preparation and magnetoelectric properties of pzt-nf composites - oral presentation anmm 2011_pt...

8/13/2019 Preparation and Magnetoelectric Properties of PZT-NF Composites - Oral Presentation ANMM 2011_pt Conf

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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!

preparation and magnetoelectric properties of pzt-nf composites - oral presentation anmm 2011_pt...

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