Preparation and magnetoelectric

properties of NiFe
2
O
4
-PZT ceramic
composites
Cristina E. Ciomaga
1*
, M. Airimioaei
2
, V. Nica
1
,
L.M. Hrib
1
, O.F. Caltun
1
, A. R. Iordan
2
, C. Galassi
3
,
L. Mitoseriu
1
and M. N. Palamaru
2
1
Faculty of Physics, Al. I. Cuza University Iasi 700506, Romania
2
Faculty of Chemistry, Al. I. Cuza University Iasi 700506, Romania
3
ISTEC-CNR, Via Granarolo no. 64, I-48018 Faenza, Italy
5th International Workshop on
Iai, 5-7 September 2011
*Corresponding Author email: cristina.ciomaga@uaic.ro
Outline
I. Introduction
- Magnetoelectric composite ceramics - the concept of
synergy effect. Reported results.

II. Our approach: preparation by citrate-nitrate gel-
combustion using template powders obtained by mixed
oxides methods in order to induce new functional properties.

III. The PZT with NiFe
2
O
4
ceramic composite
Powder and ceramic preparation
Structural and microstructural characterization by XRD and
SEM
Magnetic properties
Dielectric properties
Magnetoelectric effect

IV. Conclusions and future work.
ME
effect
Diel/FE
FM/AF/Ferri
Composite materials: combining di-similar materials in compact
structures in order to obtain new properties (sum, combinatory
or product properties) and multifunctionality.
I. Introduction
J . Van Suchetelene, Philips Res. Rep. 27, 28 (1972)
Magnetoelectric (ME) composites coupling via
magnetostrictive-piezoelectric effect:
Idea: (1972) 2 phases individually not showing a property can
achieve it, if appropriately combined or coupled in a composite.
Conditions for the ME composites:

Homogeneous, well dispersed diphase microstructures;

No chemical reactions between the two phases;


High density, no mechanical defects (pores, craks) for good
mechanical coupling, dielectric and ME properties;


High resistivity of the M phase, compositions below the
percolation limit and/or no connectivity for the M phase.
J. Ryu et al., Magnetoelectric effect in composites of magnetostrictive and piezoelectric
materials, 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, and
future 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 thin
films, J. Mater Sci, 44:5080 (2009).
J.Ma et al., Recent progress in Multiferroic Magnetodielectric Composites: from Bulk to Thin
Films, Adv. Mater., XX, 1-26 (2011).
formed by:
- BaTiO
3
with:
CoFe
2
O
4

NiFe
2
O
4
LiFe
5
O
8
Ni(Co,Mn)Fe
2
O
4
,

MnFe
1.8
Cr
0.2
O
4,
LaMnO
3
, terphenol-D, etc.


- PZT, PMN-PT with CoFe
2
O
4,
NiFe
2
O
4
and Ni(Co,Mn)Fe
2
O
4

- Bi
4
Ti
3
O
12
with CoFe
2
O
4

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 (2003
M.I. Bichurin et al., Phys. Rev. B68, 132408 (2003)
L. Mitoseriu and V. Buscaglia, Phase Trans. 79 (2006) 10951121
Q.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) 13
fiber/rod composite.
- Reported results:
(a)
(c) (b)
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.
Methods for producing ME composites
Mixing of the phases separately prepared

The large majority of publications reported the use of this
method to obtain ME composites.

In situ preparation of the composites:

- coprecipitation, gel-combustion
P. 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 composites
C. 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.
II. Our approach:

to produce ME ceramic composites with 0-3 connectivity using
wet-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.
III. Preparation and functional
properties of Pb(Zr,Ti)O
3
-NiFe
2
O
4

magnetoelectric ceramics
prepared in situ
by gel-combustion method
- NiFe
2
O
4
: inverse spinel structure
- PbZr
x
Ti
1x
O
3
: ferroelectric perovskite ABO
3
NiFe
2
O
4
(NFO) with Pb(Zr,Ti)O
3
(PZT): xNF-(1-x)PZT
ceramic composites
x=2, 5, 10, 20 and 30 %
using pure PZT-based template powders;
NFO by citrate-nitrate gel-combustion method.
Investigated ceramics
Powder and ceramic preparation
NiFe
2
O
4


Pb(Zr
0.47
Ti
0.53
)O
3

Pb(Zr,Ti)O
3
powder
(ss)
Fe
3+
, Ni
2+
,
nitric salts
C
6
H
8
O
7
.H
2
O
Viscous
gel
Self-
combustion at
350
0
C
Ni(NO
3
)
2
.6H
2
O Fe(NO
3
)
3
.9H
2
O
C
6
H
8
O
7
.H
2
O
PZT template
powder
Stirring (60 min)
Continuous stirring & heating
at 80C
Viscous gel
Self-combustion
Heating
treatment
PZT-NiFe
2
O
4
composites
Stirring & pH adjusting
Nitrate solution
Mixture PZT-(nitrate-
citric acid solution)
Foamy
product
Structural characterization by XRD
indicates the presence of NiFe
2
O
4

spinel phase and preserving the
Pb(Zr,Ti)O
3
ferroelectric phase;

after sintering at 1200
0
C/1h -
diphase ceramic composites (the
lack of secondary phases at
interfaces).
Pure di-phase powder composites
with a good crystallinity were
obtained after the calcination step.
20 30 40 50 60 70 80
0
500
1000
1500
2000
2500
3000
3500
4000
x=30%
x=20%
x=10%
x=5%
xNF-(1-x)PZT after calcination
2 Theta (CuKo)
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
x=2%
NiFeO
4

