Professional Documents
Culture Documents
1 s2.0 S025405840800521X Main
1 s2.0 S025405840800521X Main
a r t i c l e i n f o a b s t r a c t
Article history: In this paper, the magnetic properties of Fe3 O4 nanoparticles at different temperatures were investi-
Received 17 April 2008 gated. It was found that the magnetism of Fe3 O4 nanoparticles vanished at 550 ◦ C when exposed in the
Received in revised form 20 May 2008 atmosphere for 2 h. X-ray diffractometer, Fourier transform infrared spectroscope and scanning electron
Accepted 9 July 2008
microscope were employed to explain the change of magnetism of Fe3 O4 nanoparticles. The route of
phase transitions from Fe3 O4 to ␣-Fe2 O3 along with the increasing temperature was brought out. In order
Keywords:
to maintain the magnetism of Fe3 O4 nanoparticles at a higher temperature, a simple method was intro-
Magnetic materials
duced to deposit BaSO4 shell on the Fe3 O4 cores to prepare Fe3 O4 /BaSO4 multi-core/shell particles. The
Chemical synthesis
Magnetic properties
magnetism of Fe3 O4 /BaSO4 multi-core/shell particles did not vanish till 750 ◦ C. The change of magnetism
Phase transitions of Fe3 O4 /BaSO4 multi-core/shell particles was proved to be related to the appearance of “holes” on the
surfaces of BaSO4 shells.
© 2008 Elsevier B.V. All rights reserved.
0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.07.054
J.H. Li et al. / Materials Chemistry and Physics 113 (2009) 140–144 141
the iron ion, which is diffusing out of the crystals of magnetite dur- 3. Results and discussion
ing the oxidation process. Jolivet and Tronc [22] showed that in acid
media magnetite crystals were oxidized to ␥-Fe2 O3 by an adsorp- 3.1. Magnetic properties analysis
tion reaction which traps mobile electrons from the bulk material
and reduces the interfacial FeIII . The magnetic properties were characterized by a Gouy magnetic
However, to the best of our knowledge there are few balance, in which magnetic weight is linear with the magnetism
publications trying to maintain the magnetism of Fe3 O4 nanopar- of the samples [15]. The magnetic weight of the two samples
ticles at a higher temperature [23]. In order to make it, we calcined at different temperatures was measured under different
have investigated the oxidation behavior of Fe3 O4 nanoparti- external magnetic field, due to the easier magnetization of pure
cles at different temperatures in the atmosphere and synthesized Fe3 O4 nanoparticles. The magnetic weight related to temperature
Fe3 O4 /BaSO4 multi-core/shell particles by depositing BaSO4 shell is illustrated in Fig. 1. From Fig. 1, one can find that the magnetism
onto the Fe3 O4 cores. The results show that the thermody- of pure Fe3 O4 nanoparticles reaches maximum when calcined at
namical stability of Fe3 O4 /BaSO4 multi-core/shell particles was 250 ◦ C for 2 h in the atmosphere and vanishes when calcined at
improved obviously and their magnetism did not vanish till 550 ◦ C under the same conditions. In order to determine whether
750 ◦ C. the magnetism vanishment is instantaneous or not, pure Fe3 O4
nanoparticles were calcined at 550 ◦ C for 20 min in the atmo-
2. Experimental sphere and the magnetism vanishment happens again. Besides,
pure Fe3 O4 nanoparticles were calcined at 500 ◦ C for 2 h in the
2.1. Materials atmosphere, and the particles still show magnetism. Thus, one can
All chemicals were of analytical grade and used without further purifica-
conclude that the magnetism vanishment of pure Fe3 O4 nanopar-
tion. Ferric chloride (FeCl3 ·6H2 O), ferrous sulfate (FeSO4 ·7H2 O), ammonium iron ticles is instantaneous when the temperature is equal to or above
(II) sulfate hexahydrate ((NH4 )2 Fe(SO4 )2 ), ammonia (NH4 OH, 25%v/v aqueous), 550 ◦ C.
