Ceramics-Silikáty 62 (4), 382-388 (2018)

www.ceramics-silikaty.cz doi: 10.13168/cs.2018.0034

HYDROTHERMAL CORROSION RESISTANCE OF SILICON NITRIDE

WITH O'-SIALON GRAIN BOUNDARY PHASE
#
MICHAL VETRECIN*, ZOLTÁN LENČÉŠ*, DAGMAR GALUSKOVÁ**, PAVOL ŠAJGALÍK*

*Institute of Inorganic Chemistry, Slovak Academy of Sciences, 84536 Bratislava, Slovak Republic
**Vitrum Laugaricio – Joint Glass Centre of the IIC SAS, TnU AD, FChFT STU and RONA j.s.c.,
91150 Trenčín, Slovak Republic

#
E-mail: [email protected]

Submitted June 13, 2018; accepted August 7, 2018

Keywords: Ceramic, Silicon nitride, Sialon, ICP-OES, Corrosion

Dense Si3N4-based composites with O’-SiAlON bonding phase were prepared by hot pressing of the mixture of Si3N4 matrix
and polysiloxane (samples SA) and polysilazane (samples SB) based sintering aids. In both samples α-Si3N4 and β-Si3N4 were
identified as major phases and O'-SiAlON with a chemical formula Si1.84Al0.16O1.16N1.84 as a minor phase. The hydrothermal
corrosion tests were performed in subcritical conditions at 250°C for 100 hours. The weight loss was rather low, 0.96 wt. %
and 1.32 wt.  % for samples SA and SB, respectively. The corrosion rate of samples SA and SB was 206  mg·m-2·h-1 and
233 mg·m-2·h-1. The higher corrosion rate of sample SB prepared with polysilazane-based sintering aid is most probably due
to the hydrothermal dissolution of Si3N4 grains producing ammonia, as the pH value of eluate of this sample was higher, 8.5
compared to pH = 8.0 determined for sample SA. In sample SA a continuous SiO2-based passivation layer was formed, while
in sample SB the passivation layer was discontinuous and the corrosion medium could easily attack the Si3N4 grains. As the
corrosion solution was more basic in sample SB, the SiO2 passivation layer did not form so effectively, or dissolved faster
than in sample SA. The higher corrosion resistance of sample SA was partly improved also by using Y2O3 sintering additive,
which formed a rather stable Y2SiO5 phase.

INTRODUCTION The hydrothermal oxidation of Si3N4 can be descri-

bed by the following general equation [7]:
Silicon nitride and SiAlON-based ceramics have Si3N4 + 6 H2O = 3 SiO2 + 4 NH3 (1)
a wide spread structural applications due to their
excellent mechanical properties like strength and frac- The oxidation/corrosion resistance of Si3N4 cera-
ture toughness, good thermal shock and creep resistan- mics can be enhanced by appropriate selection of sin-
ce, good tribological and wear properties [1]. These tering aids, e.g. using rare-earth oxides (Y2O3, Yb2O3,
properties predestine the Si3N4-based ceramics for appli- Lu2O3) to create a corrosion resistant grain boundary
cations such as engine components, heat exchangers, phase or crystalline silicates at the triple junctions [16].
pump seal materials, ball bearings, cutting tools, etc. It is known that the grain boundary phase and triple point
However, recently there is an increasing demand on phases play a critical role on high-temperature proper-
materials, which can withstand attack by hot aqueous ties of Si3N4 ceramics, including their oxidation and
solutions for applications in geothermal production corrosion resistance [13, 17]. Therefore, high attention
units (heat exchangers, pumps, armatures), subcritical should be paid also to the design of the grain boundaries
and supercritical water oxidation units for waste composition, i.e. to the selection of sintering additives.
management, hydrolysis or gasification of biological Linck et al. has reported a very good hydrothermal
substances, units for the desalination of seawater, etc. corrosion resistance of polymer-derived silicon oxy-
[2-4]. Several studies have shown that the hydrothermal carbide-based ceramics (SiOC, SiZrOC and SiHfOC)
corrosion resistance of Si3N4-based materials is rather [18]. In our earlier work we have used the preceramic
low [5-14]. The general conclusion was that the SiAlOC polymer-derived ceramic (PDC) material as
oxidation rate of Si3N4 by hot water vapour depends a sintering aid for the densification of Si3N4 and the
on the sintering aids, sintering process, porosity and material showed good mechanical proper-ties with a
impurities [8]. In our previous work on the hydrothermal hardness of 19 GPa and fracture toughness 5 MPa·m1/2
corrosion of Si3N4 and SiAlON it was observed that the [19].
Si–N bonds in Si3N4 and both the Si–N and Al–N bonds In this work we have studied the hydrothermal
in SiAlON are attacked preferentially resulting in severe corrosion resistance of Si3N4/O’-SiAlON-based compo-
pitting corrosion [15]. sites in subcritical water at 250°C. The composites were
382 Ceramics – Silikáty 62 (4) 382-388 (2018)
 Hydrothermal corrosion resistance of silicon nitride with O'-SiAlON grain boundary phase

