JOURNAL OF RARE EARTHS

Vol. 2 5 , Suppl. , Jun. 2007, p . 147

Hf03
Preparation and Study on Spectrum Characteristics of Sro.9,CeoSol
Nanopowders
Bai Zhaohui ( j f S S A T ) ' " , Ba Xuewei ( G ~ & , ) " 'Zhang
, Xiyan (%*%I1, Lu Liping (P$!JT)',
Mi Xiaoyun (.k-dS)'
( 1 . School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun
130022 , China ; 2 . Chemistry and Chemical Engineering Institute , Qiqihar University, Qiqihar 161006, China )

Abstract : The Sro.&eo,o, Hf03nanopowders were synthesized by the co-precipitation method. The calcination temperature
and time of the powders were 1200 "c and 2 h , respectively. The powder size of Sro.9&eo.olHfO3 nanopowders was 15 -
30 nm. There were two excitation bands in the excitation spectra of the Sro.wCeo.olHf03 nanopowders, which peaking at
216 and 309 nm, respectively. There were two emission bands in the emission spectra excited by the 220 nm light, which
peaking at 398 and 467 nm. And they were corresponding to the 5d-+'F5,2 and the 5d4'F7/2 transitions of Ce3+ ions. But
there was only one emission band in the emission spectrum excited by the 309 nm light which peaking at 392 nm.
Key words: Sro.&eo,olHf03 ; nanopowders ; spectrum characteristics; rare earths
CLC number: TQ134.13; TL812.1 Document code: A Article ID: 1002 - 0721(2007) - 0147 - 04

Ceramic scintillator is a novel type of functional Strontium hafnates ( SrHf03 ) have larger density
ceramics. It is one of the important research fields in and effective atomic number. SrHf03 has excellent
scintillators. Compared with scintillating crystals, ce- ability of absorbing high-energy ray or particles. It can
ramic scintillators have many superiority, such as the be used as the matrix of s~intillator[~'
.I'' In this paper,
stability of physical and chemical properties, simple Sro,sCeo.olHf03 nano-powders were synthesized by the
fabrication technology, low cost, superior properties of co-precipitation method. TG-DTA , XRD and TEM
mechanical processing. And it can be doped uniform- were employed to characterize the nano-powders . The
ly. Ceramic scintillators have been regarded as the excitation spectrum and the emission spectrum were
substitute of the scintillant crystals"] . The scintillant
discussed. This work will be used as the base of further
crystals using in commercial are NaI :Tl, CaF2 : Eu ,
research in Sro,99Ceo,olHf03 ceramic scintillator.
BGO , CsI :T1 and CdW04. There are some shortcom-
ings in these crystals, for example, the problem of af- 1 Experimental
terglow, air slacking, cleavage, toxicity, larger heat
expansion, low mechanical intensity, high cost of raw 1.1 Synthesis of nano-powders
materials, and so on. Some crystals with potential
HfOCI2*8H20(9 9 . 9 9 % ) , Sr( NO3),( A . R . ) and
scintillating properties cannot be prepared by using the
Ce02(9 9 . 9 9 % ) were used as the starting materials.
techniques of crystal growth. With the development of
Ammonia was the precipitant. The raw materials were
the technology of transparent ceramics, it is possible to
fabricate transparent ceramic scintillators . Some ceram- weighted following the stoichiometric proportion of Sr0,*
ic scintillators have been developed, for example, ( Y , Ceo.olHf03.Ce(N03)3solution was obtained by dissolv-
( 3 1 2 0 3 : Eur2], Gd202S : Eu, Tb[31, Gd3Ga5OI2: Cr, ing CeOz with dense HN03 and Hz02. HfOC12 8H20
Ce[41, BaHf03 : Ce"', YAG : Cef6], Lu203 : E u ' ~ ] , and Sr( N 0 3 ) 2were put into Ce(N03)3solution, keeping
BGO[*' . As the basic radiation sensors, ceramic scintil- stirring, and the mixed solution was prepared. The val-
lators can be used in nuclear medicine (X-CT, PET), ue of pH was adjusted using ammonia. The concentra-
high-energy physics, nondestructive evaluation of mate- tion of the mixed solution was modularized by de-ion-
rials, safety inspection and geologic exploration. ized water. The ultimate density of the mixed solution

