- Email: [email protected]
Microstructure and magnetic properties of cobalt ferrite nano powder prepared by solution combustion synthesis
Accepted Manuscript Microstructure and magnetic properties of cobalt ferrite nano powder prepared by solution combustion synthesis Alireza Mazrouei, Ali Saidi PII:
S0254-0584(18)30082-8
DOI:
10.1016/j.matchemphys.2018.01.075
Reference:
MAC 20347
To appear in:
Materials Chemistry and Physics
Received Date: 20 November 2017 Revised Date:
19 January 2018
Accepted Date: 26 January 2018
Please cite this article as: A. Mazrouei, A. Saidi, Microstructure and magnetic properties of cobalt ferrite nano powder prepared by solution combustion synthesis, Materials Chemistry and Physics (2018), doi: 10.1016/j.matchemphys.2018.01.075. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Microstructure and magnetic properties of cobalt ferrite nano powder prepared by solution combustion synthesis Alireza Mazrouei٭1, Ali Saidi ¹´
RI PT
Advanced Materials Research Center, Faculty of Materials Engineering, Najafabad Branch, Islamic Azad University, Najafabad, Iran
1. Introduction
TE D
M AN U
SC
Abstract In this study, cobalt ferrite nanoparticles (CoFe O NPs) were prepared by solution combustion synthesis using urea and glycine as fuels. The magnetic properties of the CoFe O powders were modified by using various amounts of extra fuel (above the stoichiometric value). Thermodynamic calculations indicates that as the extra fuel increases, the amount of gases produced and the adiabatic flame temperature (T ) rise. To investigate effect of urea, glycine and amount of extra fuel on the structural and magnetic properties of CoFe O powders, the produced samples were studied by using X-ray diffraction (XRD), vibrating sample magnetometer (VSM), field emission scanning electron microscopy (FESEM), thermo gravimetric analysis and differential scanning calorimetry (TGA-DSC), and Brunauer-Emmett-Teller (BET) technique. XRD results of the produced sample indicated that the single phase CoFe O with an average crystallite size between 17 and 33 nm was synthesized. By using two different type of fuel, the specific surface area of the produced powders were increased from 1.6 (glycine fuel) to 56.2 m /g (urea fuel). By changing the type of fuel and the amount of extra fuel, the CoFe O coercivity (H ) ranges between 870 and 1667.8 O and the saturation magnetization (M ) varies between 31.6 and 83.7 emu/g. The solution combustion synthesized CoFe O powders exhibit a hard ferrimagnetic behavior. Based on the results, Urea is the proper fuel for producing cobalt ferrite nanoparticles (with a particle size less than 100 nm) and in case of using glycine, the minimum amount of this fuel should be 2 times the stoichiometric amount. Keywords: Cobalt ferrite nanoparticles, Solution combustion synthesis, Magnetic properties.
AC C
EP
Cobalt ferrite is well known to have significant magnetic anisotropy, moderate saturation magnetization and remarkable chemical stability [1]. These properties make CoFe O particles a good candidate for the technological applications such as magnetic recording devices, gas sensors, catalysis, ferrofluids and medical applications such as hyperthermia, drug delivery, and contrast enhancers in magnetic resonance imaging [2-8]. The cationic distribution for nanophase cobalt ferrite is different from its bulk counterpart. Bulk state is purely inverse spinel with general formula of (Fe ) (Co Fe )! (T indicating tetrahedral and O indicating octahedral sites) [9]. For cobalt ferrite nanoparticles the cationic states and distribution are complicated. CoFe O nanoparticles as mixed spinel which can be represented as (Co " Fe #$" ) (Co #$" Fe # " )! where δ is the degree of inversion [1,9]. The magnetic properties of CoFe O particles are mainly dominated by particle size, specific surface area, morphology and cationic distribution in the two interstitial sites (tetrahedral and octahedral) [3]. Cobalt ferrite nanoparticles were produced so far by various 1
٭Corresponding author at: Advanced Materials Research Center, Faculty of Materials Engineering, Najafabad Branch, Islamic Azad University, Najafabad, Iran. Tel.: +989130605114 E-mail address: [email protected] (Alireza Mazrouei).
1
ACCEPTED MANUSCRIPT
SC
RI PT
methods including co-precipitation [9,10], solvothermal [11]. mechanical alloying [12,13], sol-gel [4,7,14] etc. In addition, solution combustion synthesis has recently been developed to synthesize nanoparticles of ceramic oxides [15-18]. This method is very simple, costeffective and fast [5,19]. In this method, ceramic oxide powders is produced due to an exothermal reaction between metal nitrate (oxidizer) and fuel (reducing agent) [20]. In solution combustion synthesis, the type and amount of fuel plays a major role in the structural properties of the product. So far, cobalt ferrite powders have been produced with different fuels, such as Urea [21-23], alanine [2,24], citric acid [25], glycine [26-28], 5-aminotetrazole [29], Polyvinyl alcohol [30], hexamethylene tetramine [31], arginine [32]. On the other hand, given that urea and glycine are cost-effective and commercially available fuels, no comparison has been made regarding the production of CoFe O powders with these fuels by solution combustion synthesis. The purpose of this study is to compare the structural and magnetic properties of cobalt ferrite nanoparticles produced by solution combustion synthesis method using urea and glycine fuels. 2. Experimental
M AN U
2.1. Sample preparation
→ CoFe O
(
+ 2Fe(NO ) ) + 6.67CO
(
+ 6.67CH N O(
(2) + 10.67N
(Glycine fuel) Co(NO ) ( /) + 2Fe(NO )
→ CoFe O
( /)
) + 8.88C9
( /)
+ 4.446 7& 89
(<) + 6.228
/)
(2) + 13.34H O(2)
(1)
(:;)
(<) + 11.17 9(<) + 0.019
(<)
(2)
AC C
/)
EP
(Urea fuel) Co(NO ) (
TE D
To prepare the cobalt ferrite particles, based on combustion reactions (1) and (2) stoichiometric amounts of Fe(NO ) . 9H O (Merck, 99%), Co(NO ) . 6H O (Merck, 99%), CH N O (Merck, 99%) and C H& NO (Applichem, 98%) were dissolved in 20 ml of distilled water (at 80 ℃) in a glass beaker. The aqueous solution was stirred for one hour (at 80 ℃). The beaker was then kept on hot plate preheated to 350 ℃. The whole solution combustion reaction process was performed in less than 4 minutes whereas time of ignition was less than half a minute. Various amounts of extra fuel were added to the reaction mixture in different proportions (0-100 wt%), in order to investigate its influence on the CoFe O properties.
