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Fusion Engineering and Design 86 (2011) 1719–1723

Contents lists available at ScienceDirect

Fusion Engineering and Design

journal homepage: www.elsevier.com/locate/fusengdes

Manufacturing of self-passivating W-Cr-Si alloys by mechanical alloying and HIP

P. López-Ruiz a , F. Koch b , N. Ordás a , S. Lindig b , C. García-Rosales a,∗
a
CEIT and Tecnun (University of Navarra), E-20018 San Sebastian, Spain
b
Max-Planck-Institut für Plasmaphysik, EURATOM Association, D-85748 Garching, Germany

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

Article history: Self-passivating tungsten-based alloys may provide a major safety advantage in comparison with pure
Available online 30 April 2011 tungsten, which is presently the main candidate material for the plasma-facing protection of future
fusion power reactors. WCrSi alloys were manufactured by mechanical alloying (MA) and HIP at 1300 ◦ C
Keywords: and 200 MPa for 1 h. Different MA conditions were investigated to obtain powders with lowest possible
Tungsten alloys amount of contaminants and small and homogeneous particle and crystallite size. Milling in WC vials
Mechanical alloying
under Ar without process control agent provided best results. After HIP densities close to 100% were
HIP
obtained. First oxidation tests on preliminary alloys showed self-passivating behavior with rates com-
Oxidation resistance
Armor material
parable to WCrSi thin films at 800 ◦ C but worse performance at 1000 ◦ C. In all cases a Cr2 WO6 protective
layer is formed at the surface.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Tungsten is presently the main candidate material for the
plasma exposed areas of future fusion reactors (DEMO) mainly
due to its low erosion yield by sputtering with plasma particles
[1]. However, the use of W as first wall (FW) material implies a
safety concern in case of a loss-of-coolant accident with air ingress
into the reactor vessel. In this situation, temperatures up to 1100 ◦ C
would be achieved in the in-vessel components of a He-cooled reac-
tor within 10 to 30 days due to the decay heat [2], leading to the
formation of WO3 and subsequent evaporation of (WO3 )x -clusters
[3,4]. A possible way for avoiding this would be the addition to W
of stable oxides-former alloying elements, so that at high temper-
ature in the presence of oxygen a self-passivating layer is formed
protecting the material from further oxidation. In previous works
[5,6] different binary and ternary W alloys have been manufac-
tured via magnetron sputtering, demonstrating that W thin films
containing about 10 wt.% Si and 10 wt.% Cr exhibited excellent self-
passivating behavior when exposed to air at temperatures up to
1000 ◦ C. However, the PVD route is not applicable to DEMO because
for the blanket FW, coatings or tiles with a thickness of several mm
are required for economic reactor operation [2].
Powder metallurgy is a suitable and relatively low cost route
for the production of alloys of complex composition with the
desired microstructure. In this paper, first results on the manufac-
turing of W-Cr-Si alloys by powder metallurgy (mechanical alloying
∗ Corresponding author. Tel.: +34 943 212 800; fax: +34 943 213 076.
E-mail address: cgrosales@ceit.es (C. García-Rosales).
(MA) + hot isostatic pressing (HIP)) are presented. First results of
oxidation tests up to 1000 ◦ C are shown.
2. Experimental
Elemental powders of pure W (99.9%, 10 ␮m), Cr (99%, 40 ␮m)
and Si (99.5%, 40 ␮m) were mechanically alloyed in a SPEX 8000D
mill, using vials and grinding media of both hardened steel (HS)
and WC with ball-to-powder weight ratios (BPR) of 4:1 and 10:1,
respectively and balls of two different diameters: 12 and 5 mm. Two
different compositions were studied: WCr10Si10 and WCr5Si5 (wt.
%). Initially, milling was performed in air (only HS vials), and later
on, in Ar to minimize powder contamination by O. Grinding was
performed both using hexane as process control agent (PCA) and
without PCA (only WC vials). Different milling times (15 min to 6 h)
were investigated. The powders were uniaxially pressed at 100 MPa
to cylinders of ∅ 16 mm and ∼4 mm height. HIP of glass encapsu-
lated compacts was carried out at 1300 ◦ C for 1 h and 200 MPa.
The O and C content of the powders was measured using a
LECO analyzer. Powders and sintered samples were characterized
by FEG-SEM, EDX mapping, cross sectioning FIB and XRD. The open
porosity of the samples was measured by He pycnometry, and the
density was determined from the geometrical and the He densities
assuming no residual porosity. Vickers microhardness measure-
ments were performed applying a load of 9.8 N for 15 s. Finally, first
oxidations experiments were performed at 600, 800 and 1000 ◦ C
with synthetic air at atmospheric pressure. The mass gain of the
samples due to oxide formation was measured by a thermobalance
Netzsch STA 449 F1 with a sensitivity of 0.025 ␮g. The procedure is
described in detail in [5].

