Available online at www.sciencedirect.

com
JOURNAL OF

ScienceDirect
JOCRNAL OF RARE EARTHS 25 (2007) 79 - 83

www.elsevier .com/locate/jre

Structural Analysis and Magnetic Properties of Gd-Doped Li-Ni Ferrites

Prepared Using Rheological Phase Reaction Method
'%)
Jiang Jing ( % *), Li Liangchao ( * k&) * , Xu Feng ( j +
( Department

OJ

Chemistri , Institute of Phlszcal Chemistry, Zhepang Vormul CTniversity, Jmhua 321004, China)

Recelled 26 Ipnl 2006; reiised 20 October 2006

Abstract: A wries of Gd-doped Li-Ni ferrites with the formula of LiNio.sGd,Fe2-x04 where x = 0.00 - 0 . 0 8 in steps of
0 . 0 2 , were pre'iared by thermolyis of oxalate precursors obtained by rheological phase reaction. The structure, morpholog y , and the ma :netic properties of the samples were characterized by powder X-ray diffraction (XRD) , atomic force microscopy ( LIFM) and a vibrating sample magnetometer (VSM) . A single spinel phase was obtained in the range of x =
0 . 0 0 0 . 0 4 . The lattice parameters of the Gd-doped samples were larger than that of pure Li-Ni ferrite, and increased in
the range of 0 . I )0< s 0 . 0 4 , then decreased up to x = 0 . 0 8 , because of the formation of the secondary phase (GdFeO3) . All san ples were spheric particles with an average size of about 100 nm, but agglomerated to some extent. The
h+eresis loops indicated that the saturation magnetization decreased gradually with increasing Gd content, while the vanation of coercivi ty was related to the microstructure of the Gd-doped samples.

Key words : rheological phase ; Li-Ni ferrite ; Gd-doped ; structure ; magnetic properties ; rare earths
CLC number: TM273
Document code: A
Article ID: 1002 - 0721 (2007)Ol- 0079 - 05

Lithium f t n i t e s have attracted considerable attention for their pl Itential applications in microwave devices such as is0 ators, circulators, and phase shifters,
because of the r high resistivity, low dielectric losses,
and high Curi: temperature. These are used as replacements for expensive magnetic garnets because of
their low costs . It is interesting that the electromagnetic propertiei of spinel ferrites can be tailored by
controlling the type and amount of transition metallic
substitutes. C ntil now, several investigations have
been carried o i t to make further improvements on the
dielectric and magnetic properties of substituted lithium ferrites-'.3- It is known that rare earth ( R E ) ions
have unpaired 3f electrons, which have the role of
originating maj;netic anisotropy because of their orbital

'

shape. The magnetocrystalline anisotropy in ferrite is

related to the 4f-3d couplings between the transition
metal and rare earth ions; thus doping rare earth ions
into spinel lithium ferrite can improve their electrical
and magnetic properties.
In this study, Gd-doped Li-Ni ferrite powders
were obtained using thermolysis of oxalate precursors
that prepared by the rheological phase r e a ~ t i o n ',~and
their structural and magnetic properties were investigated. The rheological phase reaction method is a process of preparing compounds or materials from solidliquid rheological mixture, that is, the solid reactants
are fully mixed in proper molar ratio, made by adding
the required amount of water or other solvent to a solid-liquid rheological body in which the solid particles

Corresponding author (E-mail: skv52@zjnu. c n )

Foundation item: Project supported by the Natural Science Foundation of China (Y405038) and Science and Technology Key Project of Zhejiang
Projince (2006C21080)

Biography : Jiang Jinp i1982 - ) , Male. Master randidate

Cop!right j 2007, by Editorial Committee of Journal of the Chinese Rare Earths Society. Published by Elsevier B . V . All rights reserved.

JOURNAL OF RARE EARTHS, Vol. 2 5 , N o . 1 , Feb . 2007

80

and liquid substance are uniformly distributed. The

precursors obtained using this method have the advantages of excellent stoichiometry and homogeneity,
trace impurities, and relatively lower thermal-decomposition temperature. This method is inexpensive and
simple.