2.2. Sample characterization Crystallite size and phase identification of the powders were carried out by using Philips X-ray diffractometer equipped with a crystal monochromator employing Cu- Kα radiation of wavelength 1.54 ºA. The average crystallite size (D>?@) was calculated based on XRD patterns using Debye Scherrer formula 0.9λ
D = ß cosθ
(3)
Where ß is the full-width at half maxima of the strongest intensity diffraction peak, λ is the wavelength of radiation (1.54 ºA) and θ is the angle of diffraction. Morphology was investigated by FESEM (Mira3-Xmu). BET (Brunauer-Emmett-Teller) surface area of the powders (SGH ), was measured by the nitrogen gas adsorption technique using a sorptometer 1042-costech instrument.
2
ACCEPTED MANUSCRIPT Assuming that the CoFe O particles have a spherical shape, the equivalent particle size ( DGH ) was calculated using Eq. (4) DGH =
IJJJ ρKLMN
(4)
RI PT
Where DGH is the equivalent particle size (nm), ρ is the theoretical density of CoFe O (5.3g/cm ), and SGH is the BET surface area (m /g) [2]. Magnetic properties were measured at room temperature with a vibrating sample magnetometer (VSM, Meghnatis Daghigh Kavir, Iran) in an operating range of ± 15 KO . Thermo gravimetric analysis and differential scanning calorimetry (TGA-DSC) of the stoichiometric mixture of metal nitrates with urea and glycine fuel was carried out using a STA-503 Bahar instrument operated in temperature range 30 -1000 ℃ with heating rate of 20 ℃ per minute in flowing air ambience.
3. Results and discussion
M AN U
SC
The observed high flame temperature of the solution combustion reaction is due to the exothermicity of the reaction between the gaseous decomposition products of metal nitrate as NOP and fuel as HNCO, NH , etc. In solution combustion reactions, extremely high temperatures can be achieved within a very short time. Therefore, it is reasonable to assume that a thermally isolated system exists because there is very little time for the heat to disperse to its surroundings. Consequently, the maximum temperature to which the product is raised is assumed to be adiabatic temperature (T ). The heat liberated during the reaction is the enthalpy of the system [19]. The equation 5 and the
thermodynamic information of Table 1 were used to calculate T . Thermodynamic data of reactants and products is available in literature [33].
TE D
WX CT (Product)dT (5) Q = - ∆H° (reaction) = S YZ Where Q is the heat absorbed by products under adiabatic condition, and CT is the heat capacity of the products at constant pressure.
Table 1 Thermodynamic data required for calculating adiabatic flame temperature. ∆H° (Kcal/mole )
C[ (cal/mole .K)
EP
Compound
-160.3
----
Co(NO )
-100.5
----
CH N O
-79.61
----
C H& NO
-126.31
----
CoFe O
-252
10.34 + 0.00274 T
H O(2)
-57.79
7.2 + 0.0036 T
-94.05
35.36
CO N O
(2)
(2) (2)
AC C
Fe(NO )
0
6.5 + 0.001 T
0
5.92 + 0.00367 T
Based on thermodynamic calculations, T and number of mole of gases produced, increase with the amount of extra fuel used during combustion reactions (Table 2). Adiabatic flame temperature increases in samples from 1494 ℃ (sample A# ) to 1726 ℃ (sample A ) and from 1530 ℃ (sample A ) to 1758 ℃ (sample AI ). However, the actual flame temperatures are lower than the theoretically calculated values owing to incomplete combustion and 3
ACCEPTED MANUSCRIPT
Table 2 Samples specifications, experimental data, and some obtained results.
A#
Urea
A
Urea
A
Urea
A
Glycine
A&
Glycine
AI
Glycine
100
M^
time (s)
T (° C)
Gases produced (moles)
D>?@ (nm)
DGH (nm)
SGH (m /g)
(emu/g)
0
5
1494
30.68
17
20
56.2
31.6
9.6
870
50
35
1647
44
16
53
21.4
48.7
17.5
957.5
100
15
1726
57.36
30
48
23.7
66.4
27.1
877.7
0
10
1530
26.21
30
707
1.6
45.6
23.7
1667.8
50
11
1680
37.3
33
339
3.3
78.6
39.6
1292.7
20
1758
48.4
31
80
14.1
83.7
43
1516.1
Reaction
M
SC
Extra Fuel (wt%)
M AN U
Fuel & Extra Fuel
(emu/g)
H (O )
EP
TE D
Sample Code
RI PT
heating of air [5]. The amount of gases produced increases in samples from 30.68 (sample A# ) to 57.36 moles (sample A ) and from 26.21 (sample A ) to 48.4 moles (sample AI ). Solution combustion reactions is substantially influensed by the type and amount of extra fuel. Fig. 1 illustrated the process of synthesizing of the samples A# and A . In sample A# , the combustion reaction was carried out as bulk within 5 s, while In sample A , the combustion reaction was performed in the combustion front within 10 s. The variation of the reaction times is presented in Table 2. In other samples, with increasing the amount of extra fuel, combustion reaction changes from a strong incandescence process, which is accompanied by flames to a smoldering process, where no flames appeared.
