Accepted Manuscript

Key step in the synthesis of ultrafine strontium ferrite powders (SrFe12O19) by

sol-gel method

Tran Thi Viet Nga, Nguyen Phuc Duong, To Thanh Loan, Than Duc Hien

PII: S0925-8388(14)01026-3
DOI: http://dx.doi.org/10.1016/j.jallcom.2014.04.193
Reference: JALCOM 31158

To appear in:

Received Date: 17 March 2014

Revised Date: 23 April 2014
Accepted Date: 25 April 2014

Please cite this article as: T.T. Viet Nga, N. Phuc Duong, T. Thanh Loan, T. Duc Hien, Key step in the synthesis of
ultrafine strontium ferrite powders (SrFe12O19) by sol-gel method, (2014), doi: http://dx.doi.org/10.1016/j.jallcom.
2014.04.193

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 Key step in the synthesis of ultrafine strontium ferrite powders

(SrFe12O19) by sol-gel method

Tran Thi Viet Nga*, Nguyen Phuc Duong, To Thanh Loan, and Than Duc Hien

International Training Institute for Materials Science (ITIMS), Hanoi University of Science and

Technology, No. 1 Dai Co Viet road, Hanoi, Vietnam

Abstract

Submicron strontium hexaferrite (SrFe12O19) particles were synthesized using the sol-gel route.

Magnetic properties and structure of strontium ferrite powders were studied at various ranges of

calcination temperature (Tca) (750 °C to 900 °C), calcination time (3 min to 2 h), Fe/Sr molar ratios

(RM) (10.5 to 12), and pH (1 to 8). The resultant particles were investigated using X-ray diffraction,

scanning electron microscopy, and vibrating sample magnetometer. At 750 °C, the Sr-M phase

could be obtained for 3 min in air. However, single-phase Sr-M, which had stabilized magnetic

properties, was obtained at Tca of 850 °C for 2 h. In solutions at pH 1, magnetic properties of the

obtained sample at RM = 10.5 were found to be optimal with maximum saturation magnetization of

56 emu/g and intrinsic coercive force of 6.7 kOe.

Keywords: Sol-gel synthesis; hexaferrite, scanning and transmission electron microscopy; X-ray

diffraction; magnetic measurements

* Corresponding author: International Training Institute for Materials Science (ITIMS), Hanoi

University of Science and Technology, No. 1 Dai Co Viet road, Hanoi, Vietnam. Tel.: +84

438680787; Fax: +84 438692963.

E-mail address: vietnga@itims.edu.vn (Tran Thi Viet Nga)

1
1. Introduction

Submicron hexagonal ferrite particles with high coercivity, high uniaxial magnetocrystalline

anisotropy with easy axis of magnetization along the hexagonal c-axis, and good chemical stability

are promising materials for applications in permanent magnets, microwave devices, and magnetic

recording, among others. Numerous efforts have recently been made into the fabrication of

submicron hexagonal ferrite particles to improve their magnetic properties by controlling the

particle size and shape, and reducing the sintering temperature, which typically exceeds 1200 °C for

the conventional ceramic approach. To achieve highly homogeneous ultrafine strontium hexaferrite

particles, multiple low-temperature chemical methods have been used, such as co-precipitation [1–

3], hydrothermal [4, 5], sol-gel [6–8], micro-emulsion [9], citrate precursor [10], glass

crystallization [11], and sono-chemical [12]. However, these chemical methods have numerous

factors that affect the characteristics of the resulting hexagonal ferrite, including the mole ratio of

Fe3+/Sr2+ (RM), mole ratio of citric acid to the metal nitrate AC/(Fe3+ + Sr2+) (RA), pH of the starting

solution, and calcination temperature (Tca). In previous studies [13], single-phase BaFe12O19

powders were achieved by decreasing the Fe3+/Ba2+ molar ratio from the stoichiometric value of 12

to 8, and the achieved maximum saturation magnetization (MS) was 50.2 emu/g. Hsuan-Fu Yu et al.

[14] also showed the effect of pH and calcination temperature on the characteristics of BaFe12O19

particles, and reported that pure single-domain BaM particles with M (at 3T) = 54 emu/g and

intrinsic coercivity force (iHc) = 3717 Oe are produced at pH 9. Yu and Huang studied the effects of

pH and citric acid/metallic ion molar ratio of the starting solution, as well as Tca, on the

characteristics of BaFe12O19 particles. Single-domain magnetic BaM particles can be obtained at

800 °C at a starting pH of the solution of 7 and citric acid/metallic ratio = 1.5 [15, 16]. In this paper,

we systematically studied the influence of technological parameters, such as Tca, RM , pH, and

calcination time (tca), on the structure and magnetic properties of SrFe12O19 particles prepared by

sol-gel precursor. The relations between the parameters and structure, as well as magnetic
2
properties, were investigated.