1 Experimental
Samples with chemical formula LiNi, Gd, Fez0, ( x = 0.00 - 0.08 ) were prepared using the rheological phase method. Analytical grade chemical reagents Li,CQ3, NiSO, * 6 H 2 0 , Gd203, Fe203, and
H,C,O, * 2H,O were weighed in stoichiometric proportions and thoroughly mixed by being ground in an agate mortar for 30 min; appropriate amount of ethanol
was then added to form a mixture in rheological state.
The mixture was sealed in a teflonlined stainless-steel
autoclave and reacted at 120 'C for 48 h in an oven.
The obtained precursors were washed for several times
with deionized water and ethanol, dried at 60 "c for
12 h and sintered at 1000 "c for 2 h in air, followed
by cooling with furnace to room temperature at a
cooling rate of 5 'C * min . Polycrystalline LiNi,
Gd, Fez 0, powders were obtained.
The X-ray diffraction patterns of samples were
collected using a PW3040/60 diffractometer with a
graphite monochromator and Cu Ka radiation ( A =
0.15418 nm) at a scanning rate of 4 (") srnin-' in the
range of 2 0 from 20" to 80". The morphology and particle sizes of the samples were examined using atomic
force microscopy ( AFM , P47H-SPM-MDT) . Magnetization measurements were carried out using a vibrating
sample magnetometer (VSM , Lakeshore 7404) under
applied magnetic field at room temperature .
~

'

than that of the Fe3+ ions (0.064 nm ) ; the amount of

Fe3+ions substituted by Gd3+ ions h a w a limit, therefore redundant Gd" ions will aggregate on the grain
boundaries forming the GdFeO? phase during the sintering process'6,7' .
The dependence of the lattice parameter on the
Gd content x is shown in Fig. 2. The lattice parameters of all Gd-doped samples are larger than that of
pure Li-Ni ferrite. This is because l a r y r Gd3+ ions replace Fe3+ ions on the octahedral site5 , leading to the
expansion of the spinel lattice. Howex e r , when the Gd
content x is beyond 0.04, the lattice parameter decreases up to x = 0.08. A possible explanation for the
decrease in the lattice parameter can be the compiession of the spinel lattice induced by vxondary phases
because of the difference in the thermal expansion
coefficients"' .
The X-ray density d , was calculated by the for-

8M

mula d, = 7 ,
where M , N , and a represent the
Na
molecular weight, the Avogadro' s number, and the
lattice parameter, respectively. It is Seen from Fig. 2
that the X-ray density increases linearly with the Gd
content x . Both the molecular weight and the volume
of the unit cell for the doped ferrite increase with

+ Spinel

I i

1 GdFeO,

.-cx
4

A ' '

al
u

2 Results and Discussion

b _ _ ..

11

30

40

. A

~0.06

x=0.04

yru

n.

50

60

F0.02

.%=0.00

70

80

2a/(")

2 . 1 X-ray diffraction analysis

Fig. 1

The X-ray diffraction patterns of LiNio,sGd.Fez

0, ferrites are given in Fig. 1. All diffraction peaks of
the samples correspond to the cubic spinel structure
(ICDD PDF # 86-2267). A single spinel phase is
obtained for the samples with x = 0.00 0.04, indicating that introducing an appropriate amount of Gd3+
ions into ferrite can replace the Fe3+ions on the octahedral sites, which obeys Vegard's law'" . However,
with the Gd content increasing further ( x > 0 . 0 4 ) , a
small amount of secondary phase is formed with the
diffraction peak (28 = 32.87") identified as the peak
of the GdFe03 phase (ICDD PDF # 78-0451 ) , because the ionic radius of Gd3+ ( 0 . 0 9 4 n m ) is larger

0.8364

XRD patterns of LiNio 5Gd,Fel. .Oq ferrites

- 4.83
0.00

0.02

0.04

0.06

0.08

Gd content x

Fig.2

Dependence of lattice parameter (C and X-ray density

( 0 )on Gd content x

81

Jiang J et al . Analysis and Properties of Gd-Doped Li-Ni Ferrites

the Gd content s , because of the replacement of larger

Gd3+for Fe'& , and the molecular weight has more increment when compared to the volume of the unit cell,
therefore, tht X-ray density increases with the Cd
content s.

2 . 2 Cation distribution
Energy calculations show that the size and valency of cations md the oxygen parameters of the anions

are the impo.-tant parameters in deciding the cation

distribution i l l ferrites . The cation distribution for
lithium ferritt has been suggested as ( Fe:+ ) [ Li&
Fe:; 10, l o . [n general, Li + and hi'+ ions have preference for tht. octahedral B sites; Fe3+ ions are distributed betwtaen .A and B sites, and Gd3' ions with
larger ionic radii replace Fe'+ ions on the octahedral B
sites. Based in this and Neel's tWo sublattice model,
the cation distribution of Cd-doped ferrites can be as,Yii',Gd: + Fe:I ] 0, , where
sumed as (Ft + ) [ Li;?