AC C
Fig. 1. Images taken during the solution combustion reactions of samples A1 and A4.
XRD analysis, as shown in Fig. 2, indicates that the combustion synthesized powders consists of single phase CoFe O having a face-centered cubic structure. The obtained peaks are well matched with standard JCPDS card no. 22-1086. Weak diffraction peak corresponding to formation of FeO was observed in case of sample A (glycine fuel). The average crystallite size (D>?@ ) of the samples A# (17 nm), A (16 nm), A (30 nm), A (30 nm), A& (33 nm), and AI (31 nm) was calculated by Debye Scherrer formula (Table 2). The adiabatic flame temperature of urea-produced samples is smaller than glycine, and by decreasing the growth of crystallites, D>?@ of urea-produced samples (A# - A ) is smaller than glycine-produced samples (A - AI ). On the other hand, by increasing the amount of extra fuel and T , D>?@ increases in samples (except A ) from 17 nm (A# ) to 30 nm (A ) and from 30 nm (A ) to 31 nm (AI ). In sample A combustion heat was released in 35 s, compared with sample A# (5 s), 4
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
SC
RI PT
so in sample A the growth of crystallites decreases. one can say that the absence of a tangible difference between the average crystallite size (D>?@ ) of the samples A (30 nm), A& (33 nm), and AI (31 nm) can be justified by their releasing time of the combustion heat, A (10 s), A& (11 s) and samples AI (20 s). By increasing the weight percentage of extra fuel the intensity of the XRD patterns increase, which indicates an increase in crystallinity of the produced samples.
Fig. 2. XRD patterns of solution combustion synthesized CoFe O powders.
The simultaneous TGA-DSC curves of the stoichiometric metal nitrates with urea fuel (sample A# ) and stoichiometric metal nitrates with glycine fuel (sample A ) were shown in Fig. 3. The TGA-DSC curve of sample A# (urea fuel) contains two exothermic peaks at 200 and 251℃ with sharp weight loss that indicates occurrence of combustion reaction and two endothermic peaks at below 200℃, related to vaporization of water and inner water. The total weight losses observed in TGA plot of sample A# (urea fuel) is ∼80%. No weight loss is observed after the combustion reaction giving a product free of residual reactants and carbonaceous matter. The TGA-DSC curve of sample A (glycine fuel) contains sharp 5
ACCEPTED MANUSCRIPT exothermic peak at 188℃ that indicates occurrence of solution combustion reaction and two endothermic peaks at below 188℃, related to vaporization of water and inner water. The total weight losses observed in TGA plot of sample A (glycine fuel) is ∼82%.
M AN U
SC
RI PT
A# (Urea Fuel)
AC C
EP
TE D
A (Glycine Fuel)
Fig. 3. TGA-DSC curves of the stoichiometric mixture of metal nitrates with urea fuel (sample A# ) and stoichiometric mixture of metal nitrates with glycine fuel (sample A ).
The BET surface area (SGH ) of the obtained powders varies between 1.6 and 56.2 m /g (Table 2). As expected, by increasing the weight percentage of extra fuel and thus increasing the number of mole of gases produced, SGH values increased in samples A (21.4 m /g) to A (23.7 m /g) and A (1.6 m /g) to AI (14.1 m /g). on the other hand, the high value of SGH in sample A# (56.2 m /g) was acceptable due to the exhaust of 30.68 moles of gases produced in 5 s, compared to the samples A (exhaust of 44 moles of gases produced in 35 s) and samples A (exhaust of 57.36 moles of gases produced in 15 s). In all samples except A# , 6
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
SC
RI PT
the equivalent particle size (DGH ), calculated from the BET surface area is larger than the crystallite size (D>?@ ), therefore these samples are polycrystalline (Table 2). The FESEM images of samples A# and A are shown in Fig. 4. These images indicate remarkable changes in microstructure, particle size, particle distribution, and porosity by changing fuel from urea (sample A# ) to glycine (sample A ). The evolution of BET surface area as a function of fuel type is confirmed by the FESEM images. In solution combustion synthesis, evolution of large quantities of gases like carbon dioxide, water, and nitrogen results in the formation of fine and porous particles. The main factor chainging the porosity of samples is the number of mole of gases produced (CO , H O, N ) [19]. One can say that, the porosity of sample A# (exhaust of 30.68 moles of gases produced in 5 s) is more than the sample A (exhaust of 26.21 moles of gases produced in 10 s). Energy dispersive spectroscopy (EDS) of samples A# and A evidenced O, Fe and Co as the only present elements. The elemental composition of samples A# (50.31% O, 33.16% Fe, 16.53% Co) and A (48.03% O, 34.01% Fe, 17.97% Co), expressed in atomic percents, is close to the theoretical composition of CoFe O (57.1% O, 28.6% Fe, 14.3% Co).
Fig. 4. FESEM Images of samples A1 and A4.
