Surface & Coatings Technology 207 (2012) 461–466

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Surface & Coatings Technology

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Performance of gas nitrided and AlTiN coated AISI H13 hot work tool steel in
aluminium extrusion
Yucel Birol ⁎, Behiye Yuksel
Materials Institute, Marmara Research Centre, TUBITAK, Kocaeli, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: The performances of nitrided and AlTiN coated AISI H13 hot work tool steel samples were investigated under
Received 28 March 2012 conditions similar to those encountered in aluminium extrusion. The compound layer on the surface of the
Accepted in revised form 14 July 2012 gas nitrided tool steel is entirely removed during sliding contact with aluminium after a sliding length of
Available online 22 July 2012
3900 m, under a contact load of 60 N exposing the underlying diffusion zone to the aluminium counterface.
Aluminium is known to have a strong tendency to adhere to steel and forms an adhesive layer leading to a
Keywords:
Aluminium extrusion
very high friction coefficient. This results in high shear stresses that are responsible for the fracturing of the
Tooling diffusion zone which is intrinsically brittle owing to a dispersion of nitrides. Fracture events followed by
Wear spallation produces a substantial material loss in the nitrided sample. The AlTiN coating, on the other
Nitriding hand, resists delamination and protects the underlying steel substrate against a chemical interaction with
PVD the aluminium counterface. This is reflected by the wear rates measured to be 1.21 × 10 −3 mm 3 and
9.36 × 10 −7 mm 3 for the nitrided and AlTiN coated samples, respectively.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction Physical Vapour Deposition (PVD) is capable of depositing ceramics

Extrusion is by far the predominant manufacturing route to pro-
duce aluminium profiles for a variety of structural applications [1,2].
Profiles of almost any shape and size can be produced by forcing a
preheated billet through the opening of a die assembly. This process
involves high loads and elevated temperatures and exposes the die
bearing surface to substantial mechanical and thermal stresses, abrasion
and adhesion as well as chemical attack [3–5]. Extrusion dies are thus re-
quired to possess good resistance to wear, thermo-mechanical fatigue
and oxidation, as well as chemical stability against hot aluminium [6,7].
The AISI H13 hot work tool steel, quenched and tempered to a hard-
ness of about 500 HV, is the standard tool material as it offers high
strength and ductility, good tempering resistance at moderate cost [8].
However, hot work tool steels suffer poor resistance to sliding wear [9].
The die has to be replaced or reworked once the dimensions and surface
finish of the extrudate deteriorate beyond tolerable limits. The improve-
ment of the service life of extrusion dies warrants dramatic savings and
represents an important strategy for the economics of this process [4].
Hence, there is a growing interest in using surface engineering tech-
niques to improve the wear resistance of the hot work tool steel [10–12].
While nitrided dies remain the preferred tools for hot forming of alumin-
ium parts in the extrusion industry [13,14], thin hard coatings have been
attracting increasing attention in recent years [11,15,16]. Of the several
modern thin film coating technologies widely used in tooling industries,
⁎ Corresponding author. Tel.: +90 262 677 3084; fax: +90 262 641 2309.
E-mail address: yucel.birol@mam.gov.tr (Y. Birol).
below the temper softening temperature of tool steels providing supe-
rior wear and high temperature resistance [17–20]. Hence, it has re-
ceived a great deal of attention for surface engineering of forming and
cutting tools in recent years [21,22]. Among the several PVD coatings
tested, the aluminium-rich thin hard AlTiN coatings offer a very attrac-
tive combination of hardness and oxidation resistance at elevated tem-
peratures as well as high fatigue resistance [23]. The present work was
undertaken to test the performances of gas nitrided and additionally
AlTiN coated AISI H13 hot work tool steel samples under conditions
similar to those encountered in aluminium extrusion.
2. Experimental
Wear test samples were machined from a premium grade AISI H13
hot work tool steel widely employed in extrusion tooling. They were
subsequently austenized at 1025 °C for 30 min, quenched in circulating
air and finally tempered twice at 625 °C for 2 h yielding a hardness of
480±20 HV. The samples thus obtained were polished to a mirror-like
finish and cleaned ultrasonically before they were coated on the contact
face.
The first set of samples were gas nitrided in a stream of ammonia gas
(NH3) at 530 °C to a case depth of approximately 200 μm while the sec-
ond set of samples were additionally coated with a thin hard AlTiN film.
The Cathodic Arc Physical Vapour Deposition (CAPVD) process was
employed for the deposition of thin hard AlTiN coatings on the second
set of tool steel samples after the compound layer from gas nitriding
was removed. Hence, the difference between the two types of samples

