Materials and Design 99 (2016) 412–420

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Materials and Design

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Structural properties of MgO–ZrO2 ceramics obtained by conventional

sintering, arc melting and field assisted sintering technique
E. Śnieżek a,⁎, J. Szczerba a, P. Stoch a, R. Prorok a, I. Jastrzębska a, W. Bodnar b, E. Burkel b
a
AGH University of Science and Technology, Faculty of Materials Science and Ceramics, al. A. Mickiewicza 30, 30-059 Krakow, Poland
b
Institute of Physics, University of Rostock, Albert-Einstein-Str. 23, 18059 Rostock, Germany

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

Article history: MgO–ZrO2 ceramics were obtained by three different methods: conventional sintering, arc melting and field
Received 13 December 2015 assisted sintering. The present study was undertaken in order to determine the influence of the different
Received in revised form 17 March 2016 sintering techniques on the structural properties of MgO–ZrO2 ceramics. The phase compositions of the obtained
Accepted 18 March 2016
samples consisted of MgO and ZrO2 cub. ss (doped by MgO). The amount of all phases in the final product and
Available online 22 March 2016
their average crystallite sizes are strongly influenced by the sintering method. The smallest crystallites were re-
Keywords:
alized for ceramics consolidated by the field assisted sintering method (20.1 ± 2.5 nm for MgO and 27.0 ± 2.7 nm
ZrO2 for ZrO2 cub. ss). About ten times larger crystallites resulted by conventional sintering. The average crystallite size
MgO in the material obtained by arc melting technique was around 116 ± 20.4 nm. It was observed that the micro-
Sintering structures of the samples prepared by arc melting and field assisted sintering are similar.
Arc melting © 2016 Elsevier Ltd. All rights reserved.
Field assisted sintering

1. Introduction hydrothermal methods, combustion synthesis, etc. Materials based on

ZrO2 can be prepared by various methods which significantly influence
ZrO2-based ceramics are one of the most important contemporary their properties. Coupling the mechanochemical reaction of precursor
construction and functional materials [1]. This is due to the conscious materials (ZrCl4 and CaO) with the suitable annealing process results
control of extensive polymorphism of ZrO2 by the possibility of stabili- in the preparation of nanocrystalline ZrO2 with an average crystallite
zation each polymorph and due to unique properties of ZrO2 like high size smaller than 100 nm at temperatures up to 1100 °C [15]. Next syn-
mechanical strength, Young's modulus, hardness, fracture toughness, thesis method of cubic ZrO2 nanoparticles, which can be used for large
corrosion and wear resistance, tribological properties, and high ionic scale is the thermolysis of [Zr(HAP)3(H2O)2](NO3) as a precursor in
conductivity. [1–13]. ZrO2 shows three low pressure crystallographic oleylamine (C18H37N) and triphenylphosphine (C18H15P). Depending
structures, namely, monoclinic (m-P21/c) which is stable at room tem- on the time and temperature of the process, this method allows to re-
perature up to approximately 1170 °C, tetragonal (t-P42/nmc) between ceive quesi-spherical nanoparticles with size about 30–50 nm [16].
1170 °C and 2370 °C and cubic (c-Fm3m) for higher temperatures up to Moreover, pure cubic ZrO2 nanopowder can be obtained in a one step
2700 °C. The densities of these three phases vary significantly, especial- low temperature solution combustion method leading to average crys-
ly, of the monoclinic and tetragonal phases and they are 5.68 g/cm3, tallite sizes of cubic zirconia ranging from 6 nm to 12 nm. The ZrO2 crys-
6.10 g/cm3 and 6.20 g/cm3, respectively. During cooling, below tallites formed irregular agglomerates and created porous structure
1070 °C zirconia undergoes a martensitic transformation. Such transfor- [17].
mation of tetragonal to monoclinic form results in about 3–4% volume The high density, homogeneous microstructure and appropriate
change [1,14]. The phase transformation of zirconia has also significant grain size of the ZrO2 based ceramics are required for high quality mate-
influence on mechanical properties like strength or toughness of zirco- rials. As reported in [18] the most significant difference between YSZ
nia ceramics. (yttria–stabilized zirconia) bulk materials compacted by field assisted
The stabilization of the tetragonal and the cubic phases can be sintering technique, hot pressing and conventional sintering is the aver-
achieved by addition of other suitable oxides which randomly occupy age grain size. The field assisted sintering technique (FAST), also known
the Zr-sites [14]. It may be obtained by using different stabilization ox- as spark plasma sintering (SPS) [19,20], enables preparation of mate-
ides. In recent years, a number of well know techniques has been devel- rials with smaller grain size in compare to hot pressing and convention-
oped to produce stabilized ZrO2 powder: powder mixing, sol-gel, al sintering. This technique allows compacting dense and fine-grained
materials in a very short time at relatively low temperature [18]. In con-
⁎ Corresponding author. trast, obtaining dense MgO–ZrO2 materials, as a result of sintering re-
E-mail address: [email protected] (E. Śnieżek). quires the use of high temperature and a relatively long time [21–23].

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 E. Śnieżek et al. / Materials and Design 99 (2016) 412–420 413