7
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
SC
RI PT
The hysteresis curves of the obtained powders are presented in Fig. 5. The saturation magnetization (M ), remanence magnetization (M^ ) and coercivity (H ) were summarized in Table 2. The saturation magnetization (M ) of CoFe O powders ranges between 31.6 and 83.7 emu/g. The coercivity (H ) of CoFe O powders ranges between 870 and 1667.8 O . With increasing SGH , the spin canting phenomenon is created due to the change in the position of the ions in the particle surface relative to the corresponding ions in the particle core. The spin canting phenomenon leads to the formation of a 1.69 nm dead surface layer on the surface of cobalt ferrite particles and reduces the saturation magnetization [10,25]. Difference in combustion and crystallizaton process could influence the distribution of Co ions at octahedral, Fe ions between octahedral and tetrahedral sites, and then more affect the super-exchange interaction between two sites [27]. By increasing the weight percentage of extra fuel and so T , the crystallite size and crystallinity of samples increased. Thus, the value M in samples A# (31.6 emu/g) to A (66.4 emu/g) and A (45.6 emu/g) to AI (83.7 emu/g) increased. The critical size of cobalt ferrite particles was reported at 70 nm with a blocking temperature of 235 ° K [3,10]. The particles smaller than the critical size, exhibit a super-paramagnetic behavior and the coercivity of super-paramagnetic particles is zero. The equivalent particle size (DGH ) in samples A# (20 nm), A (53 nm), and A (48 nm) is smaller than the critical size (70 nm), but the coercivity (H ) of samples A# (870 O ), A (957.5 O ), and A (877.7 O ) is not zero. This can be the result of particles that are agglomerated and the presence of ferrimagnetic particles in the wide particle size distribution. This fraction of ferrimagnetic particles increases coercivity and magnetization.The equivalent particle size (DGH ) in samples A (707 nm), A& (339 nm), and AI (80 nm) is larger than the critical size (70 nm), thus, these samples exhibit a ferrimagnetic behavior. By comparing DGH of the produced powders with critical size, it can be concluded that glycine-produced samples have ferrimagnetic behavior, while a part of the urea-produced samples have ferrimagnetic behavior and the other part of the urea-produced samples have superparamagnetic behavior. Therefore, by using urea and glycine fuels and adding extra fuel, the particle size, specific surface area and magnetic properties of the cobalt ferrite particles can be modified and optimized in a wide range.
8
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 5. Magnetic hysteresis curves of solution combustion synthesized CoFe O powders.
TE D
4. Conclusion
AC C
EP
In this study, cobalt ferrite nanoparticles (CoFe O NPs) were produced by solution combustion synthesis method using urea and glycine fuels. The major difference in combustion reaction with urea fuel that was carried out as bulk in 5 s with a large amount of gas exiting, than the glycine fuel that was done in the combustion front in 10 s, made SGH in the urea-produced sample (56.2 m /g) much larger than that of glycine (1.6 m /g). According to thermodynamic calculations, by increasing the weight percentage of extra fuel, T increased in the process of Solution combustion synthesis leading to the growth of crystallites in products and increase of crystallite size and crystallinity of the produced samples. As expected, the amounts of saturation magnetization of the samples increased by increasing the weight percentage of extra fuel. On the other hand, by increasing the weight percentage of extra fuel, the number of moles of gases produced, increased leading to the increase of SGH in produced samples. The superparamagnetic behavior of particle fraction in urea-produced samples reduced the amount of magnetization of these samples. In addition, the glycine-produced samples had a hard ferrimagnetic behavior. It can be concluded that urea fuel should be used to produce cobalt ferrite nanoparticles (with a particle size less than 100 nm) by using solution combustion synthesis and in case of using glycine, the minimum amount of this fuel should be 2 times the stoichiometric amount.
9
ACCEPTED MANUSCRIPT References
AC C
EP
TE D
M AN U
SC
RI PT
[1] Mathew, D. Shin Juang, R, ’An overview of the structure and magnetism of spinel ferrite nanoparticles and their synthesis in microemulsions’, Chemical Engineering Journal, No. 129, pp. 51-65, 2007. [2] Ianos, R. Bosca, M. Lazau, R,’ Fine tuning of CoFe O properties prepared by solution combustion synthesis’, Ceramics International, No. 40, pp. 10223-10229, 2014. [3] Naik, S.R. Salker, A.V. Yusuf, S.M. Meena, S.S, ’Influence of Co distribution and spin–orbit coupling on the resultant magnetic properties of spinel cobalt ferrite nanocrystals’, Journal of Alloys and Compounds, No. 566, pp. 54-61, 2013. [4] Toksha, B.G. Shirsath, S.E. Patange, S.M. Jadhav, K.M, ’Structural investigations and magnetic properties of cobalt ferrite nanoparticles prepared by sol–gel auto combustion method’, Solid State Communications, No. 147, pp. 479-483, 2008. [5] Hajarpour, S. Gheisari, Kh. Honarbakhsh Raouf, A, ’Characterization of nanocrystalline Mg J.I ZnJ. Fe O soft ferrites synthesized by glycine-nitrate combustion process ’, Journal of Magnetism and Magnetic Materials, No. 329, pp. 165-169, 2013. [6] Wan, C. Li, J, ’Synthesis of well-dispersed magnetic Cofe O nanoparticles in cellulose aerogels via a facile oxidative co-precipitation method ’, Carbohydrate Polymers, No. 134, pp. 144-150, 