2. Experiment

The strontium powders were synthesized by sol-gel method. Fe(NO3)3 (1 M) and Sr(NO3)2 (1 M)

were dissolved in deionized water with various RM , ranging from 10.5 to 12 (step 0.5). Citric acid

was then added into the solution at a fixed [Sr2++Fe3+] : C3 H4(OH)(COOH)3 molar ratio of 1:3. We

used NH4OH to adjust the pH from 1 to 8. After the pH had been stabilized, the solution was stirred

at 1000 rpm and gradually evaporated at 80 °C. As the water evaporated, the remainder became

highly viscous gels with a brown color as a result of the chelation process. These gels were dried at

100 °C for 24 h, and then heated at 500 °C for 2 h to eliminate the remaining residual water and

other organic impurities. To form the hexaferrite phase, the gels were calcined in air at Tca of

750 °C, 800 °C, 850 °C, and 900 °C for different tca.

Differential thermal and thermogravimetric analyses (DTA/TGA) were employed to study thermal

behavior using a Universal V2960T with a heating rate of 10 °C/min in air, whereas pure alumina

powder was used as the reference specimen. X-ray diffraction (XRD, Cu-Kα, Siemens D-5000) was

used to identify the crystalline structure. To examine the particle size and morphology, we used

scanning electron microscopy (SEM). The magnetic parameters and temperature dependence of

magnetization were measured using a vibrating sample magnetometer with maximum field (H) of

13.5 kOe and temperatures ranging from room temperature to 800 K.

3. Results and discussion

3.1. Thermal analysis

The TGA and DTA of the gel precursor at pH 1 and RM of 10.5 are shown in Fig. 1. The experiment

was performed using 5.102 mg of gel precursor and a heating rate of 5 °C/min in static air. In the

DTA curve, the first two exothermic peaks at approximately 142 °C and 219 °C were attributed to

the decomposition of NH4NO3 to liberate NO, O2, and H2O. At approximately 340 °C, the third

exothermic peak showed the decomposition of the remaining unreactive organic material induced
3
by excess citric acid and occurrence off the crystallization process off the main phase following Eq.

3.1. The TGA curve indicates a weight loss of 23% in this reaction.

6Fe2O3 + SrCO3 = SrFe12O19 + CO2 ↑ (3.1)

3.2. Effect of calcination temperature and calcination time

To monitor phase development with increasing Tca, the obtained gel precursor was calcined in air at

various temperatures between 500 °C and 950 °C. Figure 2 shows the XRD patterns of strontium

ferrite powders with RM of 10.5 calcined at different Tca with different tca. Based on the results

obtained from thermal analysis of the precursors (Fig. 1), we selected 500 °C as the minimum Tca to

ensure that all organic components in the precursors were completely removed. Fig. 2a shows the

XRD pattern of the Sr-ferrite powder calcined at 500 °C for 5 h. The obtained powder contained the

γ-Fe2O3 phase and Sr(NO3)2 phase at 2θ = 25.2°. According to Wei Zhong et al. [17], γ-Fe2O3 is a

cubic spinel with a chemical formula of Fe[Fe3/5□1/3]O4, where □ denotes the hole of the cation. Its

structure is similar to that of the S block in Ba-ferrite, so γ-Fe2O3 can react with BaCO3 easily to

form BaFe2O4, thereby producing a single BaFe12O19 phase at a low temperature. The ultrafine γ-

Fe2O3 phase obtained by heating the gel at temperatures between 300 °C and 500 °C (preliminary

heating process) could further enhance the development of Sr-ferrite after calcination at higher

temperatures. Figures 2b and 2c show the XRD pattern of specimen powders calcined at 750 °C for

60 min and 2 h, respectively. The powders contained both the Sr-ferrite phase and α-Fe2O3 phase,

which were characterized by Miller indices (104), (113), (024), (116), (214), and (300). This

observation was also reported by other authors, and may be attributed to the occurrence of local

combustion during calcination [18, 19]. The intensity ratio between (104) peak of α-Fe2O3 phase

and (114) of hexaferrite phase ranged from 15% to 30% as tca increased from 3 min to 2 h at

750 °C. At Tca of 850 °C and 950 °C, a single-phase M-type ferrite was formed with no other

characteristic diffraction peaks. The crystallinity of SrFe12O19 was further enhanced with increasing

Tca.
4
XRD refinements were carried out using the Rietveld method with the help of the Fullprof program.

