, is relatively soft (Vickers
hardness 2.5 GPa), lightweight (4.6 g/cm3), and machinable. Its Young’s and shear moduli are 310
and 127 GPa, respectively. The compressive and flexural strengths at room temperature are 475 and
350 MPa, respectively. At 1000 8C, the deformation is plastic, with a maximum compressive stress
of '450 MPa. Ti4AlN3 thermal shocks gradually, whereby the largest strength loss (50 pct) is seen
at a DT of 1000 8C. Further increases in quench temperature, however, increase the retained strength
before it ultimately decreases once again. This material is also damage tolerant; a 100 N–load diamond
indentation, which produced an '0.4 mm defect, reduces the flexural strength by only '12 pct. The
thermal-expansion coefficient in the 25 8C to 1100 8C temperature range is 9.760.2 3 1026 8C21.
The room-temperature electrical conductivity is 0.5 3 106 (V ? m)21. The resistivity increases linearly
with increasing temperature. Ti4AlN3 is stable up to 1500 8C in Ar, but decomposes in air to form
TiN at '1400 8C.

I. INTRODUCTION pressed, annealed under dynamic vacuum at 900 8C for

9 hours (to dehydride the TiH2), sealed under vacuum in
RECENTLY , we reported on the fabrication of a fully borosilicate glass tubes, and hot isostatically pressed
dense, polycrystalline, single-phase layered nitride,
(hipped) at 1275 8C for 24 hours under 70 MPa of pressure.
Ti4AlN3.[1] Initially, this ternary was believed to have a
To obtain single-phase material, the samples were further
Ti3Al2N2 chemistry and a hexagonal structure.[2] More
annealed at 1325 8C for 168 hours under Ar. All samples
recently, it was proposed, based on chemical analysis, that
were fully dense, with a measured density of 4.58 mg/m3,
this compound had a Ti3AlN2 chemistry instead and was
which compares favorably to the theoretical density of 4.61
isostructural with Ti3SiC2.[3] Most recently, we have conclu-
Mg/m3. The grain structure of Ti4AlN3 was resolved by
sively shown by high-resolution transmission electron
etching a polished surface with a 1:1:1 by volume solution
microscopy, chemical analysis, and Rietveld refinement of
of H2O, HNO3, and HF for 15 seconds (Figure 1(a)). The
neutron diffraction that this compound was layered, wherein
average grain size is on the order of '20 mm.
layers of pure Al atoms are separated from each other by
The mechanical tests were completed on a servohydraulic
four layers of Ti. The nitrogen atoms occupy the octahedral
MTS testing machine. All measurements were carried out
sites between the Ti layers.[4,5]
using a constant crosshead displacement speed of 0.0035
Based on its structure and the results presented herein,
mm/s, which corresponds to an initial strain rate of 1023
there is little doubt that Ti4AlN3 represents a member (the
s21. The compression tests were carried out on samples of
only one to date) of a third family of the layered carbides
dimensions 2 3 2 3 3 mm3. The flexural samples used in
and nitrides, with the general formula Mn11 AXn , where n 5
the thermal-shock and damage tolerance measurements were
1 to 3, M is an early transition metal, A is an A-group (mostly
cut to the ASTM-C1161 specification of 2 3 1.5 3 25
groups III-A and IV-A) element, and X is either C or N, as
mm3. The flexural strength (s) was calculated using the
reported elsewhere.[6–9] The purpose of this article is to
following equation:
report on the properties of this newly synthesized ternary.
Information regarding the oxidation is briefly summarized 3P(l1 2 l2)
in this article; a complete account can be found elsewhere.[10] s5 [1]
2BW 2

II. EXPERIMENTAL DETAILS
The synthesis of Ti4AlN3 is described elsewhere.[1] In
brief, TiH2 (TIMET, Henderson, NV; 99.3 pct, 2325 mesh),
TiN (Alfa Aesar; 99.8 pct, 2 to 5 mm), and AlN (Alfa Aesar,
N 32.0 wt pct minimum, dm ' 3 mm) powders were mixed
to the desired stoichiometry. The mixed powders were cold
where P is the fracture load; l1 and l2 are the outer and inner
spans, respectively; B is the specimen width (2 mm); and
W is the specimen thickness (1.5 mm). The aforementioned
samples were cut using a diamond wheel and used as is
(i.e., the corners were not beveled).
The Vickers hardness was measured at a load of 100 N;
the microhardness (LECO* M-400) tester was measured at
*LECO is a trademark of LECO Corporation, St. Joseph, MI.