2015. [7] Zhang, R. Sun, L. Wang, Z. Hao, W. Cao, E. Zhang, Y, ’ Dielectric and magnetic properties of CoFe2O4 prepared by sol-gel auto-combustion method’, Materials Research Bulletin, No. 98, pp. 133-138, 2018. [8] Amiri, S. Shokrollahi, H, ’ The role of cobalt ferrite magnetic nanoparticles in medical science’, Materials Science and Engineering C, No. 33, pp. 1-8, 2013. [9] Chakrabarty, S. Dutta, A. Pal, M, ’Enhanced magnetic properties of doped cobalt ferrite nanoparticles by virtue of cation distribution’, Journal of Alloys and Compounds, No. 625, pp. 216-223, 2015. [10] Bensebaa, F. Zavaliche, F. L’Ecuyer, P. Cochrane, R.W. Veres, T, ’Microwave synthesis and characterization of Co–ferrite nanoparticles’, Journal of Colloid and Interface Science, No. 277, pp. 104-110, 2004. [11] Tan, X. Wang, X. Liu, Q. Zhou, J. Zhang, P. Zheng, S. Miao, S, ’ Bio-gel template synthesis of CoFe O nano-catalysts and application in aerobic oxidation of cyclohexane’, Journal of Hydrogen Energy, No. 42, pp. 19001-19009, 2017. [12] Waje, S.B. Hashim, M. Yusoff, W.D. Abbas, Z, ’X-ray diffraction studies on crystallite size evolution of Cofe O nanoparticles prepared using mechanical alloying and sintering’, Applied Surface Science, No. 256, pp. 3122-3127, 2010. [13] Shi, Y. Ding, J. Yin, H, ’ CoFe O nanoparticles prepared by the mechanochemical method’, Journal of Alloys and Compounds, No. 308, pp. 290-295, 2000. [14] Shobana, M.K. Rajendran, V. Jeyasubramanian, K. Kumar N.S, ’Preparation and characterisation of NiCo ferrite nanoparticles’, Materials Letters, No. 61, pp. 2616-2619, 2007. [15] Thorat, N.D. Shinde, K.P. Pawar, S.H. Barick, K.C. Betty, C.A. Ningthoujam, R.S, ’ Polyvinyl alcohol: an efficient fuel for synthesis of superparamagnetic LSMO nanoparticles for biomedical application’, Dalton Transactions, No. 10, pp. 3060-3071, 2012. [16] Vojisavljevic, K. Wicker, S. Can, I. Bencan, A. Barsan, N. Malic, B, ’ Nanocrystalline cobalt-oxide powders by solution-combustion synthesis and their application in chemical sensors’, Advanced Powder Technology, No. 28, pp. 1118-1128, 2017. [17] Zhou, Q. Xue, L, Wang, Y. Li, H. Chikada, T. Oya, Y. Yan, Y, ’ Preparation of Li TiO ceramic with nano-sized pores by ultrasonic-assisted solution combustion’, Journal of the European Ceramic Society, No. 37, pp. 3595-3602, 2017. [18] Sherikar, P. Sherikar, B, ’Synthesis Of Yttrium Ferrite (YFeO ) By Solution Combustion Synthesis Using Alanine As A Fuel’, Materials Today: Proceedings, No. 4, pp. 10792-10797, 2017. [19] Patil, K.C. Hegde, M.S. Rattan, T. Aruna, S.T ,Chemistry of Nanocrystalline Oxide Materials Combustion Synthesis Properties and Applications, World Scientific Publishing Co, Singapore, 2008. [20] Borisov, A.A. Luca, L. Merzhanov, A , Self-Propagating High-Temperature Synthesis of Materials , Vo. 5 ,Taylor & Francis, New York, 2002. [21] kasapoglu, N. Baykal, A. Koseoglu, Y. Toprak, M.S, ’ Microwave-assisted combustion synthesis of CoFe O with urea and its magnetic characterization’, Scripta Materialia, No. 57, pp. 441-444, 2007. [22] Franco Jr, A. Zapf, V, ’ Temperature dependence of magnetic anisotropy in nanoparticles of CoP Fe( $P) O ’, Journal of Magnetism and Magnetic Materials, No. 320, pp. 709-713, 2008.
10
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
SC
RI PT
[23] Gabal, M.A. Juaid, A.A. Rashed, S. Hussein, M.A, ’ Synthesis and characterization of nano-sized Cofe O via facile methods: A comparative study’, Materials Research Bulletin, No. 89, pp. 68-78, 2017. [24] Prabhakaran, T. Hemalatha, J, ’ Combustion synthesis and characterization of cobalt ferrite nanoparticles’, Ceramics International, No. 42, pp. 14113-14120, 2016. [25] Wahba, A.M. Mohamed, M.B,’Structural and magnetic characterization and cation distribution of nanocrystalline CoP Fe( $P) O ferrites ’, Journal of Magnetism and Magnetic Materials, No. 378, pp. 246-252, 2015. [26] Salunkhe, A.B. Khot. V.M. Thorat, N.D. Phadatare, M.R. Sathish, C.I. Dhawale, D.S. Pawar, S.H,’ Polyvinyl alcohol functionalized cobalt ferrite nanoparticles for biomedical applications’, Applied Surface Science, No. 264, pp. 598-604, 2013. [27] Salunkhe, A.B. Khot, V.M. Phadatare, M.R. Pawar, S.H,’ Combustion synthesis of cobalt ferrite nanoparticles-Influence of fuel to oxidizer ratio’, Journal of Alloys and Compounds, No. 514, pp. 91-96, 2012. [28] Pourgolmohammad, B. Masoudpanah, S.M. Aboutalebi, M.R, ’ Synthesis of CoFe O powders with high surface area by solution combustion method: Effect of fuel content and cobalt precursor’, Ceramics International, No. 43, pp. 3797-3803, 2017. [29] Ianos, R,’ Highly sinterable cobalt ferrite particles prepared by a modified solution combustion synthesis’, Materials Letters, No. 135, pp. 24-26, 2014. [30] Anazi, A. Abdelraheem, H.W. Han, C. Nadagouda, M.N. Sygellou, L. Arfanis, M.K. Falaras, P. Sharma, V.K. Dionysiou, D.D,’ Cobalt ferrite nanoparticles with controlled composition-peroxymonosulfate mediated degradation of 2-phenylbenzimidazole-5-sulfonic acid’, Applied Catalysis B: Environmental, No. 221, pp. 266279, 2018. [31] Khandekar, M.S. Kambale, R.C. Latthe, S.S. Patil, J.Y. Shaikh, P.A. Hur, N. Suryavanshi, S.S,’ Role of fuels on intrinsic and extrinsic properties of CoFe O synthesized by combustion method’, Materials Letters, No. 65, pp. 2972-2974, 2011. [32] Sundararajan, M. Kennedy, L.J. Aruldoss, U. Pasha, S.K. Vijaya, J.J. Dunn, S,’ Microwave combustion synthesis of zinc substituted nanocrystalline spinel cobalt ferrite: Structural and magnetic studies’, Materials Science in Semiconductor Processing, No. 40, pp. 1-10, 2015. [33] Dean, J.A , lange's handbook of chemistry, McGRAW-HILL, USA, 1999.