prepared by hot pressing of the mixture of Si3N4 matrix homogenized in a Si3N4-based planetary ball mill in
and SiAlOCN-based polymer-derived ceramic sintering hexane and after rotary evaporation of solvent dried
aids. in vacuum drier at 80°C and 200  mbar for 6  h. Soft
agglomerates were crushed in agate mortar. From the
prepared powders pellets (φ = 12 mm) were pressed by
EXPERIMENTAL uniaxial pressing (100 MPa).
Samples were densified in a graphite resistance
Preparation of the sintering hot-pressing furnace. The sintering conditions and den-
additives sification behaviour of the produced samples are summa-
Commercial α-Si3N4 powder (SN-E10, Ube Indust- rized in Table 2. Due to the lower viscosity of polysilo-
ries Ltd., Tokyo, Japan, α-phase > 95 %, d50 = 0.5 µm) xane-based additives samples SA could be densified at
was used as a matrix for the preparation of Si3N4-based lower temperature and shorter time (1600°C/15  min)
composites. Two types of sintering aids have been used, compared to samples SB containing polysilazane-based
both were composed of preceramic polymers combined additives with higher viscosity (1700°C/30  min). The
with very fine inorganic fillers (Table 1). The preparation load of 30 MPa was applied at 1200°C during the heating
of sintering aids is described in details elsewhere [19]. up to the final processing temperature and released at
Briefly, the sintering additive A was prepared from the 1300°C during cooling. Nitrogen gas inlet started at
mixture of polysiloxane (Silres H44, Wacker-Chemie 300°C and was adjusted to constant 0.105  MPa in the
GmbH, Müchen, Germany), γ-Al2O3 (Aeroxide Alu C, furnace during the whole experiment.
Evonik Industries AG, Essen, Germany, d50 = 13 nm),
amorphous Si3N4 (Goodfellow, Huntingdon, England, Table 2. Hot pressing conditions (temperature T, dwell time td,
d50  =  20  nm), carbon black (Vulcan XC-72, Cabot, load P) and weight loss (Δm) of samples SA and SB.
Leuven, Belgium, mean particle size of 20 - 50 nm) and
Samples Tmax (°C) td (min) P (MPa) Δm (%)
Y2O3 (Inframat Advanced Materials, Manchester, CT,
USA, mean particle size of 30 - 50  nm) in isopropyl SA 1600 15 30 -5.87
alcohol. The homogenized slurry was dried for 8  h at SB 1700 30 30 -4.33
60°C. The fillers were active, because they formed a
SiAlON-based solid solution during sintering. Carbon
Materials characterization
acted as a reducing agent to produce in situ AlN from
γ-Al2O3, which was incorporated into the structure of Density measurements were carried out by the
SiAlON. Y2O3 served as a common sintering aid and Archimedes method in mercury. Each sintered sample
should decrease the viscosity of SiAlON-based liquid was measured three times and the standard deviation
phase during sintering. of density values was less than 0.02 g·cm-3. The micro-
The sintering aid B was prepared from the mixtu- structures were observed by scanning electron microsco-
re of polysilazane precursor (Ceraset PSZ20, KiON py (EVO 40HV; Zeiss, Oberkochen, Germany). Phase
Defense Technologies Inc., Huntigdon Valley, PA, USA) composition was investigated by X-ray diffraction ana-
and γ-Al2O3 nanopowder (Aeroxide Alu C) in hexane. lysis (D8-Discover; Bruker, Madison, WI, CuKα radia-
After drying the mixture was crosslinked at 300°C for 1 tion), and applying the X’Pert HighScore Plus 3.0 soft-
h and pre-pyrolysed at 600°C for 30 min in flowing N2. ware (PANalytical, Inc., Westborough, MA).
Finally, the heat treated powder mixtures A and B were Vickers hardness and indentation fracture resistance
separately ball milled in Si3N4 milling container with were measured using Leco hardness tester (LV-100, Leco
Si3N4 balls. Co., St. Joseph, MI) by indentation method applying a
load of 9.8 N and 98 N, respectively. The indentation
fracture resistance was calculated according to Shetty’s
Preparation of composites equation [20]:
The starting powders for the preparation of Si3N4- KIC = 0.0889(H · P/4l)0.5 (2)
based composites were composed of 82 wt. % of α-Si3N4
(SN-E10, Ube Ind. Ltd., Japan) and 18 wt. % of sintering where H is the hardness, P is the applied load, and l is
additives (A or B, Table 1). The powder mixtures were the crack length.