The densification behavior of MgO–ZrO2 with zirconia amount of 2–

50 mol% was presented in [21]. The samples were prepared using
conventional sintering at 1100 to 1600 °C. The maximum density was
achieved for samples sintered at 1500 °C with 8 mol% of MgO. The
higher amount of MgO make difficult to consolidate the material. It re-
sulted from a precipitation of MgO at the grain boundaries [21].
The ZrO 2–MgO solid solution and ceramics based on MgO and
cubic ZrO2 have drawn lots of attention. The MgO–ZrO2 ceramics ma-
trix were investigated for use as an inert matrix fuel for a light water
reactor [24–26]. Medvedev et al. [24,25] prepared the ceramics from
a mixture of ZrO2 and MgO (30, 40, 50 and 60 wt% of MgO) by a con-
ventional two step heat treatment at 1000 °C and 1700 °C. The ob-
tained samples consisted of cubic ZrO2 solid solution and MgO as
main phases with traces of monoclinic ZrO 2 . The composition of
ZrO2 solid solution depends on the amount of MgO in the starting
mixture. The solubility of MgO in ZrO2 at 1700 °C increases with
the mass content of MgO. Likewise, the lattice parameters of cubic
ZrO2 phase and MgO is slightly different for each compositions [24, Fig. 1. Particle size distributions of MgO, ZrO2 and MgO-ZrO2 mixture.
25]. Furthermore, the MgO–ZrO2 ceramics degradation in water
and nitric acid depended mainly on compositions, grain size and
the nature of the grain boundaries [24–26]. The ZrO2 content above main grain populations with median sizes around 0.1 μm, 0.9 μm and
62.5 wt% stabilized grain boundaries. Moreover, the hydration of 40 μm. The volume fraction of particles smaller than 1 μm is much
MgO occurred only on the surface [26]. The microstructure plays a higher for the mixture than for the pure ZrO2 and MgO powders.
key role and effects on the hydration resistance [24–26]. The MgO–ZrO2 powder was uniaxially pressed into cylindrical pel-
Sarikaya and Celik [27] produced MgO–ZrO2 coating with a very lets with 20 mm in diameter and 10 mm in thickness at a pressure of
dense structure on Ni metal and on AlSi alloys using an atmospheric 60 MPa. In the first method, the pellets were sintered at four different
plasma spray technique. The thickness of obtained ceramic coating de- temperatures: 1400 °C, 1500 °C, 1600 °C, and 1700 °C under air atmo-
termined the residual stress [27]. On the contrary, the evaporation in- sphere with 24 h soaking time at the maximum temperature. The
duced self assembly (EISA) technique allows to obtain mesoporous heating rate was of 5 °C/min. The pellets were cooled within the furnace
MgO–ZrO2 solid solution which characterized by very small crystallite after sintering.
sizes. Depends on Mg/Zr molar ration, the crystallite size were from In the second method, the arc melting technique was used in order
3.67 nm (Mg/Zr = 1) to 5.97 nm (Mg/Zr = 0.25). The obtained MgO– to obtain the samples. Before the melting process, the mixture was
ZrO2 solid solution could be further used as a heterogeneous catalyst pressed into pellets. In order to improve melting, samples were
[28]. compacted into cylindrical pellets, as described above, except that
The purpose of the present work was to characterize MgO–ZrO2 ce- they were thinner (5 mm in thickness). Melting in an arc furnace
ramics prepared by three different techniques: conventional sintering, (SpekoArc 300) equipped with tungsten electrode was conducted in
arc melting and field assisted sintering, since the sintering occurs in rad- the high purity argon atmosphere with contactless ignition in the
ically different conditions and environments. The microstructure of the enclosed copper crucible. The electric arc was set perpendicular to the
samples obtaining by each techniques will be like enough differ. The mi- pellet surface. The distance between the tip of tungsten electrode and
crostructure translate to physical, chemical and mechanical properties. the pellet surface was approximately 5 mm. The electric current was in-
Therefore, it is of great interest to understand the influence of the vari- creased from 20 A until the pellet started to melt. The maximum electric
ous synthesis conditions on the final microstructure and structural current reached the value of 230 A. It corresponds to a temperature
properties of MgO–ZrO2 ceramic composites. when the MgO–ZrO2 mixture was completely melted. The 230 A was
equivalent to the temperature about 3000 °C. At this temperature the
2. Material and methods samples were kept for about 60 s. To obtain better homogeneity, the
samples were melted twice, once on each side.
2.1. Preparation of MgO–ZrO2 ceramics In the third approach, the field assisted sintering technique was used
in order to consolidate MgO–ZrO2 composites. 10 g of the powder mix-
Magnesia–zirconia ceramics were obtained by three different tech- ture were stacked into a graphite die with an inner diameter of 20 mm
niques: conventional sintering, arc melting and field assisted sintering. and separated from inner walls of the die and the punches by means of a
Commercial monoclinic zirconia (ZrO2: Acros Organics, 98.5% purity) graphite foil in order to prevent the material from reacting with the die
and magnesia (MgO: Acros Organics, 99.0%) powders in 1:1 mol ratio and to ensure an electrical contact. Furthermore, the graphite die was
were used as precursor raw powders. A mechanochemical treatment covered with a porous carbon felt to reduce heat radiation losses from
of the mixtures was carried out in a planetary ball-mill (FRITSCH, the outer surface of the die. The application of the carbon felt also re-
Pulverisette 6) using tungsten carbide grinding jars. The ball (tungsten duces possible gradients of temperature within the sample and it en-
carbide) to powder weight ratio was 30:1. The mixture was blended sures maximal possible in-plane homogeneity of the obtained sample
with a rotation speed of 400 rpm under inert atmosphere for 5 h. [29,30]. The sintering procedure was performed in Tycho Sinterlab
There was no contamination in the mixture originating from the mill Rostock using the HP D5 unit from FCT Systeme GmbH Rauenstein,
and grinding jars. The particle size distributions of ZrO2, MgO and Germany. Fig. 2 presents real-time data of the temperature (black
the MgO–ZrO2 mixture, presented in Fig. 1, were estimated using line) variation and the plunger displacement (red line), corresponding
Mastersizer 2000 (Malvern Instruments). The initial ZrO2 powder was to the densification of material [19], during the sintering procedure.
characteristic of a unimodal grain size distribution of d50 = 20.8 μm. The consolidation process was divided into six characteristic phases
The MgO curve can be easily deconvoluted into two overlapped peaks marked in Fig. 2 with vertical dashed lines. In the first phase, the
which correspond to population about 2.4 μm and 25 μm. In the case sintering chamber was evacuated to approximately 1 mbar and an ini-
of the MgO powder a wide range (from 0.6 μm to 60 μm) was observed. tial pressure of 10 MPa was applied to the plunger system. During the
After the mechanochemical treatment the mixture consisted of three second and the third phase, the pressure and the temperature were
414 E. Śnieżek et al. / Materials and Design 99 (2016) 412–420

