Sie sind auf Seite 1von 5
ARTICLE IN PRESS Physica B 390 (2007) 23–27 www.elsevier.com/locate/physb Preparation of a -Fe 2 O

ARTICLE IN PRESS

ARTICLE IN PRESS Physica B 390 (2007) 23–27 www.elsevier.com/locate/physb Preparation of a -Fe 2 O 3

Physica B 390 (2007) 23–27

ARTICLE IN PRESS Physica B 390 (2007) 23–27 www.elsevier.com/locate/physb Preparation of a -Fe 2 O 3

Preparation of a -Fe 2 O 3 nanoparticles by high-energy ball milling

Li-Li Wang, Ji-Sen Jiang

Department of Physics, Center of Functional Nanomaterials and Devices, East China Normal University, Shanghai 200062, PR China

Received 8 May 2006; received in revised form 14 July 2006; accepted 19 July 2006

Abstract

a-Fe 2 O 3 nanoparticles were prepared by high-energy ball milling using a-FeOOH as raw materials. The prepared samples were characterized by transmission electron microscopy (TEM), Mo¨ssbauer spectroscopy, X-ray diffraction (XRD) and differential thermal analysis–thermogravimetric analysis (DTA–TGA). The results showed that after 90 h milling a-Fe 2 O 3 nanoparticles were obtained, and the particle size is about 20 nm. The mechanism of reaction during milling is supposed that the initial a-FeOOH powder turned smaller and smaller by the high-speed collision during ball milling, later these particles turned to be superparamagnetic, at last these superparamagnetic a-FeOOH particles were dehydrated and transformed into a-Fe 2 O 3 . r 2006 Elsevier B.V. All rights reserved.

PACS: 78.67.Bf; 76.80.+y; 78.30.Hv

Keywords: High-energy ball milling; Nanomaterials; a -FeOOH; a-Fe 2 O 3 ; Mo¨ssbauer spectroscopy

1. Introduction

a -Fe 2 O 3 (hematite) is not only a strategic industrial material, but also one of the most used metal oxides with various applications in many scientific and industrial fields. It is one of the most frequently used catalysts in chemical industry [1] and a potential candidate as a photoanode for possible photoelectrochemical cells [2]. Moreover, a -Fe 2 O 3 can be used as gas sensor material to detect the combustible gases such as CH 4 , C 3 H 8 and i-C 4 H 8 [3,4]. There are many kinds of methods to prepare a -Fe 2 O 3 nanoparticles, e.g. hydrothermal reaction [5–7], microwave [8], sol–gel method [9], microemulsion method [10], forced hydrolysis [11] and solid-phase grinding [12]. High-energy ball milling is an important way to produce nanoparticles. It has many advantages, e.g. low cost, simple operation, high yield and so on. At the same time, the influence of ball milling on the phase transition and reaction of inorganic nonmetal materials is an interesting topic for researchers. Randrianantoandro et al. [13] studied the direct phase transition of a -Fe 2 O 3 to g -Fe 2 O 3 . Uehara et al. [14] studied the structure changes of iron oxide in

Corresponding author. E-mail address: jsjiang@phy.ecnu.edu.cn (J.-S. Jiang).

0921-4526/$ - see front matter r 2006 Elsevier B.V. All rights reserved.

different media by ball milling. Sanchez et al. [15] and Lee et al. [16] found that a -Fe 2 O 3 could be produced by ball milling g -Fe 2 O 3 . Jiang et al. [17] prepared 10 nm a -Fe 2 O 3 nanoparticles directly from crude a -Fe 2 O 3 by high-energy ball milling, and found that the surface anisotropy constant of a -Fe 2 O 3 nanoparticles produced by this method is higher than bulk material. Gonzalez et al. [18] studied the structure and phase changes of a -FeOOH during ball milling mainly by XRD. In this report, a -FeOOH was milled in air at room temperature, and the resultant particles, the phase change and the reaction mechanism of a -FeOOH during ball milling were mainly analyzed by Mo¨ssbauer spectroscopy as well as by TEM, XRD and DTA–TGA.