hydrazine hydrate (N2 H4 ·H2 O, wt% = 50%), barium chloride (BaCl2 ), anhydrous However, for Fe3 O4 /BaSO4 multi-core/shell particles, there are
ethanol (C2 H5 OH) and potassium thiocyanate solution (KSCN) were all purchased
two points of maximal magnetism, and one is at 250 ◦ C and the
from Sinopharm Chemical Reagent Co. Ltd. (SCRC). Deionized water was used
throughout experiments. other at 550 ◦ C. The magnetism vanishment of the composite par-
ticles takes place at 750 ◦ C for 2 h in the atmosphere. Experiments
2.2. Synthesis of Fe3 O4 nanoparticles
reveal that the magnetism vanishment of Fe3 O4 /BaSO4 multi-
core/shell particles is also instantaneous when the temperature is
Fe3 O4 nanoparticles were synthesized according to our previous report [24]. equal to or above 750 ◦ C.
Simply, 136 ml of deionized water and 2 ml of N2 H4 ·H2 O were put into a three-
neck, 250 ml, round bottom flask equipped with a mechanical stirrer, and agitated
for 30 min to eliminate the oxygen. Aqueous solutions of FeSO4 and FeCl3 were
3.2. XRD studies
dropped into the flask with agitation. Immediately after the addition of the
iron salts solution, 8 ml of NH4 OH and 10 ml of deionized water were quickly To find the reason of magnetism vanishment of pure Fe3 O4
syringed into the flask with vigorous stirring. The solution turned from grass- nanoparticles, X-ray diffraction was performed using Cu K␣ radi-
green to orange-yellow, and finally to black quickly, indicating the formation of
ation. The XRD patterns of pure Fe3 O4 nanoparticles calcined at
magnetite. At the same time, turn on the microwave oven, circulate the cool-
ing water, and modulate the heating power to gain an invariable temperature different temperatures are shown in Fig. 2. From Fig. 2, one can find
of 80 ◦ C for 30 min. The precipitates were filtered and washed with deionized that there is almost no difference among the diffraction peaks of
water and anhydrous ethanol for several times, and dried under vacuum for the particles calcined at 150 ◦ C and 250 ◦ C except the weakening
24 h.
in intensity of magnetite, especially for (3 1 1) peak. From 350 ◦ C
to 550 ◦ C, the (3 1 1) peak keeps reduction, while (1 0 4) peak of
2.3. Synthesis of Fe3 O4 /BaSO4 multi-core/shell particles hematite develops and becomes stronger and stronger. When at
550 ◦ C, magnetite (Fe3 O4 ) transforms to hematite (␣-Fe2 O3 , [25])
A simple method was produced to synthesize Fe3 O4 /BaSO4 multi-core/shell
particles. In a typical synthesis process, 50 ml of ammonium iron (II) sulfate hex- completely [26].
ahydrate solution (0.2 M), 10 ml of 50% hydrazine hydrate and 5 ml of ammonia
were mixed together with vigorous stirring at 80 ◦ C for 1 h. Elevate the temperature
to 100 ◦ C and then 40 ml of barium chloride solution (0.5 M) were slowly dropped
into the mixture. After 1 h vigorous stirring, keep the system immovable for 1 h at
80 ◦ C. Finally, the resultants were filtered with a magnete and washed with deion-
ized water and anhydrous alcohol for several times, and dried under vacuum for
24 h.
2.4. Characterization
The obtained Fe3 O4 /BaSO4 multi-core/shell particles and pure Fe3 O4 nanopar-
ticles were calcined at different temperatures (150 ◦ C, 250 ◦ C, 350 ◦ C, . . ., 750 ◦ C)
for 2 h in the atmosphere. X-ray diffractometer (XRD, X‘Pert-Pro MPD, Holand)
and Fourier transform infrared spectroscope (FT-IR, Nicolet FT-IR Avatar 360,
America) were employed to analyze the phase transitions of pure Fe3 O4 nanopar-
ticles after calcined at different temperatures. The qualitative analysis of the
change of magnetism of the calcined particles was performed on a Gouy
magnetic balance (FDTX-FM-A, Nanjing University Plant, China). Some calcined
particles were dissolved in hydrochloric acid (HCl, 0.1 M) and potassium thio-
cyanate solution (KSCN, 0.1 g ml−1 ) was added as a color-developing agent to
form a red solution. U-2810 spectrophotometer (Hitachi, Japan) was used to
measure the absorbency of the red solution that implying the concentration
of Fe3+ in each calcined particles. All the data are obtained through at least
three times of experiments. Scanning electron microscope (SEM, Hitachi S-4700,
Japan) was used to observe the morphology of Fe3 O4 /BaSO4 multi-core/shell parti-
cles. Fig. 1. Relationship of magnetic weight of different samples and temperature.
