Magnetic and structural properties of Cu0.85Fe0.

15O system synthesized by coprecipitation

H. D. Colorado & G. A. Prez Alczar

Hyperfine Interactions ISSN 0304-3843 Hyperfine Interact DOI 10.1007/s10751-011-0354-0

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Hyperfine Interact DOI 10.1007/s10751-011-0354-0

Magnetic and structural properties of Cu0.85 Fe0.15 O system synthesized by co-precipitation

H. D. Colorado G. A. Prez Alczar

Springer Science+Business Media B.V. 2011

Abstract Cu0.94 Fe0.06 O and Cu0.85 Fe0.15 O samples were synthesized by using the coprecipitation chemical method. Starting from aqueous solutions of copper nitrate, CuO (NO3 )2 3H2 O, iron nitrate, Fe (NO3 )3 9H2 O and sodium hydroxide as precipitating agent, NaOH. The precipitate of three samples for Cu0.94 Fe0.06 O and five for Cu0.85 Fe0.15 O of fine powder were calcined for 5 h at different temperatures. The obtained X rays diffraction patterns refined by the Rietveld method show the CuO characteristic pattern, showing that the Fe atoms enter to replace Cu atoms. Furthermore, it was obtained that the crystallite size decreases with calcination temperatures for Cu0.94 Fe0.06 O. The transmission Mssbauer spectroscopy showed that the samples present a disordered paramagnetic behavior due to the big value of the half-width of line of the quadrupolar splitting. Vibrating sample magnetometry confirms the paramagnetic character. The XRD results indicate that the material is nanostructured, due that the crystallite sizes are of the order of 10 nm for Cu0.94 Fe0.06 O and 40 nm for Cu0.85 Fe0.15 O. Keywords Mssbauer spectroscopy X rays diffraction Vibrating sample magnetometry Copper oxide Co-precipitation Nanostructure material

1 Introduction The thorough investigation of the properties of CuO was stimulated by the discovery of high temperature superconductors (HTSC). This is because CuO is the basis of the HTSC cuprates and exhibits properties similar to the semiconducting phase of the HTSC. Both are nearly insulating and present antiferromagnetic order at

H. D. Colorado (B G. A. Prez Alczar ) Departamento de Fsica, Universidad del Valle, A.A. 25360, Cali, Colombia e-mail: herdacom@gmail.com

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H.D. Colorado, G.A. Prez Alczar

relatively high temperatures [1, 2]. Copper oxide awake increasingly interesting from the standpoint of practical and fundamental aspects. It has proved to be an important industrial material that can be widely used in applications such as gas sensors, magnetic storage media in solar energy transformation, semiconductors and catalysis [36]. By reducing the crystal size of copper oxide to a nanometric scale, unique properties that may occur tend to be significantly different from those of a bulk sample; examples of such properties are the optical, electrical, magnetic and catalytic properties. It is therefore necessary to know the physical and chemical characteristics for different grain sizes of CuO particles in the development of practical applications [7]. On the other hand, it also highlights the interest in methods of synthesis of nanoparticles directly to control the physical and chemical properties. Consequently, we have studied several methods to obtain nanostructured materials, being among the more traditional solgel [8], co-precipitation [9], Pechini [10, 11], and other chemical methods [12]. And because it is well established synthetic method in this work are prepared CuO samples doped with 6% and 15% Fe using co-precipitation, which has the advantage of being an easy and low budget. Although the CuO system had been widely studied, there is very little information available of this system doped with iron. This paper presents the magnetic behavior of samples at room temperature obtained by transmission Mssbauer spectroscopy (MS) and vibrating sample magnetometry. The structural properties were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM).

2 Experimental The production process of copper monoxide doped with Fe, was arisen by co-precipitation method. We used stoichiometric amounts of copper nitrate, Cu(NO3 )2 .3H2 O, and iron nitrate, Fe (NO3 )3 .9H2 O, starting salts for an aqueous solution under magnetic stirring at 600 rpm for 40 min at 40 C. Then, with the addition of sodium hydroxide (NaOH), co-precipitation occur releasing heat to stabilize and eventually kill a temperature of 40 C. NaOH is also used to control the pH which remained at 12.53 in the aqueous solution on magnetic stirring for 1 h. The precipitate resulting from the chemical reaction is slowly cooled to room temperature, and then transferred to a centrifuge at 2,000 rpm for 10 min in order to decant the Cu(FeOH)2 and remove the NaNO3 formed. This process is repeated 4 times until complete removal of NaNO3 . After the precipitate is dried for 192 h at 50 C and calcined for 5 h at 150 C, 200 C and 250 C for Cu0.94 Fe0.06 O and at 100 C, 150 C, 200 C, 250 C and 300 C for Cu0.85 Fe0.15 O. Mssbauer measurements were performed in a conventional spectrometer 57Co/Rh source of 25 mCi. All the spectra were fitted with the MOSFIT program. The Cu0.94 Fe0.06 O XRD pattern was performed on a Bruker D8 Advance diffractometer with a Cu anode tube and graphite monochromator input Cu0.85 Fe0.15 O detector and a pro PANalytical XPert diffractometer with tube Cu anode. The diffractometer was calibrated with a sample of alumina and the radiation used was Cu K-. The 2 angular scan was performed discretely in steps of 0.02

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Magnetic and structural properties of Cu0.85 Fe0.15 O system

1,00
250 C D1 D2

Relative Transmission

0,99 1,00
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Fig. 1 Transmission Mssbauer spectra (left) and hysteresis cycles (right) of the Cu0.94 Fe0.06 O and Cu0.85 Fe0.15 O systems, respectively, at different calcination temperatures

every 30 s. The diffractograms were refined with the GSAS program which uses the Rietveld method.

