DOI :
10.2240/azojomo0322
May 19 2012
Michelina Catauro, Flavia Bollino, Ishu Kansal, Elie Kamseu, Isabella
Lancellotti, Cristina Leonelli
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This is an AZo Open Access Rewards System (AZo-OARS) article distributed
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Submitted: 28 March, 2011
Posted: 19 May, 2012
Topics Covered
AbstractKeywordsIntroductionMethods
and Materials Geopolymer
Preparation Geopolymer
Characterization Bioactivity
TestsResults and
Discussion Sodium Based
Geopolymers Potassium Based
GeopolymersConclusionsReferencesContact Details
Abstract
In this study three different geopolymer compositions have been investigated
and characterized as potential biomaterials. The first two geopolymer
formulations are mainly composed of metakaolin, with some silica additions in
order to achieve a Si/Al molar of 2.10 while the third one contains a reduced
amount of metakaolin and comprises mainly of silica gel with composition:
H24AlK7Si31O79 with Si/Al = 31.
Further, NaOH pellets and sodium silicate (Na2SiO3) were
added in the first two formulations in different concentrations as activator and
ligand, respectively, while KOH additions were made to the third geopolymer
formulation (separately or jointly with potassium silicate solution). Room
temperature consolidation was followed by thermal activation of composition with
Si/Al=31 at 60 °C for 150 min and at 500 °C for 180 min. The work presents
exhaustive microstructural characterization (infrared spectroscopy, electron
microscopy and X-ray diffraction) of as synthesized geopolymer samples in
conjunction with their mechanical and in vitro bioactivity evaluation. The
materials were composed of amorphous aluminosilicates with a limited amount of
zeolitic phases, found on the top surface. The compressive strength of the first
two compositions was higher than 15 MPa and flexural strength around 2 MPa after
2 days of curing at room temperature. Compressive strength tests were carried
out on composition with on Si/Al = 31 geopolymer on both activated sample series
and demonstrated that when added separately the activator leads to more fragile
specimens (0.90 MPa vs. 1.95 MPa). To the best of authors’ knowledge the effect
of geopolymer preparation on mechanical properties of thermally activated Si/Al
= 31 formulation has never been proved before. The bioactivity was successfully
tested with the soaking of the samples in a simulated body fluid (SBF) for 3
weeks. The formation of a layer of hydroxyapatite on the surface of the
materials was shown both by SEM micrograph and EDS analysis.
Keywords
Geopolymers, FTIR, Bioactivity, Compressive Strength, Molar Ratio Si/Al =
31
Introduction
In the biomaterials field, some systems based on amorphous silicate network
like bioactive glasses1, calcium phosphates2,3,
aragonite4, are successfully applied in bone surgery. As a matter of
fact numerous synthetic aluminosilicates5,6, possess chemical
properties which offer employment as bone graft biomaterials. Among these
aluminosilicates also geopolymers can be listed. They can be defined as
cementitious materials that are formed by mixing aluminosilicate powders (e.g.,
metakaolin) with alkali or alkali-silicate solution7-10.
The formation of
[Mz(AlO2)x(SiO2)y.MOH.H2O]
gel, which essentially relies on the dissolution of aluminosilicates materials,
is a dominant step in geopolymerisation. When the gel phase hardens, the
separate aluminosilicate particles are bound together with the gel which acts as
binder11. Authors12,13 have described the reaction process
of the gel formation indicating that Al-Si solid particles in alkaline solution
conduct to the formation of monomers -OSi(OH)3 and
Al(OH)4-. The successive reactions between these monomers, alkali
ions and water results in the formation of dimer and longer chains14.
The final geopolymers are then formed with tightly packed 3D semi-crystalline
microstructure with good mechanical properties15,16. Typically,
better strength behaviour is obtained for mixtures with Si/Al molar ratio in the
range of 1.65-2.10 combined with Na/Al ratio near 1. Increased silica content
usually reduces the mechanical strength while multiple alkali sources, KOH and
NaOH, can act in a synergistic way to promote samples of optimal chemical and
mechanical characteristics13,14,17. The compressive strength of
geopolymer materials depends on a number of factors including gel phase
strength, the ratio of gel phase/undissolved Al-Si particles size, the
distribution and the hardness of the undissolved Al-Si particles, the amorphous
nature of geopolymers or the degree of crystallinity as well as the surface
reaction between the gel phase and the undissolved Al-Si particles.
