Ceramics International 44 (2018) 11048–11059

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Ceramics International
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Liquid phase sintering and characterization of SiC ceramics T

⁎
A.C. Santos , S. Ribeiro
Engineering School of Lorena (EEL), University of São Paulo (USP), Pólo Urbo Industrial, Gleba AI6, CP 116, 12608-970 Lorena, SP, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: The present study focuses on the sintering of silicon carbide-based ceramics (SiC) by liquid phase sintering (LPS)
B. Microstructure-final followed by characterization of the produced ceramics. AlN/Re2O3 mixtures were used as additives in the LPS
C. Toughness process. In the first step, the LPS-SiC materials were produced in a graphite resistance furnace in the form of discs
Flexural strength at different temperatures. The conditions with the best results regarding real density and relative density were
Weibull module
taken as reference for sintering in the form of prismatic bars. In the second step, these samples were evaluated
D. SiC
Liquid phase sintering
regarding fracture toughness (KIC), by the Single Edge V Notch Beam – SEVNB – method, and flexural strength.
KIC behavior was evaluated according to the depth and curvature radius of the notches. Reliable KIC values were
presented when the ceramic displayed a small curvature radius at the notch tip. When the radius was large, it did
not maintain the square root singularity of the notch tip. Tests were carried out to determine KIC values in
atmospheric air and water. KIC results were lower in water than air, with a decrease ranging between 2.56% and
11.26%. The observations indicated a direct grain size correlation between KIC values and fracture strength of
the SiC ceramics.

1. Introduction
Silicon carbide (SiC) has been recognized as an attractive material
for applications in new technologies that require high performance in
aggressive environments, such as the aerospace, aeronautics, biome-
dical, automotive and mechanical industries. However, its use in
structural applications is often restricted by fluctuations in mechanical
resistance and susceptibility to fracture, thereby limiting applications
when service-induced surface cracks or defects are generated in the
silicon carbide [1–5].
One of the ways to minimize this problem is by controlling the
processing steps of the ceramic materials, in order to obtain ceramics
with minimum impurities and extrinsic defects. The adopted processing
parameters, such as the type and amount of additives, temperature,
time and sintering method also exert great influence on ceramic quality.
For example, the presence of a liquid phase can accelerate the sintering
process, allowing temperature reductions, as well as decreasing the
time required for effective material densification [6]. These precautions
contribute to an appropriate ceramic microstructure, in which tough-
ening mechanisms absorb energy and hinder or even prevent crack
propagation and extend ceramic shelf life [7–14].
Since SiC-based ceramics are difficult to sinter via solid phase, it is
imperative to use substances that promote the formation of an optimum
amount of liquid phase in the microstructure at relatively low tem-
peratures. This condition improves SiC particle flow, due to the fact that
the liquid reduces friction among the particles and introduces capillary
forces, allowing the dissolution of sharp edges, the rapid rearrangement
of the solid particles and increases in the sintering rate, thus resulting in
shrinkage, densification, phase transformation, grain growth and better
final properties [15–18].
In a previous study, the contact angles of Dy2O3/AlN and Yb2O3/
AlN mixtures on a SiC substrate exhibited low final values, lower than
10°, i.e. conditions that guarantee wetting and spontaneous liquid
spreading, consequently allowing these mixtures to be applied as effi-
cient SiC liquid phase sintering additives [19]. A peculiar characteristic
occurs regarding the use of AlN as a sintering additive together with
SiC, since there is a similarity in the crystalline structure of both
compounds, since both have hexagonal structures and analogous net-
work parameters. Although SiC and AlN have strong covalent bonds,
their crystalline structure similarity can form a solid solution over a
wide range of compositions and temperatures. The formation of a so-
lution between SiC and AlN contributes to decrease their bonding en-
ergies, promoting the displacement and migration of the Si, C, Al and N
atoms in the lattice and the improvement of the sintering properties of
these materials [20–22].
Another important feature in SiC sintering is the use of a powder
bed – a mixture of powders used to cover the samples and maintain the
partial pressure equilibrium of the compounds – since it inhibits vola-
tilization, reduces mass loss and maintains a uniform microstructure. In
addition, studies have demonstrated that sintered samples with

⁎
Corresponding author.
E-mail address: alinecorecha@yahoo.com.br (A.C. Santos).