The crystal structure for all samples was well-refined in the hexagonal space group P63/mmc with

a = 5.87 Å and c = 23 Å. Fig. 3 shows the diffraction plot and Rietveld refinement pattern of

samples calcined at 950 °C. For this sample, the lattice parameters were refined to be

a = 5.8738(5) Å and c = 23.0221(15) Å. In the case of processing with the presence of impurities,

only a slight percentage (<0.4%) of impurities (α-Fe2O3 and Sr(NO3)2), which could be ignored,

was observed in the sample. Thus, the sample calcined at 950 °C was confirmed to have a single

phase. The percentages of phases present in these samples, lattice parameters (a, c), unit cell

volume (V), and crystallite sizes (D) are listed in Table 1.

The dependence of iHC on tca and Tca are shown in Fig. 4. iHC markedly increased with increasing tca

and Tca. However, at low Tca, such as 750 °C and 800 °C, iHC reached a stable value when tca

exceeded 30 min. At 850 °C, iHC stabilized after calcination for 12 min. Thus, a higher Tca value

required a lower tca value. This result was mainly attributed to the improvement in Sr-ferrite

crystalline and phase homogeneity during calcination at higher temperatures and longer times. In

addition, the presence of the α-Fe2O3 phase at low Tca and development of particle size with

increasing Tca in the range of the critical single domain of SrM hexagonal ferrite (270 nm) [20]

could also be the main reasons for the enhancement in coercivity in samples at higher Tca. A similar

increase in coercivity was also observed for samples prepared at pH 7 and 8. iHC at 850 °C for 2 h

reached 5.9 kOe, which was approximately 4% larger than that of samples reported by Hsuan-Fu

Yu et al. [21].

3.2. Effect of pH on magnetic properties

To investigate the effect of pH on magnetic properties, we selected samples with RM = 10.5 and

RM = 11.5. Fig. 5a and 5b show the values of iHC and MS of samples with RM of 10.5 and 11.5

derived from solutions of varying pH at Tca of 850 °C, respectively. In generally, iHC generally

decreased with increasing pH, whereas MS changed slightly. The samples obtained from the solution
5
at pH 1 exhibited better magnetic properties with iHC of 6.7 kOe and MS of 59 emu/g (with

RM=10.5); with iHC of 6.6 kOe and 56 emu/g (with RM = 11.5) than those obtained from solutions

with other pH values. For the sample with RM = 11.5, the lowest iHC of samples was 5 kOe, which

was obtained at pH 3. At a solution of pH 2, MS of this sample decreased by 18% compared with

that in the sample obtained from a solution of pH 1. While for the sample with RM = 10.5, the

lowest iHC of samples was 5.7 kOe and higher 14% than of sample RM = 11.5. The chemical phases

presented in the samples could be the main reason for the change in magnetic properties.

Therefore, to determine for the presence of impurities and explain for the change magnetic

properties of these samples, the XRD patterns of samples with RM = 11.5 annealed at 850 °C were

analyzed using the Rietveld refinement program. The results are shown in Table 2 and Fig. 6. For

the samples derived from solutions at pH 1 and 5, SrFe12O19 was the major crystalline phase with

94.1% and 96.2%, respectively. Furthermore, α-Fe2O3 was the only intermediate phase in these

samples. In samples from solutions at pH 2 and 3, the intermediate phases consisted of α-Fe2O3,

Sr2Fe2O5, and Sr4Fe6O13. The presence of these phases was attributed to an incomplete calcination

reaction of these sample prepared at pH 2 and 3 [22]. At a solution of pH 3, α-Fe2O3 appeared as the

major crystalline phase, with more than 50% in the obtained specimens (Fig. 6). Therefore, higher

Tca (>850 °C) and longer tca are required to obtain a single phase in these samples. However, Hsuan-

Fu Yu et al. [14] reported a specimen obtained from a solution at pH 3 that consisted of α-Fe2O3

and BaM. iHC from our research was larger by approximately 8.7% than that of Hsuan-Fu Yu et al.

in the same pH of a solution.

The SEM images of samples prepared at a solution of pH 1 are shown in Fig. 7a and 7b, and the

results indicate that the particles had a proper hexagonal platelet shape. The average particle size

was evenly distributed in the range of 80 nm to 100 nm. The sizes of all particles were smaller than

the critical single domain of SrM hexagonal ferrite (270 nm).