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Table 1
MA conditions of manufactured alloys, contaminants after MA and some properties after HIP.

Sample code Composition MA conditions Impurities after MA (wt.%) Properties after HIP

Vial Atmos. PCA time (h) Fe O C Density (%) HV1.0

8W-HS-ah-2 WCr10Si10 HS air hexane 2 1.9 0.76 0.22 93.5 −

9W-HS-ah-2 WCr5Si5 2 0.9 0.71 0.21 95.6 −
8W-HS-ih-2 WCr10Si10 HS Ar hexane 2 1.9 0.32 0.15 87.5 1413 ± 28
9W-HS-ih-2 WCr5Si5 2 0.9 0.23 0.14 99.3 1126 ± 16
8W-WC-ih-2 WCr10Si10 WC Ar hexane 2 − 0.38 0.40 75.9 472 ± 7
9W-WC-ih-2 WCr5Si5 2 − 0.25 0.38 93.9 750 ± 21
8W-WC-i-1 WCr10Si10 WC Ar − 1 − 0.29 0.04 97.4 1144 ± 28
9W-WC-i-1 WCr5Si5 1 − 0.17 0.06 98.4 1095 ± 14

3. Results and discussion
First trials of MA were carried out in HS vials (BPR 4:1) under
air with milling time ranging from 15 min to 6 h, using hexane as
PCA to achieve effective particle fracture and avoid excessive cold-
welding [7]. With increasing milling time Fe contamination from
the vial and balls (measured by EDX) rose steadily, reaching val-
ues as high as 6.1 wt.% after 6 h milling. Also C contamination from
hexane increased steadily up to 0.31 wt.% after 6 h MA. On the other
hand, the O content of the powders (initially 0.16% for WCr10Si10,
0.11% for WCr5Si5) increased up to 0.76% after 2 h and then sta-
bilized at 0.50% after 6 h MA. Under all conditions, contamination
of WCr5Si5 was slightly lower than that of WCr10Si10. XRD spec-
tra of the powders showed the peaks of the elemental powders
without formation of new phases, indicating that no alloying but
energetic milling took place. Estimation of the crystallite size from
the W peaks width using the Williamson-Hall method [8] indi-
cated a strong decrease of crystallite size with milling time, which
stabilized between 2 and 3 h. This result is in line with SEM obser-
vation of the powders. Therefore, 2 h milling time was selected for
future work at the SPEX as a good compromise between an effective
milling and tolerable amount of contamination.
In Table 1 the milling conditions and contaminants after MA of
the materials prepared during this work are listed. First samples
for HIPing were prepared with WCr10Si10 and WCr5Si5 powders
milled in HS under air with hexane as PCA for 2 h (8W-HS-ah-2 and
9W-HS-ah-2). Densities above 93% were achieved, proving that it
is feasible to obtain dense alloys by this method.
To reduce the O content, powders of both compositions were
milled under the same conditions than before but in inert atmo-
sphere (Ar) (8W-HS-ih-2 and 9W-HS-ih-2). As shown in Table 1,
the O content could be reduced by a factor of 2-3. Thus, all fur-
ther powders were milled in Ar. Surprisingly the C content of these
powders was also reduced by a factor of ∼1.5.
To eliminate Fe contamination, subsequent millings were per-
formed using WC vials and balls (BPR 10:1), and maintaining
hexane as PCA (8W-WC-ih-2 and 9W-WC-ih-2). However, while
the HS vials are tight, the WC vials do not completely ensure leak
tightness. Nevertheless, after several trials it was possible to obtain
powders with an O content comparable to that of previous powders
milled in HS and Ar (s. Table 1). Additionally, a significant increase
in the C content, coming now not only from hexane but also from