https://doi.org/10.1016/j.ceramint.2018.03.083
Received 4 January 2018; Received in revised form 22 February 2018; Accepted 11 March 2018
Available online 15 March 2018
0272-8842/ © 2018 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
A.C. Santos, S. Ribeiro
protective bedding display higher relative density and greater flexural
strength than those without protective bedding [23].
Microstructural and densification developments that occur during
isothermal sintering include increase in grain size and changes in pore
shape, size and number, usually leading to decreases in porosity. Grain
growth is the process by which the average grain size increases con-
tinuously during heat treatment, with the decrease and disappearance
of some smaller grains. This process involves a difference in energy
among the small and larger grains, resulting in the reduction of the
grain boundary area and the total boundary energy. The total grain
growth process associated with this free energy difference across a
curved grain boundary and the diffusion jump frequency of the atoms
across the grain boundary indicates that the grain growth rate increases
exponentially with temperature, a well known parameter in the sin-
tering process [24,25].
In fracture mechanics, resistance is defined by the size of defects
such as pores, inclusions and microcracks, as well as by fracture
toughness. However, with regard to defects, there are limitations in the
studies due to the nature of the ceramic microstructure, where a grain
boundary may be responsible for a fragile fracture, while the service-
induced surface defects generated also reduce material resistance [2,3].
The fracture toughness test (KIC) allows understanding the behavior of
materials containing cracks or other small internal defects, by analyzing
the maximum stress that a material can withstand in the presence of
such defects [26]. Therefore, it can be stated that fracture toughness is
the resistance of the material to unstable crack propagation.
Although it is a very important property in ceramic materials,
fracture toughness is a discussion topic, since there are several methods
and equations available for determining fracture toughness. The SEVNB
(Single Edge V-Notch Beam) method consists of bending fracture
toughness measurements, in which introducing the defect in the sample
is very important and requires a precise technique. The tests comply
with the method execution guidelines established by the ISO 23146:
2008 standard and are easily applied in practice for most dense ceramic
materials at different temperatures and environments, while also al-
lowing less dispersed data than other methods, independently of the
type of bending [27,28]. This independence regarding the type of ap-
plied load, either at four or three point bending, is due to the fact that
there is no need for a high precision position of the sample in the load
support, since, regardless of the area subject to mechanical stress, the
produced notch directs the crack propagation [29].
Concerning several materials in the form of notched bars, it has
been observed that the extent of the notch, and particularly the notch
radius, affect the measured KIC values [30–34]. KIC values of covalent
ceramics, such as silicon carbide and silicon nitride, decrease with a
radius reduction of approximately 30 µm, although there is still high
dispersion of the values. Thus, it is suggested that the radii should be
smaller than 20 µm, as dispersion becomes smaller. Other studies,
however, support the idea that the radii should be at most between 10
and 15 µm [29,35,36].
The major difficulty in applying this method is with regard to pro-
ducing the thin "V" notch. However, a machine with alternating rota-
tional movement (pendulum movements), coupled to a micrometer and
a razor blade of adequate thickness has been proposed, which deepens
the notch and refines it when using diamond paste [37]. The photo-
graphs displayed in Fig. 1 illustrate details of the notch tip of a silicon
carbide sample. Fig. 1(a) displays the height of the pre-notch b and the
radius size r obtained with the razor blade and 6 µm diamond paste. It is
possible to create a thinner "V" notch and consequently decrease the
radius size r when the paste granulometry is decreased, as displayed in
Fig. 1(b) and (c). Usually, a square notch is produced with a razor blade
and 6 µm diamond paste and finished with a 1 µm paste or one with
finer granulometry [38].
Work environments generally evaluated in crack propagation stu-
dies as a function of the intensity factor (K) for SiC ceramics are air
heated or air and water at room temperature [1,39,40]. Mechanisms
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Ceramics International 44 (2018) 11048–11059
b
S
r = S/2
Fig. 1. Photographs produced by stereoscopic magnification of the notches
obtained with 6, 1 and 0.25 µm pastes, indicating sequential thinning as a
function of paste granulometry [37].
that occur before reaching the critical intensity factor (Kc) may promote
their effect on the final fracture process.
A mechanism with justified crack growth behavior has included
chemical reactions kinetics, which is known as stress corrosion
cracking, where the bonds in the system governed by dissociative re-
actions occur with the mixing of the surrounding atmosphere [41–43].
As a result, hydration stresses cause the increase of normal stress on the
crack surface, leading to K increases and crack propagation with hy-
drolysis progress, observed as surface energy increases [44,45].
When evaluating the flexural strength of a ceramic, the method
consists in applying a constant loading rate at the center of a specific
specimen supported on two points that undergoes slight flexion fol-
lowed by a catastrophic failure. Thus, the flexural strength can be de-
fined as the maximum tensile stress or compression in the external fi-
bers of the specimen volume (V) in the flexural test. An important
consequence of the theory that fragile rupture is initiated with Griffith
failures is that the fracture strength of a brittle solid is statistical in
nature, with the best-known and applied material resistance developed
by Ernst W. Weibull in 1939 [46,47]. Mathematically, to estimate the
Weibull (m) parameters of the material, a regression between the cu-
mulative probability (P) and the experimental values of the tensions
obtained experimentally that caused the material failure is necessary.
To calculate the probability of failure, it is necessary to first order the
experimental data with increasing values and then apply an estimator.
The higher the m value, the more reliable the material. Consequently,
the more m approaches zero, P(σ,V) approaches the unit so that the
probability of failure is equal for all tension values (σ > σc). When m
tends to infinity, P(σ,V) is zero for all σ values smaller than σ0 (σ < σc).
For modest resistances in which commercial products fail the most,
statistical theoretical predictions are generally confirmed by experi-
mental data [40,48,49].
In this context, the main objective of this study was to investigate
process parameter influences, such as sintering temperature and types
of additives, on liquid phase sintered SiC ceramics properties, as well as
to evaluate the fracture toughness of SiC samples after shaving with a
razor blade and 3-point bending resistance.
2. Material and methods
A 90% SiC volume in the blend was used, while 10% volumes of
Dy2O3/AlN or Yb2O3/AlN were used as additives. The weight compo-
sition of each mixture is displayed in Table 1 and represents the 10%
point below the eutectic point of the phase diagram taken as reference
[19]. The SiC powders and additives were blended for 6 h in an attrition
mill with a water-cooled nylon jug using silicon carbide balls and iso-
propyl alcohol as the carrier. The suspensions were dried in a rotary
evaporator at 90 °C, and, subsequently, the blend powders were passed
through an ASTM 20 sieve and pressed into 15 mm diameter discs and
in the form of prismatic bars (65 × 5 mm2). A double-acting uniaxial
piston pressing under 60 MPa was applied using a Marconi MA098/C
hydraulic press and then a Paul Weber KIP 100E isostatic press at
300 MPa.
A.C. Santos, S. Ribeiro
Table 1
Weight (g) and percentage composition (%) of the AlN-Re2O-SiC mixtures to prepare the samples to be sintered and the weight composition (g) of the powder bed
used for the compact sintering.
Codes AlN-Re2O-SiC
AlN Dy2O3 Yb2O3 SiC
NDySiC 3.15 25.36 – 120
2.12% 17.07% 80.81%
NYbSiC 3.42 – 29.14 120
2.24% 19.10% 78.66%
Sintering was performed using a 1000-4560-FP20ASTRO Thermal
Technology Inc. oven. The samples were placed in a graphite crucible
and surrounded by a powder bed (see Table 1). Argon atmosphere at
1 atm and sintering temperatures of 1850 °C, 1900 °C, 1950 °C and
2000 °C were applied. To evaluate the mechanical properties of the
ceramics by the flexural test, the prismatic bars were sintered at the
temperatures in which the discs presented higher real density and re-
lative density values.
The furnace heating rate was of 24 °C/min up to 1000 °C under
vacuum and of 5 °C/min above 1000 °C under an argon atmosphere
until reaching the highest temperature: 1850 °C, 1900 °C, 1950 °C or
2000 °C, with a 2 h isotherm. Cooling was performed at room tem-
perature at a rate of 25 °C/min.
To reach the dimensions of 4 mm in height, 3 mm in width and
50 mm in length, in order to meet the ISO 23146: 2008 standard [28]
for determining fracture toughness, the sintered samples were first
glued with thermal glue on a steel plate and rectified in a FERDIMAT
TA42 tangential rectifier using diamond D121 and D91 grinding wheels
(Winter Abrasives).
The apparent density was determined according to Eq. (1) using a
pachymeter, and the real density was determined by the Helium gas
pycnometry method in an Ultrapyc 1200e apparatus. Relative density
was calculated by the ratio between the apparent density and the real
density of the sintered samples. The shrinkage values of the materials
after sintering were also obtained with a digital pachymeter.
ρ = wsample / Vsample
where: w is weight and V is volume.
The crystalline phases were analyzed by X-ray diffraction by the
powder method. A Panalytical Empyrean diffractometer with Cu Kα
radiation, nickel filter, 40 kV voltage and 35 mA current was used. Peak
indexing was obtained by comparison to microchips from the Pearsons
Crystal Data database by the PANalytical software (X′Pert HighScore
Plus) [50,51].
For the microstructure analysis, the rectified samples were
sanded and polished on a Jean Wirtz PHOENIX 4000 Polishing System
with 70, 45, 30, 15 µm diamond sand and 15, 9, 6, 3, 1 µm polishing
cloths/suspensions. For better disclosure of the polished discs grains,
the material was attacked with sodium tetraborate decahydrate
(B4Na2O7·10H2O) in alumina crucibles for 5 min at 770 °C, with heating
and cooling rates of 2 °C/min, in an Inti oven. The samples were then
covered with gold film (50 mA current, 60 s) in an MED 020 metallizer
and analyzed under a 1450VP LEO microscope, in the secondary elec-
tron mode, with a 20 kV acceleration voltage and 3.2 mA tungsten fi-
lament current. For the fracture surface analysis, the fracture char-
acteristic was maintained.
The toughening tests obeyed the method execution guidelines es-
tablished by the ISO 23146: 2008 standard. To this end, a sharp notch
was introduced, simulating the critical defect in the sample, using the
"V" notched bar technique.
Each group of seven rectified and measured samples (4 × 3 ×
50 mm3) were glued, side by side, to a small steel plate and notched at
the center of the length measurement (L) with the razor blade attached
to a special machine with eccentric movements, with a 3 N load, using
Ceramics International 44 (2018) 11048–11059
Powder bed
Graphite AlN Dy2O3 Yb2O3 SiC
5 1.57 12.68 – 60
5 1.71 – 14.57 60
6 µm grain size Arotec diamond paste. Finally, to promote the thinning
of the "V" groove, the other side of the same blade was used, but ap-
plying 1 µm diamond paste [37].
The ISO 23146:2008 standard determines that the final depth of the
notch should be between 0.8 and 1.2 mm. Based on this, this study was
divided into two parts in order to evaluate the effect of depth size on
fracture toughness. The first part consisted in obtaining notches with
depths ranging from 0.8 mm to 1.2 mm, as determined by the
ISO 23146:2008 standard. These samples with variable notches were
tested in air, according to the standard, as well as in potable water. The
choice to evaluate the fracture toughness of ceramics in water is due to
the fact that SiC ceramics become potential candidates for applications
in which they are subjected to long periods of stress, generating mi-
crocracks, and because they are also applied in humid environments,
such as orthopedic implants, mechanical seals in hydraulic systems and
tubes applied in incinerators for energy production. The second part of
the study consisted of evaluating the effect of notches with the specific
depths of 0.8 mm, 1.0 mm and 1.2 mm on fracture toughness in air.
These groups were named “notched specimens”.
The influence of notch width on ceramic fracture toughness was also
evaluated. In order to obtain the radius of each notch curvature, a
HITACHI TM – 3000 bench scanning electron microscope was used to
capture images of the notch tip of each notched bar. The process follow-
up to obtain the desired notch depths was performed on a Quimis ste-
reoscopic microscope coupled to a KC-512D&N camera. The notched
samples were then submitted to the 4-point flexural test using a MTS
(1) 64205 A-01 Bend Fixture devices with 40- to 20-mm roller spacings,
fitted in a universal EMIC DL-3000 test machine with a load cell of
5 kN. The bending test in potable water was performed at room tem-
perature (25 °C) using the same MTS and load cell devices as those used
in the atmospheric air test, however, inserted in a machined steel vessel
containing the water and aligned within the vessel using rigid foam.
The specimens were centralized with the notch facing the traction side
and the tests were controlled by the displacement of the actuator at a
speed of 0.5 mm/min.
Table 2 shows the physical-chemical composition of the water used
in the bending test.
The KIC, SEVNB calculations were performed according to the fol-
lowing equations [28]:
KIC, SEVNB = [F /(B √W )]. [(S1 − S2)/ W ]. [(3√a)/(2(1 − α )3/2)]. Y * (2)
α = a/W (3)
Y * = 1, 9887 − 1, 326α − [((3, 49 − 0, 68α + 1, 35α 2) α (1 − α ))
/(1 + α )2] (4)
where: KIC, SEVNB is the fracture toughness in mode I, F is the fracture
load at the rupture moment of the notched and flexed bar at 4 points, B
is the thickness of the sample, W is the height of the sample, S1 is the
distance of the two most distant rollers, S2 is the distance of the two
nearest rollers, α is the ratio of the size (depth) of the sample notch to
the height of the sample and Y is the form factor.
To determine flexural strength, the samples were subjected to the
flexural test using MTS 642.05 A-01 Bend Fixture devices, fitted in an
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Table 2 (a)
Composition of the potable water used in the flexural tests. 20
Parameters Value Unit Reference Method 100