Received date: 2006 - 12 - 01 ; revised date: 2007 - 04 - 26

Foundation item: Project supported by the Jilin Provincial Natural Science Foundation (YJ0417035)
Biogrttphy: Bai Zhaohui (1967- ), Female, Master, Associate professor; Research field : photoelectric functional materials
* Corresponding author (E-mail: zhaohuibai @ 126.com)
148 JOURNAL OF RARE EARTHS, Vol. 25, Suppl. , Jun . 2007

and the ammonia aqueous solution were 4 and 0.6 mol HfO2. The exothermic peak at about 340 “c should be
L-’ , respectively. The opposite titration method was due to the decomposition of Ce ( O H ) 3 . And the de-
employed. The mixed precipitate of Hf ( O H ) 4 , Sr composed product may be amorphous Ce203or crystal
(OH),.8H20 and Ce(OHI3 appeared to be white floc- Ce203. This phase cannot be distinguished according
cule. The precipitate was washed with de-ionized water to the XRD patterns because of the little content of
for 3 to 5 times in order to remove the C1- ions. Then it CeO2. The endothermic peak at 505 “c is generated by
was washed with absolute ethyl alcohol for 2 times in the decomposition of Sr( OH), . And the peak indicates
order to remove the residual water. The mixed precipi- that the cubic SrO is obtained. The more intensive exo-
tate was dried in the vacuum drying oven at 90 “c for 8 thermic peak at about 740 “c indicates a phase transi-
h . The dry precursor was grinded in the agate crucible. tion: from amorphous Hf02to tetrahedral HfOz. And
The fine precursor powders were put into the corundum this transition is an exothermic process. The feeble exo-
crucible and calcined at 1200 “c for 2 h . thermic peak at about 927 “c is the proof of the solid
1.2 Characterization of samples reaction between HfOZand SrO . The reaction product is
SrHf03 of tetrahedral crystal lattice. At the temperature
The XRD patterns and particle size of the dry of 1081 “c, there is an exothermic peak in the DTA
precursor and powders calcined at different tempera-
curve. The exothermic peak is due to the phase transi-
ture were performed with X-ray diffractometer (Rigaku
tion of SrHf03 from tetrahedral to cubic crystal
D/max-rA , Japan ) . The TG-DTA curves of the pre-
structure“’]. The part of DTA curve (above 1092 “c) is
cursor were tested with thermal analyzer ( TA-
a false peak because of the matter of the instrument.
SDT2960, America). The morphology of the nanop-
owders was examined with transmission electron micro- 2.2 XRD patterns
scope ( TEM , JEM-2010, Japan ) . The excitation
Fig. 2 is the XRD patterns of the samples heat-
spectrum and emission spectrum were examined with
treated at different temperature of Sro.&eo.ol Hf03 pre-
spectrometer (F-4500, Japan) .

2 Results and Discussion

2.1 Thermal analysis
Fig. 1 is the TG-DTA curves of Sro.99Ceo.olHf03
precursor. The TG curve is composed with 4 different
parts. First, the weight losses very fast from 30 to 147
“c , and the weight lost is about 8 % . This can be due
- 8 7 -4
to the evaporation of planar water and the decomposi- 0 m 4w By) 837 rax,rm1m
tion of Sr( OH), 8 H 2 0 . Second, the weight loss be- Temperature/%
comes slower from 147 to 360 “c . In this step, the Fig. 1 TG-DTA curves of Sro,sCeo.olHf03precursors
weight loss is caused by the loss of water from the
thermal decomposition of Hf ( OH )4 and Ce ( OH ) 3 .
Third, the TG curve appears gently from 360 to 556
“c . The decomposition of Sr(OH), induces the loss of
structural water and the weight loss. The decomposed
products are SrO and H 2 0 . The last step is the course
of the high temperature volatilization of SrO from 556
to 1167 “c . The TG curve becomes plainer when the
temperature is higher than 1167 “c . This phenomenon
indicates that SrO reacts with Hf02 completely and the
main crystal phase of SrHf03 is obtained.
There is an intensive endothermic peak at about 204”)
108 “c in the DTA curve. The endothermic reaction is Fig.2 XRD patterns of Sro.%Ceo.olHfO3precursors heat treated
composed with the evaporation of planar water and the at different temperatures
decomposition of S r ( O H ) 2 * 8 H 2 0and Hf(OH),. The ( I ) Uncalcined; (2) 400 T;(3) 600 “c; (4) 800 F;
decomposed products are Sr ( O H )2 and amorphous ( 5 ) lo00 “c; (6) 1200 T
 Bai 2 H et a1 . Preparation and Study on Spectrum Characteristics of SrCeHfO Nanopowders 149

