Journal of Alloys and Compounds 602 (2014) 346355

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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

TEM analysis, mechanical characterization and oxidation resistance

of a highly refractory ZrB2 composite
Laura Silvestroni , Diletta Sciti
CNR-ISTEC, Institute of Science and Technology for Ceramics, Via Granarolo 64, I-48018 Faenza, Italy

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

Article history: The microstructure of a dense ultra-high-temperature ceramic, namely ZrB2 containing 15 vol% of WSi2,
Received 20 January 2014 was characterized by X-ray diffraction, scanning and transmission electron microscopy. ZrB2 displayed a
Received in revised form 20 February 2014 coreshell structure: the core was constituted by the original MB2 grain and the shell by a (Zr,W)B2 solid
Accepted 21 February 2014
solution which grew epitaxially on the core. According to the nal microstructure with mixed
Available online 28 February 2014
Zr,W-silicides, -borides and -carbides at the triple points and clean grain boundaries, a densication
mechanism for ZrB2 in presence of WSi2 is proposed. This composite displayed excellent thermo-
Keywords:
mechanical properties, like strength retention of 84% at 1500 C in air and moderate oxidation up to
ZrB2
Silicides
1650 C. Correlation between microstructure and properties are here presented in relationship to other
TEM ultra-refractory ceramics available in the literature.
High temperature mechanical properties 2014 Elsevier B.V. All rights reserved.
Oxidation

1. Introduction magnetic eld during slip casting process enabled to achieve

The impelling demand of reusable and long lasting materials,
able to operate at high temperature and for long time pushes the
scientic research towards continuous search of materials possess-
ing a combination of properties always more challenging. The new
concept of hypersonic vehicles actually lies on the availability of
these new materials. Like most of parts of motors, the components
of propulsion or hypersonic vehicles are exposed to signicant
heating ux where mechanical solicitations are present too. There-
fore the main requirement that a material for such applications
should satisfy is a combination of refractoriness at high tempera-
ture in oxidizing environment and sufcient mechanical resistance
in such environment. The class of compounds commonly known as
ultra-high temperature ceramics (UHTCs) has been identied as
potential candidate for operating in harsh conditions owing to
their melting point exceeding 3000 C and their resistance to abla-
tion [1].
Among the most investigated systems, ZrB2-based composites
certainly hold supremacy in literature and overall knowledge of
the microstructure-properties relationships over the other borides
and carbides compounds. It has been shown that strength up to
1 GPa [2] can be achieved upon a tailored design of composition
and processing. A recent work reported that texturing of ZrB2 by
Corresponding author. Tel.: +39 546 699723; fax: +39 546 46381.
E-mail address: laura.silvestroni@istec.cnr.it (L. Silvestroni).
strength overcoming 800 MPa at 1600 C [3]. It has further been
demonstrated that the addition of dopants, in particular silicides
and carbides of transition metals in groups V and VI, can induce
a strength retention at high temperature by altering the micro-
structural features [4,5]. For example, strength of 640 MPa at
1500 C in argon has been reported after introduction of WC [5].
In another paper, WC-doping was introduced in ZrB2ASiC compos-
ite in amounts ranging from 3 to 7 vol% and again increased oxida-
tion performances of the W-doped ceramics as compared to pure
ZrB2ASiC were reported [6]. The reasons for this improvement
were ascribed to the formation of a eutectic between WO3 and
ZrO2 at 1275 C, that acted as liquid phase sintering and decreased
the porosity of the scale, or WO3 acted as barrier itself due to the
volume increase associated with oxidation of W to WO3. In a ded-
icated study, the oxidation behavior of ZrB2 with 0, 4, 6, or
8 mol% W was studied at 8001600 C and pointed out that the
addition of W into B2O3 increased the stability of the protective
glassy layer, which resulted in higher oxidation resistance [7].
Other authors suggested that tungsten oxide species form strong
acid sites in ZrO2 and inhibit ZrO2 tetragonal to monoclinic struc-
tural transformations [8].
In this work, a ZrB2 ceramic was hot pressed through addition of
WSi2 which enabled the densication and the development of a
microstructure possessing high mechanical strength at 1500 C in
air and relatively low oxidation rate up to 1650 C. WSi2, with a
tetragonal structure, has been the focus of considerable attention
as an attractive material for electronics and high temperature

http://dx.doi.org/10.1016/j.jallcom.2014.02.133
0925-8388/ 2014 Elsevier B.V. All rights reserved.
 L. Silvestroni, D. Sciti / Journal of Alloys and Compounds 602 (2014) 346355 347