Antimony 0.001 mg/L VIS 18

Relative Density (%)

Aluminum < 0.118 mg/L VIS 90
Ammonia (as NH3) 0.3 mg/L VIS

Shrinkage (%)
Arsenic < 0.0002 mg/L VIS 16
Barium 0.02 mg/L VIS 80
Cadmium < 0.004 mg/L VIS
Lead < 0.009 mg/L VIS
14
Cinanide < 0.005 mg/L VIS 70 NDySiC
Chloride 10 mg/L Titulometry
Copper < 0.010 mg/L VIS relative density
Apparent color 115 uH VIS 60 12
shrinkage
Chromium < 0.023 mg/L VIS
Total hardness 20 mg/L Titulometry
Iron 0.19 mg/L VIS 50 10
Fluoride < 0.170 mg/L VIS 1800 1850 1900 1950 2000 2050
Manganese 0.03 mg/L VIS Sintering Temperature (°C)
Mercury < 0.0002 mg/L VIS
Nickel < 0.042 mg/L VIS
Nitrate (as N) 1 mg/L VIS (b)
Nitrite (as N) 0.01 mg/L VIS 20
pH (potable) 7.50 – Potentiometry 100
Selenium < 0.0002 mg/L VIS
Sodium 10.27 mg/L VIS 18
Total dissolved solids 480 mg/L Gravimetry 90
Relative Density (%)
Sulphate 15 mg/L VIS

Shrinkage (%)
Hydrogen sulphide < 0.05 mg/L VIS 16
Turbidity 21.8 uT Turbidimetry 80
Uranium < 0.001 mg/L Ion chromatography
Zinc 0.06 mg/L VIS
14
70
VIS = visible spectrophotometry. NYbSiC
relative density 12
60
EMIC DL-3000 universal testing machine with a 5 kN load cell. The shrinkage
three-point configuration was adopted and the calculation was per-
formed according to Eq. (5). The rectified samples on the four surfaces 50 10
were sanded with diamond sand and suspensions of up to 6 µm in order 1800 1850 1900 1950 2000 2050
to remove stress concentrator defects and possible defects caused by the Sintering Temperature (°C)
boundary section [52].
Fig. 2. Effect of sintering temperature on the density and retraction of SiC
S3 = 3PL/2bd 2 (5) sintered with (a) AlN + Dy2O3 and (b) AlN + Yb2O3.

where: S3 is the three-point flexural strength in MPa, P is the fracture

load in MN at the flexion moment of the bar rupture, L is the distance
between the two rollers for the three-point bending, b is the sample
width in meters, d is the sample thickness in meters.
Once considerable variation of the tensile strength values of the
ceramic materials occurs, the statistical treatment is performed using
the Weibull statistic. For data treatment, the set of samples with con-
stant volume (V/V0 = 1), the two-parameter method and an estimator
to express the probability of failure, equal to P = (i–0.5)/N, with linear
adjustment of the points [12,48] were applied.
3. Results and discussion
3.1. Densification, phases and microstructures
Fig. 2 shows the effect of sintering temperature on the relative
density and shrinkage of the materials. The relative density increased
with increasing sintering temperature. The SiC with the Dy2O3/AlN
additive displayed a 3.2% increase in density, reaching an adequate
value of 98.6% at both 1950 °C and 2000 °C. When Yb2O3/AlN was
added, densification increased by 7.9%, with a 91.6% increase at
1850 °C to 99.5% at 2000 °C, demonstrating that the NYbSiC2000
ceramic showed a lower degree of porosity.
Ceramic densification was assisted by the formation of the liquid
phase obtained from the reaction of the oxides/AlN during the tem-
perature increase that involved the SiC and allowed for greater mi-
crostructural packing. The hypothesis that the reaction of the additives
occurred with SiO2, always present on the SiC surface, leading to the
formation of a liquid phase when forming a molten silicate, is also valid
for one of the densification reasons [16,17]. NDySiC ceramics shrinkage
between 16.2% and 17.2%, while NYbSiC ranged between 14.5% and
18.8%.
The conditions under which the highest values of real density
(NDySiC1900 and NYbSiC1850) and relative density (NDySiC1950 and
NYbSiC2000) were obtained were adopted for SiC sintering in the form
of prismatic bars and subsequent property evaluations by flexion.
The diffractograms of SiC containing additives Dy2O3/AlN and
Yb2O3/AlN are shown in Fig. 3(a) and (b), respectively. NDySiC pre-
sents peaks that are characteristic of the secondary Dy4Al2O9 and
Dy3Al5O12 phases at the four sintering temperatures. At 1900 °C, the
Dy4Al2O9 phase peaks are less intense at the 2θ positions of 29.29° and
30.58°, suggesting that a phase transformation occurred, while at
27.93° the characteristic Dy3Al5O12 peak phase became more intense.
The two phases were consumed at 1950 °C, with the Dy4Al2O9 peaks
remaining at 11.70° and 52.74°, referring to the overlapping peaks of
the two phases. At 2000 °C, other Dy4Al2O9 peaks ceased to exist at
18.77°, 26.67°, 29.29° 30.58° and 49.51°. In addition, peaks became
more intense at 34.64°, 43.06° and 48.09° for NDySiC2000, character-
istic of the DyAlO3 phase. No characteristic AlN peaks were detected,
since the mass fraction was very small, of less than 3%. However, it is
probable that a trace of AlN is still present up to 1900 °C, since the
phase diagram taken as reference shows the formation of liquid phase
and the remaining AlN phase between 1850 °C and 1900 °C at the

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A.C. Santos, S. Ribeiro Ceramics International 44 (2018) 11048–11059

(a) (b)
10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
α α
β β SiC β β SiC
100 NDySiC1850 α SiC
100 NYbSiC1850 α SiC
* Dy Al O * Yb Al O
Dy Al O Yb Al O

