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Revista Romn de Materiale / Romanian Journal of Materials 2011, 41 (3), 240 - 247
Institutul Naional de Recuperare Medicin Fizic i Balneoclimatologie, Str. Ion Mihalache Nr. 11, sect. 1, Bucureti, Romnia
2
Universitatea Politehnica Bucureti, Str. G. Polizu nr. 1, sector 1, Bucureti, Romnia
3
Metav, Str. C.A.Rosetti Nr.31, sector 2, Bucureti, Romnia
1.
Introducere
1. Introduction
Zirconium oxide (ZrO2) is a ceramic material
that is often studied because it posseses excellent
properties (excellent mechanical properties at
elevated temperatures, high density and hardness,
high wear resistance, good chemical inertia, tensile
stregth)[1]. Zirconia is used in implants as hip
femoral head component due to it high strength,
high capacity to be polished and low friction
coeficient. Because it is chemically inert in
physiological environment the risk of infection is
reduced. As a material for implants, zirconia can be
used alone, mixed or coated with other oxide
materials [2,3]. There are well known polymorphic
forms of zirconia: monoclinic (M), which is
thermodynamically stable from room temperature
to about 1170oC, tetragonal (T) and cubic (C).
Monoclinic phase transformation of tetragonal
phase (T) occurs in the temperature range 1100oC
- 1200oC and is stable up to 2370oC and the cubic
shape (C) appears at 2370oC to 2689oC. To
eliminate the appearance of microcracks durring
cooling, ZrO2 must be stabilized with oxides such
as those of yttrium, calcium, magnesium, etc.[4,5]
Several
methods
(sol-gel
method,
hydrothermal, evaporation and condensation
processes, precipitation) have been described in
R.Rogojan, E. Andronescu, I.Iliescu, R. Truc, B.. Vasile / Sinteza i caracterizarea nano-pulberii de zircon stabilizat
cu oxid de calciu, obinut prin metoda sol-gel
241
2. Experiment
Metoda sol-gel a fost utlizat pentru
prepararea nanopulberii de zircon stabilizat cu
oxid de calciu. Precursorii folosii pentru obinerea
zirconei au fost clorura de zirconiu i propoxidul de
zirconiu.
2.1. Prima sintez a ZrO2 prin metoda solgel s-a realizat pornind de la clorura de zirconiu i
etanol. Pentru stabilizarea zirconei cu CaO (8%
procente masice) s-a adugat azotat de calciu.
Reacia a fost condus prin amestecarea soluiilor
de ZrCl4 (1M) (Merck) i Ca(NO3)2 (0,03M)
(Chimopar) i adugarea, n cantiti mici, a
etanolului (p.a., Chemical Company) pe baie de
ap la 60oC.
2.2. A doua sintez prin metoda sol-gel s-a
realizat pornind de la propoxid de zirconiu
(C12H28O4Zr 0,025M) (p.a., Fluka) i etanol (p.a.,
Chemical Company). Pentru stabilizarea zirconei
cu CaO (8% procente masice) s-a adugat
izopropoxid de calciu. Reacia a fost condus prin
adugarea izopropoxidului de calciu n soluia de
propoxid de zirconiu i adugare de etanol, n
picturi, cu amestecare pe baie de ap.
Vscozitatea solului a crescut pe msur ce
temperatura n baie a atins valoarea de 90oC.
Gelurile obinute prin rutele II.1 i II.2 au fost
lsate la maturare timp de 24 ore, apoi au fost
uscate la 100oC, timp de 24 de ore. Pulberile
obinute au fost tratate termic la 1000 oC/2 ore.
3. Rezultate i discuii
Pentru caracterizarea microstructural i
compoziional a nanopulberilor au fost utilizate
difracia de raze X (XRD), analiza termic com-
242
R.Rogojan, E. Andronescu, I.Iliescu, R. Truc, B.. Vasile / Synthesis and characterization of calcia stabilized zirconia
nano-powder, obtained by sol-gel method
2000
20
40
60
3000
I
x
20
60
1500
80
2000
I(cps)
I
I(cps)
40
1000
I
1000
500
I
U
100
400
80
I(cps)
I(cps)
300
60
200
40
100
20
0
20
40
60
2 theta/deg
20
40
60
80
2 theta/deg
R.Rogojan, E. Andronescu, I.Iliescu, R. Truc, B.. Vasile / Sinteza i caracterizarea nano-pulberii de zircon stabilizat
cu oxid de calciu, obinut prin metoda sol-gel
243
Dimensiunile de cristalit, conform relaiei Debye-Scherrer, pentru fazele cristaline ale C-ZrO2, tratat termic la 1000 C
0
Dimensions of crystallites according to Debye-Scherrer relation for C-ZrO2 cristaline phase of samples treated at 1000 C/2h.