application, as its properties provide the desirable combination of 3. Results

high melting temperature (2160 C), good strength at high temper-
ature, good creep resistance and high oxidation resistance which 3.1. Densication behavior
relies on the formation of vitreous, dense, adherent SiO2 scale
[9]. Following previous positive results obtained with other transi- The densication curve recorded during hot pressing run is de-
tion metal silicides [10] and in view of the above mentioned phys- picted in Fig. 1a where density and temperature are reported as a
ico-chemical features, WSi2 could be an adequate sintering function of time. It can be read that signicant shrinkage started
additive for ZrB2 for applications in ultra-high temperature just above 1750 C (TON), which is a relatively high temperature
environments. as compared to other transition metal silicides (ZrSi2: 1350 C,
Different analytical techniques were used in order to elucidate MoSi2: 1500 C [10]). The inset in Fig. 1a shows the maximum den-
the composition and structure of the newly formed W-based sication rate for different ZrB2 composites containing the same
phases. Besides the conventional characterization by X-ray diffrac-
tion and scanning electron microscope, transmission electron
microscope was here used as main tool to explore microstructures
on a small length scale to give information about the densication
mechanisms and to establish correlations between microstructural
features and bulk material properties.

2. Experimental procedure

A composite containing 15 vol% of sintering additive was prepared using the

following commercial powders: hexagonal ZrB2, Grade B (H.C. Starck, Germany),
specic surface area 1.0 m2/g, impurity max content: C: 0.25 wt%, O: 2 wt%, N:
0.25 wt%, Fe: 0.1 wt%, Hf: 0.2 wt%, particle size range 0.18 lm; tetragonal WSi2,
(Sigma Aldrich, Milano, Italy), 325 mesh, 99.5%, traces of metals <6000 ppm.
The powder mixture was ball milled with zirconia media in a polyethylene
jar for 24 h in absolute ethanol at 130 rpm. The ratio between powder, solvent
and milling media was 1:1:1 in weight. Subsequently the slurry was dried in a
rotary evaporator. Sintering was conducted in a hot pressing in low vacuum
(100 Pa) using an induction-heated graphite die with a constant uniaxial
pressure of 30 MPa, heating rate 20 C/min and free cooling. The maximum
sintering temperature was 1930 C. The bulk density was measured by Archimedes
method.
To identify the crystalline phases formed, the sample was examined using X-ray
diffraction (Siemens D500, Karlsruhe, Germany), with Cu Ka radiation, step size of
0.04 and 1 s counting rate.
The microstructure was analyzed on fractured and polished surfaces by
scanning electron microscopy (FE-SEM, Carl Zeiss Sigma NTS Gmbh berkochen,
Germany) and energy dispersive X-ray spectroscopy (EDS, INCA Energy 300, Oxford
instruments, UK). TEM samples were prepared by cutting 3 mm discs from the bulk
of the sintered pellets. These were mechanically ground down to about 20 lm and
then further ion beam thinned until small perforations were observed by optical
microscope. Local phase analysis was performed using transmission electron
microscopy (TEM) equipped with an energy-dispersive X-ray system. TEM analysis
was performed by a FEI Tecnai F20 ST, with an acceleration voltage of 200 kV,
equipped with an EDAX EDS X-ray spectrometer PV9761 with super ultra-thin
window.
Quantitative calculations of the microstructural features, such as residual
porosity and secondary phases content, were carried out via image analysis with
a commercial software package (Image Pro-plus 4.5.1. Media Cybernetics, Silver
Spring, MD, USA).
Vickers microhardness (HV1.0) was measured with a load of 9.81 N using a
Zwick 3212 tester.
Fracture toughness (KIc) was evaluated using chevron-notched beams (CNB) in
exure. The test bars, 25  2  2.5 mm3 (length by width by thickness, respec-
tively), were notched with a 0.1 mm-thick diamond saw; the chevron-notch tip
depth and average side length were about 0.12 and 0.80 of the bar thickness,
respectively. The specimens were fractured using a semi-articulated silicon carbide
four-point xture with a lower span of 20 mm and an upper span of 10 mm using a
screw-driven load frame (Instron mod. 6025). The specimens were loaded with a
crosshead speed of 0.05 mm/min. The slice model equation of Munz et al. [11]
was used to calculate KIc. On the same machine and with the same xture, the ex-
ural strength (r) was measured at room temperature and at 1500 C in air on cham-
fered bars 25  2.5  2 mm3 (length  width  thickness, respectively), in 4-point
bending using a crosshead speed of 0.5 mm/min. Before the bending test, a soaking
time of 18 min was set to reach thermal equilibrium. 5 specimens were tested at
room temperature and 3 at high temperature.
The oxidation resistance was tested at 1200, 1350, 1500 and 1650 C on
13  2.5  2 mm3 bars in static air in a bottom loading furnace box (Nannetti FC/
18, Faenza, Italy). The specimens were located in the furnace on ZrO2 supports Fig. 1. (a) Densication curve recorded during hot pressing. TON: temperature at
when the maximum temperature was reached and then removed and air quenched which shrinkage begins, TLP: temperature at which liquid phase forms. In the inset:
after an exposure time of 15 min. All the specimens were previously cleaned in ace- plot of the maximum densication rate as a function of the temperature for
tone. The mass of the specimens was measured before and after exposure. The different silicides; Z: ZrSi2, T: TaSi2, M: MoSi2, W: WSi2. (b) X-ray diffraction pattern
microstructural modications induced in the oxidized specimens were evaluated of the sintered composite showing the crystalline phases and (c) ZrB2 peaks
by XRD and SEMEDS on surface and cross section. splitting at high 2-Theta angles.
348 L. Silvestroni, D. Sciti / Journal of Alloys and Compounds 602 (2014) 346355
amount of various silicides, i.e. ZrSi2, MoSi2, TaSi2 and WSi2 [10]. It
is evident that WSi2, besides favoring the sintering process at the
highest temperature, also enables the densication at the lowest
speed. The sintering process proceeded at the same rate up to
1850 C, after which a steeper slope indicated the improvement
of densication mechanisms, possibly assisted by liquid phases
(TLP). At 1930 C the relative density was around 87% of the theo-
retical value, but a dwell at this temperature for 25 min enabled
the achievement of the full density.
3.2. Microstructural features of the as sintered ceramic
The X-ray diffraction pattern of the composite is reported in
Fig. 1b; a Si standard was placed on the top of the specimen in or-
der to detect any peak shift. In the whole 2-Theta range, ZrB2 was
the main crystalline phases, but reections of tetragonal WB were
found too, whilst WSi2 was present just in traces. At high 2-Theta
angles, above 80 (Fig. 1c), another phase is clearly visible on the
right of ZrB2 (PDF# 34-0423). The unit cell parameters of this new-
ly formed phase were a = 3.1653 and c = 3.5244 , i.e. slightly
shorter than those of pure ZrB2 (a = 3.1690 and c = 3.5300 ),
which indicates a contraction of the unit cell. The presence of these
additional reections was interpreted as due to the formation of a
(Zr,W)B2 solid solution. However, the exact composition of this
new phase was not computable through Vegards rule, owing to
the too small amount of W entered into ZrB2 lattice, within the
instrumental error.
Images of the microstructure by SEM are shown in Fig. 2. Fig. 2a
shows an overall view of the polished section: the grains are
rounded with average dimensions of 3.1 0.8 lm and are homoge-
neously surrounded by a brighter gray phase. Different gray levels
in the matrix are due to different grains orientation. The main sec-
ondary phases are about 2 vol% of silica, with dark contrast, and
3.5% of a white phase containing W,B,C,O. Small SiC grains were
Fig. 2. SEM images of the sintered ceramic showing (a) the overall microstructure, (b) the matrix morphology with (c) EDX spectra of core and shell. (d) Elemental mapping of
the matrix showing the distribution of W in the shell. (e)(g) secondary W-based phases.
often found next to silica pokets. No major defects or porosity were
observed. Fig. 2b discloses the morphology of the matrix: the core
is ZrB2, whilst the outer brighter region, the shell, is ZrB2 contain-
ing 2 at.% of W, resulting in a solid solution like (Zr0.98W0.02)B2, as
the EDS spectra and elemental mapping in Fig. 2c and d demon-
strate. The presence of carbon in the spectra is due to beam
contamination. Images acquired with in-lens electrons, Fig. 2eg,
revealed that the bright phase observed by backscattered electrons
in Fig. 2a is actually composed by several other phases: the largest
areas are WCO and WBC, always adjacent to each others and with
low dihedral angles suggesting solidication from liquid phase. At
the extremities, brighter regions with generally elongated shape
are WB with Zr traces, Fig. 2e and f, whilst the bright phases found
at the triple points with concave shape are mixed Zr,W-silicides
with stoichiometry difcult to identify owing to the superimposi-
tion of W and Si lines, Fig. 2g.
TEM investigations enabled a more precise denition of the
constituent phases. Examples of the matrix grain morphology are
reported in Fig. 3ac. A peculiar feature of the diboride grains
was the presence of dislocations in the shell. Similarly to previous
study on analogous composites [10,12], core and shell were
epitaxial, as disclosed by electron diffraction patterns, Fig. 3. In
spite of that, no modication of lattice parameters was detected
by SAEDP technique, owing to the small differences in atomic radii
between Zr and W (0.160 and 0.137 nm, respectively) and to the
little W content in the shell. The boundary between core and shell
was quite sharp and dened by dislocations pile up, as depicted
in Fig. 3ac. W-rich precipitates were occasionally found at the
core-shell interface, as the inset in Fig. 3c shows. TEM EDS
quantitative analyses performed on core and shell, conrmed
around 2 wt% of W in the solid solution, Fig. 3. The study of
secondary phases and triple points by electron diffraction and
EDS conrmed the formation of large WB grains, with WC or
WSi2 smaller grains at the apical parts, Fig. 4ae and the
 L. Silvestroni, D. Sciti / Journal of Alloys and Compounds 602 (2014) 346355 349

Fig. 3. (a)(c) TEM images showing the coreshell structure of the matrix of the sintered ceramic with EDX spectra at low and high voltage and SAEDP taken from (a)
conrming epitaxy between ZrB2 and (Zr,W)B2. The inset in (c) shows a W-rich precipitate occasionally found at the coreshell interface.