142 J.H. Li et al. / Materials Chemistry and Physics 113 (2009) 140–144
Fig. 2. XRD patterns of pure Fe3 O4 nanoparticles at room temperature (a) and
It is well known that Fe3 O4 is a mixed cubic oxide which contains
calcined at 150 ◦ C (b), 250 ◦ C (c), 350 ◦ C (d), 450 ◦ C (e), 550 ◦ C (f) for 2 h in the
atmosphere. 2/3 Fe3+ and 1/3 Fe2+ cations whereas ␣ and ␥-Fe2 O3 contain only
Fe3+ cations. In order to validate the gradual transformation from
Fe3 O4 to ␣-Fe2 O3 (550 ◦ C for 2 h), Fe3+ concentration of every cal-
3.3. FT-IR studies cined samples was reflected via measuring the absorbency of the
sample solution. Fig. 4 shows the results of the absorbency mea-
XRD cannot show the change of pure Fe3 O4 nanoparticles after surement. The inserted illustration demonstrates that the maximal
calcined at 150 ◦ C and 250 ◦ C. In order to reveal it, IR spectra (as absorbency of the sample solution occurs at 480 nm. Along with the
shown in Fig. 3) of magnetite samples calcined at different tempera- increase of temperature from 150 ◦ C to 550 ◦ C, Fe3+ concentration
tures were obtained using Fourier transform infrared spectroscope of the calcined samples increases. After calcined at 550 ◦ C for 2 h in
(FT-IR). From Fig. 3, one can find the absorption peak of Fe–O in the atmosphere, the Fe3+ concentration keeps the same, implying
Fe3 O4 at 571.1 cm−1 [27]. After calcined at 150 ◦ C for 2 h, the peak the complete transformation from Fe3 O4 to ␣-Fe2 O3 .
at 571.1 cm−1 splits into two peaks at 632.9 cm−1 and 563.4 cm−1 ,
respectively. The new arisen absorption peaks at 632.9 cm−1 and 3.5. SEM analysis
563.4 cm−1 which are associated with Fe–O bond, are the char-
acteristic peaks of ␥-Fe2 O3 [28]. XRD is not sensitive enough to SEM images were obtained to observe the morphology of the
differentiate between Fe3 O4 and ␥-Fe2 O3 , due to extreme similar- Fe3 O4 /BaSO4 multi-core/shell particles. Fig. 5(a) shows the image
Fig. 3. IR spectra of pure Fe3 O4 nanoparticles at room temperature (a) and calcined at 150 ◦ C (b), 250 ◦ C (c), 350 ◦ C (d), 450 ◦ C (e), 550 ◦ C (f) for 2 h in the atmosphere.
J.H. Li et al. / Materials Chemistry and Physics 113 (2009) 140–144 143
4. Conclusions
Acknowledgments
Key Laboratory of Coal Conversion, CAS (No. 2006-902), the Key [11] Y.C. Chang, D.H. Chen, J. Colloid Interface Sci. 283 (2005) 446.
Laboratory of Organic Synthesis of Jiangsu Province, the Chemical [12] C.Q. Hu, Z.H. Gao, X.R. Yang, Chem. Phys. Lett. 429 (2006) 513.
[13] H. Iida, K. Takayanagi, T. Nakanishi, T. Osaka, J. Colloid Interface Sci. 314 (2007)
Experiment Center of Soochow University and R&D Foundation of 274.
Nanjing Medical University (NY0586). [14] F.Q. Hu, Z. Li, C.F. Tu, M.Y. Gao, J. Colloid Interface Sci. 311 (2007) 469.