High mechanical strength of geopolymers results on the rapid solidification
within hours and rapid early strength development, as it is already known for
phosphatic dental cements18. In addition a good level of porosity can
be easily introduced at room temperature by adding specific
additives19. Both these characteristic make these materials
attractive for hard tissue prostheses or bone fillers and bindings.
Even though these types of materials are particularly interesting for their
fast strength development, their bioactivity or at least biocompatibility has
not yet been investigated extensively. The aim of the present paper is to
investigate the application of metakaolin based geopolymers as potential
biomaterials as well as studying the effect of sample preparation on silica rich
metakaolin geopolymer already proposed in literature as bony
filling6. The preparation and characterization of a total of three
different formulations are reported.
Methods and Materials
Geopolymers Preparation
Metakaolin (MK) was used as the principal source of aluminosilicate. The
choice was based on the fact that it improves mechanical strength and reduces
the transport of water and salts in the final product. Metakaolin, with a molar
ratio Si/Al = 2.10, was prepared by calcining kaolinitic clay at 700 °C in
muffle oven for 2 hrs.
Two different formulations of geopolymer materials, containing different
amount of NaOH and with two different Na/Al ratios, were prepared as shown in
Table 1.
Laboratory grade NaOH pellets and distilled water were used to prepare 8M
alkaline solution. Sodium silicate solution (grade N, RM3, 0 from Ingessil
s.r.l., Verona, Italy) with a mol/mol ratio of SiO2/Na2O
equal to 2.99 was used.
Designated quantities of sodium hydroxide and silicate solutions were mixed
with 100 g batches of metakaolin (solid/liquid ratio of 1.66). No additional
water was added apart from that of NaOH and Na-silicate20. Overall
porosity, 60vol%, is visible in Figure 1a.
Table 1. Formulation of the two geopolymers, with Si/Al =
2.10, prepared for this study (Na silicate solution used: 30 ml per 100 g
MK)
Composition |
NaOH 8M
Solution |
Na/Al |
Curing
time (days) |
GP120 |
20 ml/100g MK |
0.77 |
15 |
BGP130 |
30 ml/100g MK |
1.05 |
30 |
.jpg)
Figure 1. Optical micrograph of (a) GP120 (BGP130 has
similar microstructure) and (b) BGP3 P (BGP3 S has similar microstructure) bulk
samples.
The resulting slurries were stirred mechanically for about 10 min to reach
good homogenization, and then poured in a closed polyethylene mould for 12 hrs
at room temperature before demoulding. The curing time was 30 days for both the
compositions.
In order to reduce the impact of non-bonded Al atoms in the final product, an
increase of silica was operated by SiO2 additions to MK. Thus the
percentage of Al present in the final formulation decreased to Si/Al =31, but,
at the same time, the effect of 3D bonded silica chains increased the network
connectivity, decreasing Al release4-6.
Table 2. Silica rich formulation and details of
activation: P refers to sample prepared using pellets of KOH directly added to
K- silicate (water added =35ml). S refers to sample prepared using 8M KOH
solution (water added =25ml).
SAMPLE |
Activ. |
Label |
Consolidation |
Thermal
treatment |
B-GP1 |
P |
B-GP1P |
3 or 4 days in a closed plastic bag |
none |
|
S |
B-GP1S |
3 or 4 days in a closed plastic bag |
none |
B-GP 2 |
P |
B-GP2P |
1 day in Teflon® container prior thermal treatment |
60°C in Teflon® for 150 min |
|
S |
B-GP2S |
1 day in Teflon® container prior thermal treatment |
60°C in Teflon® for 150 min |
B-GP 3 |
P |
B-GP3P |
treated after one week from preparation |
Same as B-GP 2 plus 500°C for 180 min |
|
S |
B-GP3S |
treated after one week from preparation |
Same as B-GP 2 plus 500°C for 180 min |
Following literature formulation of Oudadesse et al.4-6 a third
geopolymer sample is here proposed with theoretical formula:
H24AlK7Si31O79. The raw materials
used were KOH, K2SiO3 and SiO2 apart from the
previously mentioned metakaolin. Laboratory grade KOH pellets and distilled
water were used to prepare 8M alkaline solution (4.45 g of solution in 1.225 g
of MK) or were directly added to the potassium silicate solution (1.995 g in
7.164 mol). Potassium silicate solution (grade N, RM3, 0 from Ingessil s.r.l.,
Verona, Italy) with a mol/mol ratio of SiO2/K2O equal to
3.10 was used. In both procedures, 1.225 g MK was added with 14.655 g of
SiO2 and consolidation was performed as reported in Table 2. The
SiO2 added was completely amorphous in nature which was produced
hydrothermally from natural silicates21.