Fig. 4. TEM images of the secondary phases with EDX spectra and diffraction patterns showing the presence of WB, WC, WSi2 and residual ZrO2.
350 L. Silvestroni, D. Sciti / Journal of Alloys and Compounds 602 (2014) 346355
segregation of ZrO2 or impurities, like Fe-rich phases, at the triple
junctions, Fig. 4f. Analyses of the interfaces revealed non wetted
grain boundaries between adjacent (Zr,W)B2 grains, Fig. 5af, and
between WB and (Zr,W)B2, Fig. 5gi. Clean interfaces were found
both in case of simple triple junctions, Fig. 5ac, and in case of
segregation of secondary phases at the triple points, Fig. 5df.
Strain contrasts were generally observed in ZrB2 grains when other
phases crystallized at the junctions, Fig. 4a and e. To obtain
statistically valid results, several interfaces were analyzed and no
amorphous lm was found between (Zr,W)B2, (Zr,W)C, (W,Zr)Si2
and WB grains, as conrmed in Fig. 6.
3.3. Mechanical properties
The mechanical properties measured on the ZrB2AWSi2 compos-
ite are reported in Table 1 together with properties of other ZrB2
ceramics sintered with addition of silicides (MoSi2, TaSi2) or W-com-
pounds (WC) [5,10,13,14]. As expected, the fracture toughness of
this composite was in the range of other ZrB2-based ceramics mea-
sured with the same chevron v-notched method, 3.6 MPa m1/2 [10].
The hardness, around 18 GPa, resulted higher than other ZrB2-
ceramics sintered with addition of other transition metal silicides
[10], despite coarser grain size and 2 vol% of silica, probably thanks
Fig. 5. TEM and HRTEM images of the triple point junctions showing clean grain boundaries between (a)(f) adjacent (Zr,W)B2 grains and (g)(i) between WB and (Zr,W)B2.
to the presence of other hard secondary phases, like WB and WC. The
room temperature exural strength was 640 with very low standard
deviation, less than 3%, conrming a uniform microstructure with-
out large aws. Interesting results were obtained for exural
strength tests at 1500 C in air: a retained strength of more than
84% was preserved, outdoing most of ZrB2 compounds available in
the literature. Excellent results were obtained also by Zou and co-
workers [5] who even measured a strength increase, however those
data are not directly comparable with those of the present work,
since their tests were performed in argon and in 3-point bending.
3.4. Microstructural features of the oxidized ceramic
When we deal with oxidation of dark ceramics like borides, an in-
crease of the oxidation temperature induces the modication of the
gray color, typical of the as sintered material, to dark gray, index of
glass formation, to whitish-yellow, index of formation of the corre-
sponding metal oxide. In the present case, the oxidized specimens
remained of gray color up to 1350 C, but when the ceramic was oxi-
dized above 1500 C it nished with whitish-yellowish aspect.
The main crystalline phase detected by X-ray diffraction on the
oxidized samples, was monoclinic ZrO2. In addition tungsten oxide
was detected at all temperatures, Fig. 7. Traces of WB were instead
 L. Silvestroni, D. Sciti / Journal of Alloys and Compounds 602 (2014) 346355 351

Fig. 6. HR-TEM images showing clean grain boundaries between (Zr,W)B2, (Zr,W)C, (W,Zr)Si2 and WB.

Table 1
Composition, mean grain size and mechanical properties of ZrB2AWSi2 ceramic compared to other ZrB2-composites containing either transition metal silicides or W-compounds.
m.g.s.: mean grain size, KIc: fracture toughness measured by chevron notch technique, HV: microhardness (1 kg), r: 4-point exural strength at room temperature or at 1500 C in
air.

Composition (vol%) ZrB2 m.g.s. (lm) KIc (MPa m0.5) HV (GPa) rRT (MPa) r1500 (MPa) Ref.
ZrB2 + 15 WSi2 3.1 0.8 3.62 + 0.35 18.3 + 0.4 641 + 19 537 + 16 This work
ZrB2 + 15 MoSi2 2.4 3.50 0.60 14.9 0.5 704 98 333 31 [10]
ZrB2 + 15 TaSi2 2.0 3.80 0.10 17.8 0.5 840 33 374 5 [10]
ZrB2 + 3 WC (PLS) 9.1 5.6 14.5 2.6 444 30 [13]
ZrB2 + 3 WC (HP) 4.0 1.2 23.0 0.9 565 53 [13]
ZrB2 + 20SiC + 5 WC 1.1 605b 640b,c [5]
(ZrB2 + 20SiC) + 10 WC 6.5 0.2a 13.9 0.2 518 10b [14]
a
SEVNB.
b
3-pt Beniding strength.
c
Ar.