Table 1. Composition of preceramic-polymer-based sintering additives.

H44 HTT
Powder polysiloxane polysiloxane γ-Al2O3 a-Si3N4 C Y2O3
mixture (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %)
A 35.7 – 37.1 21.6 1.1 4.4
B – 67.0 33.0 – – –

Ceramics – Silikáty 62 (4) 382-388 (2018) 383

 Vetrecin M., Lenčéš Z., Galusková D., Šajgalík P.

Corrosion experiments under diffractions. The results of quantitative phase analysis

static conditions are listed in Table 3. The main difference is in the content
of α and β-Si3N4, as the O’-SiAlON content was around
The sintered samples were cut and ground to rec- 19 - 24 %. While in sample SA the ratio α/(α+β) Si3N4
tangular bars. Their faces were polished with 3  μm was 69.7 %, in sample SB it was only 34.7 %. The higher
diamond paste and the edges were chamfered. The bars β-Si3N4 content in sample SB is caused by the higher
were ultrasonically cleaned in acetone for 15 min, rinsed sintering temperature (1700°C), longer dwell time
in distilled water and dried in vacuum drier at 80°C for (30  min) and “nitrogen-rich” polysilazane-based sin-
12 h. tering aid. All these parameters enhance the α → β-Si3N4
As the reference medium deionized water was used phase transformation. The size of α-Si3N4 grains in
(conductivity 25 ± 5 × 10-4 S·m-1 prepared in the reverse sample SA was approximately 0.3  μm and in sample
osmosis purification system (CHEZAR, Bratislava, SB their size was a little bit smaller, 0.1 - 0.2  μm
Slovak Republic). The bars were placed in teflon-lined (more etched grains are α-Si3N4 in the microstructures
pressure corrosion reactors with the inside volume in Figure  1). The O’-SiAlON phase is homogeneously
26 cm3 filled with corrosion liquid of pH 7.4 and heated distributed on the grain boundaries and in triple junctions
in laboratory drying oven. The ratio between the sample (unetched areas in Figures 1a, b). There is a remarkable
surface and the volume of corrosive liquid (S/V) was held difference in the grain size of β-Si3N4 due to the higher
constant at 0.17 ± 0.05 × 10-3 cm-1. The corrosion tests sintering temperature and longer holding time applied
were carried out at 250°C (pressure cca 3.9  MPa) for during the sintering of sample SB. The needle-like
100 hours. The weight of bars and pH value of corrosion elongated β-Si3N4 grains are well visible in this sample
medium were measured before and after each corrosion (Figure  1b) having a length of 1 - 2 μm and width of
test. about 0.2 - 0.4 μm.