[15] R.Y. Hong, T.T. Pan, H.Z. Li, J. Magn. Magn. Mater. 303 (2006) 60.
[16] M.J. Meziani, P. Liu, P. Pathak, J. Lin, S.K. Vajandar, L.F. Allard, Y.P. Sun, Ind. Eng.
References Chem. Res. 45 (4) (2006) 1539.
[17] Z.Q. Liu, H. Hashimoto, M. Song, K. Mitsuishi, K. Furuya, Acta Mater. 52 (2004)
[1] S. Zhou, E.S. Garbett, R.F. Boucher, Ind. Eng. Chem. Res. 35 (11) (1996) 4257. 1669.
[2] A. Holzwarth, J.F. Lou, T.A. Hatton, P.E. Laibinis, Ind. Eng. Chem. Res. 37 (7) (1998) [18] J.H. Liu, J. Wei, S.M. Li, Mater. Lett. 61 (2007) 1529.
2701. [19] U. Colombo, G. Fagherazzi, F. Gazzarrini, G. Lanzavecchia, G. Sironi, Nature 219
[3] J. Bao, W. Chen, T.T. Liu, Y.L. Zhu, P.Y. Jin, L.Y. Wang, J.F. Liu, Y.G. Wei, Y.D. Li, Nano (1968) 1036.
1 (4) (2007) 293. [20] M.A. Nejad, M. Jonsson, J. Nucl. Mater. 345 (2005) 219.
[4] J.-H. Park, K.-H. Im, S.-H. Lee, D.-H. Kim, D.-Y. Lee, Y.-K. Lee, K.-M. Kim, K.-N. [21] P.S. Sidhu, R.J. Gilkes, A.M. Posner, J. Inorg. Nucl. Chem. 39 (1977) 1953.
Kim, J. Magn. Magn. Mater. 293 (2005) 328. [22] J.P. Jolivet, E. Tronc, J. Colloid Interface Sci. 125 (1988) 688.
[5] S. Dubus, J.F. Gravel, B.L. Drogoff, P. Nobert, T. Veres, D. Boudreau, Anal. Chem. [23] R.Y. Hong, S.Z. Zhang, G.Q. Di, H.Z. Li, Y. Zheng, J. Ding, D.G. Wei, Mater. Res. Bull.
78 (12) (2006) 4457. 43 (2008) 2457–2468.
[6] M. Brahler, R. Georgieva, N. Buske, A. Muller, S. Muller, J. Pinkernelle, U. Teich- [24] R.Y. Hong, J.H. Li, H.Z. Li, J. Ding, Y. Zheng, D.G. Wei, J. Magn. Magn. Mater. 320
graber, A. Voigt, H. Baumler, Nano Lett. 6 (11) (2006) 2505. (2008) 1605.
[7] E.-H. Kim, H.-S. Lee, B.-K. Kwak, B.-K. Kim, J. Magn. Magn. Mater. 289 (2005) [25] J.-B. Shi, C.-W. Lee, J.-W. Guo, M.-J. Cheng, C. Wu, C.-J. Chen, Y.-C. Chen, Y.-T. Lin,
328. C.-C. Chang, Mater. Lett. 61 (2007) 5268.
[8] H.-S. Lee, E.-H. Kim, H.P. Shao, B.-K. Kwak, J. Magn. Magn. Mater. 293 (2005) [26] S. Nasrazadani, H. Namduri, Spectrochim. Acta Part B 61 (2006) 565.
102. [27] R.Y. Hong, J.H. Li, J. Wang, H.Z. Li, Particuol. 5 (2007) 186.
[9] Y.S. Kim, K. Nakatsuka, T. Fujita, T. Atarashi, J. Magn. Magn. Mater. 201 (1999) [28] R.Y. Hong, H.P. Fu, G.Q. Di, Y. Zheng, D.G. Wei, Mater. Chem. Phys. 108 (2008)
361. 132.
[10] A.M. Donia, A.A. Atia, K.Z. Elwakeel, Hydrometallurgy 87 (2007) 197. [29] S. Nasrazadani, A. Raman, Corros. Sci. 34 (8) (1993) 1355.