2. Experimental

For the milling experiment, 10 g of goethite powder (a - FeOOH, yellow powder) was used. High-energy ball milling was carried out in a planetary ball mill. The milling was performed in a closed container with a hardened-steel vial of 100 ml volume and 100 hardened-steel balls of a diameter of 8 mm at ambient temperature in air without any additives. The milling intensity was 200 rpm and the

24

ARTICLE IN PRESS

L.-L. Wang, J.-S. Jiang / Physica B 390 (2007) 23–27

ball-to-powder weight ratio of 20:1 was chosen. After selected milling times, the mill was stopped and a small amount of powder was taken from vial for measurement. The milling lasted for 90 h in all. The 57 Fe Mo¨ssbauer spectra were obtained from powdered samples in the transmission mode with the 57 Co in Cr matrix as the source moving in constant- acceleration regime. Hyperfine interaction parameters were derived from the Mo¨ssbauer spectra using a least-squares method. The spectrometer was calibrated using a standard 25 m m a -Fe foil. For low-temperature measurement, liquid nitrogen was used. XRD were performed on a diffract- ometer manufactured by Rigaku with Cu K a radiation ( l ¼ 0.15406 nm) in the range of 2 y ¼ 10–80 1 by a step of 0.02 1 . TEM observations were carried out using a JEM- 100CX at 200 kV. DTA–TGA analyses were obtained in a TGA/SDTA851e manufactured by METTLER in nitrogen atmosphere and with a heating rate 10 K/min.

3. Results and discussion

3.1. Characterization of the structure and morphology of nanoparticles

Fig. 1 (a) is an X-ray diffraction pattern of the initial powders. The diffraction pattern is consistent with a - FeOOH (JCPDs card 29–713). Therefore, a -FeOOH is the main component of the initial powders. Fig. 1 (b) is an X- ray diffraction pattern of the sample milled for 90 h. The diffraction pattern of the sample is consistent with a -Fe 2 O 3 (JCPDs card 13–534). This means during the milling process the mechanochemical reaction occurred, i.e. after milled for 90 h a -FeOOH transformed into a -Fe 2 O 3 .

for 90 h a -FeOOH transformed into a -Fe 2 O 3 . Fig. 1. XRD

Fig. 1. XRD of initial powder (a) and sample milled for 90 h (b).

a -Fe 2 O 3 was synthesized through the following reaction:

(1)

The particle size of the prepared sample (milled for 90 h) is about 20 nm by Sherrer’s formula. The TEM image of sample milled for 90 h (Fig. 2) shows the morphology of particles is nearly spherical. The particle size from the picture is about 18 nm, which is consistent with the result by XRD.

2 a FeOOH ! a 2 O 3 þ H 2 O :