the WC vials, was observed. Hence, new powder batches were pre-
pared under the same conditions without hexane as PCA and for a
milling time of 1 h (8W-WC-i-1 and 9W-WC-i-1). It was managed
to produce powders of both compositions with relatively low O
content (< 0.3 wt.%) and with a C content (< 0.06 wt%) 6-10 times
lower than in the previous case. Nevertheless, it should be taken
into account that the milling time was lower. Besides, whereas WC
was clearly detected by XRD in 8W-WC-ih-2, no WC peaks were
visible in the XRD spectra of the 8W-WC-i-1 powder (Fig. 1). More-
over, the Si peaks almost disappeared in the 8W-WC-i-1 powders,
which may indicate a more effective milling; this was actually the
reason for a reduction of the milling time. These observations were
the same for the other composition.
In Fig. 2 powders 9W-WC-ih-2 and 9W-WC-i-1 at different
magnifications are shown. After 2 h milling in hexane, a very effec-
tive reduction in particle size is observed, more pronounced than
in powders milled in HS vials because of the larger density of
WC and the higher BPR. In addition, the initial Cr and Si parti-
cles cannot be distinguished anymore with BSE. Most W particles
are flake-shaped. After 1 h milling without PCA, a larger and less
homogeneous particle size is observed, most probably because the
absence of PCA promotes cold welding; this can be verified at larger
magnification (Fig. 2 (d)), where cold-welded flakes forming lamel-
lar structures are visible (yellow arrow). Again, no Cr and Si can be
detected by BSE.
According to these results, future work in a planetary ball mill
with larger amounts of powders will be performed in WC vials
under Ar without PCA.
All powders milled in Ar were compacted, encapsulated and
HIPed, achieving in most cases a densification above 93%, and in
some cases close to 100%. The exceptions are samples 8W-HS-
ih-2 (87.5%) and especially 8W-WC-ih-2 (75.9%), where possibly
some encapsulation problems occurred. No clear correlation of the
densification after HIP with the manufacturing conditions can be
deduced from these results. Samples with composition WCr5Si5,
i.e. with larger amount of W, seem to densify better. Fig. 3 shows the
microstructure of samples 9W-WC-ih-2 and 9W-WC-i-1 (milled in
WC vials with and without hexane for 2 and 1 h, respectively) after
HIP. As expected from the powder morphology, the microstruc-
ture of sample 9W-WC-ih-2 is finer and more homogeneous, while
sample 9W-WC-i-1 exhibits larger W flake-shaped particles. A
larger amount of dark phase is present in sample 9W-WC-ih-2,
which had a significantly higher amount of C (s. Table 1). Accord-
ing to EDX mapping, this dark phase corresponds to carbides and
oxides in sample 9W-WC-ih-2, and to oxides in sample 9W-WC-
i-1. Cross-sectioning by FIB demonstrated the practical absence of
porosity. At higher magnification, ultrafine intergranular oxides can
be detected, which may have a beneficial effect by preventing grain
Fig. 1. XRD spectra of the 8W-WC-ih-2 and 8W-WC-i-1 powders milled in WC vials
under Ar with and without hexane as PCA and for 2 and 1 h, respectively.
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P. López-Ruiz et al. / Fusion Engineering and Design 86 (2011) 1719–1723 1721