3.3. Effect of input Fe/Sr molar ratio on structure and magnetic properties
6
 At the same pH of a solution, the dissociation of Fe(NO3)3 and Sr(NO3)2 differed markedly,

so the phase composition and magnetic properties differed significantly between samples with

different RM. Table 3 shows the magnetic properties of samples with different RM at 850 °C for 2 h

at pH 1. These results reveal that RM greatly affected the magnetic properties of strontium ferrite

powders. iHC of samples with RM of 10.5 and 11.5 reached 6.7 and 6.6 kOe, respectively. The

specimen with RM = 12 exhibited the lowest values among specimens with other RM. These results

were in agreement with those reported by Y-P. Fu et al. [19]. The iHC values obtained for our

samples were lower than the theoretical limit of Sr-M (7.5 kOe) [23]. However, the iHC values

observed in our work were considerably higher than those reported by Rezlescu et al. [24] and

García-Cerda et al. [25] (3.4 and 4.2 kOe, respectively) for Sr-M ferrite particles, which were also

prepared by sol-gel method. MS and remanent magnetization (Mr) at room temperature of samples

also varied with RM, and their maximal values were observed at RM = 10.5. To investigate the effect

of RM on magnetic properties, the effects of RM on the phase composition of powders were also

monitored by XRD measurements (Fig. 8). Powders with RM = 10.5 and 11.5 were observed to be

of a single phase, with 98.6% and 92.6% of the SrFe12O19 phase, respectively. The intermediate

hematite α-Fe2O3 appeared as a major phase in the sample with RM = 12 (37.5%). This result could

be attributed to the coordination probability of metal cations and the citric anion, which occurred

strongly at RM = 10.5 and 11.5, so these samples were significantly pure. These XRD results were

in agreement with the magnetic property results listed in Table 3.

4. Conclusions

The sol-gel technique is a useful method to prepare homogeneous ultrafine SrFe12O19 powders with

improved magnetic properties. Results of this study show that magnetization, coercive force, and

size distribution were dependent on technological parameters. Appropriate pH, Fe/Sr molar ratio,

and Tca were adjusted and determined to produce a single-phase nanosized SrM with optimized

magnetic properties. The single-phase SrM was formed at Tca of 850 °C with Fe/Sr molar ratio of
7
10.5 and pH of the solution of 1. The sample exhibited a specific Ms of 56 emu/g and iHC of

6.6 kOe.

Acknowledgments

This research was funded by the Vietnam National Foundation for Science and Technology

Development under grant number 103.02-2014.19

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[10] V.K. Sankaranarayanan, D.C. Khan, J. Magn. Magn. Mater. 153 (1996) 337.

[11] L Rezlescu, E Rezlescu, P.D Popa, N Rezlescu, J. Magn. Magn. Mater. 193 (1999), 288–290.

[12] K.V.P.M. Shafi, A. Gedanken, Nanostruct. Mater. 12 (1999) 29.

[13] M.M. Rashad, M. Radwan, M.M. Hessien, J. Alloys Compd. 453 (2008) 304–308.

[14] Hsuan-Fu Yu, Pei-Chi Liu, J. Alloys Compd. 416 (2006) 222 – 227.

[15] H. Yu, K. Huang, J. Magn. Magn.Mater. 260 (2003) 455.

[16] H. Yu, K. Huang, J. Mater. Res. 17 (2002) 199.

[17] Wei Zhong , Weiping Ding, Ning Zhang, Jianming Hong, Qijie Yan, Youwei Du , J.

Magn. Magn. Mater. 168 (1997) 196-202.

8
[18] Y. Fu, C. Lin, K. Pan, J. Alloys Compd. 364 (2009) 221.

[19] Y.-P. Fu, C.-H. Lin, J. Alloys Compd. 386 (2005) 222–227.

[20]. R. J. Parker, Ferrite, Proceedings of ICF-3. (1980).

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[22] Nobuyoshi Koga, Takanori Tsutaoka, J. Magn. Magn.Mater. 313 (2007) 168 – 175

[23] V.V. Pankov, M. Pernet, P. Germi, P. Mollard, J. Magn. Magn. Mater. 120 (1993) 69–72.

[24] N. Rezlescu, C. Dorof tei, E. Rezlescu, P.D. Popa, J. Alloys Compd. 451 (2008) 4 92–4 96.

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369 (2004) 182–184.