50 α ° DyAlO 50 α
° YbAlO
β β
α α
α β β ** α β β
* α *
* ** ** ** α * *
β * * * * * α β
* * * * α * * * * * *
0 0
α α
100 NDySiC1900 β 100 NYbSiC1900 β

α 50 α
50

Intensity (%)
β α
β α β
Intensity (%)

β β α
α β
* * * *
* ** α * * α * *
* * ** ** * α β * *
* * * * α β
* * * *
0 0
α α
β NYbSiC1950 β
100 NDySiC1950 100

α
50 α
50 β α β
α
β β
α β α β
* α * ** α *
* * ** ** ** * α β * * * α β
* * * * *
0 0
α α
β NYbSiC2000 β
100 NDySiC2000 100

α
β α
50 α 50 β
β α
α β β
α α
*°
α
°* β *° β
°* *
* * °* α * * α β
0 *
*
0
* *
°* *

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80

2θ (°) 2θ (°)
Fig. 3. X-ray diffractograms patterns of sintered SiC with Dy2O3/AlN (a) and Yb2O3/AlN (b) at different sintering temperatures.

chosen study point of this work (10% below the eutectic point), while
there is only formation of liquid and vapor above 1900 °C [18,19].
The peaks for SiC with Yb2O3/AlN, according to the diffractograms
of Fig. 3(b), show very similar behavior to that in the SiC with Dy2O3/
AlN, shown in Fig. 3(a). When sintered at 1850 °C, the material also
presented peaks characteristic of the Yb4Al2O9 and Yb3Al5O12 phases.
The lowest Yb4Al2O9 peaks occurred at 1900 °C, with the presence of
other peaks concerning the formation of Yb3Al5O12 at 17.32°, 33.64°
and 40.51°. The Yb4Al2O9 phase peaks became less intense when the
sintering temperature was increased to 1950 °C, while others ceased to
exist at 11.96°, 50.87°, 53.93° and 61.41°, while Yb3Al5O12, peaks
ceased to exist at 40.45° and 53.93°. The NYbSiC2000 diffractogram
also shows peaks characteristic of the Yb4Al2O9 phase at position 2θ,
similar to those in DyAlO3 displayed in the NDySiC2000 diffractogram.
The following equations suggest the possible formation reactions of
the Re4Al2O9 (6) and (7), Re3Al5O12 (8)–(10) and ReAlO3 (11) phases.
Rare earth oxide (Re2O3) may have reacted with the decomposition
products of aluminum nitride (Al) and of the oxide and/or silica itself
(O) present on the SiC surface [22]. The ReAlO3 phase was probably
formed from the reaction between Re4Al2O9 and Re3Al5O12 [23].
2Re2O3 + 2Al + 3/2O2 → Re4Al2O9
2Al + 3/2O2 → Al2O3 ∴ Al2O3 + 2Re2O3 → Re4Al2O9
3/2Re2O3 + 5Al + 15/2O → Re3Al5O12
5Al + 15/2O → 5/2Al2O3 ∴ 5/2Al2O3 + 3/2Re2O3 → Re3Al5O12
3/4Re4Al2O9 + 7/2Al + 21/4O → Re3Al5O12
Re4Al2O9 + Re3Al5O12 → 7ReAlO3
The intensity of the peaks characteristic of α-SiC became higher
with increasing temperature. The formation of a larger number of α-SiC
hexagonal plates with increasing temperature is confirmed in the mi-
crographs presented in the Fig. 4. This behavior usually contributes to
material tenacification mechanisms.
The Bragg reflections of the more intense peaks, characteristic of SiC
in the 2θ region between 35.4 and 35.8, show a discreet shift to lower
2θ values with increases in sintering temperature, as shown in Fig. 4,
with magnifications of these peaks for (a) NDySiC and (b) NYbSiC. This
displacement may be indicative of the formation of a solid solution
between α-SiC and AlN due to similar network structures [20,21],
causing an increase in the interplanar distance (d) of the crystals and an
increase of the network parameters (a and c), justifying the displace-
ment of the SiC peak in the low angle direction.
Fig. 5 shows the NDySiC (a–d) and NYbSiC (e–h) micrographs sin-
tered at (a and e) 1850 °C, (b and f) 1900 °C, (c and g) 1950 °C and (d
and h) 2000 °C.
All ceramics had pores in their bodies. The B4Na2O7·10H2O attack
eventually dissolved the secondary phase of the surface, facilitating a
certain amount of SiC grain debonding, although the use of sodium
tetraborate decahydrate allowed for a much better visualization of the
grain boundaries of the materials compared to surface sanding and
(6)
polishing with diamond suspensions.
(7) The smaller grains are more spherical due to the dissolution step of
the sintering process, while the larger grains show a slightly elongated
(8) and also irregular shape, in addition to hexagons (indicated by arrows).
The hexagonal plates refer to α-SiC grains, which originated from the
(9) dissolution of β-SiC in the additive and their subsequent precipitation in
the alpha form. These hexagonal plates showed a slightly larger aspect
(10) ratio for NYbSiC than the hexagonal plates in the sintered NDySiC at the
same temperature. These plates are observed at larger numbers in the
(11)
micrographs obtained at 2000 °C.
The growth of activated grains is also observed for a large

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A.C. Santos, S. Ribeiro Ceramics International 44 (2018) 11048–11059

(a) smaller size than NDySiC2000. This difference is due to the relationship
found for the lower viscosity of the ceramics processed with dysprosium
NDySiC 2000°C [19], contributing to the higher grain growth rate whose growth ki-
1950°C netics is controlled by diffusion [25]. NYbSiC2000 displayed larger
100
1900°C pores, but in smaller numbers, as well as hexagonal plates, when
Intensity (%)

1850°C compared to NDySiC2000.

3.2. Mechanical properties: fracture toughness and flexural strength

80
Fracture toughness (KIC) was evaluated as a function of notch depth
in order to verify any difference in KIC values when working with
specific depths −0.8 mm, 1.0 mm and 1.2 mm – in the depth range
required by the ISO 23146:2008 standard.
Since the size of the notch radius affects the KIC values, fracture
60
toughness was also evaluated as a function of the notch tip radius size
35.4 35.6 35.8 for the compositions studied at different temperatures [27,30–32,34].
2θ (°) Fig. 6(a) shows illustrative micrograph obtained by scanning elec-
tron microscope of notche produced with razor blade and diamond
(b) pastes with notch depth ranging from 0.8 mm to 1.2 mm and (b–e)
widening the tip width of some notches.
NYbSiC 2000°C Generally, when obtaining the thin notch at longer times, the dia-
100 1950°C meter of the notch tip tends to increase. This indicates that small
1900°C changes regarding the notching time have a pronounced effect on the
Intensity (%)

1850°C diameter of the notch tip.