Thermal cycles for consolidation the 3D silica network were applied, as
reported in Table 2, following literature indications4-6.
Microstructure of BGP3 P sample is visible in Figure 1b.
Geopolymer Characterization
The final geopolymers were tested for crystalline phases evolution with X-Ray
diffraction (XRD) on both surface and bulk of each sample (Philips Electronic
Instruments, model PW 1730).
The compressive strength was determined by using mechanical testing machine
Instron, USA. The end surfaces of specimens and surface were polished flat and
parallel to avoid the requirement for capping. The cylinders (2 cm diameter x 4
cm thickness) were centred in the compression-testing machine and loaded to
complete failure. The compressive strength was calculated by dividing the
maximum load (N) at failure by the average cross-sectional area (m2).
The final result is the average value of three tested specimens.
Fourier transform infrared (FTIR) transmittance spectra were recorded in the
400-4000 cm-1 region using a Prestige 21 Shimatzu system, equipped
with a DTGS KBr (Deuterated Tryglycine Sulphate with potassium bromide windows)
detector, with resolution of 2 cm-1 (45 scans). KBr pelletised disks
containing 2 mg of sample and 200 mg KBr were prepared. FTIR spectra were
elaborated by Prestige software (IRsolution).
Bioactivity Tests
In order to study their bioactivity, one disc per each composition was soaked
in a simulated body fluid (SBF) solution with ions concentration nearly equal to
those in human blood plasma (Table 3), at 37 °C and in a polystyrene bottle, as
scheduled by bioactivity test in vitro22. The SBF solution was
prepared by dissolving reagent grade chemicals NaCl, NaHCO3, KCl,
MgCl2•6H2O, CaCl2,
Na2HPO4, Na2SO4 (Sigma-Aldrich) in
ultra-pure water and buffered at pH 7.4 using HEPES sodium salt
(C8H18N2O4SNa) (Sigma-Aldrich) and
1M NaOH.
Table 3. Simulated body fluid (SBF) ionic concentration
(mM).
|
Na+ |
K+ |
Mg2+ |
Ca2+ |
Cl- |
HCO3- |
HPO42- |
SO42- |
Human blood plasma |
142.0 |
5.0 |
1.5 |
2.5 |
103.0 |
27.0 |
1.0 |
0.5 |
SBF |
142.0 |
5.0 |
1.5 |
2.5 |
148.0 |
4.2 |
1.0 |
0.5 |
In these tests the ratio between the total surface (ST) of the material in
contact with the SBF solution and the volume of such solution (VSBF)
influence the reaction of formation of a hydroxyapatite layer. A constant ratio
of ST/VSBF =10 mm2/ml was used.
After an immersion periods of 21 days, the materials were removed from the
SBF, gently washed with ultra-pure water, and dried at 40 °C. The ability to
form an apatite layer was studied by Environmental Scanning Electron Microscopy
(ESEM QUANTA 200) observations coupled with energy dispersion spectroscopy- EDS
(X-EDS Oxford INCA-350) analyses.
Results and Discussion
Sodium Based Geopolymers
Sodium based geopolymer composition proposed here are capable of offering a
controlled porous material when appropriately added with a poring agent as
reported in literature19. Final bulk density value was about
1.56-1.55 g/cm3 with a porosity of 38 ± 5.1
vol. %; compressive strength 15.0 ± 4.4 MPa, bi-axial
flexural strength 8.0 ± 4.5 MPa. Since the mechanical
characterization has been reported elsewhere19,23, in this
contribution we are focused only on their application as biomaterials. With this
in mind we started with a complete microstructural characterization of the two
formulations GP120 and BGP130.