M.W. BARSOUM, Professor and T. EL-RAGHY, Research Assistant
Professor, are with the Department of Materials Engineering, Drexel Univer-
sity, Philadelphia, PA. A. PROCOPIO graduated from the Department in
June of 1999 with an MS thesis.
Manuscript submitted May 17, 1999.
loads of 3, 5, and 10 N. To measure the damage tolerance,
microhardness indentations were placed on polished (1200-
grit SiC paper) surfaces of four-point bend specimens, such
that one diagonal of the indentation was parallel to the length

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 31A, FEBRUARY 2000—333


(a)
(b)
(c)
Fig. 1—SEM micrographs of (a) polished and etched surface of Ti4AlN3;
(b) low-magnification fracture surface of Ti4AlN3; and (c) higher magnifica-
tion of (b), showing layered structure.
of the sample. The postindentation retained flexural strengths
were measured according to ASTM-C1161. Three samples
were tested for each indentation load.
For the thermal-shock experiments, the specimens were
inserted in a furnace at the testing temperature, held at that
temperature for '10 minutes to allow them to thermally
equilibrate with the furnace, and immediately quenched in
an ambient water bath. In all cases, a majority of the oxide
334—VOLUME 31A, FEBRUARY 2000
scale flaked off as a result of the quenching. The maximum
oxide layer thickness measured was on the order of '30
mm for the samples treated at 1400 8C. The quenched sam-
ples (ten for every quench temperature) were tested
according to ASTM-C1161.
To explore the thermal stability of Ti4AlN3, samples were
heat treated in Ar at various temperatures (1300 8C to 1600
8C) for 6 hours and furnace cooled. Powder samples drilled
from the bulk of the heat-treated samples were used for
phase identification by X-ray diffraction (XRD) using a
powder diffractometer (SIEMENS* D-500). Scans were
*SIEMENS is a trademark of Siemens Electrical Equipment, Toronto.
made with Cu Ka radiation at a rate of 1.2 deg (2u)/min,
using a step of 0.02 deg. To confirm the XRD results, cross
sections of the heat-treated samples were polished and exam-
ined by a scanning electron microscope (SEM) equipped
with an energy-dispersive spectroscopy (EDS) system. The
EDS work was conducted using an acceleration voltage of
20 kV and a beam current of 15 nA, at a working distance
of 25 mm.
The thermal expansions of parallelepiped samples (4 3
4 3 25 mm3) were measured under flowing Ar (25 mL/
min) in the 25 8C to 1100 8C temperature range, using a
dilatometer (Unitherm, Anter Corp.) at a heating rate of 2
8C/min. The dilatometer was calibrated using a single-crystal
sapphire rod. The thermal-expansion coefficient varied by
2 pct. To minimize oxidation, Ti foil was wrapped loosely
around the sample so as to getter any oxygen present.
The details of the thermal conductivity and specific heat–
capacity measurements are described in detail in Reference
21. The electrical resistance was measured with a micro-
ohmmeter (Model 5600, AEMC Instruments). The tempera-
ture dependence of the resistance was also measured in the
120 to 300 K temperature range by placing the sample just
above the liquid nitrogen level in a Dewar flask. The slow
evaporation of the nitrogen allowed for a slow heating of
the sample, the temperature of which was measured by a
thermocouple attached directly to the sample.
III. RESULTS AND DISCUSSION
At this time there is little doubt, and the results of this
work confirm, that Ti4AlN3 is a member of the larger family
of layered ternary nitride and carbides, with the general
formula Mn11AXn.[6–9] The layered nature of this compound
is clearly visible in Figures 1(b) and (c), in which fractured
surfaces are shown at two different magnifications. As dis-
cussed subsequently, like its cousins, this ternary is relatively
soft for a carbide or nitride, damage and thermal-shock
resistant, and a good conductor of heat and electricity. How-
ever, the most important characteristic Ti4AlN3 shares with
the other layered carbides and nitrides is the unique combina-
tion of high stiffness (E . 300 GPa) and ease of machinabil-
ity. Like the others, Ti4AlN3 is machinable with regular high-
speed tool steels, a bandsaw, or hacksaw, without lubrication
or cooling required. Hitherto, the price paid for high stiffness
has always been difficulties in machinability; this is no
longer the case.
Similar to Ti3SiC2, and in contrast to its relatively low
hardness, Ti4AlN3 is an elastically stiff solid with Young’s
METALLURGICAL AND MATERIALS TRANSACTIONS A
and shear moduli of .310 and 127 GPa, respectively.[17]
Interestingly enough, Ti4AlN3 is roughly 25 pct stiffer (Table
I) than stoichiometric TiN, which is a much harder, nonma-
chinable, refractory solid.
As shown in the top curve in Figure 2(a), the Vickers