Fig. 7. X-ray diffraction spectra of ZBW oxidized at 1200, 1350, 1500, 1650 C for 15 min.
352 L. Silvestroni, D. Sciti / Journal of Alloys and Compounds 602 (2014) 346355
visible up to 1350 C, whilst ZrB2 reections were not identied at
any oxidation temperature. The weight gain per unit surface area
(not shown) increased with the temperature, moderately up to
1350 C, 3 mg/cm2, then more at higher temperature, i.e. up to
12 mg/cm2 at 1650 C.
Images of the external surface at the various oxidation temper-
atures are given in Fig. 8ad, whilst pictures of the fractured cross
sections are reported in Fig. 8eh with EDS spectra of the men-
tioned phases. As rst observation, it can be seen that the thickness
of the oxidized layer progressively increased with the temperature
and passed from 24 lm after 1200 C, to 55 lm at 1350 C, to
135 lm at 1500 C and to 210 lm at 1650 C.
At 1200 C, Fig. 8a, the surface was characterized by large areas
of glassy B2O3 and submicrometric grains of ZrO2 which were cov-
ered by tiny WO3 whiskers, inset in Fig. 8a, bottom. Occasionally
this phase was also found in form of agglomerates with bright con-
trast among ZrO2 grains, see the inset in Fig. 8a, top. In the cross
section, Fig. 8e, about 24 lm underwent modication and this
scale was mostly constituted by ZrO2 grains with intergranular
WO3 agglomerates adherently attached to the unreacted bulk
without visible cracks and topped with discontinuous B2O3 glassy
layer.
At 1350 C boron oxide disappeared from the surface and, in the
outermost layer, only ZrO2 grains immersed in silica glass were de-
tected, Fig. 8b. Even W traces were barely detected among the crys-
tals. The scale thickness doubled as compared to the sample
oxidized at 1200 C, but maintained the same morphology,
Fig. 8f. Also in this case the oxidized layer was well adherent to
the matrix, inset in Fig. 8f.
The oxidation at 1500 C induced a notable variation of the
external morphology which appeared wavy and rutty showing
Fig. 8. SEM images of (a)(d) external surface and (e)(h) cross section of the oxidized ceramic. From left to right: 1200, 1350, 1500, 1650 C with microstructural details in
the insets. In the bottom: EDS spectra of B2O3 glass in (a), ZrB2 and ZrO2 in (f), WO3 in (g) and SiO2 from all surfaces.
bumps and craters. The ZrO2 grains coarsened to about 2 lm and
appeared aggregated and melted on a silica continuous layer,
Fig. 8c. The growing planes were well visible in ZrO2 and W-rich
phases with bright contrast were found at the grain boundary,
Fig. 8c. Differences in coefcient of thermal expansion between
zirconia and silica provoked the formation of microcracks. This
oxidation induced a diversication in morphologies of the ZrO2
sub layer, Fig. 8g. Starting from the top, 20 lm coarse ZrO2 grains
were standing on another 20 lm of columnar ZrO2, which was
topping about 95 lm of dense rounded-grains ZrO2. The whole
thickness was partially lled with silica and the ZrO2 grains were
coated with homogeneously dispersed WO3 drops which eventu-
ally turned into 5 lm big agglomerates, see the insets in Fig. 8g.
The surface of the sample oxidized at 1650 C was not notably
different from the one oxidized at 1500 C, just more bumps, cra-
ters and cabbage-like structures were noticed, Fig. 8d. Similarly,
the morphology of the various scales remained basically unmodi-
ed as compared to the features observed for the samples oxidized
at 1500 C, Fig. 8h, but each scale just increased in thickness and
columnar ZrO2 layer further developed and displayed microcracks
within the elongated grains.
4. Discussion
4.1. Microstructure evolution during densication
In the sintered material, a notable change of the microstructural
features occurred, which is strictly related to the densication
mechanisms activated by WSi2. Addition of metal disilicides, MeSi2
(Me@Ti, Cr, Zr, Mo, Ta, W), to TiB2 and ZrB2 was rst investigated
by Pastor and Meyer in 1974 [15] and, according to their studies,
 L. Silvestroni, D. Sciti / Journal of Alloys and Compounds 602 (2014) 346355 353