The two geopolymer formulations were analysed by XRD on both the surface and
bulk in order to evaluate material’s structure uniformity and the nature of the
geopolymeric gel. The bulk of both samples show traces of the kaolinitic clay
which is, not fully transformed into metakaolin, as it always happen in
industrial processes. XRD pattern of GP120 (Figure 2) is reported as an example
since for BGP130 the same crystalline phases were identified. The geopolymer
appears largely amorphous with traces of crystalline phases. In particular the
following phases were identified: monoclinic kaolin
Al2Si2O5(OH)4 (JCPDF file 05-0221),
monoclinic nacrite 2M Al2Si2O5(OH) 4
(JCPDF file 16-0606), which is a phyllosilicate clay mineral polymorph of
kaolinite, along with traces of another phyllosilicate with monovalent cation
and possibly muscovite 1M-like structure,
KAl2Si3AlO10(OH)2 (JCPDF file
07-0025). Furthermore, as a consequence of the reaction between metakaolin and
the alkaline solutions, Na-aluminosilicates were developed, such as
Na4Al2Si2O9 (JCPDF file 10-0031) and
Na6Al4Si4O17 (JCPDF file 10- 0033).
During geopolymerization the dissolution and nucleation of gel are generally
exothermic reactions so the energy of gel growth to polysialates is not enough
to conduct to crystalline phases. Therefore a significant broad band due to the
amorphous nature of the geopolimeric gel is also evident in all the XRD patterns
for both the compositions.
Kaolinite and nacrite were observed on the surface probably as traces of the
unreacted kaolinitic clay used in the synthetic process along with Na-
aluminosilicate Na2Al2SiO6 (JCPDF file 30-1148)
due to the reaction with the alkaline solution (Figure 3). In addition, a
carbonate phase, possibly trona
Na3H(CO3)2.2H2O (JCPDF file 29-1447)
was also evident, due to the reaction with the atmosphere.
.jpg)
Figure 2. XRD pattern of GP120 bulk sample (K =
kaolinite, N = nacrite, M = muscovite, Na = Na-aluminosilicates)
.jpg)
Figure 3. XRD pattern of GP120 sample surface (T = trona,
K = kaolinite, N = nacrite, M = muscovite, Na =
Na2Al2SiO6)
In the geopolymers FTIR spectra, an approximate relationship between the
frequency of the absorption bands and the ratio of Si:Al in the aluminosilicate
framework was observed by Milkey24: the higher the Al inclusions, the
lower the wavelength. In Figures 4 and 5 the spectra of samples GP120 and
BGP130, respectively, inner and surface parts are shown. All the spectra present
the strongest vibration typical of all aluminosilicates (see Table 3), which are
assigned to internal vibrations of Si-O-Si and Si-O-Al. In addition other common
feature are present: two absorption bands at about 3450 and 1650 cm-1
resulting from hydration water, a strong Si-O stretching vibration at about
1080-1100 cm-1 and Si-O bending vibration at about 450-470
cm-1. Moreover, the bands between 600-800 cm-1 are due to
Al-O-Si vibrations25,26 : in particular, the bands at 798
cm-1 are due to Al-O stretching vibrations. The surface spectra
(Figures 4B and 5B) show Al-OH stretching vibrations at 914-916 cm-1
while Si-OH bending vibrations, at 850 cm-1, are present only in
BGP130 surface spectrum (Figure 5a). The presence of a band at 1460 cm-
1 in Figure 4b and 5b indicates that sodium carbonate species are present
on the surface of this sample confirming the XRD results which shows the
reactivity of the surface with the atmosphere. The absence of this band in
Figure 4a and 5a indicates that sodium carbonate species are not present in the
samples inner part27.
.jpg)
Figure 4. FTIR of sample GP120 (a) inner and (b) surface
part
.jpg)
Figure 5. FTIR of sample BGP130 (a) inner and (b) surface
part.
Table 4. IR characteristic bands and their
interpretation
Absorption
Bands |
Interpretation |
3450 and 1650 cm-1 |
hydration water |
1080-1100 cm-1 |
Si-O stretching vibration |
450-470 cm-1 |
Si-O bending vibration |
840 cm-1 |
Si-OH bending vibration |
798 cm-1 |
Al-O stretching vibration |
914-916 cm-1 |
Al-OH stretching vibration |
600-800 cm-1 |
Al-O-Si vibrations |
1460 cm-1 |
Na2CO3 |
The microstructural characterization has been conducted by scanning electron
microscopy (ESEM/EDS) in order to compare the two geopolymer formulations and
their different behaviour (Figure 6). Both the samples do not show porosity in
the micrometric range. The overall porosity19 has been measured with
Archimede’s method. The absence of pores of micrometric size, confirmed by ESEM
micrographs, is due to a well designed formulation. In addition the good
mechanical properties are justified by the nanometric size of pores. These
pores, generally called gel pores (< 15 nm) are too small to affect the
mechanical properties28.