11
ACCEPTED MANUSCRIPT
Highlights:
RI PT
Cobalt ferrite nano powders are prepared by solution combustion synthesis using urea and glycine as fuels. The magnetic and structural properties of cobalt ferrite particles produced by the use of urea and glycine fuels are compared.
SC
The specific surface of the urea-produced sample (56.2 m /g) is much larger than that of glycine (1.6 m /g).
AC C
EP
TE D
M AN U
Urea fuel should be used to produce cobalt ferrite nanoparticles by using solution combustion synthesis and in case of using glycine, the minimum amount of this fuel should be 2 times the stoichiometric amount.
S0254-0584(18)30082-8
DOI:
10.1016/j.matchemphys.2018.01.075
Reference:
MAC 20347
To appear in:
Materials Chemistry and Physics
Received Date: 20 November 2017 Revised Date:
19 January 2018
Accepted Date: 26 January 2018
Please cite this article as: A. Mazrouei, A. Saidi, Microstructure and magnetic properties of cobalt ferrite nano powder prepared by solution combustion synthesis, Materials Chemistry and Physics (2018), doi: 10.1016/j.matchemphys.2018.01.075. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Microstructure and magnetic properties of cobalt ferrite nano powder prepared by solution combustion synthesis Alireza Mazrouei٭1, Ali Saidi ¹´
RI PT
Advanced Materials Research Center, Faculty of Materials Engineering, Najafabad Branch, Islamic Azad University, Najafabad, Iran
1. Introduction
TE D
M AN U
SC
Abstract In this study, cobalt ferrite nanoparticles (CoFe O NPs) were prepared by solution combustion synthesis using urea and glycine as fuels. The magnetic properties of the CoFe O powders were modified by using various amounts of extra fuel (above the stoichiometric value). Thermodynamic calculations indicates that as the extra fuel increases, the amount of gases produced and the adiabatic flame temperature (T ) rise. To investigate effect of urea, glycine and amount of extra fuel on the structural and magnetic properties of CoFe O powders, the produced samples were studied by using X-ray diffraction (XRD), vibrating sample magnetometer (VSM), field emission scanning electron microscopy (FESEM), thermo gravimetric analysis and differential scanning calorimetry (TGA-DSC), and Brunauer-Emmett-Teller (BET) technique. XRD results of the produced sample indicated that the single phase CoFe O with an average crystallite size between 17 and 33 nm was synthesized. By using two different type of fuel, the specific surface area of the produced powders were increased from 1.6 (glycine fuel) to 56.2 m /g (urea fuel). By changing the type of fuel and the amount of extra fuel, the CoFe O coercivity (H ) ranges between 870 and 1667.8 O and the saturation magnetization (M ) varies between 31.6 and 83.7 emu/g. The solution combustion synthesized CoFe O powders exhibit a hard ferrimagnetic behavior. Based on the results, Urea is the proper fuel for producing cobalt ferrite nanoparticles (with a particle size less than 100 nm) and in case of using glycine, the minimum amount of this fuel should be 2 times the stoichiometric amount. Keywords: Cobalt ferrite nanoparticles, Solution combustion synthesis, Magnetic properties.
AC C
EP
Cobalt ferrite is well known to have significant magnetic anisotropy, moderate saturation magnetization and remarkable chemical stability [1]. These properties make CoFe O particles a good candidate for the technological applications such as magnetic recording devices, gas sensors, catalysis, ferrofluids and medical applications such as hyperthermia, drug delivery, and contrast enhancers in magnetic resonance imaging [2-8]. The cationic distribution for nanophase cobalt ferrite is different from its bulk counterpart. Bulk state is purely inverse spinel with general formula of (Fe ) (Co Fe )! (T indicating tetrahedral and O indicating octahedral sites) [9]. For cobalt ferrite nanoparticles the cationic states and distribution are complicated. CoFe O nanoparticles as mixed spinel which can be represented as (Co " Fe #$" ) (Co #$" Fe # " )! where δ is the degree of inversion [1,9]. The magnetic properties of CoFe O particles are mainly dominated by particle size, specific surface area, morphology and cationic distribution in the two interstitial sites (tetrahedral and octahedral) [3]. Cobalt ferrite nanoparticles were produced so far by various 1
٭Corresponding author at: Advanced Materials Research Center, Faculty of Materials Engineering, Najafabad Branch, Islamic Azad University, Najafabad, Iran. Tel.: +989130605114 E-mail address: [email protected] (Alireza Mazrouei).