1
2

+ xrGdi++ ( 1 - ,x)rFf3+]

r, = - - [ 0 . 5 r 1 , - +0.5r,,'-

(1)
u=-----

TB+

''

( d 4 F ) , and the shared and unshared octahedral edge

(dBEand d,,,) can lie calculated according to Eqs.
( 3 ) (7)'13,14'
using the values of the lattice parameter a and the oxygen parameter u .
r
1
d,, = ao d 3 ( u - $
(3)

_I

Li0+5+ro
5 ! denotes that Li' ( 0 . 059 nni) replaces partially for F e ' ~( 0 . 0 6 4 nm) on the octahedral R sites,
and fills partiaiiy into the octahedral interstices.
Accordirig to the cation distribution given by Gddoped ferrite:. the average ionic radii of B sites ( r B )
and the oxygc 11 parameter 11 can be calculated by Eqs .
( 1 ) and ( 2 ) i ' :

u values depend on the chemical composition, the

,
preparation conditions, and the heating procedurerL2'
and the ideal u value is close to 0.0375 nm in spinel
ferrite. For the investigated samples, the values of u
are rnore than the ideal one, which indicates that the
crystal lattice deviates from the ideal spinel ferrite because of the difference in the preparation co.
nditions
The values of the tetrahedral and octahedral
bondlength ( d,, and d,, ) , the tetrahedral edge

Ro

where, u is he lattice parameter, and R , , is the radius of the os?-ren ion ( 0 . 1 3 4 nni) .
The valiies of the oxygen parameter u , and the
average radilri rB on the octahedral sites as a function
of the Gd co itent Y are shown in Fig. 3 . The r B increases linea .l!~ with the Gd content .Y , which corresponds to Fe substituted by Gd'+ on the B sites. The

The edge and the bondlength of the tetrahedral

and octahedral sites as a function of the Gd content x
are shown in Table 1 , respectively. It is seen that d,,
and d,, increase with the Gd content x , which may be
because of the fact that Fe3+ ions are substituted by
larger Gd3+ ions on the octahedral sites, resulting in
along with the expansion of
the increase of d,, and dR1,
the B sublattice; meanwhile the A sublattice is compressed by the B sublattice, resulting in the decrease
of dALand d A E .dBE, exhibits similar behavior as the
lattice parameter.
The distance between magnetic ions ( hopping
length) in the tetrahedral and octahedral sites is given
by E q s . ( 8 ) - (9)i'4'L5':

0.03882

- 0.03876

0 0660
c

A -

aJ3
LB=4

0 0655

=' C

Table 1

0.0650

0.03864

0.0645
0.0610

(.on

(1. u3 8 5:

0.02

0.04

0.06

0.08

.4\erag. radius r B 8 and oxygen parametrr u

~

'I

functio I of Gd content

(01

Values of d A L , d s L , d A E ,dBE.and dsEUas a

function of Gd content x
Octahedral sites

Cd rontrnt

Tetrahedral sites

(1 4, i l l l l l

d ,~llllll

dHLliiiii

dukinm

C/I(+, l n m

~~

Gd contcnt I

Fig.3

as a

0.00

0.1999

0.3264

0.1986

0.2645

0.29630

0.02

0.1991

0.3251

0.1991

0.m)

0.29635

0.04

0.1981

0.3234

0.1W

0.2678

0.2%38

0.06

0.1971

0.3219

0.2002

0.2694

0.29628

0.08

0.1%1

0.3212

0.2007

0.2710

0.2%16

.k

JOURNAL OF RARE EARTHS, Vol. 2 5 , N o . I , Feb . 2007

a2
0.36218 -

- 0.29570

E
0.36211

.C

0.36197

- 0.29550
-*-LA

0.36190

4 - L
0-2.9540
0.00

0.02

0.04

0.06

'g

0.08

Gd content x
Fig. 4

Dependence of hopping length for the A sites ( 0 )and R

sites ( 3 )on Gd content x

The dependence of the hopping length ( L A and

L B ) for the A sites and the B sites on the Gd content
x is shown in Fig. 4. It is observed that the variation
of L A and LB exhibits similar behavior as the lattice
parameter a . L A and L , increase at x = 0.04 because
the Gd3+ ions replace the Fe3+ions on the B sites in
the spinel lattice, while these decrease with the Gd
content x > 0.04, since the redundant Gd3+ ions form
the GdFe03 phase along the grain boundaries and inhibit the grain growth.

