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Preparation and magnetoelectric
properties of NiFe2O4-PZT ceramic
compositesCristina E. Ciomaga1*, M. Airimioaei2, V. Nica1,
L.M. Hrib1, O.F. Caltun1, A. R. Iordan2, C. Galassi3,
L. Mitoseriu1and M. N. Palamaru21Faculty of Physics, Al. I. Cuza University Iasi 700506, Romania
2Faculty of Chemistry, Al. I. Cuza University Iasi 700506, Romania3ISTEC-CNR, Via Granarolo no. 64, I-48018 Faenza, Italy
5th International Workshop on
Iai, 5-7 September 2011
*Corresponding Author email: [email protected]
mailto:[email protected]:[email protected] -
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OutlineI. Introduction
Magnetoelectric composite ceramics - the concept of
synergyeffect. Reported results.
II. Our approach: preparation by citrate-nitrate gel-combustion using template powders obtained by mixedoxides methods in order to induce new functional properties.
III. The PZT with NiFe2O4ceramic compositePowder and ceramic preparationStructural and microstructural characterization by XRD and
SEMMagnetic propertiesDielectric propertiesMagnetoelectric effect
IV. Conclusions and future work.
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MEeffect
Diel/FEFM/AF/Ferri
Composite materials: combining di-similar materials in compactstructures in order to obtain new properties (sum, combinatoryorproductproperties) and multifunctionality.
I. Introduction
J. Van Suc hetelene, Phil ips Res. Rep. 27, 28 (1972)
Magnetoelectric (ME) composites coupling viamagnetostrictive-piezoelectric effect:
Idea: (1972) 2 phases individually notshowing a property canachieve it, if appropriately combined or coupled in a composite.
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Conditions for the ME composites:
Homogeneous, well dispersed diphase microstructures;
No chemical reactionsbetween the two phases;
High density, no mechanical defects(pores, craks) for goodmechanical coupling, dielectric and ME properties;
High resistivityof the Mphase, compositions below thepercolation limitand/or no connectivityfor the M phase.
J. Ryu et al., Magnetoelectric effect in composites of magnetostrictive and piezoelectricmaterials, J. Electroceramics, 8, 107 (2002).M. Fiebig, Revival of the magnetoelectric effect, J. Phys. D: Appl. Phys. 38, R123 (2005);
S. Priya, Recent advancements in magnetoelectric particulate and laminate composites, J.Electroceram. 19, 147 (2007).C.W. Nan et al., Multiferroic magnetoelectric composites: Historical perspective, status, andfuture directions, J. Appl. Phys. 103, 031101(2008). Junyi Zhai et, al, Magnetoelectric Laminate Composites: An Overview, J. Am. Ceram. Soc., 91[2] 351358 (2008).Li Yan et al., Review of magnetoelectric perovskite-spinel self-assembled nano-composite thinfilms, J. Mater Sci, 44:5080 (2009).J.Ma et al., Recent progress in Multiferroic Magnetodielectric Composites: from Bulk to ThinFilms, Adv. Mater., XX, 1-26 (2011).
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formed by:BaTiO3 with:
CoFe2O4NiFe2O4
LiFe5O8Ni(Co,Mn)Fe2O4,MnFe1.8Cr0.2O4,LaMnO3, terphenol-D, etc.
PZT, PMN-PT with CoFe2O4, NiFe2O4and Ni(Co,Mn)Fe2O4Bi4Ti3O12 with CoFe2O4
J. Van den Boomgaard and R.A.J. Born, J. Mater. Sci, 13, 1538 (1978)I. Bunget and T. Raetchi, Phys. Stat. Solidi a 63, K55 (1981)K.K. Patankar et al, Mat. Sci. Eng. B87, 53 (2001)Z. Yu, C. Ang, J. Mater. Sci.: Mater. Electr. 13, 193 (2002)G. Shrinvasan et al., Phys. Rev. B 67, 014418 (2003M.I. Bichurin et al., Phys. Rev. B68, 132408 (2003)L. Mitoseriu and V. Buscaglia, Phase Trans. 79 (2006) 10951121Q.H. Jiang, Z.J. Shen, J.P. Zhou, Z. Shi, C.W. Nan, J. Eur. Ceram. Soc.27, 279, (2007)
H. Zhang, S.W. Or and H.L.W. Chan, J. Appl. Phys. 104 (2008)
Sintered bulk composites with the three common connectivity schemes:(a) 03 particulate composite, (b) 22 laminate composite, and (c) 13fiber/rod composite.