80
60
35.4 35.6 35.8
2θ (°)
Fig. 4. Amplification of the most intense SiC peaks in the NDySiC (a) and
NYvSiC (b) X-ray diffractograms.
population of grains, exhibiting growth changes as the sintering tem-
perature increased. Thus, larger grains are noticed for the ceramics
sintered at 2000 °C, due to the growth rate ratio of the grain that in-
creases exponentially with increased temperature [24]. Thus, as the X-
ray diffraction analyses indicate that the phase transformation occurred
and the micrographs demonstrate that grain growth also occurred, the
amount of additives used in the process can be considered satisfactory
[17].
For the NDySiC ceramics, micrographs (a) and (b) indicate that
these ceramic microstructure regions show mean grain diameter of
1.12 ± 0.45 µm and 1.38 ± 0.49 µm respectively, not showing much
difference in porosity. The presence of larger pores and a much larger
increase in grain size in micrograph (c) to 1.60 ± 0.59 µm can be
observed, including growth in hexagon grain nuclei orientation of α-
SiC, as indicated by the arrows. Microstructure (d) indicates larger
pores and remarkable grain growth to 2.14 ± 0.63 µm, when the re-
duction of the grain boundary area is the driving force for grain growth.
The edges of these larger grains are better defined.
Micrographs (e) and (f) for the NYbSiC ceramics also showed si-
milarities with NDySiC, with the formation of smaller and more
equiaxed grains at both 1850 °C (1.22 ± 0.38 µm) and 1900 °C
(1.24 ± 0.39 µm). The sintering temperature of 1950 °C for NYbSiC
allowed grain growth to 1.35 ± 0.40 µm, including growth in the or-
ientation of their nuclei, perpendicular to the basal plane, as displayed
in the upper right corner of the (g) micrograph; albeit to a lesser extent,
with lower porosity and several smaller hexagons regarding NDySiC.
NYbSiC2000 presented grain size of 1.62 ± 0.53 µm, however with
The graphs presented in Fig. 7 demonstrate the influence of the
square root of the curvature radii (r1/2) on KIC for the specific notches
obtained at 0.8 mm, 1.0 mm or 1.2 mm ceramic depth for (a)
NDySiC1900, (b) NDySiC1950, (c) NYbSiC1850 and (d) NYbSiC2000.
NDySiC1900 exhibited linearly distributed KIC values. It is clear that
the material, when notched to obtain a specific depth (0.8, 1.0 or
1.2 mm), showed a variation in the square root size of the radius (r1/2)
from 2.25 to 3.83 µm0.5, while allowing for very small dispersion of the
KIC, of ± 0.04. The lower values of the square root of the radius were
obtained with the 1.2 mm depth notch, due to the fact that a thick notch
produced up to the depth of 1.05 mm was obtained, followed by the
production of the fine notch in only 7 min to quickly reach the depth of
1.2 mm. For NDySiC1950, the 0.8 mm deep notches presented the
smallest r1/2 sizes, between 2.63 and 3.04 µm0.5, while the 1.0 and
1.2 mm deep notches obtained with too much notching time resulted in
much higher square roots of the radius, between 4.38 and 5.12 µm0.5, as
well as higher KIC values.
In Fig. 7(c), regarding NYbSiC1850, KIC was little affected by the
variation in square root size of the radius up to ~ 5 µm0.5, satisfying the
plane deformation condition. Such an effect is probably determined by
the sensitivity of this material to stress concentrations due to micro-
structure differences. As displayed in Fig. 5(e), SiC SFL at 1850 °C
showed a refined microstructure, with smaller grain size but lower
density (see Fig. 2(b)), suggesting the presence of high porosity, justi-
fying the low KIC values. Sintering at 1850 °C also resulted in a low
hardness, 13 MPa material, allowing greater wear of the material re-
garding the blade during notching and consequently, higher initial r0,5
values, varying between 3.5 and 4.6 µm0.5 for the 1.2 mm deep notch.
The SiCYb2000 ceramic was the toughest among the processed cera-
mics, with low deviations for the 1.2 mm deep notches, Fig. 7(d). It is
possible that the formation of hexagonal plates occurred in greater
amounts at 2000 °C and may have contributed, along with larger grain
size, to the delaying crack propagation mechanism.
It is clear from Fig. 7(b) that, when the value of the curvature radius
of the notch tip is very high, the KIC value tends to be overestimated and
is, therefore, less reliable when considering the shelf life of SiC with
sharp defects or with "V" defects introduced during the manufacture of
these components.
This trend has also been observed since the first studies using the
SEVNB method [27,28,30,36], due to the inactivation of the notch base
[32]. The inactivation of the notch tip for larger bending radii is based
on the basic fracture mechanics approach to calculate crack tip stress

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A.C. Santos, S. Ribeiro Ceramics International 44 (2018) 11048–11059

Fig. 5. Secondary electron scanning electron microscopy micrographs of the attacked surface of SiC sintered with Dy2O3 (a–d) and Yb2O3 (e–h) for 2 h at 1850 °C (a
and e), 1900 °C (b and f), 1950 °C (c and g) and 2000 °C (d and h).

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A.C. Santos, S. Ribeiro Ceramics International 44 (2018) 11048–11059

Fig. 6. Micrographs illustrating (a) the depth of the notch, that can range from 0.8 to 1.2 mm, and enlargement of the tip of some notches, with radii of approximately
(b) 2.02 µm1/2, (c) 2.26 µm1/2, (d) 3.21 µm1/2 and (e) 4.90 µm1/2.

considering the crack geometry factors in the sample, whose stress implies a sharper notch tip that will direct the beginning of the crack
concentration is directly proportional to the stress applied by the ma- propagation at that point, requiring less applied load. For larger
chine and the ratio of crack size to radius size at the crack tip. This bending radii, the angle at the crack tip will be less sharp, requiring

(a) (c)
4.5
NDySiC1900 4.5 NYbSiC1850
4.0 4.0
KIC (MPa.m1/2)

3.5 3.5
KIC (MPa.m1/2)

3.0 3.0

2.5 2.5

2.0 2.0
a = 0,8 a = 0,8
1.5 a = 1,0 1.5 a = 1,0
a = 1,2 a = 1,2
1.0 1.0
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4
1/2 0,5 1/2 0,5
r (μm ) r (μm )

(b) (d)
4.5
NDySiC1950 4.5
NYbSiC2000
4.0 4.0
KIC (MPa.m )

3.5
1/2

KIC (MPa.m )

3.5
1/2

3.0 3.0

2.5 2.5

2.0 2.0
a = 0,8 a = 0,8
1.5 a = 1,0 1.5 a = 1,0
a = 1,2 a = 1,2
1.0 1.0
2.5 3.0 3.5 4.0 4.5 5.0 2.0 2.2 2.4 2.6 2.8 3.0
1/2 0,5
1/2
r (μm )
0,5
r (μm )
Fig. 7. Dependence of KIC on r1/2 in atmospheric air, for the specific 0.8 mm, 1.0 mm and 1.2 mm notches of the following samples: (a) NDySiC1900, (b)
NDySiC1950, (c) NYbSiC1850 e (d) NYbSiC2000.

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A.C. Santos, S. Ribeiro Ceramics International 44 (2018) 11048–11059

4.5 4.5
(a) 4.0
NDySiC1900
(e)
4.0
3.5
KIC (MPa.m )

KIC (MPa.m )
1/2 3.5

1/2
3.0
3.0 2.5

2.5 2.0
1.5
2.0
KIC = 3.43 ± 0.32 1.0 KIC = 3.19 ± 0.04
1.5
0.5
NDySiC1900
1.0 0.0
3.5 3.6 3.7 3.8 3.9 4.0 3.4 3.6 3.8 4.0
1/2 0,5
1/2
r (μm )
0,5 r (μm )

4.5 4.5
NDySiC1950 (f)
(b) 4.0
4.0
3.5
KIC (MPa.m )

KIC (MPa.m )
3.5
1/2

1/2
3.0
3.0 2.5

2.5 2.0
1.5
2.0
1.0
KIC = 3.11 ± 0.15 KIC = 2.91 ± 0.10
1.5
0.5
NDySiC1950
1.0 0.0
1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.2 2.4 2.6 2.8
1/2 0,5 1/2 0,5
r (μm ) r (μm )

4.5 4.5
(c) NYbSiC1850 (g)
4.0
4.0
3.5
KIC (MPa.m )
KIC (MPa.m )

1/2

3.5
1/2

3.0
3.0 2.5

2.5 2.0
1.5
2.0
1.0 KIC = 2.66 ± 0.10
1.5 KIC = 2.73 ± 0.19
0.5
NYbSiC1850
1.0 0.0
4.60 4.65 4.70 4.75 4.80 3.8 4.0 4.2 4.4
1/2 0,5 1/2 0,5
r (μm ) r (μm )

4.5 (d) 4.5 NYbSiC2000 (h)

4.0 4.0
3.5
KIC (MPa.m )
KIC (MPa.m )

1/2

3.5
1/2

3.0
3.0 2.5
2.5 2.0
1.5
2.0
KIC = 3.55 ± 0.47 1.0 KIC = 3.15 ± 0.16
1.5
0.5
NYbSiC2000
1.0 0.0
3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 1.6 1.8 2.0 2.2 2.4 2.6 2.8
1/2 0,5 1/2 0,5
r (μm ) r (μm )
1/2
Fig. 8. Dependence of KIC on r in atmospheric air (a–d) and water (e–h), for notches varying between 0.8 and 1.2 mm for samples (a) NDySiC1900, (b)
NDySiC1950, (c) NYbSiC1850 and (d) NYbSiC2000.