2 . 3 Morphologies of samples
Fig. 5 shows the representative AFM photographs
of LiNio.5Gd,Fe2_z04(
x = 0.00, 0.04, 0.08) ferrites. It is observed that the samples are spheric particles with average size of about 100 nm , but agglomeration occurs to some extent. The grain sizes of ferrites
are related to the chemical composition, the preparation conditions, the cell volume, the secondary phase s , and the glomeration behavior of particles. It is observed from Fig. 5 that the grain size of the sample
with x = 0.04 is the largest among the three samples,
because the replacement of limited amounts of Gd3+
ions for Fe3+ ions occurs at x = 0.04, and the expan-

sion of the spinel lattice reaches its maximum. When

x > 0.04, redundant Gd3+ ions form the GdFeO, phase
along the grain boundaries to inhibit the grain growth.
It is clear that the grain size of the sample with x =
0.08 is smaller than that of the sample with x = 0.04.

2 . 4 Magnetic properties
The variation of the saturation magnetization as a
function of the Gd content x is shown in Fig.6, which
is in agreement with the literature"6' " . The saturation magnetization of the Gd-doped samples is less
than that of pure ferrite, and decreases with the increase of the Gd content. The magnetic moments of
rare earth ions generally originate from localized 4f
electrons and these are characterized by lower magnetic ordering temperatures, i . e . , lower than 40 K"";
their magnetic dipolar orientation exhibits disordered
form at room temperature. Hence, it maj be reasonable that Gd3' ions are considered as non-magnetic
ions, and make no contribution to the magnetization of
doped ferrite at room temperature. Furthermore, the
deformity of the spinel lattice produces due to Gd3+
substituted for Fe3+ , nonlinear antiferromagnetic coupling between A and B sublattice increases, and the
magnetic dilution of secondary phase ( GdFe03) becomes stronger with Gd content, consequently, saturation magnetization of samples decreases.
Fig. 6 also shows the variation of the coercivity as
a function of the Gd content. The coercivity values of
the Gd-doped samples are lower than that of pure LiNi ferrite. It is seen that the coercivitj decreases in
the Gd content x = 0.00 0.04, then increases up to
x = 0.06, and decreases thereafter. The coercivity is
influenced by factors such as magnetocq stallinity , microstrain , magnetic particle morphology and size dis. .
tribution, anisotropy , and the magnetit. domain S ~ F
The initial decrease may be related to the microstructure of samples. The coercivity is inversely proportion-

Fig. 5 AFM images of LiNio 5GdlFr2- .04samples

( a ) x =O.OO; (b) x = 0 . 0 4 ; ( c ) x =0.08

83

Jiang J et a1 . Analysis and Properties of Gd-Doped Li-Ni Fem'tes

L21 Jiao M C , Li G D, Liang I' Q. Fdfect of rare earth element ou nlicrowave ahsorption properties of nano-lithium ferrite [ J ] . J . Rare E u r t h , wo4,22: 67.
[3] -Ibo E:l Ata A M , El Nimr M K , Attia S M, et al. Studies
of AC electrical conductivity a i d initial magnetic pemeabili1) of rare-earth-substituted Ii-Co ferrites [ J ] . J . M a p .
~ a g ,n Moter . , 2006, 2V(I): 33.
141 Jiang J , Li L C , Xu F, et al. Stractural and magnetic

Fig .6 Compositional \ariation nf saturation magnetization

and coerc i \ i t \ 1

8,

a1 to the grain size . It is obsened by AFM images

( F i g . 5 ) that tl,e grain size of samples increases in the
range of .T = 0 00 0 . 0 4 . -1larger grain size makes
the motion of t ie domain walls easier, and thereb!- the
coercivit!- decrl.ases. R-ith increasing Gd coiltent. redundant Gd3- ons ma!- reside at the grain boundaries
and form secoi clan phase. The prrsrnce of secondary
phase at the p a i n boundaries ma!- not only inhibit the
motion of the I iagnetic domain walls, h i t may also induce some dis ortion Mithin the grains leading to the
initiation of th internal stress ; moreor e I , w-ith niore
Gd3* ions iniroduced into the spinel ferrite, the
strength of thr spin-orbital coupling that determines
?I1
the magnetic ,inisotropy in the ferrites increases ,
and thus the ccercivity increases w-ith the Gd rontent x
be!-ond 0.04.
14

3 Conclusion
L\

series t If LiNio 5Gd,Fe2 0, saniples were syn~

thesized by t h thrrniol!-sis of oxalate precursors ohtained b!- the rheological phase reaction. It showed
that all Gd-doled ferrites had a major spinel phase,
and a single sliiiiel phase wab obtained in the range o f
x = 0.00 0 . '91.
The lattice parameters of Gd-doped
samples were arger than those of pure Li-Ni ferrite,
and increased \rith the Gd content .x = 0 . 00 0. 04,
and then decrt ased up to .Y = 0.08. because of the formation of the ,econdafi- phase. The oxygen parameter
~1 deviated fro]ti the ideal value (0.0375 nin) . The saturation magnei izatiori decreased gradually with the increasing Gd camtent. crhile the variation of coercivity
ic'as related to the micrnstnir.tiirc~ nf the (Xciope(l saniples .