1
ACCEPTED MANUSCRIPT
SC
RI PT
methods including co-precipitation [9,10], solvothermal [11]. mechanical alloying [12,13], sol-gel [4,7,14] etc. In addition, solution combustion synthesis has recently been developed to synthesize nanoparticles of ceramic oxides [15-18]. This method is very simple, costeffective and fast [5,19]. In this method, ceramic oxide powders is produced due to an exothermal reaction between metal nitrate (oxidizer) and fuel (reducing agent) [20]. In solution combustion synthesis, the type and amount of fuel plays a major role in the structural properties of the product. So far, cobalt ferrite powders have been produced with different fuels, such as Urea [21-23], alanine [2,24], citric acid [25], glycine [26-28], 5-aminotetrazole [29], Polyvinyl alcohol [30], hexamethylene tetramine [31], arginine [32]. On the other hand, given that urea and glycine are cost-effective and commercially available fuels, no comparison has been made regarding the production of CoFe O powders with these fuels by solution combustion synthesis. The purpose of this study is to compare the structural and magnetic properties of cobalt ferrite nanoparticles produced by solution combustion synthesis method using urea and glycine fuels. 2. Experimental
M AN U
2.1. Sample preparation
→ CoFe O
(
+ 2Fe(NO ) ) + 6.67CO
(
+ 6.67CH N O(
(2) + 10.67N
(Glycine fuel) Co(NO ) ( /) + 2Fe(NO )
→ CoFe O
( /)
) + 8.88C9
( /)
+ 4.446 7& 89
(<) + 6.228
/)
(2) + 13.34H O(2)
(1)
(:;)
(<) + 11.17 9(<) + 0.019
(<)
(2)
AC C
/)
EP
(Urea fuel) Co(NO ) (
TE D
To prepare the cobalt ferrite particles, based on combustion reactions (1) and (2) stoichiometric amounts of Fe(NO ) . 9H O (Merck, 99%), Co(NO ) . 6H O (Merck, 99%), CH N O (Merck, 99%) and C H& NO (Applichem, 98%) were dissolved in 20 ml of distilled water (at 80 ℃) in a glass beaker. The aqueous solution was stirred for one hour (at 80 ℃). The beaker was then kept on hot plate preheated to 350 ℃. The whole solution combustion reaction process was performed in less than 4 minutes whereas time of ignition was less than half a minute. Various amounts of extra fuel were added to the reaction mixture in different proportions (0-100 wt%), in order to investigate its influence on the CoFe O properties.
2.2. Sample characterization Crystallite size and phase identification of the powders were carried out by using Philips X-ray diffractometer equipped with a crystal monochromator employing Cu- Kα radiation of wavelength 1.54 ºA. The average crystallite size (D>?@) was calculated based on XRD patterns using Debye Scherrer formula 0.9λ
D = ß cosθ
(3)
Where ß is the full-width at half maxima of the strongest intensity diffraction peak, λ is the wavelength of radiation (1.54 ºA) and θ is the angle of diffraction. Morphology was investigated by FESEM (Mira3-Xmu). BET (Brunauer-Emmett-Teller) surface area of the powders (SGH ), was measured by the nitrogen gas adsorption technique using a sorptometer 1042-costech instrument.
2
ACCEPTED MANUSCRIPT Assuming that the CoFe O particles have a spherical shape, the equivalent particle size ( DGH ) was calculated using Eq. (4) DGH =
IJJJ ρKLMN
(4)
RI PT
Where DGH is the equivalent particle size (nm), ρ is the theoretical density of CoFe O (5.3g/cm ), and SGH is the BET surface area (m /g) [2]. Magnetic properties were measured at room temperature with a vibrating sample magnetometer (VSM, Meghnatis Daghigh Kavir, Iran) in an operating range of ± 15 KO . Thermo gravimetric analysis and differential scanning calorimetry (TGA-DSC) of the stoichiometric mixture of metal nitrates with urea and glycine fuel was carried out using a STA-503 Bahar instrument operated in temperature range 30 -1000 ℃ with heating rate of 20 ℃ per minute in flowing air ambience.
3. Results and discussion
M AN U
SC
The observed high flame temperature of the solution combustion reaction is due to the exothermicity of the reaction between the gaseous decomposition products of metal nitrate as NOP and fuel as HNCO, NH , etc. In solution combustion reactions, extremely high temperatures can be achieved within a very short time. Therefore, it is reasonable to assume that a thermally isolated system exists because there is very little time for the heat to disperse to its surroundings. Consequently, the maximum temperature to which the product is raised is assumed to be adiabatic temperature (T ). The heat liberated during the reaction is the enthalpy of the system [19]. The equation 5 and the
thermodynamic information of Table 1 were used to calculate T . Thermodynamic data of reactants and products is available in literature [33].
TE D
WX CT (Product)dT (5) Q = - ∆H° (reaction) = S YZ Where Q is the heat absorbed by products under adiabatic condition, and CT is the heat capacity of the products at constant pressure.
Table 1 Thermodynamic data required for calculating adiabatic flame temperature. ∆H° (Kcal/mole )
C[ (cal/mole .K)
EP
Compound
-160.3
----
Co(NO )
-100.5
----
CH N O
-79.61
----
C H& NO
-126.31
----
CoFe O
-252
10.34 + 0.00274 T
H O(2)
-57.79
7.2 + 0.0036 T
-94.05
35.36
CO N O
(2)
(2) (2)
AC C
Fe(NO )
0
6.5 + 0.001 T
0
5.92 + 0.00367 T
Based on thermodynamic calculations, T and number of mole of gases produced, increase with the amount of extra fuel used during combustion reactions (Table 2). Adiabatic flame temperature increases in samples from 1494 ℃ (sample A# ) to 1726 ℃ (sample A ) and from 1530 ℃ (sample A ) to 1758 ℃ (sample AI ). However, the actual flame temperatures are lower than the theoretically calculated values owing to incomplete combustion and 3
ACCEPTED MANUSCRIPT
Table 2 Samples specifications, experimental data, and some obtained results.