Dimensiunea de cristalit (nm), corespunztoare distanei interplanare
Precursor
Dimensiunea medie de cristalit,
The size of crystallites (nm), corresponding to the distance interplanare
Average crystallite size (nm)
Precurso
ZrCl4
7.67
6.55
7.63
7.28
C12H28O4Zr
8.44
5 77
4.28
6.16
Exo
DTG
100
750
172
90
TG
60
74
80
600
800
1000
Temperature [ C]
TG
125
70
65
400
DTA
493
85
75
110
200
DTG
490
95
80
70
105
100
DTA
364
90
Weight loss [%]
114
200
400
600
800
1000
Temperature [ C]
b
a
Fig. 3 - Analiza termic complex a pulberilor de zircon obinute prin metoda sol - gel din clorura de zirconiu (a) i
propoxid de zirconiu (b) / Advanced Thermal Analysis of zirconia powder obtained by sol-gel method from anorganic (a) and
organic precursor (b).
244
R.Rogojan, E. Andronescu, I.Iliescu, R. Truc, B.. Vasile / Synthesis and characterization of calcia stabilized zirconia
nano-powder, obtained by sol-gel method
a
o
Fig. 4 - Imagini SEM pentru zircona obinut prin metoda sol-gel din ZrCl4, la 1000 C/2h / SEM images of zirconia obtained by sol-gel
o
method at 1000 C/2h started from ZrCl4 (a-x100000, b-x200000).
b
a
o
Fig. 5 -Imagini SEM pentru zircona obinut prin metoda sol-gel din C12H28O4Zr, la 1000 C/2h / SEM images of zirconia obtained by solo
gel method at 1000 C/2h started from C12H28O4Zr (a-x100000, b-x200000).
R.Rogojan, E. Andronescu, I.Iliescu, R. Truc, B.. Vasile / Sinteza i caracterizarea nano-pulberii de zircon stabilizat
cu oxid de calciu, obinut prin metoda sol-gel
245
c
0
Fig. 6 - a Imagine TEM pentru zircona obinut din precursori anorganici, tratat termic la 1000 C/2h, b imagine de nalt rezoluie,
c imagine de difracie de electroni pe arie selectat / a - Bright field TEM image of zirconia obtained, from inorganic precursors
o
0
at 1000 C/2h, b - High resolution TEM image of zirconia obtained at 1000 C/2h, c SAED (Selected area electron diffraction)
0
image of zirconia obtained at 1000 C/2h.
c
0
Fig 7 - a - Imagine TEM pentru zircona obinut din precursori organici, tratat termic la 1000 C/2h, b imagine de nalt rezoluie,
c imagine de difracie de electroni pe arie selectat / a - Bright field TEM image of zirconia obtained, from organic precursors at
0
0
1000 C/2h, b - High resolution TEM image of zirconia obtained at 1000 C/2h, c SAED (Selected area electron diffraction) image
0
of zirconia obtained at 1000 C/2h.
246
R.Rogojan, E. Andronescu, I.Iliescu, R. Truc, B.. Vasile / Synthesis and characterization of calcia stabilized zirconia
nano-powder, obtained by sol-gel method
Transmission
electron
microscopy
analysis shows that both powders have sizes
below 100 nm, and the precursor nature has a big
influence on the morphology of the obtained
powders. To be noticed is the fact that the
nanometric powder obtained from inorganic
precursors has an approximative dimension of 35
nm, lower than the powder obtained from organic
precursors (50 nm).
**********************************************************
Maris Berzins, Preparation and characterization of ZrO2
Al2O3 particulate nanocomposites produced by plasma
technique, Proc. Estonian Acad. Sci. Eng., 2006, 12 (4),
349.
4. Adrian Volceanov, Enik Volceanov, and Petru Ni, ZrO2
stabilization with complex rare-earth oxides mixture,
Roumanian Journal of Materials, 2004, 34 (2), 99.
R.Rogojan, E. Andronescu, I.Iliescu, R. Truc, B.. Vasile / Sinteza i caracterizarea nano-pulberii de zircon stabilizat
cu oxid de calciu, obinut prin metoda sol-gel
5. Bogdan tefan Vasile, Ecaterina Andronescu, Daniel Florea,
and Cristina Ghiulic, Structural investigations of scandiadoped zirconia nanopowders obtained by sol-gel method, Sci.
Bull., Series B, 2010, 72 (1), 81.
6. D.H. Aguilar, L.C. Torres-Gonzalez, L.M. Torres-Martinez,
T. Lopez, and P. Quintana, Ciencia UANL, Marzo 2003, VI
(1), 53.
7. Radu Piticescu, Claude Monty, Marija Kopsec, Adrian Motoc,
Ctlin Georgescu, and Barbara Malic, Zirconia based
nanoceramics - synthesis, processing and characterization,
Roumanian Journal of Materials, 2002, 32(2), 103.
8. S. K. Malhotra, Paramanand Singh, and A. Thirunavukkarasu,
Synthesis of Alumina-Zirconia Nanocomposites by Solgel
Process Materials and Manufacturing Processes, October 2006,
21(7), 652.
247
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Deformation mechanisms
Modelling with focus on molecular dynamics, discrete dislocation dynamics and crystal plasticity
Future directions
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