0257-8972/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2012.07.051
462 Y. Birol, B. Yuksel / Surface & Coatings Technology 207 (2012) 461–466

(Fig. 1). The test chamber was heated to 550 °C. A normal force of 60 N
was applied to the coated test sample to establish a dry sliding contact
with the rotating aluminium cylinder. This level of normal force was se-
lected with a consideration of the forces that act on the die bearing dur-
ing aluminium extrusion. The sliding speed was 0.52 ms−1 and the
4 total sliding distance was 3900 m. The sliding contact between the coat-
7 ed test samples and the aluminium cylinder was interrupted for 10 s
3 after every 50 s to reproduce the start-and-stop cycle encountered in
6
the industrial aluminium extrusion process when a new billet is loaded
5 to the press. The normal force, the friction force and the temperature
1 were also selected with a consideration of the actual extrusion process
2 and were continuously recorded throughout the wear tests. The wear
test samples were submerged in a NaOH solution at 80 °C to remove
the aluminium from the surface after the wear test.
Standard metallographic practices were employed to characterise
the nitrided and AlTiN-coated samples. The samples were examined
1: aluminium cylinder both in the as-polished state and after chemical etching in a 2% nital
2: coated hot work tool steel sample solution. The coating morphology and composition were determined
3: normal force using a JEOL 6335F model field emission gun scanning electron mi-
4: friction force
5: heating element
croscope (FEG-SEM) fitted with an Oxford INCA model energy disper-
6: thermocouple sive X-ray analyzer (EDS). The phase structure of the surface layers
7: ceramic insulation were examined with a Philips PW 3710 grazing incidence X-ray dif-
fractometer equipped with CuKα radiation. A scan rate of 0.02° s −1
Fig. 1. Testing unit used in the sliding wear tests.
was used with a grazing incidence of 0.5 o. Hardness across the section
of the nitrided samples was measured with a microhardness tester
was the type of nitride on the 200 μm thick diffusion zone. The CAPVD under a load of 300 g (HV0.3) and a time of 20 s. An ultra micro hardness
process offers high ionisation levels in the plasma and thus leads to a tester was used to measure the hardness of the AlTiN coating. 20 mN
dense coating structure [24]. The chamber was evacuated to approxi- was applied in 120 steps every 0.5 s with load and depth sensitivities
mately 10−3 Pa before the deposition step. Substrates were heated of 0.2 mN and 0.01 nm, respectively.
and ion-etched with Cr bombardment by applying bias voltage up to The worn surfaces were investigated with optical microscopy (OM)
−1000 V for 5 min. The temperature of the substrate samples in- and field emission scanning electron microscopy (FE-SEM) both on the
creased to approximately 400–450 °C due to IR and plasma heating. surface and across the section of tested samples. The topology of the
Pure chromium was deposited on the substrate first at a bias voltage coated surfaces and of the wear tracks in worn samples was investigated
of − 400 V for 10 min to improve the adhesion of hard films. The with a VeecoWyko NT1100 3-D model optical profilometer.
cathode current was 60 A. High purity (99.999%) nitrogen was used for
a deposition time of 30 min at a N2 pressure of 1 Pa and at a bias voltage 3. Results
of −100 V. 99.99 at.% purity Cr and 67/33 at.% Al–Ti cathodes were used
for the deposition of AlTiN coating on a CrN bond coat on heat-treated The structural features of the nitrided hot work tool steel sample
and polished tool steel samples. are shown in Fig. 2. The gas nitriding process employed in the present
The wear test in the present work employed the common block-on work has produced an approximately 6 μm thick compound layer
cylinder configuration assembled inside a heating chamber [25]. Hot (Fig. 2a and b). This is the outermost layer which appears white in
work tool steel samples, 5 mm× 10 mm× 30 mm, heat treated and, ei- Fig. 2a and was shown by XRD to consist predominantly of the γ′ nitride
ther gas nitrided or AlTiN coated on the contact face, served as the die (Fe4N) (Fig. 3a). Several weak reflections of the ε nitride (Fe2–3N) were
bearing while an aluminium cylinder, ϕ 100 mm × 50 mm, machined also noted. The ε phase is known to be hard and brittle, while the γ′ phase
from a commercial 6063 alloy billet served as the aluminium extrudate is hard and tough [26,27]. The dark zone underneath the compound layer