densication of borides with MeSi2 was successful because it was and also silica glass at such high temperatures tends to be carbo-
conducted at temperatures close to the MeSi2 melting point. For reduced to SiC. In addition, the study of the interfaces also reveals
WSi2, however, full densication is achieved although the temper- that the liquid does not wet the matrix, as all the grain boundaries
ature range is well below its melting point, 2160 C [16]. However, were clean from any intergranular phases.
low dihedral angles suggest WSi2 was ductile at the sintering
temperature.
According to the phase diagrams involving WASi [16], WAB 4.2. Fracture strength
[17], WAC [17], no liquid phases are predicted to form below
1930 C. Also the eutectic at 1275 C [18] between the oxides cov- The featuring characteristic of this composite is its very high
ering the particles, WO3 and ZrO2, does not seem to affect the refractoriness at 1500 C in air, as testied by fracture strength of
beginning of the shrinkage occurring at 1750 C, TON in Fig. 1a. Only 540 MPa at this temperature, namely 84% of the room temperature
Si, SiO2 and B2O3 are liquid below the sintering temperature. How- value, and the linearity of the loaddisplacement curve, displayed
ever, the presence of W-based phases at the triple junctions con- in Fig. 9a. An example of the fracture surface after bending test at
taining Zr traces suggests the existence of some liquid phases in 1500 C is shown in Fig. 9b. On the cross section, about 150 lm of
which ZrB2 is partially soluble in. Similar to MoSi2, and TaSi2 material underwent oxidation and this layer was formed by ZrO2
[10,12], the densication of ZrB2AWSi2 composite is presumed to rounded grains containing W traces and covered by H3BO3 acicular
be assisted by a transient liquid phase, due to the reaction between crystals deriving from hydration of B2O3 after exposure to humid-
WSi2 and the oxide impurities covering the diboride powders, ity in the environment. This feature is quite surprising, since B2O3
according to reaction (1): has low vapor tension and evaporates above 1000 C. The fact that
we still see crystalline boron oxide in the oxide scale could be due
2 WSi2 B2 O3 l ! 2 WB 2:5 Sil 1:5 SiO2 l 1 to the presence of tungsten oxide which reduced the volatility of
Reaction (1) implies removal of B2O3 from the surface of the the borate glass, as previously stated in a dedicated study [7].
diboride particles, formation of SiA and SiAO-based liquids and The strength retention at high temperature is usually attributed
is favorable in the whole sintering temperature range, 48 kJ/ to the formation of a protective oxide scale [20], crack healing or to
mol at 1700 C. Reaction (1) is not exhaustive and, in the reducing the release of internal residual stresses [21]. In this system, neither
environment of the hot pressing chamber, it is likely that variants amorphous phase nor glassy phases were found in the microstruc-
of the same reaction locally occur, for example resulting in the for- ture. Crack healing can be therefore ruled out as strengthening
mation of WO3, reaction (2): mechanism. Regarding the relaxation of the internal residual stres-
ses, the test temperature of our specimens, 1500 C, was not close
9 WSi2 4 B2 O3 9 COg ! 8 WB WO3 9 SiC
9 SiO2 l 2
which has a negative Gibbs free energy as well, 36 kJ/mol at
1700 C.
Nevertheless, all these intermediate phases concur to the for-
mation of liquid phase at temperature around 1850 C, TLP in
Fig. 1a, that promotes mass transfer mechanisms, by partial disso-
lution of the boride matrix.
A distinctive feature of the ZrB2AWSi2 composites is the forma-
tion of (Zr,W)B2 solid solution around ZrB2 grains, which was al-
ready found for other ZrB2AMeSi2 and it was also assessed that
(Zr,Me)B2 shells grow epitaxially onto ZrB2 cores [10,12]. This
grains morphology suggests again a solution re-precipitation
mechanism, summarized by reaction (3), even if diffusion of W into
the diboride lattice and Zr into the silicide cannot be ruled out, as
previously observed for analogous systems involving different
transition metal cations which are close in the periodic table [19]:

ZrB2 WSi2 ! Zr; WB2 W; ZrSi2 3

During cooling the transient liquid-phase solidies, resulting in
the formation of discrete crystalline phases, such as the observed
WB, WC. At the same time, the carbo-reduction of SiO2A and
WO-based species to SiC and WC is favorable too:

SiO2 C ! SiC CO2 g 4

WO3 2C ! WC COg CO2 g 5

The chemistry of the crystalline phases at the triple point junc-
tions seems to conrm the above reactions to occur.
We can state that, compared to previously studied systems, the
densication of this one with WSi2 proceeds through more slug-
gish mechanisms even if the sintering temperatures is higher, see
the inset in Fig. 1a. This can be determined by combination of fac-
tors: the initial liquid amount is limited and more refractory, its Fig. 9. (a) Loaddisplacement curves for exural strength at room temperature and
viscosity progressively increases owing to the incorporation of at 1500 C in air. (b) SEM images of the cross section of a bar after exural strength
higher and higher amount of cations from boride and silicides, testing at 1500 C showing the presence of acicular BO-based crystals.
354 L. Silvestroni, D. Sciti / Journal of Alloys and Compounds 602 (2014) 346355
to the material sintering temperature, 1930 C, so that the relaxa-
tion could not have been truly effective.
In a recent TEM study conducted upon high temperature ex-
ural strength on ZrB2AB4C composites with clean grain boundaries
like in the present case [3], it was pointed out that, below a testing
temperature of 1600 C, no interconnected cavities developed at
the grain junctions and that the stress induced by the load was pro-
gressively accommodated by ZrB2 grains plastic deformation, due
to the generation and ow of dislocations. This mechanism pro-
moted a strength increase at high temperature in that composite
[3]. In the ceramic of the present work, we observed dislocation
networks already after sintering, as Fig. 3 clearly shows. The
absorption of small amount of mechanical energy during the ex-
ural test by dislocation ow and multiplication could give a partial
contribution to the remarkable high temperature strength of
ZrB2AWSi2 composite. Also the clean grain boundaries and the
presence of highly refractory secondary phases at the triple points,
like WB, possessing a melting point of 2655 C [17], or WC, 2870 C
[17], Fig. 4, could be benecial for the high temperature strength
by preventing grain boundary sliding at high temperature.
In conclusion, the high refractoriness of the ZrB2AWSi2 ceramic
is very likely a combination of multiple factors: the formation of a
stable and protective borate glass on the surface during oxidation,
the intrinsic refractoriness of the crystalline compounds, the
absence of amorphous phases at the grain boundaries and the
tendency of the matrix grains to absorb energy by plastic deforma-
tion due to dislocations ow.
4.3. Oxidation behavior
From the microstructure evolution presented in Section 3.4, it is
obvious that multiple and various phenomena occur upon oxida-
tion of ZrB2 doped with WSi2 implying melting, formation of glassy
phases, phase transformation and vaporization. The benecial ef-
fect of tungsten on the oxidation behavior of ZrB2 and ZrB2ASiC
composites has been already outlined in previous works [57].
The improved behavior of W-doped ceramics was ascribed to dif-
ferent phenomena:
 The formation of an eutectic between WO3 and ZrO2 at 1275 C,
that acted as liquid phase sintering and decreased the porosity
of the outer scale [5,6].
 The fact that WO3 performed as barrier itself due to the volume
increase associated with oxidation of W-species to WO3 [6].
 The incorporation of W in the borate glass which increased its
stability [7].
In the present case, at 1200 C, boride, carbide and silicide and
are expected to oxidize according to:
ZrB2 5=2O2 ! ZrO2 B2 O3
WSi2 7=2O2 ! WO3 2SiO2
WC 2O2 ! WO3 CO
2WB 9=2O2 ! 2WO3 B2 O3
In this temperature range, a subsurface oxidation layer is al-
ready formed, mainly composed of ZrO2, for around 25 lm.
This picture remains essentially the same at 1350 C.
At 1500 C the ceramic starts to oxidize readily and both weight
gain and oxide thickness notably increase, probably owing to the
formation of liquid phases. When W-compounds are present, li-
quid phase can form at temperatures lower than 1300 C, due to
the WO3AZrO2 eutectic [18]. Additional sources of liquid come
from mixed (Zr,W)-silicides, oxides and carbides present as
secondary phases in the sintered microstructure. Liquid phases
provide a fast path for oxygen transport and enhance oxidation.
In addition, the condensation of tungsten oxide, coming from reac-
tions (7)(9), from vapor phase is well evident, as it is found as
nanosized rounded particles on ZrO2 grains, Fig. 8g and h.
At 1650 C, the aforementioned phenomena are further en-
hanced. Liquid phases cause convection phenomena which make
zirconia grow in columnar structures, as consequence of convec-