-1

Parda\-i Hoiiath 51.

Allow Compd., 1998, 275-277: 657.

[91 Kharabe K G , Jadhav S -4, Shaikh A M, et al. Magnetic
properties of mixed Ii-Ni-Cd ferrites [J].Muter. Chem.
Ph!s . , 2001, 72( I ) : 77.
L 101 Jarihav S A . Structural and magnetic properties of Zn substituted Li-Cu ferrites [ J ] . M a t u . C h e n . Phys . , 2000, 65
( 1 ) : 120.
[ I 1 Standley K J . Oxide Maguetic Materials [ M I . Oxford:
Claretidon Press, 1972.
[ 121 Ahmed M A , Atria E , Salah L M . Structural and electrical studies on La3 + substituted Ni-Zn ferrites LJ] . Mater .
Cheni . Phys . , 2005, !?2(2 - 3) : 310.
1131 Ahbas T. Khan Y , Ahmad M , et al. X-ray diffraction
study of the cation distribution in the Mn-Zn-ferrites [ J 3 .
Solid Stute C o m n . , 1992, 82(9): 701.
[I41 Shitrr ,4 R , Kawade V 3, Bichile G K . X-ray diffraction
and dielectric study of Co,_, Cd,Fe2.* Cr,O, femte system
[ J ] . Marer. Lett . , 2002, 56(3) : 188.
'151 h e r M A , El H i t i M . Mfisshauer and X-ray studies for
Nin 2 Z ~ i k M8-zFe204
a
ferrites [J]. J . Mugn. Mugn . Mat e r . . Z O I , W 4 ( 1 ) :118.
!I61 Zhao 1, J , Cui Y , Yang H , et al. The magnetic properties
of Ni,, ,Mn, ,CA,Fe:. ,O, ferrite [J] . M a e r . I ~ t .t, u)o6,60
( 1 ) : 104.
[ 171 Panda R N, Shih J C, Chin T S. Magnetic properties of
nanecrystalline '3-or Pr-substituted CoFe204 synthesized
hy the citrate precursor technique [ J ] . J . ,Vugn . Magn .
Mnter., 2003, 251(I): 79.
[ ISj N d i s W J , Legvold S. Thermal conductivities and lorenz
functions of gadolinium, terbium and holmium single crysPhys. R w . , 1%9, 180(2): 581.
[ 191 Rana M L , Abhm T. Thr effrrt of Zn substitution on mic,iostiuctuir a i d uq,urlic pimpvrtic.r of Cu, , h i , F v L 0 4 fcrI

tals [ J ] .

ritr

[ J j . 1. Mngn. Mugn. Muier., 2"2, 246(1 - 2):

110.

References :
-

properties of la-dooped ti-Ni ferrite [ J ] . J . Rare Earths,

2005. 23: 259.
[ 5 ] Cahn K VC . Physical Metallurgy [ M I . Amsterdam: NorthHolland, 1985. 184.
161 Sileo E E , Jacob) S E. Gadolinium-nickel fenites preparrd from metal citrates precursors [ J 1. P h y . B , 2004,
354(1-3): 241.
[7: Ahnled M ,A, -4teia E , El Ilek S I . Rare earth doping effect on the structural and e1ec:trical properties of Mg-Ti ferritr [ J ] . Mater . Lett . , u)(33, 57(26 - 27) : 4256.
is] Krz1rsc.u 1,Rezlescir E , Popa P D, et al. Effects of rare
earth oxides on physical properties of Li-Zn ferrite [ J ] . J.

Clirnwa\e applicatinns of soft ferrites

[ J ] . J . l/i,gn. Ilr~g:rt. I l n t w . ,

Uxx). 215-216: 171.

kahii M I., Zhang Z J . Synthesis and magnetic properties

of CoFc204spinel ferrite nanopxticles doped with larithanide
ions LJ!. Appl. Ph,ys. L e l l . , wO1, 78(23): 3651.