Fig. 2. Temperature variation and the plunger displacement against the process time of the
MgO-ZrO2 ceramics. Six characteristic phases of the sintering process, described in detail
in text, are marked with vertical dashed lines.

increased to 100 MPa and 400 °C, respectively. Here, it is worth to men-
tion that due to technical limitations the heating process below 400 °C
was controlled by a thermocouple mounted in the graphite die and
above 400 °C by an optical pyrometer focused on a surface approxi-
mately 4 mm away from the sample, in a hole drilled in the upper
graphite plunger. Next, the temperature was increased to 1600 °C
with a controlled heating rate of 150 K/min and this temperature was
held for 10 min. In the last phase of the process the pressure of
100 MPa was kept and the sample was cooled down with a natural
cooling rate of approximately 200 K/min between 1600 °C and 400 °C.
The post-sintered sample was cleaned from a protective graphite foil
using a sand blaster.
Fig. 3. X-ray diffraction patterns of samples prepared by conventional sintering at 1400 °C,
2.2. Characterization techniques 1500 °C, 1600 °C and 1700 °C (ZrO2 cub. ss - cubic form of ZrO2 stabilized by MgO; ZrO2 tet.
- tetragonal ZrO2; ZrO2 mon. - monoclinic ZrO2).

Crystalline phases were analyzed by X-ray diffraction (XRD, Philips

Panalytical X'Pert-Pro MPD diffractometer). XRD patterns of the samples intensity of the diffraction peaks corresponding to the monoclinic
obtained by three different methods were collected at room temperature ZrO2 phase decreased with the increasing sintering temperature
using Cu-Kα radiation with a scan step size of 0.02°/2θ and an average and they were not observed above 1600 °C. The sample sintered at
time of 10 s/step. The obtained data was analyzed using the X'Pert Pro 1700 °C was composed of only two crystalline phases. All the diffraction
Highscore Plus software. The crystalline parameters were refined by the peaks could be assigned to the cubic ZrO2 and MgO phases. There was
full-profile Rietveld method [31] implemented in the FullProf software no evidence of any diffraction lines corresponding to other polymorphs
package [32]. Structural parameters, including scale factor, zero shift, of ZrO2 (monoclinic or tetragonal). Thus, based on XRD results, the sam-
background function, lattice parameters, atomic coordinates and peak ple sintered at 1700 °C was selected for further investigations.
profile were taken into account in the course of refinement. The XRD patterns of the MgO–ZrO2 ceramics sintering by three differ-
Infrared spectra were collected in the mid infrared (MIR) region ent methods are shown in Fig. 4. All the reflections of the XRD patterns
(4000 cm−1–400 cm−1) after 512 scans with 1 cm−1 resolution using were indexed by JCPDS card no. 89-4248 and 80-0964 correspond to
Bruker Vertex 70v spectrometer. Samples were prepared using the stan- MgO and cubic ZrO2 stabilized by MgO (Zr0.86Mg0.14O1.86), respectively.
dard KBr pellets method. The baseline correction has been carried out The XRD diffraction patterns show two major diffraction peaks at 2θ =
before the decomposition process. 42.9° and 63.5° belonging to MgO and four at 2θ = 30.5°, 35.4°, 50.9°,
The microstructures of the fractured surfaces of the samples were in- 60.5° and 62.3° belonging to cubic ZrO2. There was no evidence of other
vestigated using a scanning electron microscope (SEM, FEI NovaNanoSem polymorphic forms of ZrO2 in the collected XRD patterns. Fig. 5 shows
200) equipped with an energy dispersive X-ray spectrometer (EDS). the powder X-ray diffraction patterns in the 2θ range of 27°–33°. Addi-
tionally, theoretical positions of the main diffraction lines for monoclinic
3. Results and tetragonal ZrO2 were marked in the picture. The XRD analysis dem-
onstrated that monoclinic and tetragonal phases of ZrO2 are not present
3.1. X-ray diffraction in the examined materials.
The only differences in the XRD patterns (Figs. 4 and 5) were in the
Fig. 3 shows a sequence of XRD patterns demonstrating the phase relative peak intensities and their half widths. Therefore, the average
evolution of the MgO–ZrO2 samples sintered at 1400 °C, 1500 °C, crystallite size was estimated from the full width half maximum
1600 °C and 1700 °C. A transformation of ZrO2 from monoclinic to te- (FWHM) of the diffraction lines using Scherrer equation (Eq. 1) [33].
tragonal and cubic form was observed in the studied temperature The instrumental apparent peak broadening was corrected.
range. At 1400 °C only two starting phases: monoclinic ZrO2 and MgO
were identified. At 1500 °C the diffraction lines corresponding to tetrag- Dhkl ¼ 0:9λ=ðβ cosθÞ ð1Þ
onal and cubic ZrO2 appeared. The intensity of the cubic ZrO2 peaks sig-
nificantly increased with the increasing temperature of sintering. The where:
 E. Śnieżek et al. / Materials and Design 99 (2016) 412–420 415