Table 3. XRD phase composition of sintered samples including

RESULTS AND DISCUSSION the ratio of α and β-Si3N4 phases α/(α+β).
Microstructure and phase α-Si3N4 β-Si3N4 O'-SiAlON α/(α+β)
composition (%) (%) (%) (%)
All samples were densified to nearly full density SA 56.6 24.6 18.8 69.7
with a remaining porosity on the level of 1 - 2 %. Based SB 26.2 49.4 24.3 34.7
on the XRD and SEM analysis (Figure 1) in both SA and
SB samples α-Si3N4, β-Si3N4 and O’-SiAlON (general
formula Si2-xAlxO1+xN2-x, where 0.04 ≤ x ≤ 0.4 [21]) were
detected as the major phases. The X-ray diffraction data Properties of sintered samples
were evaluated by Rietveld refinement using the X’Pert The sintered samples were nearly fully dense with
HighScore Plus 3.0 software. The crystallographic infor- a remaining porosity of 1 - 2 %. The Vickers hardness
mation file (CIF) of Si1.84Al0.16O1.16N1.84 phase was used was rather high for the prepared Si3N4-based materials,
for O’-SiAlON, i.e. with x = 0.16 in a general formula Si2- close to 19  GPa (Table 4). The hardness of α-Si3N4
xAlxO1+xN2-x, as this phase fitted the best to the obtained

a) SA b) BA
Figure 1. SEM micrographs of the plasma-etched cross-sections of sintered samples SA (a) and SB (b).

384 Ceramics – Silikáty 62 (4) 382-388 (2018)

 Hydrothermal corrosion resistance of silicon nitride with O'-SiAlON grain boundary phase