3.2. Analysis of milling process

Some selected Mo¨ssbauer spectra recorded at 300 K are presented in Fig. 3. A set of asymmetrically broadened sextet presents in the spectrum of the sample before milling (0 h). The fitting parameters are shown in Table 1. According to the value of hyperfine field [19] and the shape of the spectrum [20], sextets 2–5 (Table 1) are attributed to a -FeOOH. Another small sextet with 506.62 kOe hyperfine field (sextet 1 in Table 1) is also presented in the spectrum of raw material. This sextet is estimated to be a -Fe 2 O 3 from the value of hyperfine field [19]. From the analysis above we conclude that the initial powder consists of a -FeOOH mostly and a trifle a -Fe 2 O 3 . It shows in Fig. 3 that as the milling time prolongs, the sextet area for a -Fe 2 O 3 becomes larger, and the area for a - FeOOH becomes smaller. These changes indicate that the content of a -Fe 2 O 3 becomes larger and the content of a - FeOOH becomes smaller as the milling time prolongs. Meanwhile, there are obvious doublets in the spectra of samples milling for 3, 5 and 10 h, and the doublet in spectrum of sample milled for 10 h is the biggest. The doublet and the sextet for a -FeOOH both have disappeared from the spectrum of sample of milled for 90 h (Fig. 3), which indicates the completeness of the reaction. The analysis can also be supported by the hyperfine field distribution of samples milled for different time. Fig. 4 is the hyperfine field distribution of samples corresponding to Fig. 3. The peaks around 500 and 370 kOe represent a - Fe 2 O 3 and a -FeOOH, respectively. Besides, the peaks with small hyperfine field values about 30 kOe represent doub- lets. Fig. 5 shows the area changes of hyperfine field peaks of doublet, sextet for FeOOH and sextet for a -Fe 2 O 3 with different milling time. This picture also illustrates that the longer the milling time is, the more intensive the peak representing for a -Fe 2 O 3 is, and the weaker the peak representing for a -FeOOH is. The intensity of doublet increases before 10 h and then decreases. Samples milled for 3, 5 and 10 h all have obvious doublet. It can help us understand the mechanism of mechanochemical reaction to analyze the corresponding substance of the doublet. The sample milled for 10 h that has the biggest doublet is chosen. There are visual peaks of a -Fe 2 O 3 (peaks with crosses in Fig. 6) in the XRD pattern of this sample, which indicates that part of a -FeOOH has transformed into a -Fe 2 O 3 . Fig. 7 is the Mo¨ssbauer spectra of this sample at room temperature (300 K) and liquid

ARTICLE IN PRESS

L.-L. Wang, J.-S. Jiang / Physica B 390 (2007) 23–27

25

L.-L. Wang, J.-S. Jiang / Physica B 390 (2007) 23–27 25 Fig. 2. TEM photo of

Fig. 2. TEM photo of sample milled for 90 h.

23–27 25 Fig. 2. TEM photo of sample milled for 90 h. Fig. 3. Mo¨ssbauer spectra

Fig. 3. Mo¨ssbauer spectra of different samples at room temperature.

Table 1 Parameters of Mo¨ssbauer spectra of raw material

 

Hyperfine

I.S (mm/s)

QS (mm/s)

Area

field (kOe)

Sextet 1

506.62

0.81

1.00

0.030

Sextet 2

372.65

0.37

0.26

0.245

Sextet 3

347.10

0.37

0.26

0.440

Sextet 4

311.23

0.37

0.27

0.086

Sextet 5

279.82

0.41

0.19

0.199

0.086 Sextet 5 279.82 0.41 0.19 0.199 Fig. 4. Hyperfine field distribution of different samples.

Fig. 4. Hyperfine field distribution of different samples.

nitrogen temperature (77 K). Table 2 shows the parameters of the Mo¨ssbauer spectra. The spectrum at 77 K is completely composed of magnetic sextets. The areas of the sextets with the largest hyperfine field representing for a -Fe 2 O 3 , both at 300 and 77 K, are nearly the same, which indicates the doublet at room temperature is mainly due to superparamagnetic particles of a -FeOOH. From the hyperfine field distribution of the sample at room temperature and 77 K (Fig. 8), we can draw the same conclusion. From the distribution curve of hyperfine field of the sample at low temperature (77 K), we can also see that the doublet has disappeared. The hyperfine field value of a -Fe 2 O 3 at low temperature is a little larger than that at room temperature, while the value of FeOOH at low

26

ARTICLE IN PRESS

L.-L. Wang, J.-S. Jiang / Physica B 390 (2007) 23–27

PRESS L.-L. Wang, J.-S. Jiang / Physica B 390 (2007) 23–27 Fig. 5. The area changes

Fig. 5. The area changes of hyperfine field peaks of doublet, sextet for FeOOH and sextet for a-Fe 2 O 3 with differrent milling time.

for a -Fe 2 O 3 with differrent milling time. Fig. 6. XRD of the sample

Fig. 6. XRD of the sample milled for 10 h. The peaks with crosses are the diffraction peaks of a-Fe 2 O 3 .

crosses are the diffraction peaks of a -Fe 2 O 3 . Fig. 7. Mo¨ssbauer spectra

Fig. 7. Mo¨ssbauer spectra at 300 and 77 K of the sample milled for 10 h.