PZT
(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
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
2 Theta (CuKo)
NiFe
2
O
4

x=2%
x=5%
x=10%
x=20%
x=30%
(211) (201)
(002)
(220)
(311) (222)
(203)
(422)
(511)
(440)
(620)
(533)
(444)
(001)
(101)
(110)
(111)
(200)
(102)
(112)
(202)
(220)
(103)
Microstructural charaterization by
SEM
x=2% x=5%
x=10%
x=20%
increasing the
addition of Ni ferrite,
the grains of ferrites
phase are dispersion in
PZT ferroelectric
matrix;
two different phases
of PZT and NFO
distinctly with particle
size of NFO ~2-4m.
NiFe
2
O
4

Pb(Zr,Ti)O
3

x=30%
Magnetic properties
f = 1MHz-3GHz,
Agilent E4991A RF Impedance/Material Analyzer
increase with increasing the Ni
ferrite amount;
at f=2,52,7x10
9
Hz multiple
resonances;
10
8
10
9
0
1
2
3
4
5

2,4x10
9
2,6x10
9
-600
-400
-200
0
200
400
600
R
e
a
l

p
a
r
t

o
f

p
e
r
m
e
a
b
i
l
i
t
y
Frequency (Hz)
xNF-(1-x)PZT
x=2%
x=5%
x=10%
x=20%
x=30%
R
e
a
l

p
a
r
t

o
f

p
e
r
m
e
a
b
i
l
i
t
y
Frequency (Hz)
5,0x10
8
1,0x10
9
1,5x10
9
2,0x10
9
2,5x10
9
0,0
0,5
1,0
1,5
2,0

2,2x10
9
2,4x10
9
2,6x10
9
0
200
400
600
800
1000
1200
1400

'
'
Frequency (Hz)
xNF-(1-x)PZT
I
m
a
g
i
n
a
r
y

p
a
r
t

o
f

p
e
r
m
e
a
b
i
l
i
t
y
x=2%
x=5%
x=10%
x=20%
x=30%
Frequency (Hz)
Magnetic hysteresis loops at room temperature
The magnetic hysteresis loops M(H) at room temperature show the
presence of the ordered magnetic structure derived from the unbalanced
antiparallel spins as in the pure NiFe
2
O
4
system.
M
s
45emu/g for NFO


M
r
increases from 0.11
emu/g to 0.63 emu/g with
increasing the NFO phase.

H
c
increases with
increasing of NiFe
2
O
4

addition.
-10000 -5000 0 5000 10000
-50
-40
-30
-20
-10
0
10
20
30
40
50

-400 -300 -200 -100 0 100 200 300 400
-40
-30
-20
-10
0
10
20
30
40
M

(
e
m
u
/
g
)
H (Oe)
xNF-(1-x)PZT
M

(
e
m
u
/
g
)
H (Oe)
x=2%
x=5%
x=10%
x=20%
x=30%
NiFe
2
O
4
at room temperature, f = 1Hz-10
5
Hz.
Maxwell-Wagner relaxation for f<10 Hz;
Debye relaxation 10
2
-10
4
Hz;
the dielectric loss are <0.2%;
Magnetoelectric composites of nickel ferrite and lead zirconnate titanate prepared by spark
plasma sintering, Q.H. Jiang, Z.J. Shen, J.P. Zhou, Z. Shi, Ce-Wen Nan, Journal of the
European Ceramic Society 27 (2007) 279284
Multiferroic properties of Ni
0.5
Zn
0.5
Fe
2
O
4
PbZr
0.53
Ti
0.47
O
3
ceramic Composites, H. Zhang,
S.W. Or and H.L.W. Chan, J. Appl. Phys. 104 (2008) 104-109
Dielectric properties
10
0
10
1
10
2
10
3
10
4
10
5
300
400
500
600
700
800
900
xNF-(1-x)PZT
R
e
a
l

p
a
r
t

o
f

p
e
r
m
i
t
t
i
v
i
t
y
Frequency (Hz)
x=2%
x=5%
x=10%
x=20%
x=30%
10
0
10
1
10
2
10
3
10
4
10
5
0,00
0,05
0,10
0,15
0,20
xNF-(1-x)PZT
x=2%
x=5%
x=10%
x=20%
x=30%
D
i
e
l
e
c
t
r
i
c

l
o
s
s
Frequency (Hz)
10
0
10
1
10
2
10
3
10
4
10
5
0
50
100
150
xNF-(1-x)PZT
x=2%
x=5%
x=10%
x=20%
x=30%
I
m
a
g
i
n
a
r
y

p
a
r
t

o
f

p
e
r
m
i
t
t
i
v
i
t
y

(
c
'
'
)
Frequency (Hz)
at room temperature, f = 10
6
Hz-10
9
Hz.
The multiple resonances are
explained with the dielectric
resonant cavity model as being TM
fundamental and superior modes