Fig. 5. X-ray diffraction patterns of MgO–ZrO2 ceramics prepared by (a) conventional

sintering at 1700 °C, (b) arc melting, (c) FAST in 27–33 2θ range (ZrO2 cub. ss — cubic
Fig. 4. X-ray diffraction patterns of MgO–ZrO2 ceramics prepared by (a) conventional form of ZrO2 stabilized by MgO; m — ZrO2 — monoclinic ZrO2; t — ZrO2 — tetragonal ZrO2).
sintering at 1700 °C, (b) melting, (c) FAST (ZrO2 cub. ss — cubic form of ZrO2 stabilized
by MgO).
sample processed by arc melting exhibited slightly different shapes
than the spectra of the samples prepared by conventional sintering
D — crystallite size along (hkl) direction, and FAST.
β — full width half maximum (FWHM) of the most intense diffraction
line, 3.4. Microstructure analysis
λ — wavelength of X-ray,
θ — the Bragg angle. Figs. 9–11 show scanning electron microscopy (SEM) micrographs
of the MgO–ZrO2 ceramics processed by sintering, arc melting and
The evolution of the crystallite sizes in the MgO–ZrO2 ceramics was FAST, respectively. The chemical analysis in microareas with energy dis-
investigated after each sintering and it is summarized in Table 1 for ZrO2 persive spectroscopy (EDS) of the fracture surface of the materials indi-
cub. ss and MgO. The crystallite size varied considerably. The largest es- cated that the samples consisted of two well distributed phases: MgO
timated crystallites were found in the sample consolidated by conven- (black areas) and ZrO2 cub. ss stabilized by MgO (grey areas). As is
tional sintering and the smallest in the material processed by FAST. clear from Fig. 9(a) and (b), the grains of ZrO2 formed agglomerates
with maximum grain size about 50 μm. The grains of ZrO2 were strongly
3.2. Crystal structure parameters sintered. Those of MgO are homogeneously distributed in the ZrO2 ma-
trix. The grains size of MgO is approximately up to 10 μm. It was ob-
The lattice parameters of the two major cubic phases: MgO (JCPDS served that in comparison to Fig. 9, the microstructures presented in
89-4248) and ZrO2 cub. ss (JCPDS 80-0964) were calculated using Figs. 10 and 11 are similar. The microstructure of the melted MgO–
Rietveld refinement by assuming the Fm-3 m (No. 225) space group ZrO2 ceramic is presented in Fig. 10(a) and (b). It is difficult to distin-
for both identified phases. No impurity crystalline phases were found. guish the grain boundaries. In Fig. 10(b), with the bigger magnification,
The measured diffraction patterns and theoretical fits are presented in MgO grains strongly interconnected with ZrO2 were observed. Further-
Fig. 6 and the obtained crystal structure parameters are summarized more, Fig. 11(a) shows agglomerated microstructure with small grains
in Table 2. The obtained unit-cell parameters were slightly different of MgO which were surrounded by larger ZrO2 grains. Zirconia is the
than those reported in the literature (Table 2). continuous phase and MgO acts as inclusions in the matrix.

3.3. Vibrational spectroscopy Table 1

Average crystallite size in MgO–ZrO2 samples prepared by three different methods.
The infrared (MIR) spectra of the differently prepared MgO–ZrO2 ce- Conventional sintering at 1700 °C Melting FAST
ramics, recorded in the range from 4000 cm−1 to 400 cm−1, are pre-
Crystallite size calculated on basis of XRD method [nm]
sented in Fig. 7. The most intense bands located in the range of about
1200 cm−1–400 cm−1 are additionally presented in detail in Fig. 8. Ac- MgO 241.8 ± 5.1 149.7 ± 29.9 20.1 ± 2.5
ZrO2 cub. ss 220.8 ± 3.0 116.0 ± 20.4 27.0 ± 2.7
cording to the MIR spectra it can be noted that the spectrum of the
416 E. Śnieżek et al. / Materials and Design 99 (2016) 412–420

Fig. 7. MIR spectra of MgO-ZrO2 ceramics prepared by conventional sintering at 1700 °C,
arc melting and FAST in the range of 4000 cm−1 −400 cm−1.

Fig. 6. The Rietveld analysis of samples prepared by (a) conventional sintering at 1700 °C,
(b) arc melting and (c) FAST. The differences between the observed and the calculated
patterns are presented at the bottom of each pattern.

Open porosity and apparent density of the obtained materials was

measured by a water displacement method (Archimedes principle).
Rather low porosity was observed in the all samples. It was found that
open porosity of the samples obtained by conventional sintering, melt-
ing and FAST was 1.5%, 0.8% and 1.2% respectively, which corresponds to
the density: 4.90 g/cm3, 4.98 g/cm3 and 4.94 g/cm3, respectively.
Fig. 8. MIR spectra of MgO-ZrO2 ceramics prepared by conventional sintering at 1700 °C,
arc melting and FAST in the range of 1200 cm−1 −400 cm−1.
4. Discussion

Mixtures of MgO and ZrO2 powders in the 1:1 mol ratio were Fig. 3, a polymorphic transformation of ZrO2 occurred during heating.
sintered at 1400 °C, 1500 °C, 1600 °C and 1700 °C in order to obtain bi- The monoclinic and tetragonal phases were observed up to 1600 °C.
phasic material (cubic ZrO2 and MgO). This temperature range was cho- The diffractogram of the sample sintered at 1700 °C, Fig. 3, showed
sen based on the analysis of the MgO–ZrO2 phase diagram, Fig. 12 [34]. MgO and ZrO2 cub. ss as the principal crystalline phases.
According to the MgO–ZrO2 phase diagram, above 1406 °C (MgO con- The X-ray patterns, shown in Figs. 4 and 5, present sharp and well
tent ≥ 12.55%) cubic ZrO2 is observed in the system and it is in equilib- defined peaks for sintered and arc melted samples which is an evidence
rium with MgO [34]. MgO is a typical oxide used to achieve stabilized of a high degree of crystallinity. The diffraction lines became broader in
zirconia [35–38]. Moreover, the liquid phase is present at 2108 °C the case of the sample consolidated by the field assisted sintering tech-
with the MgO content of about 55 mol% [34]. As it is obvious from nique. This fact indicated that the crystallite sizes of the MgO–ZrO2

Table 2
Crystal structure parameters of MgO and ZrO2 cub. ss phases (a — unit cell parameter, V — unit cell volume, A — phase share percentage).