Table 2 Parameters of Mo¨ssbauer spectra at 300 and 77 K of the sample milled for 10 h

 

Temperature

Hyperfine

IS (mm/s)

QS (mm/s)

Area

 

field (kOe)

300 K

Doublet

0.31

0.82

0.237

Sextet 1

456.74

0.33

0.15

0.148

Sextet 2

371.30

0.31

0.25

0.080

Sextet 3

343.69

0.32

0.24

0.064

Sextet 4

289.19

0.29

0.14

0.471

77 K

Sextet

1

495.51

0.39

0.10

0.141

Sextet 2

435.90

0.44

0.12

0.601

Sextet 3

431.46

0.29

0.58

0.081

Sextet 4

349.98

0.31

0.41

0.176

0.081 Sextet 4 349.98 0.31 0.41 0.176 Fig. 8. Hyperfine field distribution of the sample milled

Fig. 8. Hyperfine field distribution of the sample milled for 10 h at room and low temperature.

temperature is much larger than that at room temperature. It is reasonable, for the standard hyperfine field values of a - FeOOH and a -Fe 2 O 3 at 77 K are both larger than those at 300 K, respectively. The standard hyperfine field values of a -FeOOH and a -Fe 2 O 3 at 300 K are about 377 and 514 kOe, respectively, and at 77 K are about 509 and 535 kOe, respectively [19]. In the sample milled for 10 h, the hyperfine field values of a -FeOOH and a -Fe 2 O 3 at 300 K are 371 and 456 kOe, respectively, and at 77 K the values shift to 435 and 495 kOe, respectively. The area ratio of hyperfine field of a -FeOOH to a -Fe 2 O 3 is 0.86:0.14 after normalization at low temperature. And the area ratio of peaks of doublet: sextet a -FeOOH : sextet a Fe 2 O 3 in Fig. 8 is 0.24:0.61:0.15 after normalization. The area of a -Fe 2 O 3 peak hardly changed as the temperature changed from room temperature to liquid nitrogen temperature. Only the areas of doublet and sextet a -FeOOH changed. So we estimate that the main substance of doublet at room temperature is due to superparamagnetic particles of a -FeOOH. The mechanism of mechanochemical reaction during milling

T

Δ

ARTICLE IN PRESS

L.-L. Wang, J.-S. Jiang / Physica B 390 (2007) 23–27

27

0h 1.00 TGA 10h 0.96 90h 0.92 0.88 0.84 WL(%)
0h
1.00
TGA
10h
0.96
90h
0.92
0.88
0.84
WL(%)

5

0

-5

-10

-15

-20

0 200

400

600

800

SDTA
SDTA

0 200

400

600

Tempreture(° C)

800

Fig. 9. TGA–DTA curves of samples milled for 0, 10 and 90 h.

can be supposed that the initial a -FeOOH powder turned smaller and smaller by the high-speed collision during ball milling, later these particles turned to be superparamag- netic; at last these superparamagnetic a -FeOOH particles were dehydrated and transformed into a -Fe 2 O 3 . Fig. 9 is DTA–TGA curves of the samples milled for 0, 10 and 90 h. There is a weight loss possessing 2.3% of total weight between 50 and 120 1 C in the TGA curve of sample milled for 0 h. This weight loss is due to the evaporation of water in the sample absorbed from the air. Another weight loss possessing 11.4% of total weight appears between 120 and 350 1 C. The largest weight loss ratio is at the temperature around 265 1 C. An endothermal peak appears in the corresponding region in DTA curve, and this peak is attributed to the decomposition of a -FeOOH during heating. According to Eq. (1), when a -FeOOH decomposes to a -Fe 2 O 3 , 10% weight will lose. The weight loss value here is close to the theoretic value. There are also two weight loss regions for the sample milled for 10 h. The first weight loss region is also due to the loss of water. The amount of weight loss is larger in the sample milled for 10 h than in raw material for water is created in the reaction during ball milling. The loss amount in the second weight loss region is 8.6%, which corresponds to the decomposi- tion of a -FeOOH remaining in the sample. We can deduce from the loss amount that 15.2% a -FeOOH have conversed to a -Fe 2 O 3 after milling for 10 h. This result is consistent with that got from Mo¨ssbauer spectrum. Only water loss can be seen in the TGA curve of sample milled for 90 h. There is no weight loss between 120 and 350 1 C,