cursor. ( I ) , (21, ( 3 ) , (41, ( 5 ) and ( 6 ) represent

the XRD pattern of the samples uncalcined and cal-
2.3 Spectrum analysis
cined at 400, 600, 800, 1000 and 1200 “c , respec- There were two excitation bands in the excitation
tively. According to the XRD patterns, it can be be- spectra of the So,, Ceo.olHfo3 nanopowders according to
lieved that there are not only amorphous materials but Fig.4, which peaking at 216 and 309 nm, respectively.
also crystal materials. Compared with the JCPDS They are the results of the transition of Ce3’ ions from 4f
cards, it can be affirmed that the crystal matter is Sr to 5d energy level. Ce3+ions occupy the lattice sites of
( OH)2.8H20. The amorphous materials is the mixture Sr2+ ions in the matrix crystal lattice. The 5d energy lev-
of Hf ( OH), and Ce ( OH ), . The product calcined at el splitted into several separated energy level by the in-
400 “c is amorphous materials. This is because of the fluence of crystalline field. With the shielding of the out-
decomposition of Sr(OH)2*8H20and the product of Sr er 5s25$ electrons, 4f energy level of ce3+ions were af-
(OH), is also amorphous material. SrO of face-cen- fected slightly and they keep the characteristics of LS
tered cubic system appears in the XRD pattern of the coupling energy level (2F7j2and ’Fji2) of free ions.
sample calcined at 600 “c for 2 h . This can be attrib- Figs.5 and 6 are the emission spectra of Sr0.,
uted to the decomposition of .%(OH)*. HfOz of mono-
clinic system appears in the XRD pattern of the sample
heat-treated at 800 “c for 2 h . This phenomenon
should be explained that Hf ( OH ), decomposes during
-
600 800 “c . With the elevating of the temperature,
the feeble diffraction peaks of SrHf03 emerge in the
XRD pattern of the sample heat-treated at 1000 “c for
2 h . In the pattern of the sample heat-treated at 1200
“c for 2 h , there are only the diffraction peaks of
SrHf03. This fact indicates that the reaction of SrO
4 O d . , . , . , - , . , . , . , . ,
mmma3m3333m3493eJ

and Hf02 is very complete. Wavelengthlnm

The particle size was calculated with Scherrer for- Fig. 4 Excitation spectrum of Sro.,&eo.~lHfO, nanopowders
mula. The micrograph of the nanopowders was exam- m, I

ined with transmission electron microscope (TEM) .

Sherrer formula
-3
K/\
D M i --
-pcOse
Fig.3 is the TEM image of Sro.~~Ceo.olHf03 nan-
opowders calcined at 1200 “c for 2 h . The particle di-
ameters of So., Ceo.olHf03 nanopowders are 15 30 -
nm. The particles show good dispersity and spheric
shape. 3 0 0 4 0 3 5 c h ) 6 0 0 7 0 3
WavelengtWnm
Fig. 5 HfO, nanopowders ex-
Emission spectrum of Sro.wCeo.ol
cited at 220 nrn
3ooo
392 I

0
3504004505M550800660m
Wavelengttdmn
Fig. 3 ‘ E M image of Sro.99Ceo.olHf03
nanopowders Fig. 6 Hf03 nanopowden ex-
Emission spectrum of Sro,wCeo,ol
cited at 309 nm
150 JOURNAL OF RARE EARTHS, Vol. 2 5 , Suppl. , Jun . 2007

Ceo.olHf03nanopowders excited at 220 and 309 nm,

respectively. There is a wider emission band between
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