a b

100µm
100µm 10µm

Fig. 2. Microstructure across the section of the gas nitrided hot work tool steel samples.
 Y. Birol, B. Yuksel / Surface & Coatings Technology 207 (2012) 461–466 463

substrate bond coat top coat

a tool steel CrN AlTiN
intensity (a.u.)

1 2 3 1µm
b
wt% 1 2 3
−
intensity (a.u.)

Al 23.77 39.71
Ti − 16.40 29.03
Cr 87.68 34.36 −
N 12.32 25.47 32.26

Fig. 5. Microstructure across the section of the CAPVD AlTiN coating.

20 30 40 50 60 70 80
2θ (degrees)

Fig. 3. X-ray diffraction spectra from (a) the surface and (b) at 25 μm from the surface
intensity (a.u.)

of the gas nitrided hot work tool steel sample.

is the diffusion zone where the nitrogen atoms predominantly occupy in-
terstitial sites in the body centred cubic (bcc) lattice [28]. A fraction of the
grain boundaries in the immediate vicinity of the compound layer are
decorated with nitrides (Fig. 2b). The relatively faster diffusion of nitrogen
atoms along the grain boundaries promotes nitrogen enrichment and ni-
tride precipitation once the solid solubility limit is exceeded in the diffu-
20 30 40 50 60 70
sion zone. The XRD spectrum at 25 μm from the surface shows the
2 (degrees)
reflections of the matrix only (Fig. 3b). The matrix reflections are slightly
displaced to higher 2θ values implying a change in the lattice parameter of Fig. 6. X-ray diffraction spectrum of the CAPVD AlTiN coating.
the matrix due to macro strains associated with the compressive stress
state introduced by nitriding. The microstructure further inside is typical
of heat treated tool steels with fine carbides dispersed in a tempered mar-
tensitic matrix (Fig. 2a).
a b

3500

3000

2500 gas nitrided

hardness (HV)

AlTiN coated
2000

1500

1000

500

0
0 100 200 300 400 500 600 5 mm
distance from surface (µm)