11056
A.C. Santos, S. Ribeiro
greater force applied to the crack propagation, thus leading to higher
fracture toughness values.
Taking into account that the actual KIC values obtained experimentally
are within a region with the lowest r1/2 values , the results show that the
most reliable fracture toughness values for the design level obtained for
the processed ceramics are of 2.98 ± 0.04 MPa m1/2 (SiCDy1900),
3.11 ± 0.15 MPa m1/2 (SiCDy1950), 2.58 ± 0.19 MPa m1/2 (SiCYb1850)
and 3.39 ± 0.1 MPa m1/2 (SiCYb2000).
Fig. 8 shows the fracture toughness behavior obtained by the con-
ventional ISO 23146: 2008 methodology, where notches should vary
between 0.8 and 1.2 mm, as a function of the square root of the curvature
radius of the notch tip (KIC X r0,5) of ceramics DySiC1900, NDySiC1950,
NYbSiC1850 and NYbSiC2000, with tests performed in atmospheric air
(star) and potable water (lozenge) for comparison purposes.
In air the ceramic (a) NDySiC1900 presented notches with r1/2 size
varying very little, between 3.71 and 3.78 µm0.5 but with highly dis-
persed KIC values. Regarding (b) NDySiC1950, the r1/2 size varied
slightly more, between 1.88 and 2.29 µm0.5, although with less KIC
dispersion when compared to NDySiC1900. The dispersion of the re-
sults is a function of the curvature radius of the notch. Therefore,
smaller radii will increase the probability that the crack begins at the
tip of the notch, leading to less dispersion, whereas larger radii tend not
to direct the beginning of crack propagation to the notch tip, reducing
the probability for a specific point and increasing the dispersion values.
Concerning (c), NYbSiC1850 showed an r1/2 ranging from 4.66 and
4.77 µm0.5 with little KIC dispersion, while (d) NYbSiC2000 presented
little r1/2 variation, from 3.64 to 3.97 µm0.5, and little KIC dispersion.
However, when the square root of the radius was much higher, of
4.97 µm0,5 the KIC value was very high in this case, leading to greater
dispersion. These values indicate that when the ceramic has a toughness
fracture plain as a function of the size of the radius, the radius will exert
little influence up to a critical value.
The notches of the samples tested in water were all less than 20 µm
(< 4.5 µm0,5). Evaluating the data in Fig. 8(e)–(h), it is noted that as r1/
2
is increased, the KIC values are not affected, providing planar behavior
of the data, however, in relation to the KIC values obtained in air (a, b, c,
d), a small decrease in fracture toughness occurred for all ceramics. The
reason for this is based on arguments that oxide ceramics are inclined to
slow crack growth due to stress corrosion assisted by water molecules
[1,40].
This has been easily inferred for materials with a polar surface, i.e.
some planes of materials with mainly ionic bonds are more sensitive to
water than covalent materials [44].
Considering the percentage of the ionic character (%IC) of the
materials produced in this work, the value found using the Pauling scale
for Si–C is low, of 12% IC, thus indicating that the sintered materials
have a covalent or polar characteristic of predominantly covalent
character. The bonds of the elements Dy–O; Yb–O and Al–O for the
phases formed with the ReAlO elements Re = Dy, Yb) provide ap-
proximately 71%, 74% and 57% ionic values, respectively. Based on
this, it is likely that water exerted some influence on ionic bonds.
During the experiment, the water diffused into the ceramic struc-
ture, penetrating from the tip of the crack during its growth. In this
case, water diffusion occurs due to the high tension at the crack tip,
significantly increasing the diffusion speed [43].
If the water molecule hydrolyzed the weaker bonds at the crack tip,
the dissociative reactions that may have occurred at the crack tip are as
follows:
(H–O–H) + (–Al–O–Al) → (–Al–OH·HO–Al–) (12)
(H–O–H) + (–Dy–O–Dy) → (–Dy–OH·HO–Dy–) (13)
(H–O–H) + (–Yb–O–Yb) → (–Yb–OH·HO–Yb–) (14)
It is possible that the three stages predicted in the dissociative in-
teraction at the crack tip, i.e. water adsorption by the Al–O, Dy–O and
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Ceramics International 44 (2018) 11048–11059
Yb–O bonds, reaction with water after the high applied load and bond
stretching, would result in proton and electron transfer, and finally the
final separation process, wherein the polar terminal bonds repulse and
complete the rupture process of the bonds [42].
Thus, the variation of free Gibbs energy (-ΔG) coupled to the dis-
sociative reactions that occur between the solid-liquid interface at the
crack tip due to the wet environment is a contributing part in the
transformations of the fracture system, favoring the crack opening. This
condition requires less machine loads for the crack opening, leading to
lower KIC values.
It has also been stated that liquid phase sintered ceramics show a
complex transition in the grain boundary, because the equilibrium in-
terfacial state, which does not satisfy the Gibbs definition of a phase,
allows for a heterogeneous interface in the grain boundary, with dif-
ferences in terms of structure, composition and properties. An example
is the formation of intergranular films in the grain boundary, which are
disordered nanoscale films and more enriched with impurities than the
grains [3].
Therefore, since the ceramics used in this work have a pre-
dominantly covalent character and these bonds are more resistant to
the corrosive attack by water, it is very probable that the ceramics have
failed at the boundary of the SiC grains, since it is the grain limit
chemistry that dominates the sensitivity to water [40].
This water diffusion may have caused the hydration and weakening
of the cohesive forces between the grains, reducing SiC grain boundary
cohesion, thus reducing fracture toughness [45].
It is also noted that the higher the KIC of the ceramic, i.e, the ceramic
withstood the higher required load at the beginning of the rupture in
air, the greater the water influence, causing the greatest material re-
sistance loss.
Therefore, the greater the ceramics toughness, the greater the in-
fluence of the water, which was decisive in promoting the free Gibbs
energy and favoring the crack opening, leading to the greater decrease
in KIC values. The decrease in KIC values indicates the need to evaluate
ceramic materials in the environments they will be used.
Fig. 9 shows the Weibull distribution curves for NDySiC1900,
NDySiC1950, NYbSiC1850 and NYbSiC2000. The samples were sub-
mitted to 3-point bending strength and the results are displayed in
Fig. 9. The σ values are also shown, the mean flexural strength, σ0
which is the characteristic or intrinsic strength where the probability of
failure is equal to 63.2%; σmax, which is the highest tensile stress that
the material supported and R, Pearson's linear correlation coefficient.
The m and σ0 values were obtained from the slope and intercept of the
y-axis.
The KIC values show a direct relationship with the flexural strength
values, a relationship also found in the literature for SiC sintered with
Al2O3/Y2O3, in which very small grains were responsible for lower
resistance and lower KIC; and for AlN ceramics sintered with Re2O3 Re
= Y, La, Sm) suggesting ceramic strengthening due to toughness im-
provement [13,14].
The more the linearized lines move to the right, the greater the
strength of the material. The m value changed from 5.07 to 10.97, in
agreement with the range of typical values of 3–12 found for ceramic
materials [40,49]. The NDySiC displayed m equal to 5.07 and 6.93
when sintered at 1950 °C and 1900 °C, respectively. This dispersion in
the strength of the material, with low m values, results in lower relia-
bility, mainly due to the non-homogeneity of the material, such as
defect size variations and possible residual stresses due to anisotropic
shrinkage during cooling [48].
NYbSiC1850 displayed a higher m value, of 10.97, indicating that,
statistically, the tensile strength values are very reliable for this
ceramic and that the relation of m is not necessarily directly related to
the resistance value, but related to the homogeneity of defects in the
ceramic body. It is likely that the defects in NYbSiC1850, such as pores,
were better distributed in the ceramic body in relation to the other
ceramics. NYbSiC2000, in addition to presenting the highest resistance,
A.C. Santos, S. Ribeiro Ceramics International 44 (2018) 11048–11059