Parameters Conventional sintering at 1700 °C Melting FAST JCPDS

MgO (Fm-3 m) MgO (JCPDS 89-4248)

a [Å] 4.2098(3) 4.2164(5) 4.2430(10) 4.2109

V [Å3] 74.606(10) 74.958(15) 76.386(32) 74.67
A [mass. %] 30(3) 25(3) 23(3) –

ZrO2 cub. ss (Fm-3 m) ZrO2 cub. ss (JCPDS 80-0964)

a [Å] 5.0674(3) 5.0605(5) 5.0835(8) 5.0730

V [Å3] 130.127(13) 129.591(22) 131.364(35) 130.56
A [mass. %] 70(3) 75(3) 77(3) –
 E. Śnieżek et al. / Materials and Design 99 (2016) 412–420 417

Fig. 9. (a), (b) SEM microphotographs of fracture surface of the sample obtained by Fig. 10. (a), (b) SEM microphotographs of fracture surface of the sample processed by arc
conventional sintering at 1700 °C (M – MgO; Z – ZrO2 cub. ss). melting (M - MgO; Z - ZrO2 cub. ss).

Furthermore, it was already reported that the stabilization of the cubic

ceramics obtained by FAST are much smaller than the ones of their ZrO2 phase consist in random occupation of the Zr sites increases with
counterparts obtained with the two other methods. The average crystal- temperature to afford stabilized ZrO2 [8]. The unit cell parameter of
lite sizes, both for MgO and ZrO2 cub. ss, strongly depend on the the ZrO2 cub. ss phase reached the smallest value for the sample obtain-
sintering method. The smallest crystallites (Table 1) were recognized ed by arc melting. The lattice parameter of the ZrO2 cub. ss phase in-
for the field assisted sintering technique, with values of 20.1 ± 2.5 nm creased from 5.0605(5) Å, through 5.0674(3) Å, to 5.0835(8) Å for arc
and 27.0 ± 2.7 nm for MgO and ZrO2 cub. ss, respectively. The sintered melting, sintering and FAST, respectively. Also its amount was in-
MgO–ZrO2 ceramics were characteristic of the largest crystallites ex- creased. Therefore, the application of the arc melting technique and
ceeding 200 nm. The application of arc melting resulted in crystallites the field assisted sintering, in comparison to conventional sintering,
with an intermediate size. allowed to receive samples with the highest contents of the ZrO2 cub.
The calculated crystal structure parameters and phase share per- ss phase: 75(3) and 77(3) mass. %, respectively.
centages of MgO and ZrO2 cub. ss also depend on the sintering method The weak wide absorption band located around 3450 cm−1, Fig. 7, is
(Fig. 6; Table 2). The lattice parameter of MgO was increased for associated to the stretching of OH– groups of water. Moreover, the addi-
sintering, arc melting, as well as for the field assisted sintering tech- tional weak absorption band centered at 1635 cm−1, Fig. 7, is assigned
nique, respectively. It was already reported that there is no evidence to symmetric bending vibrations of H2O molecules. It is evident from
of the dissolution of ZrO2 in MgO from 40 to 100 mol% of MgO in the the MIR spectra that bands related to the presence of H2O in samples ob-
mixture. The lattice parameters of MgO with the value of 4.211 Å tained by arc melting are less pronounced than in the other two sam-
were constant [39]. Further investigations revealed low solid solution ples. It is well known and widely described in literature that MgO
of ZrO2 in the MgO phase [40–42]. Serena at all [40] found 1.5 wt% of easily reacts with liquid water, water vapor or moisture forming brucite,
ZrO2 dissolved in the MgO [40]. Therefore, it can be assumed that the Mg(OH)2 [43–49]. In contact with water vapor, water is adsorbed on the
lattice parameters of MgO depends on the solubility of ZrO2 in the MgO surface. In the second step, a chemical reaction between MgO and
MgO which is consequence of synthesis method and applied conditions. H2O leads to formation of brucite [43–49]. Taking this and the XRD
418 E. Śnieżek et al. / Materials and Design 99 (2016) 412–420

Fig. 12. The MgO-ZrO2 phase diagram. (M ss = monoclinic ZrO2; T ss = solid solution
based on tetragonal ZrO2; C ss = solid solution based on cubic ZrO2). The red lines
indicate the range in which the study was conducted [34].

lowest possible temperature. Arc melting and FAST are alternative

methods of sintering to the conventional sintering technique. These
two rapid sintering techniques allow the processing of materials with
fast heating rates in short times, which results in the retardation of
grain growth. In the presented work, the entire process of the field
assisted sintering lasted 36 min with only 10 min holding time at the
maximum temperature of 1600 °C. The entire melting process endured
only about 2 min. 10 g of the precursor MgO–ZrO2 powder was proc-
essed with these two methods.
The microstructures of the materials obtained by arc melting and
Fig. 11. (a), (b) SEM microphotographs of fracture surface of the sample consolidated by
FAST, Figs. 10 and 11, are closely resembling and they are significantly
FAST (M – MgO; Z – ZrO2 cub. ss). different from the microstructure of the conventionally sintered sample,
Fig. 9. In the first two cases, the sintering proceeded in the presence of
liquid phase, what is obvious in a melting technique where temperature
results into account, it can be concluded that the presence of H2O mol- of the process exceeded the melting point of the precursor powder. The
ecules results only from adsorption. The chemical reaction could have microstructure of samples obtained by melting is typical for fused ce-
taken place but the amount of brucite was under the detection limit of ramic materials, e.g. zirconia fused alumina. The melting process of
the XRD. Therefore, no significant difference of the amount of MgO the MgO–ZrO2 material lasted only 60 s and the samples were cooled
was observed for the three preparation methods. down rapidly. Due to, fine grains with tiny crystallites size microstruc-
Cubic ZrO2 is recognized by the series of bands located in the region ture were created. According to compilation of temperature of 1600 °C
of 550 cm−1 400 cm−1. The dominant absorption band is centered at and pressure of 100 MPa in field assisted sintering technique, the condi-
458 cm−1. This strong band is associated to the Zr–O–Zr bond. Experi- tions of the process were drastically different than in conventional
mental MIR spectra, Fig. 8, of the samples processed by FAST and by sintering. These non-equilibrium conditions could influence and trigger
conventional sintering at 1700 °C are similar and they both show char- the appearance of liquid phase at temperature lower than it is apparent
acteristic bands occurring at 1088 cm− 1, 920 cm− 1, 853 cm− 1, from the MgO–ZrO2 phase diagram [34]. At a ratio of 1:1 mol% of MgO:
732 cm−1, 619 cm−1 and 527 cm−1. These bands originate from the in- ZrO2, Fig. 12, the melting temperature exceeds 2000 °C [34]. In agree-
ternal vibrations of ZrO2 molecules in the unit cell. Moreover, as it was ment with the mentioned studies, it could be assumed that the evolu-
already reported [50], a strong band vibrations of Mg–O masking vibra- tion and the creation of the final microstructures during arc melting
tions of Zr–O, which should be observed at about 500 cm−1 is clearly and field assisted sintering proceeded in a similar way. The crystalliza-
shown in the MIR spectra, Fig. 7. The presented results are in good tion and creation of ZrO2 and MgO grains proceeded from the liquid
agreement with those reported in literature [50]. These characteristic phase. Due to microstructure with dendrites of ZrO2 embedded into
infrared absorption bands are more intense for the samples obtained the MgO phase was observed in Figs. 10 and 11. During arc melting
by FAST and by the conventional sintering than in the case of arc melting. and field assisted sintering technique simultaneously the stabilization
In recent years, much effort has been given to the development of of ZrO2 by MgO and grow of ZrO2 dendrites under the form of the
the synthesis methods that intensify sintering and facilitate densifica- cubic structure proceeded. This microstructure is typical of fused-cast
tion. It is important to obtain materials with highest densities at the ceramics containing ZrO2 [51].
 E. Śnieżek et al. / Materials and Design 99 (2016) 412–420 419