tive transport of low viscosity borosilicate liquid, similar to what
observed for ZrB2ASiC composites [22,23]. As a matter of fact, dif-
ferently from what reported in [6], the formation of solid solutions
between tungsten oxide and zirconia was not proved by SEMEDS,
although the amount of available W was more than double than
the minimum amount of W reported to be effective in promoting
liquid phase sintering of ZrO2 and thus hindering the oxidation
[6]. Actually, the oxidation protection imparted by W addition is
reported to be better above 1600 C [6] or even above 1800 C
[24]. Further oxidation studies at higher temperature are in pro-
gress to assess the stability of the external scale in this more severe
regime, as slightly suggested by the weight gain trend, whose slope
tends to decrease.
5. Conclusions
A ZrB2-based ceramic was hot pressed to fully density at
1930 C through addition of WSi2. Although the high sintering tem-
perature, the microstructure resulted ne and homogeneous,
thanks to the benecial effect of WSi2 and its derivatives products.
Coreshell structures were found in the boride matrix and TEM
analyses revealed the segregation of highly refractory compounds
at the triple points, like WB, WC and WASi phases with clean grain
boundaries. These features resulted favorable for the high temper-
ature performances. In particular, the mechanical strength at
1500 C in air was 540 MPa, about 84% of the room temperature
value. Possible reasons explaining this behavior were the incorpo-
ration of W in the borate glass during oxidation, which increased
the oxide layer stability and protective action, and to the presence
of clean grain boundaries and highly refractory secondary phases
at the triple junctions. The oxidation behavior was characterized
in a bottom loading furnace in the 12001650 C temperature
range and this composite underwent modications in the rst
24 lm at 1200 C up to 210 lm at 1650 C.
Acknowledgements
TEM analyses were performed thanks to the nancial support of
grant N. FA8655-12-1-3004, with Dr. Ali Sayir as contract monitor.
D. Dalle Fabbriche is greatly acknowledged for thermal treatments,
C. Melandri for mechanical tests and S. Guicciardi for useful discus-
6 sion on mechanical properties.
7 References
8 [1] E. Wuchina, M. Opeka, S. Causey, K. Buesking, J. Spain, A. Cull, J. Routbort, F.
Gutierrez-Mora, J. Mater. Sci. 39 (2004) 59395949.
[2] A.L. Chamberlain, W.G. Fahrenholtz, G.E. Hilmas, D.T. Ellerby, J. Am. Ceram. Soc.
9 87 (2004) 11701172.
[3] W.W. Wu, Y. Sakka, M. Estili, T.S. Suzuki, T. Nishimura, G.J. Zhang, Sci. Technol.
Adv. Mater. 15 (2014) 014202.
[4] D. Sciti, L. Silvestroni, C. Melandri, G. Celotti, S. Guicciardi, J. Am. Ceram. Soc. 91
(2008) 32853291.
[5] J. Zou, G.J. Zhang, C.F. Hu, T. Nishimura, Y. Sakka, J. Vleugels, O. Van der Biest, J.
Am. Ceram. Soc. 95 (2012) 874878.
[6] S.C. Zhang, G.E. Hilmas, W.G. Fahrenholtz, J. Am. Ceram. Soc. 91 (2008) 3530
3535.
[7] M. Kazemzadeh Dehdashti, W.G. Fahrenholtz, G.E. Hilmas, Corr. Sci. 80 (2014)
221228.
[8] D.G. Barton, S.L. Soled, G.D. Meitzner, G.A. Fuentes, E. Iglesia, J. Catal. 181
(1999) 5772.
 L. Silvestroni, D. Sciti / Journal of Alloys and Compounds 602 (2014) 346355
[9] G. Sauthoff, Intermetallics, VCH Publishers, Weinheim, New York, 1995. pp.
115.
[10] L. Silvestroni, D. Sciti, Effect of transition metal silicides on microstructure and
mechanical properties of ultra-high temperature ceramics, in: J. Low, Y. Sakka,
C. Hu (Eds.), MAX Phases and Ultra-High Temperature Ceramics for Extreme
Environments, IGI Global, Hershey (PA), 2013, pp. 125179.
[11] D.G. Munz, J.L. Shannon Jr., R.T. Bubsey, Int. J. Fract. 16 (1980) R137141.
[12] L. Silvestroni, D. Sciti, J. Am. Ceram. Soc. 94 (2011) 19201930.
[13] A.L. Chamberlain, W.G. Fahrenholtz, G.E. Hilmas, J. Am. Ceram. Soc. 89 (2006)
450456.
[14] J. Zou, G.J. Zhang, Y.M. Kan, J. Mater. Res. 24 (2009) 24282434.
[15] H. Pastor, R. Meyer, Rev. Int. Haut. Temp. Refract. 2 (1974) 4154.
355
[16] Z. Guo, W. Yuan, Y. Sun, Z. Cai, Z. Qiao, J. Phase Equilib. Diff. 30 (2009) 564
570.
[17] E. Rudy, Part V. Phase Diagram W-B-C. AFML-TR-69-117 (1969).
[18] L.Y. Chang, M.G. Scroger, B. Phillips, J. Am. Ceram. Soc. 50 (1967) 211215.
[19] L. Silvestroni, M. Nygren, D. Sciti, J. Eur. Ceram. Soc. 33 (2013) 28792888.
[20] F.F. Lange, J. Am. Ceram. Soc. 63 (1980) 3840.
[21] A.G. Evans, A. Rana, Acta Metall. 28 (1979) 128141.
[22] A. Rezaie, W.G. Fahrenholtz, G.E. Hilmas, J. Eur. Ceram. Soc. 27 (2007) 2495
2501.
[23] S.N. Karlsdottir, J.W. Halloran, J. Am. Ceram. Soc. 92 (2009) 481486.
[24] C.M. Carney, T.A. Parthasarathy, M.K. Cinibulk, J. Am. Ceram. Soc. 94 (2011)
26002607.