The material properties and the
geometry, shapes and dimensions
of the samples are taking into
account.
Dielectric relaxation with multiple
resonances in 10
8
-10
9
Hz frequency range:
- the position of the peaks depends
essentially on the composition
maximum of amplitude: c= 1741 for x=2
and minimum: c=567 for x=30%
2x10
8
4x10
8
6x10
8
8x10
8
10
9
-500
0
500
1000
1500
2000
xNF-(1-x)PZT
x=2%
x=5%
x=10%
x=20%
x=30%
Frequency (Hz)
R
e
a
l

p
a
r
t

o
f

p
e
r
m
i
t
t
i
v
i
t
y
2,0x10
8
4,0x10
8
6,0x10
8
8,0x10
8
1,0x10
9
0
500
1000
1500
2000
xNF-(1-x)PZT
Frequency (Hz)
I
m
a
g
i
n
a
r
y

p
a
r
t

o
f

p
e
r
m
i
t
t
i
v
i
t
y
x=2%
x=5%
x=10%
x=20%
x=30%
at room temperature, f = 1Hz-10
5
Hz.
Dielectric properties
) ( ' ' ) ( '
) ( '
) ( '
2 2
f f
f
f M
c c
c
+
=
) ( ' ' ) ( '
) ( ' '
) ( ' '
2 2
f f
f
f M
c c
c
+
=
) ( ) ( ) (
*
f M i f M f M ' ' + ' = Complex dielectric modulus:
at low frequency present an almost zero
conduction;
relaxation properties due to the hopping polaron
mechanism of ferrite.
10
2
10
3
10
4
10
5
10
6
0,0010
0,0015
0,0020
0,0025
0,0030
0,0035
x=2%
x=5%
x=10%
x=20%
x=30%
xNF-(1-x)PZT
M
'
Frequency (Hz)
10
2
10
3
10
4
10
5
10
6
0,0000
0,0001
0,0002
0,0003
0,0004
xNF-(1-x)PZT
x=2%
x=5%
x=10%
x=20%
x=30%
M
'
'
Frequency (Hz)
10
2
10
3
10
4
10
5
10
6
1E-5
1E-4
1E-3
0,01
0,1
1
xNF-(1-x)PZT
x=2%
x=5%
x=10%
x=20%
x=30%
Frequency (Hz)
C
o
n
d
u
c
t
i
v
i
t
y

(
o
x
1
0
-
3
)

(
S
/
m
)
Magnetoelectric properties
Maximal ME coefficient o
33
for the
ceramic composites on the addition x
of NF at optimal field H
dc
and f=1kHz.
o
33
- ME coefficient when the
polarization direction of the sample is
parallel 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 to
0.5mV/cmOe with increasing of NFO
addition.
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)
M
E

c
o
e
f
i
c
i
e
n
t

(
m
V
/
c
m
O
e
)
x=2%
x=5%
x=10%
x=20%
x=30%
xNF-(1-x)PZT
f=1kHz
0 5 10 15 20 25 30 35
0,0
0,1
0,2
0,3
0,4
0,5
xNF-(1-x)PZT
M
E

c
o
e
f
i
c
i
e
n
t

(
m
V
/
c
m
O
e
)
NF (% weight)
Summary
di-phase NiFe
2
O
4
with pure Pb(Zr,Ti)O
3
magnetic-ferroelectric
ceramic composites with limited reactions at interfaces were
prepared by citrate-nitrate combustion technique by using
Pb(Zr,Ti)O
3
template powders obtained by mixed oxide method.
The XRD patterns and SEM analysis confirmed the successful
formation of a di-phase composite for each composition, formed by
the spinel NiFe
2
O
4
and Pb(Zr,Ti)O
3
perovskite phase in the nominal
proportion.
The magnetic and dielectric investigations at room temperature
confirmed the formation of a composite with both dielectric and
magnetic properties, with permittivity and magnetization resulted
as sum properties from the parent PZT and ferrite phases.
Good insulating properties and relaxation due to the hopping
polaron mechanism of ferrite.
ME coefficient in the range of (0.011-0.5) mV/Oe*cm at f=1kHz.
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 effective
field theories.
Acknowledgements:
This work was financial supported by CNCSIS-UEFISCSU, project number
PN II-RU TE code 187/2010 and POSDRU/89/1.5/S/63663 project.
Thank you for your attention!