hardness decreases with increasing load and asymptotes to
'2.5 GPa. The scatter at lower loads can be attributed to
both the anisotropic nature of the structure[11,12,13] as well
as measurement scatter. A SEM micrograph of an indented
surface (10 N) is shown in Figure 2(b); neither median nor
lateral cracks emanate from the corners. The shape of the
indentation and the details of the damage mechanisms sur-
rounding it are almost identical to the ones observed in
Ti3SiC2.[11,12,13] Higher-magnification micrographs (not
shown) clearly indicate that buckling and delamination of
individual grains, grain pullout, breakup, and kink- and
shear-band formation are all operative mechanisms responsi-
ble for energy dissipation. It is worth noting here that basal
slip is operative at room temperature in Ti3SiC2,[14,15,16] and
there is every reason to believe the same is true in Ti4AlN3
as well.
The damage tolerance of Ti4AlN3 on a linear-log plot is
shown in Figure 2(a) (lower curve). The shaded area on
the left-hand side represents the strength of as-processed
samples, i.e., those containing natural flaws. At room tem-
perature, the four-point flexural strength is 350 6 15 MPa.
For comparison’s sake, the degradation in strength of a brittle
solid is depicted by a dashed line on the same plot.[18] From
the results shown, it appears that the postindentation flexural
strengths are almost independent of indentation load. This
is especially true when it is appreciated that, because of the
low hardness, a 100 N indentation translates to a defect size
of '0.4 mm. Such a defect spans '20 pct of the sample’s
width and thickness and is greater than the 12 pct decrease
(350 to 310 MPa) in flexural strength. Here again, in analogy
to Ti3SiC2, we conclude that the mechanisms enumerated
previously, and ultimately emanating from the layered nature
of these compounds, are operative.
The damage tolerance is consistent with the thermal-shock
results shown in Figure 3, where, once again, the similarities
to Ti3SiC2 are obvious.[19] Ti4AlN3 thermal shocks gradually,
and almost linearly, over a temperature range of 1000 8C,
at which point the loss in strength is '50 pct. Surprisingly,
further increases in quench temperatures increase the
retained strength before it ultimately decreases again. The
reason for this unusual behavior is unclear at this time, but
is currently under investigation.
The temperature dependencies of typical compressive
engineering stress-strain curves are shown in Figure 4. At
room temperature, the fracture stress is almost identical to
the “yield” point at 1000 8C, viz., 475 6 15 MPa. It is
important to note that the “yield” point, defined in this work
as in our previous work,[19,20] is the point at which the stress-
strain curves deviate from linearity. It is not a true yield
point in the sense of having five independent slip systems
operative, but rather the point at which damage, and the
concomitant inelastic deformation, is initiated.[19,20] At
11008C and 1200 8C the “yield” points drop to 150 6 10
and 75 6 10 MPa, respectively. The increased plasticity and
significant softening at higher temperatures (inset in Fig. 4)
is analogous to Ti3SiC2 and the other M2AX compounds.
At this time, the atomistic origin of this brittle-to-plastic
transformation is unclear, but is believed to result from an
enhancement in the ease of grain rotation, grain deformation,
delamination, and grain buckling.[14,15]
In agreement with previous results,[2,3] Ti4AlN3 was found
to be stable at 1400 8C in Ar for at least 6 hours. The XRD
of a sample annealed at '1500 8C for 6 hours, on the other
hand, revealed the presence of small amounts ('5 to 10
pct) of TiN. When heated in air, however, Ti4AlN3 is less
stable: a sample heated in air at 1300 8C for 4 hours not
only grew an oxide layer on its surface, but also a subsurface
layer of TiNx. In the 900 8C to 1200 8C temperature range,
the oxidation kinetics are parabolic. The protective layer
that forms is comprised of TiO2 and Al2O3. A full account
of the oxidation of Ti4AlN3 is reported elsewhere.[10]
The thermal expansion of Ti4AlN3 on cooling and heating
in the 25 8C to 1100 8C temperature range is shown in
Figure 5. A least-squares fit of the expansion results yields
a thermal-expansion coefficient of 9.7 6 0.2 3 1026 8C21.
This value is in the same range as TiN and the majority of
the other layered ternaries measured to date (Table I). It is
worth noting here that the thermal expansions of Ti4AlN3
along the a- and c-axes are 9.6 and 8.8 3 1026 8C21, respec-
tively.[5] In other words, like Ti3SiC2, the thermal-expansion
anisotropy is quite mild.[21] And whereas, this is somewhat
surprising given the marked anisotropy in the mechanical
properties, it is typical of the Mn11AXn phases. In contrast