Fig. 2. BSE-SEM images of WCr5Si5 powders after MA in WC vials under Ar: (a)-(b) with hexane as PCA, 2 h milling (9W-WC-ih-2); (c) -(d) without PCA, 1 h milling
(9W-WC-i-1).

growth and improving ductility. Further investigation with TEM is sponds mainly to (WCr)5 Si3 and to a small amount of pure Cr. This
required to clarify the type of oxides. EDX and XRD analysis revealed is in agreement with [9], whereby complete solid-solution of Cr5 Si3
that the brightest phase corresponds to pure W, possibly with a and W5 Si3 exists. According to [9], only the silicide and almost no
small amount of Cr in solid solution, while the grey phase corre- pure W should be found in samples of composition WCr10Si10;

Fig. 3. BSE-SEM images of HIPed WCr5Si5 samples milled in WC vials: (a)-(b) 9W-WC-ih-2; (c)-(d) 9W-WC-i-1.
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1722 P. López-Ruiz et al. / Fusion Engineering and Design 86 (2011) 1719–1723
Fig. 4. SEM cross sectional view of sample 8W-HS-ah-2 after oxidation at 1000 ◦ C
for 3 h. A Cu protection layer was deposited prior to FIB examination.
the presence of clear W peaks in the XRD patterns and of bright W
phases in the microstructure indicates that longer HIPing times are
required to achieve complete phase homogenization.
In Table 1 the Vickers hardness of samples milled in Ar is listed.
It is not easy to identify clear tendencies due to the important influ-
ence of porosity on hardness, but also of phases and grain size [10].
Nevertheless, the values exhibit the order of magnitude expected
for silicides, significantly higher than for pure W [11].
First oxidation tests have been performed only on sample 8W-
HS-ah-2, milled in HS vials under air, at 600, 800 and 1000 ◦ C. XRD
of the oxidized sample surface and EDX mapping of cross sections
produced by FIB allowed the identification of the composition of
oxide scales, as shown in Fig. 4. The oxide permeation barrier at
the outer surface consists of a thin Cr2 WO6 layer. Thicker Cr and
W rich (and Si free) oxide structures are formed just below it. The
black structure visible in the upper section of this phase, as well
as the smaller black inclusions found in every part of this sample,
consists of SiOx . The largest zone in Fig. 4, between the latter Cr
and W rich oxide layer and the bulk alloy, is nearly free of Cr, act-
ing as Cr reservoir for the formation of the outer Cr rich layers. It
contains W and Si, partly oxidized, but the original alloy structure
is still observable. The total thickness of the layers above the un-
oxidised alloy increases with oxidation time and temperature. After
10 h oxidation at 800 ◦ C this thickness is ∼1-2 ␮m, while for 3 h at
1000 ◦ C it rises up to ∼15 ␮m. Furthermore, it was observed that
large W grains at the very surface inhibit locally the formation of
the protective Cr2 WO6 layer and act as nucleus for strong oxida-
tion. Therefore, care has to be taken in the future to reduce the size
of pure W grains by an effective milling.
The parabolic oxidation rates kp for each temperature were
obtained by linear fitting of the quadratic weight increase of the
samples during oxidation versus time. Fig. 5 shows the Arrhenius
plot for the 8W-HS-ah-2 material, including, for comparison, the
corresponding kp values of pure W and WCr12Si8 thin films. Com-
pared to the results obtained for thin films of similar composition
(but without Fe contamination), the bulk material shows a signif-
icantly lower oxidation rate at 600 ◦ C, similar rate at 800 ◦ C, but
worse performance at 1000 ◦ C. In contrast to the Cr2 WO6 protecting
layer of the bulk material, the oxidation barrier developed during
oxidation of the thin films was Cr2 O3 [6]. The different slope of the
oxidation rate fits shows that the activation energy for oxidation is
higher in the bulk alloys than for alloy films or pure W.
Fig. 5. Arrhenius plot of parabolic oxidation rates of pure W and WSi8Cr12 thin
films, and of sample 8W-HS-ah-2.
To study the oxidation mechanism, Pt markers were deposited
by FIB on sample 8W-HS-ah-2 before oxidation. Their location after
oxidation helps to clarify the rate-determining diffusion process.
Cross-sectioning by FIB of the oxidized sample and EDX mapping
reveal that the Pt markers were at the surface of the oxide scale and
not between alloy and scale, indicating that the growth of the oxide
scale is governed by O diffusion and not by diffusion of the metal-
lic component. This is in contrast to thin films oxidation, where
Cr diffusion through the growing layer to the outer surface deter-
mines the oxidation process [6]. The differences in the oxidation
mechanisms can explain the higher activation energy of the bulk
alloy.
The mechanisms for the formation of the different protecting
oxide layers are not yet clear. While the elements distribution in
the sputtered thin films is nanodispersive, the bulk material con-
tains grains of pure W at the surface, which may oxidize separately;
thermo-dynamically, the reaction of WO3 and Cr2 O3 to Cr2 WO6 is
possible at 1000 ◦ C [12]. The role of the material structure as well
as a possible influence of Fe impurities on the formation of Cr2 WO6
will be further investigated.
4. Conclusions
WC10Si10 and WC5Si5 alloys were manufactured by powder
metallurgy including MA in a SPEX mill and HIP at 1300 ◦ C for 1 h
and 200 MPa. Milling in WC vials under Ar for 1 h without PCA pro-
vided the best conditions for obtaining powders with relatively
low amount of contaminants together with an effective milling.
After HIP, densification close to 100% was obtained for those pow-
ders, whose microstructure consisted mainly in (WCr)5 Si3 and
some pure W, in addition to some medium size (0.5–1 ␮m) oxides
and ultrafine intergranular oxides, which probably prevent grain
growth and improve ductility. No complete phase homogenization
was achieved, indicating that longer HIPing times are required.
First oxidation tests on latter sample revealed lower oxidation
rate than WCrSi thin films at 600 ◦ C, similar rate at 800 ◦ C, and
worse performance at 1000 ◦ C. The oxide permeation barrier at the
surface consisted in a Cr2 WO6 layer, unlike for thin films, where the
oxidation barrier consists in Cr2 O3 . The growth of the oxide scale
is governed by oxygen diffusion. The influence of Fe has to be fur-
ther investigated. Large W grains at the surface produce defects on
the Cr2 WO6 barrier layer and should be avoided by improving the
manufacturing method.
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