GP120 shows a homogeneous microstructure with some incompletely dissolved
grains embedded in a compact geopolymeric gel. EDS analysis of grains revealed
that they contain alumina and silica in an atomic ratio near to 1 suggesting
that they are metakaolin particles. On the other hands, BGP130 composition shows
a two-phase microstructure characterized by two geopolymeric gels with different
Na content. The grainy one contains higher amount of Na (average Na/Al = 0.64)
with respect to the smooth one (average Na/Al = 0.53) (Figure 6b and 6c). In
addition, a particle rich in potassium is also evident which can be attributed
to muscovite, clayey crystalline phase identify by XRD. Both the geopolymers
exhibit good mechanical properties; therefore the sample integrity is not
degraded by the presence of granular inclusions.
.jpg)
Figure 6. ESEM micrographs of (a) GP120, (b) and (d)
BGP130. (c) reports EDS data collected in area 1 and 2 of image in (b).
Moreover an evaluation of the morphology of the apatite deposition, after
bioactivity tests, and a qualitative elemental analysis were also carried out by
SEM accompanied by EDS as reported in Figure 7, which shows ESEM micrographs of
GP120 soaked in SBF for 21 days. The layer of apatite is not visible on sample
surface, proving that this particular formulation is not bioactive. BGP130, on
the contrary, is bioactive: in fact the characteristic apatite globular crystals
are clearly visible29, as shown in Figures 7,b and c. These studies
were considered sufficient to identify the presence of apatite on the geopolymer
surface; additional XRD investigations were not possible due to the extremely
low amount of the newly formed crystalline phase.
.jpg)
Figure 7. ESEM micrograph of (a) GP120 and (b) BGP130
after soak in SBF for 21 days. (c) enlargement of (b).
A possible explanation for this different bioactive behaviour is the presence
of a greater number of –Si–ONa and –Al–ONa groups on the surface of BGP130
(Na/Al = 1.05) when compared to GP120 (Na/Al = 0.77). As reported in the
literature30,31 when exposed to SBF, sodium silicate glasses and
ceramics released Na+ ions via exchange with
H3O+ ions in SBF to form Si–OH and Al–OH groups on their
surface; this reaction causes a pH increase of SBF solution and, consequently,
Si-OH and Al-OH groups are dissociated into negatively charged units Si–O-.
These groups combine with Ca2+ ions present in the fluid imposing an
increase of positive charge on the surface. In addition Ca2+ ions
combine with the negative charge of the phosphate ions to form amorphous
phosphate, which spontaneously transforms into hydroxyl-apatite
[Ca10(PO4)6 (OH)2] where the atomic
ratio Ca/P is 1.6032. The EDS analysis confirms that the surface
layer observed in the SEM micrographs consists of calcium phosphate showing
contents of Ca:P (atomic %) 3.14:1.95 for a value of Ca/P=1.61. Before
biomedical applications of this porous metakaolin based geopolymer the issue of
the potential problems caused by the alkalinity as well as the possible leaching
of Al into the SBF should be addressed. As reported in literature, the highly
alkaline nature of the material can induce cell death, and the effect of
aluminium leached from the implant in living organisms is controversial; some
authors33-35 report that low aluminium concentrations lead to brain
disease, although lower concentrations of aluminium may be beneficial and
stimulate the proliferation of osteoblasts and new bone formation31. However,
with various approaches it is possible to obtain stable geopolymers both in
vitro and in vivo5,36.
Potassium Based Geopolymers
Potassium based geopolymers have already been tested in vitro and in
vivo4-6 and they show high bioactivity/compatibility. Oudanesse et
al.5 demostrated that amorphus geopolymers of the
potassium-poly(sialate)-nanopolymer type, obtained with molar ratios Si:Al = 31,
K2O:SiO2= 0.54 and thermally-treated at 500 °C, give
excellent results in terms of biological compatibility. This geopolymer matrix
was able to reduce alkalinity and the amount of free aluminium and to provide
high porosity for biological compatibility. Hereafter the mechanical resistance
evaluation only is reported being the two activation processes used responsible
of differences in gel consolidation.
Mechanical characterization was performed on B-GP2P and B-GP2S after the
complete curing at 30 days from the preparation and thermal treatment at 60 °C
in Teflon® container for 150 min. Both formulations present a sort of plastic
behaviour showing a long plateau before rupture at 1 MPA for B-GP2P and 2MPa for
B-GP2S (Figure 8). With the high amount of silica to be activated this behavior
is expected37.