Table I. Comparison of Properties of Some Ti-Based Ternaries and Binaries

Bulk Thermal Specific Heat
Molecular Lattice Theoretical Thermal Conductivity Capacity at Electrical Young’s Shear
Com- Weight Constants
˚ Density Expansion at 25 8C 25 8C Conductivity Hardness Modulus Modulus
pound (g/mol) (A) (g/cm3) (1026 K21) (W/m-K) (J/kg-K) (V21 m21) (GPa) (GPa) (GPa)
Ti4AlN3 260.5 a 5 2.99[2] 4.61 9.7 6 0.2 12 598 0.5 3 106 2.5 310 6 2 127 6 2
c 5 23.34
Ti3SiC2 195.8 a 5 3.0665 4.531 9.2[21] 43[21] 588[21] 4.5 3 106[6] 4[6] 333[17] 139[17]
c 5 17.671
Ti2AlN 136.75 a 5 2.99 4.31 8.8[22] — — 3.2 3 106[8] 3.5[8] — —
c 5 13.61 — — 4 3 10 6[22]

Ti2AlC 134.75 a 5 3.04 4.11 8.2[22] — — 2.8 3 106[8] 5.5[8] — —

c 5 13.60 — — 2.7 3 106[22]
4.5[22] — —
TiN* 64.95 a 5 4.24 5.4 9.35 19[23] –29[24] 545 4 3 106[24] 18 to 20 251 —
TiC* 59.91 a 5 4.328 4.91 7.4 21 564 2 3 106 28 to 35 410 to 510 186
*All data are taken from Ref. 23.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 31A, FEBRUARY 2000—335


(a)
(b)
Fig. 2—(a) Semilog indentation load dependence of Vickers’ hardness
(upper curve) and postindentation flexural strength (lower curve). The
dashed line depicts the response of a perfectly brittle solid.[18] (b) SEM
micrograph of hardness indentation (10 N).
to Ti3SiC2, however, the expansion along the c-axis is less
than that along the a-axis. This is an important result, because
it implies that the average bond strength along the c-axis,
the direction that includes the Ti-Al bonds, is higher than
that along the a-axis.
At 0.5 3 106 (V ? m)21, the room-temperature electrical
conductivity of Ti4AlN3 is roughly one order of magnitude
lower than that of Ti3SiC2. The temperature dependence of
electrical resistivity in the 77 to 300 K temperature range
is shown in Figure 6. The behavior is typical of metallic
conductors, and a least-squares fit of the results yields
336—VOLUME 31A, FEBRUARY 2000
Fig. 3—Four-point flexural strength vs quench temperature. Each point is
the average of ten separate measurements.
Fig. 4—Engineering stress-strain curves during the compression of 2 3 2
3 3 mm3 at 25 8C, 1000 8C, 1100 8C, and 1200 8C. Samples were compressed
at an initial strain rate of 1023 s21. The temperature dependencies of the
maximum compressive stresses are plotted in the inset.
r (mV ? m) 5 r300 (1 2 a (DT ))
5 2(1 2 0.00075(300 2 T ))
where T, r300, and a are, respectively, the temperature in
Kelvin, the resistivity at 300 K, and the coefficient of resisti-
vity. The latter is '5 times smaller than the corresponding
value for Ti3SiC2.[8] At 12 W/m ? K, the room-temperature
thermal conductivity of Ti4AlN3 is roughly 3 times lower
than that of Ti3SiC2.[21] The specific-heat capacities, on the
other hand, are quite comparable (Table I).
Like Ti3SiC2 and the other ternary carbides and nitrides,
Ti4AlN3 appears to combine some of the more attractive
qualities associated with metals and ceramics. Like metals,
it is machinable, thermal-shock resistant, damage tolerant,
relatively soft, and is both a good electrical and thermal
METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 5—Temperature dependence of bulk dilatometric expansion of Ti4AlN3
during heating in Ar in the 25 8C to 1100 8C temperature range. Superim-
posed on the dilatometric results are the thermal expansions obtained from
high-temperature neutron diffraction results.[5]
conductor. Like ceramics, it is elastically stiff, lightweight,
has a low thermal-expansion coefficient, and maintains its
strength to relatively high temperatures. Finally, it is worth
noting that the results presented here, especially the mechani-
cal properties, are by no means optimized. It is fair to assume
that once the failure mechanisms are better understood, these
properties can be enhanced.
IV. SUMMARY AND CONCLUSIONS
The ternary nitride Ti4AlN3 represents a member (the only
one to date) of a third family of layered ternary nitrides and
carbides, with an Mn11 AXn general formula. This material
is a potentially attractive candidate for high-temperature
structural applications. It is lightweight (4.6 g/cm3) and,
despite its high modulus of elasticity, mechanically relatively
soft (2.5 GPa) and readily machinable. It is both damage
tolerant and thermal-shock resistant. At 1000 8C, the defor-
mation is plastic, with a respectable “yield” point of 450
MPa. It is also a good electrical and thermal conductor.
ACKNOWLEDGMENTS
This work was supported by the DMR division of the
NSF (DMR-9705237).
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METALLURGICAL AND MATERIALS TRANSACTIONS A
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Fig. 6—Temperature dependence of electrical resistivity of Ti4AlN3 during
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