(HV ≈ 20 - 21 GPa) and O’-SiAlON (HV ≈ 16 - 17 GPa) that the amorphous SiO2 on the grain boundaries was
is higher compared to β-Si3N4 (HV  ≈  15 - 16  GPa). more readily dissolved into solution than the Si3N4 grains
For that reason the hardness of sample SA is higher, as it and the aqueous corrosion of Si3N4 was categorized as
contains in total larger amount of these harder phases (cf. intergranular corrosion. In our earlier work we have
Table 3). Surprisingly, the indentation fracture resistance observed a lower corrosion rate for dense Si3N4 with
of sample SB is slightly lower compared to sample SA, 5  wt.  % Y2O3 sintering additive and the weight loss
although it contains larger amount of β-Si3N4 with an was 1.0 ± 0.2 mg·cm-2 after 100 hours of hydrothermal
elongated shape of grains (Figure 1b). Slight decrease of corrosion at 290°C [15]. It seems that amorphous silica
fracture resistance might be due to the larger content of was the weakest compound in the above mentioned
brittle O’-SiAlON phase (24.3 %). hydrothermal corrosion tests of Si3N4. The solubility of
SiO2 in water is temperature and pressure dependent and
Table 4. Density (ρ), Vickers hardness (HV) and indentation it is higher for amorphous silica (a-SiO2) compared to
fracture resistance (KIC) of samples SA and SB. crystalline phase. The solubility of a-SiO2  at 97°C and
340 °C is 415 mg·l-1 and 1660 mg∙l-1, respectively [25].
ρ HV KIC
amples
S Considering the linear relationship in the dependence of
(g·cm-3) (GPa) (MPa·m1/2)
log of dissolution rate vs. 1/T, the estimated solubility of
SA 3.11 19.0 ± 0.1 5.07 ± 0.12 a-SiO2 at 250°C is about 1150 mg·l-1. Perera et al. [26]
SB 3.09 18.4 ± 0.6 4.74 ± 0.15 showed that during the hydrothermal corrosion tests of
silicate glasses water penetrates into the surface layers of
the Si−O lattice and reacts with Si−O bonds:
Properties after hydrothermal Si−O−Si + H2O = SiOH + HOSi (3)
corrosion
These bond-breaking reactions destroy the structure
Both samples SA and SB exhibited a good hydro- and the silicate islands dissolve in water and form ortho-
thermal corrosion resistance. The measured weight silicic acid according to reaction:
loss in sample SA after the hydrothermal corrosion test
SiO2 + 2H2O ↔ H4SiO4 ↔ H3SiO4– +
at 250°C for 100  hours was 0.96  wt. %. In sample SB (4)
+ H+ ↔ H2SiO42- + 2H+
the weight loss was higher, 1.32  wt. % (Table 5). The
pH value of corrosion media changed from neutral to Such a corrosion could take part in a certain extent
also in our samples, especially in sample SA with higher
Table 5. The results of hydrothermal corrosion tests of samples oxygen content. However, reaction (4) decreases the pH
SA and SB at 200°C for 100 hours. of corrosion solution and we have observed an increase
of pH to 8 and 8.5 for sample SA and SB, respectively.
Δm pH Δm/A rate
amples
S
(wt. %) (GPa) (mg·cm-2) (mg·m-2·h-1) The pH value can increase by the dissolution of Si3N4
in water yielding ammonia according to reaction (1), or
SA -0.96 8.0 2.05 205.5 summarized reactions (1) and (4) [27]:
SB -1.32 8.5 2.33 233.4
Si3N4 + 12H2O = 3Si(OH)4 + 4NH3 (5)
alkaline after the corrosion test, concretely to 8.0 in Ammonia is a weak base highly soluble in water and
sample SA and 8.5 in sample SB. increases the pH of eluate. This might be a reason, why
There are several factors which could cause the the pH value of the corrosion medium of sample SB was
differences in corrosion rate of samples SA and SB. higher. While sample SA contained polysiloxane-based
The first is the phase composition, especially the much (Si–C–O) precursor as sintering additive, in sample SB
higher α-Si3N4 and lower O’-SiAlON content in sample nitrogen/rich polysilazane-based (Si–C–N) precursor
SA compared to sample SB (Table 3). It is known that was used. This resulted in a higher content of β-Si3N4 in
the lattice oxygen content is much lower in β-Si3N4 the sintered product and according to reactions (1) and/
than in α-Si3N4 [22]. Although it is not necessary that or (5) more ammonia formed and dissolved in subcritical
α-Si3N4 contain oxygen to stabilize its structure, it can water and increased the pH value of corrosion medium.
accommodate a considerable amount of oxygen [22]. It Although the hydrothermal corrosion of both samples
was found that at 1400°C ca. 0.8 ± 0.2 wt. % oxygen can SA and SB was low, the weight loss of sample SB was
dissolve in α-Si3N4 [23]. The highest oxygen solubility approximately by 38 % higher than in sample SA. The
measured in β-Si3N4 single crystal is 0.26 wt.  % [24]. higher weight loss and higher pH value of corrosion
Oda at al. have investigated the hydrothermal corrosion medium in the case of sample SB gives a hints that
of pure, hot isostatically pressed Si3N4 (containing reactions (1) and (5) prevail during the hydrothermal
1.4 wt. % O as an impurity) and observed a weight loss corrosion of Si3N4-based samples in subcritical water.
of 9 - 12 mg·cm-2 after the corrosion test at 300°C and The SEM study of the corroded samples shows that
pressure 8.6 MPa for 96 hours [7]. They have observed in sample SA very fine, almost continuous SiO2 corro-
Ceramics – Silikáty 62 (4) 382-388 (2018) 385
 Vetrecin M., Lenčéš Z., Galusková D., Šajgalík P.

sion layer was formed (Figure 2), which slows down the by Nickel et al. [30] was in the range of 190 ± 70 mg·m-2·h-1
dissolution of the sample. In sample SB the corrosion and that of dense Si3N4 with 5  wt.  % Y2O3 sintering
layer consisted of whisker-like grains, copying the additive measured at 290°C in our earlier work from
structure of original elongated β-Si3N4 grains (Figure 3). the leached amount of nitrogen was 210 ± 2 mg·m-2·h-1
In this case the corrosion layer was not compact and [15]. The corrosion rate of samples SA and SB in this
did not separate the sample surface from the corrosion work at 250°C was 206  mg·m-2·h-1 and 233 mg·m-2·h-1
media. The solubility of SiO2 is much lower in neutral (Table 5), respectively. Although the listed corrosion
and in acidic solutions than in basic solutions [28]. rates are similar, the values cannot be compared due
In the case of sample SB the pH value of eluate was to the different testing temperatures and also due to the
higher (8.5) and the SiO2 passivating layer did not form different ratio of the sample surface (S) to the volume of
so effectively than in sample SA with lower pH value corrosion media (V). If we compare only dense Si3N4-
(8.0). The lower weight loss during the corrosion tests of based samples, then in the work of Galuskova et al.
sample SA might be influenced also by the use of Y2O3 [15] the ratio S/V was 0.7, while in this work due to the
sintering aid, which increases the corrosion resistance of smaller size of tested samples the ratio was lower, 0.17.
Si3N4 under hydrothermal conditions [29]. Yuan et al. [31] have studied the influence of S/V ratio
The corrosion rate of Si3N4 powder (grade LC 12N, on the hydrothermal corrosion of SiCN-based ceramic
s.s.a. = 17 m2·g-1, H.C. Stack) in water at 300°C determined composites and reported that with decreasing S/V ratio
the weight loss increased. Therefore, higher weight loss
is expected for samples SA and SB at 290°C with S/V
ratio 0.17 compared to the corrosion rate of samples with
S/V ratio 0.7, as their corrosion rate was similar to these
samples already at 250°C.
Finally it can be concluded that both samples SA
and SB composed of α-Si3N4, β-Si3N4 and O’-SiAlON
phases have a good corrosion resistance in subcritical
water at 250°C.