Reported results:
(a) (c)(b)
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Desirable properties
Superior and/or new functional characteristics;
Preserving the intrinsic properties of the parent phases(ferroelectric and magnetic order) and inducing new properties:
- by interphase coupling in di-phase composites;
- by controlling the chemical reactions at interfaces.
Problems reported in ceramic composites:
Poor control of the microstructures;
Impossibility to isolate the magnetic phase;
Uncontrolled chemical reactions at interfaces;
Poor reproductibility of their properties.
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Methods for producing ME composites
Mixing of the phases separately prepared
The large majority of publications reported the use of thismethod to obtain ME composites.
In situ preparation of the composites:
- coprecipitation, gel-combustionP. Padmini et al., J. Mater. Chem. 4, 1875 - 1881(1994)L. Mitoseriu et al., J. Eur. Ceram. Soc. 27, 43794382 (2007)A. Iordan et al., J. Eur. Ceram. Soc. 29 (13): 2807-2813 (2009)
- core-shell powder compositesC. Huber et al., Ceram. Inter. 30, 1241-1245 (2004)
Y.S. Koo et al., Appl. Phys.Lett. 94, 032903 (2009)Y. Deng et al., Adv. Mater. 21, 1-6 (2009) M.S. Park et al., Phys. Rev.B 79, 024420 (2009)
followed by appropriate sintering to
obtain dense ceramics.
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II. Our approach:
to produce ME ceramic composites with 0-3 connectivity usingwet-chemistry and solid-state methods;
appropriate sintering strategy to control
(i) phase assemblage (isolation of the magnetic phase: 0-3 connectivity)
(ii) chemical reactions at interfaces;
expected to drive towards new functional properties.
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III. Preparation and functionalproperties of Pb(Zr,Ti)O3-NiFe2O4
magnetoelectric ceramics
prepared in situby gel-combustion method
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- NiFe2O4: inverse spinel structure
- PbZrxTi1xO3: ferroelectric perovskite ABO3
NiFe2O4 (NFO) with Pb(Zr,Ti)O3 (PZT): xNF-(1-x)PZT
ceramic compositesx=2, 5, 10, 20 and 30 %
using pure PZT-based template powders;NFO by citrate-nitrate gel-combustion method.
Investigated ceramics
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Powder and ceramic preparation
NiFe2O4
Pb(Zr0.47Ti0.53)O3
Pb(Zr,Ti)O3powder
(ss)
Fe
3+
, Ni
2+
,nitric salts
C6H8O7.H2O
Viscous
gel
Self-
combustion at
3500C
Ni(NO3)2.6H2O Fe(NO3)3.9H2O
C6H8O7.H2O
PZT template
powder
Stirring (60 min)
Continuous stirring & heating
at 80C
Viscous gel
Self-combustion
Heating
treatment
PZT-NiFe2O4composites
Stirring & pH adjusting
Nitrate solution
Mixture PZT-(nitrate-
citric acid solution)
Foamy
product
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Structural characterization by XRD
indicates the presence of NiFe2O4spinel phase and preserving thePb(Zr,Ti)O3ferroelectric phase;
after sintering at 12000C/1h -diphase ceramic composites (thelack of secondary phases at
interfaces).
Pure di-phase powder compositeswith a good crystallinity wereobtained after the calcination step.
20 30 40 50 60 70 800
500
1000
1500
2000
2500
3000
3500
4000
x=30%
x=20%
x=10%
x=5%
xNF-(1-x)PZT after calcination
2 Theta (CuK)
Intensity(a.u.)
x=2%
NiFeO4PZT
(220) (311) (222) (203) (422) (511) (440) (533)
(001)(100)
(110)(101)
(111) (200) (201) (211) (220)
(202)
20 30 40 50 60 70 80
0
1000
2000
3000
4000
5000
6000
7000
(620)
(103)
(533)
xNFO-(1-x)PZT after sintering
Intensity
(a.u.)