The materials obtained by arc melting and field assisted sintering [15] T.D. Isfahani, J. Javadpour, A. Khavandi, M. Goodarzi, H.R. Rezaie, Nanocrystalline
growth activation energy of zirconia polymorphs synthesized by mechanochemical
technique, compared to conventional sintering, were characterized by technique, J. Mater. Sci. Technol. 30 (2014) 387–393 http://dx.doi.org/10.1016/j.
very specific microstructures. It is well known, that materials with low jmst.2013.10.012.
open porosity, well compacted and with strong ceramics bonding pre- [16] M. Salavati-Niasari, M. Dadkhah, F. Davar, Pure cubic ZrO2 nanoparticles by
thermolysis of a new precursor, Polyhedron 28 (2009) 3005–3009, http://dx.doi.
vent from corrosion and erosion effects. Therefore, they can be used to org/10.1016/j.poly.2009.06.032.
improve the service life of ceramics e.g. refractories. [17] D. Prakashbabu, R. Hari Krishna, B.M. Nagabhushana, H. Nagabhushana, C.
Shivakumara, R.P.S. Chakradar, H.B. Ramalingam, S.C. Sharma, R. Chandramohan,
Low temperature synthesis of pure cubic ZrO2 nanopowder: structural and lumi-
5. Conclusions nescence studies, Spectrochim. Acta A 122 (2014) 216–222 http://dx.doi.org/10.
1016/j.saa.2013.11.043.
[18] P. Dahl, I. Kaus, Z. Zhao, M. Johnsson, M. Nygren, K. Wiik, T. Grande, M.A. Einarsrud,
In this work, MgO–ZrO2 ceramics consisting of two major phases: Densification and properties of zirconia prepared by three different sintering tech-
MgO and ZrO2 cub. ss were prepared by three different methods. The ap- niques, Ceram. Int. 33 (2007) 1603–1610, http://dx.doi.org/10.1016/j.ceramint.
plication of conventional sintering at 1700 °C, arc melting and field 2006.07.005.
[19] J.E. Garay, Current-activated, pressure-assisted densification of materials, Annu. Rev.
assisted sintering technique resulted in obtaining biphasic materials. Mater. Res. 40 (2010) 445, http://dx.doi.org/10.1146/annurev-matsci-070909-
The XRD results suggest that no other polymorph of ZrO2 (monoclinic 104433.
and tetragonal) were detected in the samples. The Rietveld analysis re- [20] A.Z. Munir, D.V. Quach, Electric current activation of sintering: a review of the
pulsed electric current sintering process, J. Am. Ceram. Soc. 94 (2011) 1–19,
vealed different average crystallite sizes in each sample. The field
http://dx.doi.org/10.1111/j.1551-2916.2010.04210.x.
assisted sintering technique made it possible to obtain the material [21] Z.S. Ahmed, F.A. Chyad, SEM-assisted thermophysical and mechanical properties of
with the smallest crystallite sizes of 20.1 ± 2.5 nm and 27.0 ± 2.7 nm sintered MgO–ZrO2 composite, Energy Procedia 36 (2013) 872–880, http://dx.doi.
for MgO and ZrO2 cub. ss, respectively. These values are much lower org/10.1016/j.egypro.2013.07.100.
[22] T. Czeppe, P. Zięba, A. Pawłowski, Crystallographic and microchemical charac-
than those obtained by conventional sintering: 241.8 ± 5.1 nm for terization of the early stages of eutectoid decomposition in MgO–partially sta-
MgO and 220.8 ± 3.0 nm for ZrO2 cub. ss. Thus, arc melting and field bilized ZrO2, J. Eur. Ceram. Soc. 22 (2002) 35–40, http://dx.doi.org/10.1016/
assisted sintering are competitive methods to classical sintering in S0955-2219(01)00239-4.
[23] E.N.S. Muccillo, M. Kleitz, Ionic conductivity of fully stabilized ZrO: MgO and
order to process zirconia ceramics. blocking effects, J. Eur. Ceram. Soc. 15 (1995) 51–55.
[24] P.G. Medvedev, S.M. Frank, T.P. O'Holleran, M.K. Meyer, Dual phase MgO–ZrO2 ce-
ramics for use in LWR inert matrix fuel, J. Nucl. Mater. 342 (2005) 48–62, http://
Acknowledgement dx.doi.org/10.1016/j.jnucmat.2005.03.017.
[25] P.G. Medvedev, M.J. Lambregts, M.K. Meyer, Thermal conductivity and acid dissolu-
The work was partially supported by the statutory funds of the Fac- tion behavior of MgO–ZrO2 ceramics for use in LWR inert matrix fuel, J. Nucl. Mater.
349 (2006) 167–177, http://dx.doi.org/10.1016/j.jnucmat.2005.10.009.
ulty of Materials Science and Ceramics — AGH University of Science and [26] K. Holliday, T. Hartmann, G. Cerefice, K. Czerwinski, Environmental behavior of
Technology in Cracow, Poland. ZrO2–MgO ceramics containing UO2, Radiochim. Acta 99 (2011) 799–806, http://
dx.doi.org/10.1524/ract.2011.1884.
[27] O. Sarikaya, E. Celik, Effects of residual stress on thickness and interlayer of thermal bar-
References rier ceramic MgO–ZrO coatings on Ni and AlSi substrates using finite element method,
Mater. Des. 23 (2002) 645–650, http://dx.doi.org/10.1016/S0261-3069(02)00047-X.
[1] C. Piconi, G. Maccauro, Review zirconia as a ceramic biomaterial, Biomaterials 20 [28] X. Tian, Y. Zeng, T. Xiao, C. Yang, Y. Wang, S. Zhang, Fabrication and stabilization of
(1999) 1–25, http://dx.doi.org/10.1016/S0142-9612(98)00010-6. nanocrystalline ordered mesoporous MgO–ZrO2 solid solution, Microporous Meso-
[2] L. Jin, L. Ni, Q. Yu, A. Rauf, C. Zhou, Theoretical calculations of thermodynamic prop- porous Mater. 143 (2011) 357–361, http://dx.doi.org/10.1016/j.micromeso.2011.
erties of tetragonal ZrO2, Comput. Mater. Sci. 65 (2012) 170–174 http://dx.doi.org/ 03.015.
10.1016/j.commatsci.2012.07.008. [29] U. Anselmi-Tamburini, S. Gennari, J.E. Garay, Z.A. Munir, Fundamental investigations
[3] T. Czeppe, P. Zieba, W. Baliga, E. Dobrev, A. Pawlowski, Microstructure and phase on the spark plasma sintering/synthesis process: II modeling of current and temper-