Fig. 4. Hardness measurements across the section of the gas nitrided and CAPVD AlTiN Fig. 7. Macrographs of the surfaces of (a) gas nitrided and (b) CAPVD AlTiN coated hot work
coated hot work tool steel samples. tool steel samples after the sliding wear test (sliding length: 3900 m, normal force: 60 N).
464 Y. Birol, B. Yuksel / Surface & Coatings Technology 207 (2012) 461–466
a b
10 mm
Fig. 8. Macrographs of the aluminium cylinders rotated against (a) the gas nitrided and
(b) CAPVD AlTiN coated hot work tool steel samples after the sliding wear test (sliding
length: 3900 m, Normal force: 60 N).
The hardness profile across the section reflects the microstructural
features outlined above (Fig. 4). The hardness near the surface is as
high as 989 HV and decreases sharply to the core hardness across the dif-
fusion zone. The surface hardening is well established to be due to the
precipitation of nitrides and to the supersaturation with nitrogen of the
bcc matrix in the diffusion zone [29]. The surface is expanded with re-
spect to the core during nitriding producing a compressive stress state
in the diffusion zone, improving the surface hardening. The case depth,
estimated from the hardness profile to be approximately 200 μm, is con-
sistent with the etching response of the surface layer. The structural state
and the hardness distribution across the diffusion zone are critical fea-
tures since the compound layer will eventually suffer spallation leaving
gasnitrided
a b
before wear test
1 µm
c d
after wear test
10 µm
Fig. 9. SEM micrographs of the gas nitrided (a, c) and CAPVD AlTiN coated (b, d) hot work tool steel samples before (a, b) and after (c, d) the sliding wear test (sliding length:
3900 m, normal force: 60 N).
the underlying diffusion zone unprotected. The diffusion zone, with
a dispersion of nitrides and a hardness well above the core value
will then be under sliding contact with the counterface aluminium
and is expected to govern the response of the gas nitrided tool steel
to sliding wear at elevated temperatures.
The section of the surface layer of the AlTiN coated tool steel sample
is shown in Fig. 5. The PVD coating reveals a multilayered character and
a dense structure, with no evidence of delamination or structural flaws.
The composition of the outermost layer was estimated by EDS to be
34.2 at.% Al, 51.8 at.% N, and 14.0 at.% Ti, giving a coating of the type
Al0.34Ti0.14N0.52. The neighbouring layer exhibits additionally a Cr signal
suggesting that a transition zone has formed before the top coat (AlTiN)
was deposited. Finally, the innermost layer reveals only Cr and N signals
and serves to improve the adhesion of the AlTiN coating to the substrate.
The total thickness of this multilayered coating was measured to be ap-
proximately 3 μm and was uniform over the surface of the coated sample.
The hardness measured on the surface was 3286 HV. The rest of the hard-
ness profile was similar to that of the gas nitrided counterpart owing to a
diffusion zone with similar features. The glancing angle X-ray diffraction
spectrum from the coating is shown in Fig. 6. The structure of the AlTiN
coating is based on the structure of NaCl–AlN with a fraction of the alu-
minium atoms substituted by titanium atoms [30].
Macrographs from the surfaces of gas nitrided and AlTiN coated
samples submitted to wear tests under a normal load of 60 N for a
total sliding length of 3900 m are shown in Figs. 7a and b, respectively.
The two surfaces are similar at overview magnifications with well de-
fined aluminized zones over the entire contact length with the alumin-
ium cylinder. The aluminium cylinders, on the other hand, are heavily
grooved by the gas nitrided and AlTiN coated samples as shown in
Figs. 8a and b, respectively. The wear track produced by the gas nitrided
sample is relatively deeper with rough inner walls implying a more ex-
tensive interaction of the aluminium alloy with the nitrided sample.
AlTiN coated
1 µm
10 µm
 Y. Birol, B. Yuksel / Surface & Coatings Technology 207 (2012) 461–466 465

These features evidence adhesive wear which eventually changes the a

dimensions of the die bearing in actual extrusion and thus degrades
the extrudate dimensions as well as the surface quality.
The wear features of the coated tool steel test blocks were investi-
gated in more detail at higher resolutions. The nitrided and AlTiN coated
surfaces before and after the wear tests are illustrated in Fig. 9. The
roughness of the nitrided surface, Ra = 11.3 nm, is relatively higher
than that of the AlTiN layer, Ra = 8.1 nm, before the wear test. The latter
reveals occasional small droplets, quite typical of the CAPVD process,
dispersed over the surface randomly, while the nitrided surface reveals
the acicular γ nitrides, typical of the gas nitriding process, sticking out
from the surface. There is a remarkable change in the features of the
gas nitrided surface after the sliding wear test. The compound layer is
no longer evident. The complete removal of the compound layer is
evidenced also by the metallographic analysis of the nitrided surface
40µm
sections (Fig. 10). Instead, there are now large and deep wear craters
over the surface that appears to have been abraded to a flat and uniform
finish (Fig. 9). b
These wear craters are believed to have been produced through a
chemical interaction between the diffusion zone and the heated alumin-
ium. The removal of the compound layer early in the sliding wear test
has allowed direct contact of the underlying diffusion zone with the
counterface aluminium. While the γ′‐Fe4N compound layer is chemical-
ly resistant to aluminium, aluminium is known to have a strong tenden-
cy to adhere to steel. Aluminium thus develops an adhesive layer on the
tool steel sample as soon as the compound layer is detached from the
surface [31]. The interaction between aluminium and tool steel leads
to a very high friction coefficient [4,7,11], which in turn results in high
shear stresses on the sample surface. In the meantime, the toughness
of the diffusion zone is intrinsically lower with respect to the substrate
tool steel owing to a dispersion of nitrides inside the diffusion zone, pro-
moting a brittle fracture mechanism [32]. The hardness measurements
40µm
across the section of the nitrided sample after the wear test show that
the original hardness profile is retained during exposure to tempera-
tures as high as 500 °C with no evidence of temper softening (Fig. 11). Fig. 10. Microstructure across the section of (a) the gas nitrided and (b) CAPVD AlTiN
The fracture of the brittle surface layers followed by spallation produces coated hot work tool steel samples after the sliding wear test (sliding length: 3900 m,
normal force: 60 N).
a substantial material loss in the nitrided sample. The deeper wear
tracks on the aluminium cylinder in contact with the nitrided surface
attest to the fact that the compound layer has spalled off earlier with re- evidencing the much superior performance of the AlTiN coating in alu-
spect to the CAPVD AlTiN coating. The stability of the compound layer minium extrusion.
appears to be critical for a superior resistance of the nitrided hot work
tool steel in sliding wear. It has been reported that a thin and pore 4. Summary
free compound layer is essential for the improved wear resistance of
the die [14]. The compound layer on the surface of the gas nitrided tool steel is
The AlTiN coating, on the other hand, is in much better shape after entirely removed during sliding contact with aluminium after a sliding
the wear test (Fig. 9). It has suffered much less damage with only
patch-wise delamination sites randomly dispersed over the surface. 3500
These spots are very small and very shallow. The AlTiN coating is
much more stable than the ferrous nitride compound layer and has ap- 3000
parently resisted delamination during the wear test. It has thus largely gas nitrided
avoided contact of hot aluminium with the tool steel and any chemical 2500 AlTiN coated
interaction between the two. The survival of the AlTiN coating on the
hardness (HV)