9
Tables

Table 1. Percentages of phases present in the obtained sample with RM = 10.5, pH 1, and different

calcination temperatures (Tca), lattice parameters (a, c), unit cell volume (V), and crystallite size

(D). Statistical errors are indicated in the last significant digit.

Tca (°C) Phase Percentage a (Å) c (Å) V (Å3) D (nm)

950 SrFe12O19 100% 5.8738(5) 23.0221(15) 687.89(9) 42.23(4)

850 SrFe12O19 ~100% 5.8723(13) 23.0247(65) 687.61(29) 25.02(2)

SrFe12O19 91% 5.8767(3) 23.0612(18) 689.74(7) 31.76(4)

750
α-Fe2O3 9% - - -

Table 2. Percentages of phases present in the samples with different pH values of solutions, lattice

parameters (a, c), unit cell volume (V), and crystallite size (D). Statistical errors are indicated in the

last significant digit.

pH SrFe12O19 α-Fe2O3 Sr2Fe2O5 Sr4Fe6O13 a (Å) c(Å) D (nm)

1 94.1% 5.9% 5.8722(2) 23.0199(9) 24.65(3)

2 71.8% 1.5% 14.2% 12.5% 5.8758(4) 23.0437(21) 35.65(3)

3 38% 50.6% 3.9% 7.5% 5.8695(9) 23.0603(58) 42.99(3)

5 96.2% 3.8% 5.8755(9) 23.0354(36) 42.89(4)

10
Table 3. Intrinsic coercivity force (iHC), saturation magnetization (MS), remanent magnetization

(Mr), and percentages of phases present in the samples with different Fe/Sr ratios prepared in the

following conditions: pH 1, Tca = 850 °C, and tca = 2 h.

RM 10 10,5 11 11,5 12

i HC (kOe) 6.197 6.725 6.279 6.577 6.131

MS (emu/g) 38.3 59.3 43.6 56 28.8

Mr (emu/g) 22 34.9 25.3 33.1 16.4

% SrFe12O19 - 98.6% 79.5% 92.9% 62.5%

% α-Fe2O3 - 1.4% 20.5% 7.1% 37.5%

11
Figure captions

Fig. 1: Thermogravimetric (TGA) curve and differential thermal analysis (DTA) curve of the gel

precursor SrFe12O19 at pH 1 and Fe/Sr mole ratio of 10.5

Fig. 2: XRD patterns of SrFe12O19 (RM = 10.5): (a) Tca = 500 °C, tca = 5 min; (b) Tca = 750 °C,

tca = 60 min; (c) Tca = 750 °C, tca = 2 h; (d) Tca = 850 °C, tca = 2 h; (e) Tca = 950 °C, tca = 2 h (●:

SrFe12O19; ○: α-Fe2O3; and γ: γ-Fe2O3)

Fig. 3: XRD pattern refinement of SrFe12O19 calcined at 950 °C. SrFe12O19 phase is indexed in the

space group P63/mmc (hexagonal structure) with a = 5.8738(5) Å, c = 23.0221(15) Å, Rwp = 9.71%,

and goodness of fit (χ2) = 1.05

Fig. 4: Effect of calcination time and temperature on intrinsic coercivity force

Fig. 5: Saturation magnetization (MS) and intrinsic coercive force (iHC) for the specimens with

RM = 11.5 obtained from solutions at different pH values, followed by annealing at 850 °C for 2 h

Fig. 6: XRD pattern refinement of SrFe12O19 with pH 3. The sample consisted of four phases:

SrFe12O19 (38%), α-Fe2O3 (50.6%), Sr2Fe2O5 (3.9%), and Sr4Fe6O13 (7.5%). The fitting quality:

Rwp = 10.7% and goodness of fit (χ2) = 1.67

Fig. 7: SEM micrographs of the SrFe12O19 samples with pH 1, Tca = 850 °C, tca = 2 h: (a) RM = 10.5

and (b) RM = 11.5 ,

Fig. 8: XRD patterns of SrFe12O19 with different RM at 850 °C for 2 h (●: SrFe12O19 and ○: α-Fe2O3)

12
Fig. 1.
Fig. 2.
Fig. 3.
Fig. 4.
Fig. 5.
Fig. 6.
Fig. 7.
Fig. 8.
Highlights

The variations in the magnetic properties of ultrafine SrFe12O19 powders, resulting from

different technique, are studied.

Appropriate pH, Fe/Sr molar ratio, and Tca were adjusted and determined to produce a single-

phase nanosized SrM with optimized magnetic properties.

13