composition of ZrO2–MgO structural ceramic after high-temperature deformation, ature distributions, Mater. Sci. Eng. A 394 (2005) 139, http://dx.doi.org/10.1016/j.
Mater. Chem. Phys. 81 (2003) 312–314, http://dx.doi.org/10.1016/S0254- msea.2004.11.019.
0584(02)00590-4. [30] X. Wang, S.R. Casolco, G. Xu, J. Garay, Finite element modeling of electric current-
[4] G.Y. Lin, T.C. Lei, Y. Zhou, In-situ TEM observations of tetragonal to monoclinic phase activated sintering: the effect of coupled electrical potential, temperature and stress,
transformation in ZrO2–2 mol% Y2O3 ceramics, Ceram. Int. 24 (1998) 307–312. Acta Mater. 55 (2007) 3611, http://dx.doi.org/10.1016/j.actamat.2007.02.022.
[5] B. Basu, J. Vleugels, O. Van Der Biest, Transformation behaviour of tetragonal zirco- [31] H.M. Rietveld, A profile refinement method for nuclear and magnetic structures, J.
nia: role of dopant content and distribution, Mater. Sci. Eng. A 366 (2004) Appl. Crystallogr. 2 (1969) 65–71, http://dx.doi.org/10.1107/S0021889869006558.
338–347, http://dx.doi.org/10.1016/j.msea.2003.08.063. [32] J. Rodriguez-Carvajal, Recent advances in magnetic structure determination by neu-
[6] I. Kuryliszyn-Kudelsk, M. Arciszewska, A. Małolepszy, M. Mazurkiewicz, L. Stobinski, tron powder, Physica B 192 (1993) 55–69, http://dx.doi.org/10.1016/0921-
A. Grabias, M. Kopcewicz, W. Paszkowicz, R. Minikaev, V. Domukhovski, N. Nedelko, 4526(93)90108-I.
W. Dobrowolski, Influence of Fe doping on magnetic properties of ZrO2 [33] P. Scherrer, Bestimmung der Größe und der inneren Struktur von Kolloidteilchen
nanocrystals, J. Alloys Compd. 632 (2015) 609–616 http://dx.doi.org/10.1016/j. mittels Röntgenstrahlen, Nachr. Ges. Wiss. Göttingen 26 (1918) 98–100.
jallcom.2015.01.257. [34] Y. Du, Z.P. Jin, Optimization and calculation of the ZrO2–MgO system, Calphad 15
[7] M.N. Tahir, L. Gorgishvili, J. Li, T. Gorelik, U. Kolb, L. Nasdala, W. Tremel, Facile syn- (1991) 59–68, http://dx.doi.org/10.1016/0364-5916(91)90026-G.
thesis and characterization of monocrystalline cubic ZrO2 nanoparticles, Solid [35] Q. Liu, S. An, W. Qiu, Study on thermal expansion and thermal shock resistance of
State Sci. 9 (2007) 1105–1109, http://dx.doi.org/10.1016/j.solidstatesciences.2007. MgO–PSZ, Solid State Ionics 121 (1999) 61–65 (PII: S0167-2738(98 )00529-3).
07.033. [36] L. Hao, J. Lawrence, The adsorption of human serum albumin (HSA) on CO2 laser
[8] K. Haberko, R. Pampuch, Influence of yttria content on phase composition and me- modified magnesia partially stabilised zirconia (MgO–PSZ), Colloids Surf., B 34
chanical properties of Y-PSZ, Ceram. Int. 11 (1958) 151, http://dx.doi.org/10.1016/ (2004) 87–94, http://dx.doi.org/10.1016/j.colsurfb.2003.12.008.
0272-8842(85)90251-2. [37] A. Glage, C. Weigelt, J. Räthel, H. Biermann, Fatigue behaviour of hot pressed austen-
[9] G. Róg, K. Haberko, A. Kozłowska-Róg, Determination of CaO activity in the mixture itic TWIP steel and TWIP steel/Mg–PSZ composite materials, Int. J. Fatigue 65 (2014)
{xCaO + (1 − x)ZrO2} at the temperature 1270 K by a galvanic cell involving 9–17 http://dx.doi.org/10.1016/j.ijfatigue.2013.11.025.
calcium-ion conducting solid electrolyte, J. Chem. Thermodyn.s 27 (1995) [38] W.C.J. Wei, Y.P. Jin, Mechanical and thermal shock properties of size graded MgO–PSZ
741–744, http://dx.doi.org/10.1006/jcht.1995.0075. refractory, J. Eur. Ceram. Soc. 20 (2000) 1159–1167 (PII: S0955-2219(99)00243-5).
[10] W. Pyda, K. Haberko, Zirconia stabilized with a mixture of the rare earth oxides, J. Eur. [39] T. Noguchi, M. Mizuno, Liquidus curve measurements in the ZrO2–MgO system with
Ceram. Soc. 10 (1992) 453–459, http://dx.doi.org/10.1016/0955-2219(92)90020-E. the solar Furnace, Bull. Chem. Soc. Jpn. 41 (1968) 1583–1587, http://dx.doi.org/10.
[11] W. Pyda, K. Haberko, CaO-containing tetragonal ZrO2 polycrystals (Ca-TZP), Ceram. 1246/bcsj.41.1583.
Int. 13 (1987) 113–118, http://dx.doi.org/10.1016/0272-8842(87)90048-4. [40] S. Serena, M.A. Sainz, S. Caballero, Experimental determination and thermodynamic
[12] R. Pampuch, W. Pyda, K. Haberko, The obtainment and properties of calcia-TZP, calculation of the zirconia–calcia–magnesia system at 1600°, 1700°, and 1750 °C, J.
Ceram. Int. 12 (1988) 245–249, http://dx.doi.org/10.1016/0272-8842(88)90028-4. Am. Ceram. Soc. 87 (2004) 2268–2274 10.1111/j.1151-2916.2004.tb07503.x.
[13] K. Witte, W. Bodnar, N. Schell, H. Lang, E. Burkel, High energy X-ray diffraction study [41] F. Grain, Phase relation in the ZrO2–MgO system, J. Am. Ceram. Soc. 50 (1967)
of a dental ceramics-titanium functional gradient material prepared by field assisted 288–290.
sintering technique, Mater. Charact. 95 (2014) 266–271 http://dx.doi.org/10.1016/j. [42] Y. Du, Z. Jin, Optimization and calculation of the ZrO2–MgO system, Calphad 15
matchar.2014.06.018. (1991) 56–68.
[14] C.J. Howard, R.J. Hill, B.E. Reichert, Structures of the ZrO2 polymorph at room tem- [43] L.F. Amaral, I.R. Oliveira, R. Salomão, E. Frollini, V.C. Pandolfelli, Temperature and
perature by high-resolution neutron powder diffraction, Acta Crystallogr. B 44 common-ion effect on magnesium oxide (MgO) hydration, Ceram. Int. 36 (2010)
(1988) 116–120. 1047–1054, http://dx.doi.org/10.1016/j.ceramint.2009.12.009.
420 E. Śnieżek et al. / Materials and Design 99 (2016) 412–420