CONCLUSIONS

Dense Si3N4/O’-SiAlON-based composites were

prepared by hot pressing of the mixture of Si3N4 matrix
and two different SiAlOCN-based polymer-derived
ceramic sintering aids. The first type of sintering aid
Figure 2. SEM analysis of SA after corrosion test.
was on the base of polysiloxane containing amorphous
Si3N4, γ-Al2O3 and Y2O3 nanopowders (sample SA),
the second one on the base of polysilazane and γ-Al2O3
(sample SB). In both sintered samples except of α-Si3N4
and β-Si3N4 also O’-SiAlON with a chemical formula
Si1.84Al0.16O1.16N1.84 was identified, but in different
proportions.
The hydrothermal corrosion tests in subcritical
water at 250°C for 100 h showed a different corrosion rate
for the two composites. Although the weight losses were
rather low, 0.96 wt. % for sample SA and 1.32 wt. % for
sample SB, the hydrothermal corrosion of later sample
was higher by 38 %. The corrosion rate of samples SA
and SB at 250°C was 206 mg·m-2·h-1 and 233 mg·m-2·h-1,
respectively.The higher corrosion rate of sample SB
prepared with polysilazane-based sintering aid is most
probably due to the hydrothermal dissolution of Si3N4
grains producing ammonia, as the pH value of eluate
of this sample was higher, 8.5 compared to pH  =  8.0
determined for sample SA. In sample SA a continuous
SiO2-based passivating layer was formed, while in
sample SB the corrosion layer was discontinuous and
Figure 3. SEM analysis of sample SB after corrosion test. the corrosion medium could attack the Si3N4 grains. As
386 Ceramics – Silikáty 62 (4) 382-388 (2018)
 Hydrothermal corrosion resistance of silicon nitride with O'-SiAlON grain boundary phase

the corrosion solution was more basic in sample SB, the 1 N H2SO4. Journal of the European Ceramic Society,
SiO2 passivating layer did not form so effectively, or 26(16), 3909–3917. doi: 10.1016/J.JEURCERAMSOC.
dissolved faster than in sample SA. The higher corrosion 2005.12.001.
13. Blugan G., Wittig D., Kuebler J. (2009): Oxidation and
resistance of sample SA was partly influenced/improved
corrosion of silicon nitride ceramics with different sintering
also by using Y2O3 sintering additive, which formed a additives at 1200 and 1500 °C in air, water vapour, SO2
rather stable Y2SiO5 phase. and HCl environments – A comparative study. Corrosion
Science, 51(3), 547–555. doi: 10.1016/J.CORSCI.2008.
12.014.
Acknowledgments 14. Galusková D., Kašiarová M., Hnatko M., Galusek D., Dusza
J., Šajgalík P. (2014): Hydrothermal corrosion and flexural
This work was supported by Slovak Grant Agencies strength of Si3N4-based ceramics. Corrosion Science, 85,
94–100. doi: 10.1016/j.corsci.2014.04.005.
APVV-14-0385 and VEGA 2/0164/18.
15. Galusková D., Hnatko M., Galusek D., Šajgalík P. (2011):
Corrosion of structural ceramics under subcritical conditions
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