tool steel is further evidenced by the metallographic analysis of surface 2000

sections of samples submitted to sliding wear tests (Fig. 10b). The opti-
cal micrographs of the section near the surface exhibit no sign of delam- 1500
ination of the AlTiN coating. This is consistent with the relatively
shallow wear track on the cylinder tested in contact with the CAPVD 1000
AlTiN coated sample. These features were confirmed with the optical
profilometry analysis of the two groups of samples (Fig. 12). The sliding 500
contact with the aluminium cylinder under a normal force of 60 N has
worn out the nitrided tool steel sample. The surface of the AlTiN coated 0
0 100 200 300 400 500
sample, on the other hand, hardly exhibits any wear damage and is much
distance from surface (µm)
smoother. The volume losses due to sliding wear were estimated from the
3-D profile measurements to be 1.21×10−3 mm3 and 9.36×10−7 mm3 Fig. 11. Hardness measurements across the section of the gas nitrided and CAPVD AlTiN
for the nitrided and AlTiN coated samples, respectively. The volume loss coated hot work tool steel samples after the sliding wear test (sliding length: 3900 m,
due to sliding wear of the latter is three orders of magnitude smaller normal force: 60 N).
466 Y. Birol, B. Yuksel / Surface & Coatings Technology 207 (2012) 461–466
Fig. 12. 2-D and 3-D topography images and 2-D surface profiles of gas nitrided and CAPVD AlTiN coated hot work tool steel, after the sliding wear test (sliding length: 3900 m,
normal force: 60 N).
length of 3900 m, under a contact load of 60 N allowing direct contact
of the underlying diffusion zone with the aluminium counterface. Alu-
minium is known to have a strong tendency to adhere to steel and
forms an adhesive layer leading to a very high friction coefficient. This
results in high shear stresses that are responsible for the fracturing of
the diffusion zone which is intrinsically brittle owing to a dispersion
of nitrides. Fracture events followed by spallation produce a substantial
material loss in the nitrided sample. The AlTiN coating, on the other
hand, resists delamination and protects the underlying steel substrate
against a chemical interaction with the aluminium counterface. This is
reflected by the marked difference in the volume loss due to sliding
wear, measured to be 1.21 × 10−3 mm3 and 9.36 × 10−7 mm3 for the
nitrided and AlTiN coated samples, respectively.
Acknowledgements
Mr. O. Çakır and Mr. F. Alageyik are thanked for their assistance
with the experimental work.
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