and no presents in this region in DTA curve. So sample milled for 90 h is completely composed of a -Fe 2 O 3 .

4. Conclusions

The experiment shows that the structure of a -FeOOH can be changed by high-energy ball milling. Using Mo¨ssbauer spectroscopy, TEM, XRD and TGA–DTA, we know that the initial a -FeOOH powder turned smaller and smaller by the high-speed collision during ball milling, later these particles turned to be superparamagnetic, at last these superparamagnetic a -FeOOH particles were dehy- drated and turned into a -Fe 2 O 3 . The resultant is a -Fe 2 O 3 nanoparticles with 20 nm in size after a certain milling time.

Acknowledgments

This work was supported by Shanghai Nanotechnology Promotion Center (0352 nm113).

References

[1] N. Mimura, I. Takahara, M. Ando, Catal. Today 45 (1998) 61.

[2] I. Cesar, A. Kay, J.A. Gonzalez Martinez, M. Gra¨tzel, J. Am. Chem. Soc. 128 (2006) 4582. [3] M. Matsuoka, Y. Nakatani, H. Ohido, Nat. Tech. Rep. 24 (1978)

461.

L. Huo, W. Li, L. Lu, H. Cui, S. Xi, J. Wang, B. Zhao, Y. Shen,

Z. Lu, Chem. Mater. 12 (2000) 790.

[5] X. Wang, X. Chen, X.C. Ma, H.G. Zheng, Chem. Phys. Lett. 384

[4]

(2004) 391.

[6] K. Kandori, T. Ishikawa, J. Colloid Interface Sci. 272 (2004) 246. [7] X.H. Kang, X.Y. Wang, H.Q. Xie, L.Z. Lu, Chin. J. Mater. Res. 17 (2003) 466. [8] Y.Z. Tang, W.M. Zhang, Chem. Res. Appl. 10 (1998) 419. [9] K. Woo, H.J. Lee, J. Magn. Magn. Mater. 272–276 (2004) e1155. [10] A. Garcia, M. Llusar, S. Sorli, J. Calbo, M.A. Tena, G. Monros,

J. Eur. Ceram. Soc. 23 (2003) 1829.

[11] J.S. Jiang, X.L. Yang, L.W. Chen, N.F. Zhou, Appl. Phys. A 45

(1988) 245.

[12] C.X. Qiu, J.S. Jiang, Z.J. Zhao, X.L. Yang, J. Inorg. Mater. 16 (2001)

957.

[13] N. Randrianantoandro, A.M. Mercier, M. Hervieu, J.M. Greneche, Mater. Lett. 47 (2001) 150. [14] Y. Uehara, Bull. Chem. Soc. Jpn. 48 (II) (1975) 3383. [15] R.M. Torres Sanchez, J. Mater. Sci. Lett. 15 (1996) 461. [16] J.S. Lee, C.S. Lee, S.T. Oh, J.G. Kim, Scr. Mater. 44 (2001) 2023. [17] J.S. Jiang, L. Gao, X.L. Yang, J.K. Guo, Acta Phys. Chim. Sinica 16 (2000) 312. [18] G. Gonzalez, A. Sagarzazu, R. Villalba, Mater. Res. Bull. 35 (2000)

2295.

[19] R.Z. Ma, Mo¨ssbauer, Spectroscopy Manual, Metallurgical Industry Press, 1993, p. 362. [20] Z. Li, Y.P. Ying, Mineral Mo¨ssbauer, Spectroscopy, Science Press,

1996, p. 133.