3 Results and discussion Figure 1 shows the Mssbauer transmission spectra and vibrating sample magnetometry for different calcination temperatures of the Cu0.94 Fe0.06 O sample. Each spectrum was fitted with two doublets indicating the paramagnetic nature of the samples. At least one doublet of each spectrum has a line half width greater than 0.50 mm/s, which confirms a disordered paramagnetic behavior of the system for the temperatures considered. Similar fit was reported by Young et al. [13]. They report two doubles corresponding to sites of Fe+3 and Fe+2 , respectively. In our case the two doublets present basically the isomer shift of Fe+3 ( 0.35 mm/s), but different quadrupole splitting ( Q1 1.25 and Q2 0.72 mm/s). Then it is proposed that the second site corresponds to the Fe+3 sites and the first one to the Fe+3 sites but with a more asymmetric charge distribution. The obtained hysteresis cycles of the samples of Cu0.85 Fe0.15 O present near zero coercive fields and a magnetization values which tend to the saturation. These results, and the Mssbauer ones, suggest the presence of a soft magnetic behavior of the samples. More measurements at different temperatures are necessary to determine what type of phase is the present. Figure 2a presents the behavior of the percentage of the spectral area of each doublet with the calcination temperature. It is noted how the area of each doublet, D1 and D2, is constant between 150 C and 200 C, then the D1 area tends to increase

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H.D. Colorado, G.A. Prez Alczar Fig. 2 Variation with the different calcination temperatures of the spectral area (a) and of the quadrupole splitting (b) of the Cu0.94 Fe0.06 O system
D1 D2
D1 D2

spectral area (%)

75 60 45 30 15 150 200 Temperature (C)

1,4
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250

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20 30 40 50 60 70 80 90

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40

50

60

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Fig. 3 XRD patterns of the Cu0.94 Fe0.06 O system (left) and of the Cu0.85 Fe0.15 O system (right) for different calcination temperatures

with temperature while the D2 decreases. It seems that between 200 C and 250 C there is a rearrangement of charges around the decreasing Fe+3 sites with greater symmetry around him. In Fig. 2b, as expected, the quadrupole splitting for different temperatures remains essentially constant. Figure 3 shows the XRD patterns for different calcination temperatures. As can be seen, only one phase, corresponding to the monoclinic structure of CuO, was obtained for the different calcination temperatures, and then this confirms that indeed Fe atoms replace some of Cu atoms. Figure 4 shows the crystallite sizes and lattice parameters of the Cu0.94 Fe0.06 O system obtained by XRD for different temperatures. Clearly seen in Fig. 4a how the crystallite size increases with calcination temperature taking the values 9.41 nm for 150 C, 9.53 nm for 200 C and 9.76 nm for 250 C. The lattice parameters a and c decrease with temperature but these values are higher than those of the CuO reference values, whereas b values are lower compared to the reference one. The lattice parameter c does not have a defined behavior. For the Cu0.85 Fe0.15 O system, crystallite sizes between 36 and 42 nm where obtained. The obtained lattice parameters can be considered as remain invariant within an error of 0.02 . Figure 5 shows SEM images obtained for the sample calcined at 200 C. According to the resolution obtained by SEM, the left image of Fig. 5 shows different particle sizes ranging from 200 nm up to about 30 m. In the write image is clearly noted the tendency of particles to agglomerate. According to these values and

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Magnetic and structural properties of Cu0.85 Fe0.15 O system
9,8
4,7255

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Parameter a ()

9,7 9,6 9,5 9,4 150

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4,7250 4,7245 4,7240 4,7235 4,7230 4,6620 4,67 150

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3,43

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5,1390 5,1380 5,1370 5,1360 5,1350 5,1200 5,12 150

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3,3700 150 200 250

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Temperature (C)

200 250 Temperature (C)

Fig. 4 a Crystallite sizes, b, c and d lattice parameters a, b and c, respectively, obtained by XRD of the Cu0.94 Fe0.06 O system for different calcination temperatures

Fig. 5 SEM images for Cu0.94 Fe0.06 O system for the sample calcined at 200 C

those obtained by XRD for the crystallite size it can be conclude that the particles must be polycrystalline.

4 Conclusions The diffraction patterns obtained by XRD, and then refined by the Rietveld method, show a characteristic pattern of CuO, where Fe atoms replace Cu atoms, with a crystallite size which decreases with the calcination temperature. Transmission Mssbauer spectroscopy results show that there is a disordered paramagnetic behavior due to the large value taken of the line half width of the quadrupole

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H.D. Colorado, G.A. Prez Alczar

splitting. XRD results indicate that the material is nanostructured, since the obtained crystallite sizes are between 10 and 42 nm. SEM results show a strong tendency of the particles to agglomerate.
Acknowledgement The authors thank the financial support of Universidad del Valle.

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