2 Theta (CuK)
NiFe2O
4
x=2%
x=5%
x=10%
x=20%
x=30%
(211)(201)(002)
(220)(311)(222)
(203) (422) (511)(440)
(620)
(001)
(101)(110)(111)
(200)(102) (112) (202) (220)
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Magneticpropertiesf= 1MHz-3GHz,
Agilent E4991A RF Impedance/Material Analyzer
increase with increasing the Niferrite amount;
at f=2,52,7x109Hz multipleresonances;
108
109
0
1
2
3
4
5
2,4x109
2,6x109
-600
-400
-200
0
200
400
600
Realpartofpermeability
Frequency (Hz)
xNF-(1-x)PZT
x=2%
x=5%
x=10%
x=20%
x=30%Realparto
fpermeability
Frequency (Hz)
5,0x108
1,0x109
1,5x109
2,0x109
2,5x109
0,0
0,5
1,0
1,5
2,0
2,2x109
2,4x109
2,6x109
0
200
400
600
800
1000
1200
1400
''
Frequency (Hz)
xNF-(1-x)PZT
Imaginarypartofpermeability
x=2%
x=5%
x=10%
x=20%
x=30%
Frequency (Hz)
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Magnetic hysteresis loops at room temperature
The magnetic hysteresis loops M(H) at room temperature show thepresence of the ordered magnetic structure derived from the unbalanced
antiparallel spins as in the pure NiFe2O4system.
Ms45emu/g for NFO
Mr increases from 0.11emu/g to 0.63 emu/g with
increasing the NFO phase.
Hc increases withincreasing of NiFe2O4addition.
-10000 -5000 0 5000 10000
-50
-40
-30
-20
-10
0
10
20
30
4050
-400 -300 -200 -100 0 100 200 300 400-40
-30
-20
-10
0
10
20
30
40
M
(emu/g)
H (Oe)
xNF-(1-x)PZT
M(em
u/g)
H (Oe)
x=2%
x=5%
x=10%
x=20%
x=30%
NiFe2O
4
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at room temperature,f = 1Hz-105Hz.
Maxwell-Wagner relaxation for f
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at room temperature, f= 106Hz-109Hz.
The multiple resonances areexplained with the dielectricresonant cavity model as being TMfundamental and superior modes
The material properties and thegeometry, shapes and dimensionsof the samples are taking intoaccount.
Dielectric relaxation with multiple
resonances in 108-109Hz frequency range:- the position of the peaks dependsessentially on the compositionmaximum of amplitude: = 1741 for x=2and minimum: =567 for x=30%
2x108
4x108
6x108
8x108
109-500
0
500
1000
1500
2000xNF-(1-x)PZT
x=2%
x=5%
x=10%
x=20%
x=30%
Frequency (Hz)
Realpartofperm
ittivity
2,0x108
4,0x108
6,0x108
8,0x108
1,0x109
0
500
1000
1500
2000
xNF-(1-x)PZT
Frequency (Hz)
Imaginarypartofpermittivity
x=2%
x=5%
x=10%
x=20%
x=30%
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Magnetoelectric properties
Maximal ME coefficient 33 for theceramic composites on the addition x
of NF at optimal field Hdc and f=1kHz.
33 - ME coefficient when the
polarization direction of the sample isparallel to the applied magnetic field.
ME output depends on the addition of
Ni ferrite and of DC magnetic field;
The maximum ME coefficient (dE/dH)varies from 0,0011mV/cmOe to0.5mV/cmOe with increasing of NFOaddition.
0 1000 2000 3000 4000 5000 6000
0,0
0,1
0,2
0,3
0,4
0,5
0,6
Static magnetic field H(Oe)
MEc
oeficient(mV/cmOe)
x=2%
x=5%
x=10%
x=20%
x=30%
xNF-(1-x)PZT
f=1kHz
0 5 10 15 20 25 30 350,0
0,1
0,2
0,3
0,4
0,5xNF-(1-x)PZT
M
Ecoeficient(mV/c
mOe)
NF (% weight)
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Future work Still to achieve good dispersion of high-concentration
of ferrite phase in piezoelectric ceramic matrix (GS,GB, density, homogeneity).
Better investigate and understand the dielectric and
magnetic properties at higher frequency (1MHz-GHz).
Investigation of the non-linear dielectric properties.
Modelling the electromagnetic properties by effectivefield theories.
Acknowledgements:
This work was financial supported by CNCSIS-UEFISCSU, project numberPN II-RU TE code 187/2010 and POSDRU/89/1.5/S/63663 project.
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Thank you for your attention!