(a) σ (MPa) (c) σ (MPa)

200 400 600 800 250 300 350 400
2 99 2 99
90 90

Failure Probability (%)

Failure Probability (%)

1 σ = 552±125 MPa 81 1 σ = 317±35 MPa 81
σ0 = 598 MPa 72 σ0 = 325 MPa 72
0 σmax = 803 MPa 63 0 σmax = 410 MPa
63
m = 5.07 54 54
lnln(1/1-F)

lnln(1/1-F)
-1 -1
m = 10.97
R = 0.9877 45
R = 0.9503
45
36 36
-2 -2
27 27
-3 18 -3 18
date NDySiC1900 9 date NYbSiC1850 9
-4 -4 fit Weibull
fit Weibull
5.0 5.5 6.0 6.5 7.0 7.5 5.0 5.5 6.0 6.5 7.0 7.5

ln σ (MPa) ln σ (MPa)

(b) σ (MPa) (d) σ (MPa)

400 600 800 400 500 600 700 800
2 99 2 99
90 90
Failure Probability (%)

date NDySiC1950

Failure Probability (%)

date NYbSiC2000
1 fit Weibull 81 1 81
fit Weibull
72 72
0 63 0 63
54 54
lnln(1/1-F)

lnln(1/1-F)

-1 45 -1 45
σ = 611±103 MPa 36 σ = 638±97 MPa 36
-2 σ0 = 663 MPa 27 -2
σ0 = 684 MPa 27
σmax = 807 MPa σmax = 808 MPa 18
-3 18 -3
m = 6.93 m = 7.92
-4 R = 0.9848 9
-4 R = 0.9809 9

5.0 5.5 6.0 6.5 7.0 7.5 5.0 5.5 6.0 6.5 7.0 7.5
ln σ (MPa) ln σ (MPa)
Fig. 9. Weibull distribution of the resistance of (a) NDySiC1900, (b) NDySiC1950, (c) NYbSiC1850 and (d) NYbSiC2000 at 3-point flexural test.

also presented an adequate value of the Weibull module, of 7.92.
Since the material submitted to the bending test did not produce
defects (notch), the origin of the fracture occurred in the region con-
taining the critical defect, leading to the formation of fracture-char-
acteristic regions. Fig. 10 displays a micrograph of the surface fracture
obtained for one of the NYbSiC2000 samples. Under small magnifica-
tion it was possible to observe the branching of the cracks and the
pronounced effect of cone cracks, forming a rougher surface. In addi-
tion, many NYbSiC2000 samples broke into 3–5 parts, due to the higher
flexural strength of this ceramic, suggesting a higher fracture energy
due to the crack deflection mechanism [12].
The fracture toughness properties by the notched bar method and
tensile strength of the NDySiC1950 and NYbSiC2000 ceramics were
very close to EKasic® silicon carbide, a sintered technical material
produced by ESK Ceramics GmbH & Co. KG, a 3 M company. The
EKasic® C, P and G types, which have mechanical properties that allow
them to be applied in corrosive environments and friction and lu-
brication systems, are the ones that most resemble the ceramics pro-
cessed and evaluated in this study [4,5].

4. Conclusions

Fig. 10. Illustrative fracture surface obtained in a scanning electron microscope
in the secondary electron mode for the other ceramics.
The additive systems indicated that rare earths resemble each other
regarding grain morphology, with a more equiaxial shape for the
smaller grains and the presence of hexagonal plates characteristic of
more developed α-SiC from 1900 °C to higher temperatures.
Evaluating the ceramic mechanical properties showed that for a
small range of radii sizes some dispersion may still occur in the KIC