[44] L.F. Amaral, I.R. Oliveira, P. Bonadia, R. Salomão, V.C. Pandolfelli, Chelants to inhibit [49] I. Jastrzębska, J. Szczerba, R. Prorok, E. Śnieżek, An experimental study on hydration
magnesia (MgO) hydration, Ceram. Int. 37 (2011) 1537–1542, http://dx.doi.org/ of various magnesia raw materials, Ceramics-Silikáty 59 (2015) 48–58.
10.1016/j.ceramint.2011.01.030. [50] Q. Wang, J. Li, X. Yang, Z. Shi, L. Xu, Investigation on performance of zirconia
[45] R. Salomão, L.R.M. Bittencourt, V.C. Pandolfelli, A novel approach for magnesia hy- and magnesia–zirconia stationary phases in hydrophilic interaction chroma-
dration assessment in refractory castables, Ceram. Int. 33 (2007) 803–810, http:// tography, Talanta 129 (2014) 438–447 http://dx.doi.org/10.1016/j.talanta.
dx.doi.org/10.1016/j.ceramint.2006.01.004. 2014.06.016.
[46] Y. Kato, N. Yamashita, K. Kobayaski, Y. Yoshizawa, Kinetic study of the hydration of [51] C. Patapy, N. Gey, A. Hazotte, M. Humbert, D. Chateigner, R. Guinebretiere, M.
magnesium oxide for a chemical heat pump, Appl. Therm. Eng. 16 (1996) 853–862, Huger, T. Chotard, Mechanical behavior characterization of high zirconia
http://dx.doi.org/10.1016/1359-4311(96)00009-9. fused-cast refractories at high temperature: influence of the cooling stage on
[47] X. Tang, L. Guo, C. Chen, Q. Liu, T. Li, Y. Zhu, The analysis of magnesium oxide hydra- microstructural changes, J. Eur. Ceram. Soc. 32 (2012) 3929–3939 http://dx.
tion in three-phase reaction system, J. Solid State Chem. 213 (2014) 32–37 10.1016/ doi.org/10.1016/j.jeurceramsoc.2012.04.043.
j.jssc.2014.01.036.
[48] G.K. Layden, G.W. Brindley, Kinetics of vapor-phase hydration of magnesium oxide,
J. Am. Ceram. Soc. 46 (1963) 518–522 http://dx.doi.org/10.1111/j.1151-2916.1963.
tb14602.x.