.jpg)
(a)
.jpg)
(b)
Figure 8. Compression resistance of (a) B-GP2P and (b)
B-GP2S after thermal treatment at 60 °C.
FTIR spectra (Figure 9) of potassium based geopolymers show the typical
alluminosilicate vibrations presented in Table 4. Depending on thermal
treatment, the bands at about 790 cm-1, due to Al(IV)-O stretching
vibrations, increase and the shoulders at about 960 cm-1, due to
Al(IV)-OH stretching vibrations, decrease. A possible explanation is that during
the geopolymerization, there is a progressive formation of Al(IV) species and a
reduction of the number of Al(IV)-OH groups. Moreover, it is evident that there
are not many differences between geopolymer matrix obtained with procedure S or
P (Figure 9), except for B-GP3S and B-GP3P. In B-GP3P spectrum an intense band
at about 1420 cm-1 is evident due to carbonate high amount. The
intensity of this band is smaller in all other spectra. Moreover, the shoulder
at about 960 cm-1 decreases in B-GP3P and disappears in B-GP3S.
.jpg)
(a)
.jpg)
(b)
Figure 9. FTIR spectra of geopolymer obtained according
to procedures (a) P and (b) S.
Chemical alkali activation according to procedure S, i.e. KOH pellets added
to K2SiO3 solution shows some un-reacted metakaolin area
in untreated B-GP1S material (Figure 10). Similar areas are present also in
B-GP1P but here the platelet typical of metakaolin morphology are not so well
defined indicating that alkali attack has already begun.
These areas completely disappear after the 60 °C-treatment when a more
uniform microstructure is reached (Figure 11). In particular S procedure lead to
more bonded microstructure as visible in Fig. 10 from the reduced number of
fracture surfaces in sample B-GP2S with respect to B-GP2P, confirming what
observed in the compression resistance tests.
.jpg)
Figure 10. ESEM micrograph of (a) B-GP1P and (b) B-GP1S
soon after preparation. Yellow circle evidence non reacted metakaolin area.
After the 500 °C, the microstructure maintains as in Figure 11, accordingly to infrared conclusions of very similar materials.
.jpg)
Figure 11. ESEM micrograph of (a) B-GP2P and (b) B-GP2S
after 60 °C thermal treatment.
Conclusions
The study presents two formulations (GP120 and B-GP130) of metakaolin based
geopolymers activated with NaOH which have been tested in vitro for bioactivity.
The hydroxyl-apatite
[Ca10(PO4)6(OH)2] formation was
observed only on the surface of geopolymer BGP130 after immersioni n SBF
solution for 21 days. Their high intrinsic compressive strength (recorded to be
> 50 MPa) and the capability to form also porous structures (~60 vol. %), is
indicative for their suitability for applications as hard tissue prostheses.
The third formulation proposed in the study, silica rich MK geopolymer
activated with KOH/K2SiO3, has been tested mechanically to
evaluate the consolidation process as a function of the activation procedure.
The activation procedure that requires the addition of KOH pellets to K-
silicate solution leads to materials with higher compressive strength. The
results indicate that the order of addition of the reactants in the activation
step is important and affects mechanical properties even though thermal
consolidation is performed.
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Contact Details
Michelina Catauro Department of Aerospace and Mechanical
Engineering, Second University of Naples, Via Roma 21, 81031
Aversa, Italy E-mail : [email protected] |
Flavia Bollino Department of Aerospace and Mechanical
Engineering, Second University of Naples, Via Roma 21, 81031
Aversa, Italy E-mail : [email protected] |
|
|
Ishu Kansal Department of Ceramics and Glass
Engineering, University of Aveiro, CICECO, 3810-193
Aveiro, Portugal. E-mail: [email protected] |
Elie Kamseu Department of Materials and Environmental
Engineering, University of Modena and Reggio Emilia, Via Vignolese
905, I-41100 Modena, Italy E-mail : [email protected] |
|
|
Isabella Lancellotti Department of Materials and Environmental
Engineering, University of Modena and Reggio Emilia, Via Vignolese
905, I-41100 Modena, Italy E-mail : [email protected] |
Cristina Leonelli Department of Materials and Environmental
Engineering, University of Modena and Reggio Emilia, Via Vignolese
905, I-41100 Modena, Italy E-mail : [email protected] |