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A.C. Santos, S. Ribeiro
values, although this was reduced when the grooves were created with
a specific 1.2 mm depth and with the smaller radius size when being
notched with the second blade in less time, ensuring greater stress
concentration at the crack tip.
The ceramic with the largest grain size was decisive in delaying the
crack propagation by deflection along the grain boundary, justifying its
greater fracture toughness. When the ceramics were tested in a humid
environment, they showed a decrease in fracture toughness due to the
dissociative interaction at the crack end between the water and the
ionic bonds of the secondary phases and the probable failure at the
grain boundary, confirming the need to evaluate the ceramics in en-
vironments that will be subjected to efforts.
The higher flexural strengths were attributed to the higher values of
the critical stress intensity factor and the lower porosity in the ceramic
body. The presence of cone cracks occurred in a pronounced manner for
ceramics with the highest characteristic strengths.
Acknowledgements
This work was work was supported by the Fundação de Amparo à
Pesquisa do Estado de São Paulo Foundation – FAPESP (Project No.
201051925-6), by the Conselho Nacional de Desenvolvimento
Científico e Tecnológico – CNPq (productivity grant No. 304760/2010-
2), and by the Coordenação de Aperfeiçoamento de Pessoal de Nível
Superior – CAPES. We also thank the Department of Aerospace Science
and Technology (AMR/DCTA), the National Institute of Space Research
(LCP / INPE Cachoeira Paulista) and the Vale do Paraíba University
(FEAU/UNIVAP) for permission to use the isostatic press, helium gas
pycnometer and universal testing machine, respectively.
References
[1] N.A.L. Nasiri, N. Ni, E. Saiz, J. Chevalier, F. Giuliani, L.J. Vandeperre, Effect of
microstructure and grain boundary chemistry on slow crack growth in silicon car-
bide at ambient conditions, J. Eur. Ceram. Soc. 35 (2015) 2253–2260.
[2] M.V. da Silva, D. Stainer, H.A. Al-Qurechi, D. Hortza, Ceramic armors for ballistic
applications: a review, Cerâmica 60 (355) (2014) 323–331.
[3] P.R. Cantwell, M. Tang, S.J. Dillon, J. Luo, G.S. Rohrer, M.P. Harmer, Grain
boundary complexions, Acta Mater. 62 (2014) 1–48.
[4] EKASIC® Silicon Carbide, Kempten: ESK Ceramics GmbH Co., T. data. KG, 2015.
[5] V. Gentil, Carbeto de silício para cada aplicação, um material, T. Data, Sealine
Cerâmicas Especiais Ltda, 2013.
[6] A.H. Rashed, Properties and Characteristics of Silicon Carbide, POCO Graphite Inc.,
Texas, 2002.
[7] S. Kumar, W.A. Curtin, Crack interaction with microstructure designing micro-
structure for damage tolerance requires a detailed, Mater. Today 10 (9) (2007)
34–44.
[8] X. Guo, H. Yang, X. Zhu, L. Zhang, Preparation and properties of nano-SiC-based
ceramic composites containing nano-TiN, Scr. Mater. 68 (2013) 281–284.
[9] C.P. Ostertag, Influence of fiber and grain bridging on crack profiles in SiC fiber-
reinforced alumina-matrix composites, Mater. Sci. Eng. A 260 (1–2) (1999)
124–131.
[10] S. Kim, W.M. Kriven, Preparation, microstructure, and mechanical properties of
silicon carbide – dysprosia composites, J. Am. Ceram. Soc. 80 (12) (1997)
2997–3008.
[11] Y. Pan, S. Tan, D. Jiang, J. Qiu, M. Kawagoe, In-situ characterization of SiC – AlN
multiphase ceramics, J. Mater. 4 (1999) 5357–5360.
[12] R.C. Bradt, D.P.H. Hasselman, D.S. Munz, V. Shevchenko, Fracture Mechanics of
Ceramic, Ya. Plenem Press, New York, 1996.
[13] Y. Hirata, N. Suzue, N. Matsunaga, S. Sameshima, Particle size effect of starting SiC
on processing, microstructures and mechanical properties of liquid phase-sintered
SiC, J. Eur. Ceram. Soc. 30 (9) (2010) 1945–1954.
[14] R. Danzer, On the relationship between ceramic strength and the requirements for
mechanical design, J. Eur. Ceram. Soc. 34 (2014) 3435–3460.
[15] H. Abderrazak, E.S.B.H. Hmida, Silicon carbide: synthesis and properties, in:
R. Gerhardt (Ed.), Properties and Applications of Silicon Carbide, InThec, Croatia,
2011, pp. 361–388.
[16] V.A. Izhevskyi, L.A. Genova, J.C. Bressiani, A.H.A. Bressiani, Review article: silicon
carbide. Structure, properties and processing, Cerâmica 46 (2000) 1–28.
[17] K. Strecker, M.J. Hoffmann, Effect of AlN-content on the microstructure and
11059
Ceramics International 44 (2018) 11048–11059
fracture toughness of hot-pressed and heat-treated LPS-SiC ceramics, J. Eur. Ceram.
Soc. 25 (6) (2005) 801–807.
[18] A. Jeutter, Untersuchung der Phasenbeziehungenim System Aluminiumoxid-
Yttriumoxid (Master), University of Stuttgart, Germany, 1993.
[19] A.C. Santos, A.P. Luz, S. Ribeiro, Melting temperature and wetting angle of AlN/
Dy2O3 and AlN/Yb2O3 mixtures on SiC substrates, Mater. Res. 18 (5) (2015)
957–962.
[20] J. Hu, H. Xiao, W. Guo, Q. Li, W. Xie, B. Zhu, Effect of AlN–Y2O3 addition on the
properties and microstructure of in-situ strengthened SiC–TiB2 composites prepared
by hot pressing, Ceram. Int. 40 (1) (2014) 1065–1071.
[21] J. Kuang, W. Cao, S. Elder, Synthesis of α-SiC particles at 1200 °C by microwave
heating, Powder Technol. 247 (2013) 106–111.
[22] L. Kwang-Young, K. Young-Wook, N. Toshiyuki, S. Won-Seon, High temperature
strength of silicon carbide sintered with 1 wt% aluminum nitride and lutetium
oxide, J. Eur. Ceram. Soc. 33 (2013) 345–350.
[23] H. Liang, X. Yao, X. Liu, Z. Huang, The effect of powder bed on the liquid phase
sintering of a-SiC, Mater. Des. 56 (2004) 1009–1013.
[24] W.D. Kingery, D.R. Bowen, Introduction to Ceramics, John Wiley, New York, 1976.
[25] T. Nishinaga, Handbook of Crystal Growth: Fundamentals, Elsevier, Tokyo, 2014.
[26] A. Garcia, J.A. Spim, C.A. Santos, Ensaio de tenacidade à fratura, Ensaios dos ma-
teriais, LTC, Rio de Janeiro, 2000.
[27] G.A. Gogotsi, Fracture of ceramics and ceramic composites, Ceram. Int. 29 (2003)
777–784.
[28] International Organization for Standardization, ISO 23146: Fine Ceramics
(Advanced Ceramics, Advanced Technical Ceramics) – Test Methods for Fracture
Toughness of Monolithic Ceramics, S.E.V.N.B.S Method, 2008.
[29] G.A. Gogotsi, Fracture toughness studies on V-notched ceramic specimens, Strength
Mater. 32 (1) (2000) 81–85.
[30] R. Damani, R. Gstrein, R. Danzer, Critical notch-root radius effect in SENB-S frac-
ture toughness testing, J. Eur. Ceram. Soc. 16 (1996) 695–702.
[31] T. Fett, Influence of a finite notch root radius on fracture toughness, J. Eur. Ceram.
Soc. 25 (2005) 543–547.
[32] W. Zhao, C. Peng, M. Lv, M. Bai, P. Raon, Effect of notch depth on fracture
toughness of Y-TZP and determination of its actual value, Ceram. Int. 41 (1) (2015)
869–872.
[33] H. Fischer, A. Waindich, R. Telle, Influence of preparation of ceramic SEVNB spe-
cimens on fracture toughness testing results, Dent. Mater. 24 (2008) 618–622.
[34] H. Özcoban, H. Jelitto, G. Schneider, Influence of finite notch root radius and op-
tically determined crack length on the measured fracture toughness of brittle ma-
terials, J. Eur. Ceram. Soc. 30 (2010) 1579–1583.
[35] M. Mizuno, J.I. Kon, Fracture Toughness Measurement of Ceramic Matrix
Composite, VAMAS Report, Japan, 1997.
[36] J. Kuebler, Fracture Toughness of Ceramics Using the SEVNB Method; Round Robin.
Switzerland, V. Report, ESIS Report D2-99, EMPA, CH-8600 Duebendorf, 1999.
[37] S. Ribeiro, I. Atílio, M. Oliveira, G. Garcia, J. Rodrigues, Notching of ceramics as
preparation of specimens for fracture toughness measurements using the SEVNB
method, Cerâmica 59 (2013) 285–292.
[38] R. Morrell, Fractography and fracture toughness measurement, Key Eng. Mater. 409
(2009) 17–27.
[39] A.G. Evans, F.F. Lange, Crack propagation and fracture in silicon carbide, J. Mater.
Sci. 10 (10) (1975) 1659–1664.
[40] N.A.L. Nasiri, E. Saiz, F. Giuliani, L.J. Vandeperre, Effect of microstructure and slow
crack growth on lifetime prediction of monolithic silicone carbide, Mater. Sci. Eng.
A 627 (2015) 290–295.
[41] W. Nakao, Effect of self-healing on fatigue behaviour of structural ceramics and
influence factors on fatigue strength of healed ceramics, in: R. Gerhardt (Ed.),
Properties and Applications of Silicon Carbide, InThec, Croatia, 2011, pp. 251–258.
[42] B. Lawn, Fracture of Brittle Solids, Cambridge University Press, Cambridge, 1993.
[43] S.M. Wiederhorn, T. Fett, G. Rizzi, M.J. Hoffmann, J.P. Guin, The effect of water
penetration on crack growth in silica glass, Eng. Fract. Mech. 100 (2013) 3–16.
[44] C. Olagnon, J. Chevalier, V. Pauchard, Global description of crack propagation in
ceramics, J. Eur. Ceram. Soc. 26 (2006) 3051–3059.
[45] L. Liang, J. Xiong, X. Liu, Experimental study on crack propagation in shale for-
mations considering hydration and wettability, J. Nat. Gas Sci. Eng. 23 (2015)
492–499.
[46] W.A. Weibull, Statistical distribution functions of wide applicability, J. Appl. Mech.
18 (1951) 293–297.
[47] W.A. Weibull, Statistical distribution functions of wide applicability, J. Appl. Mech.
19 (1952) 233–234.
[48] A.D. Papargyris, Estimator type and population size for estimating the weibull
modulus in ceramics, J. Eur. Ceram. Soc. 18 (5) (1998) 451–455.
[49] R. Terao, J. Tatami, T. Meguro, K. Komeya, Fracture behavior of AlN ceramics with
rare earth oxides, J. Eur. Ceram. Soc. 22 (7) (2002) 1051–1059.
[50] The Highscore Suite, Powder Diffraction, 29, 2014.
[51] PEARSON’s Crystal Data (PCD), Bonn, Crystal Impact, 2013.
[52] M. Medraj, R. Hammond, M.A. Parvez, R.A.L. Drew, W.T. Thompson, High tem-
perature neutron diffraction study of the Al2O3–Y2O3 system, J. Eur. Ceram. Soc. 26
(2006) 3515–3524.