A#
Urea
A
Urea
A
Urea
A
Glycine
A&
Glycine
AI
Glycine
100
M^
time (s)
T (° C)
Gases produced (moles)
D>?@ (nm)
DGH (nm)
SGH (m /g)
(emu/g)
0
5
1494
30.68
17
20
56.2
31.6
9.6
870
50
35
1647
44
16
53
21.4
48.7
17.5
957.5
100
15
1726
57.36
30
48
23.7
66.4
27.1
877.7
0
10
1530
26.21
30
707
1.6
45.6
23.7
1667.8
50
11
1680
37.3
33
339
3.3
78.6
39.6
1292.7
20
1758
48.4
31
80
14.1
83.7
43
1516.1
Reaction
M
SC
Extra Fuel (wt%)
M AN U
Fuel & Extra Fuel
(emu/g)
H (O )
EP
TE D
Sample Code
RI PT
heating of air [5]. The amount of gases produced increases in samples from 30.68 (sample A# ) to 57.36 moles (sample A ) and from 26.21 (sample A ) to 48.4 moles (sample AI ). Solution combustion reactions is substantially influensed by the type and amount of extra fuel. Fig. 1 illustrated the process of synthesizing of the samples A# and A . In sample A# , the combustion reaction was carried out as bulk within 5 s, while In sample A , the combustion reaction was performed in the combustion front within 10 s. The variation of the reaction times is presented in Table 2. In other samples, with increasing the amount of extra fuel, combustion reaction changes from a strong incandescence process, which is accompanied by flames to a smoldering process, where no flames appeared.
AC C
Fig. 1. Images taken during the solution combustion reactions of samples A1 and A4.
XRD analysis, as shown in Fig. 2, indicates that the combustion synthesized powders consists of single phase CoFe O having a face-centered cubic structure. The obtained peaks are well matched with standard JCPDS card no. 22-1086. Weak diffraction peak corresponding to formation of FeO was observed in case of sample A (glycine fuel). The average crystallite size (D>?@ ) of the samples A# (17 nm), A (16 nm), A (30 nm), A (30 nm), A& (33 nm), and AI (31 nm) was calculated by Debye Scherrer formula (Table 2). The adiabatic flame temperature of urea-produced samples is smaller than glycine, and by decreasing the growth of crystallites, D>?@ of urea-produced samples (A# - A ) is smaller than glycine-produced samples (A - AI ). On the other hand, by increasing the amount of extra fuel and T , D>?@ increases in samples (except A ) from 17 nm (A# ) to 30 nm (A ) and from 30 nm (A ) to 31 nm (AI ). In sample A combustion heat was released in 35 s, compared with sample A# (5 s), 4
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
SC
RI PT
so in sample A the growth of crystallites decreases. one can say that the absence of a tangible difference between the average crystallite size (D>?@ ) of the samples A (30 nm), A& (33 nm), and AI (31 nm) can be justified by their releasing time of the combustion heat, A (10 s), A& (11 s) and samples AI (20 s). By increasing the weight percentage of extra fuel the intensity of the XRD patterns increase, which indicates an increase in crystallinity of the produced samples.
Fig. 2. XRD patterns of solution combustion synthesized CoFe O powders.
The simultaneous TGA-DSC curves of the stoichiometric metal nitrates with urea fuel (sample A# ) and stoichiometric metal nitrates with glycine fuel (sample A ) were shown in Fig. 3. The TGA-DSC curve of sample A# (urea fuel) contains two exothermic peaks at 200 and 251℃ with sharp weight loss that indicates occurrence of combustion reaction and two endothermic peaks at below 200℃, related to vaporization of water and inner water. The total weight losses observed in TGA plot of sample A# (urea fuel) is ∼80%. No weight loss is observed after the combustion reaction giving a product free of residual reactants and carbonaceous matter. The TGA-DSC curve of sample A (glycine fuel) contains sharp 5
ACCEPTED MANUSCRIPT exothermic peak at 188℃ that indicates occurrence of solution combustion reaction and two endothermic peaks at below 188℃, related to vaporization of water and inner water. The total weight losses observed in TGA plot of sample A (glycine fuel) is ∼82%.
M AN U
SC
RI PT
A# (Urea Fuel)
AC C
EP
TE D
A (Glycine Fuel)
Fig. 3. TGA-DSC curves of the stoichiometric mixture of metal nitrates with urea fuel (sample A# ) and stoichiometric mixture of metal nitrates with glycine fuel (sample A ).
The BET surface area (SGH ) of the obtained powders varies between 1.6 and 56.2 m /g (Table 2). As expected, by increasing the weight percentage of extra fuel and thus increasing the number of mole of gases produced, SGH values increased in samples A (21.4 m /g) to A (23.7 m /g) and A (1.6 m /g) to AI (14.1 m /g). on the other hand, the high value of SGH in sample A# (56.2 m /g) was acceptable due to the exhaust of 30.68 moles of gases produced in 5 s, compared to the samples A (exhaust of 44 moles of gases produced in 35 s) and samples A (exhaust of 57.36 moles of gases produced in 15 s). In all samples except A# , 6
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
SC
RI PT
the equivalent particle size (DGH ), calculated from the BET surface area is larger than the crystallite size (D>?@ ), therefore these samples are polycrystalline (Table 2). The FESEM images of samples A# and A are shown in Fig. 4. These images indicate remarkable changes in microstructure, particle size, particle distribution, and porosity by changing fuel from urea (sample A# ) to glycine (sample A ). The evolution of BET surface area as a function of fuel type is confirmed by the FESEM images. In solution combustion synthesis, evolution of large quantities of gases like carbon dioxide, water, and nitrogen results in the formation of fine and porous particles. The main factor chainging the porosity of samples is the number of mole of gases produced (CO , H O, N ) [19]. One can say that, the porosity of sample A# (exhaust of 30.68 moles of gases produced in 5 s) is more than the sample A (exhaust of 26.21 moles of gases produced in 10 s). Energy dispersive spectroscopy (EDS) of samples A# and A evidenced O, Fe and Co as the only present elements. The elemental composition of samples A# (50.31% O, 33.16% Fe, 16.53% Co) and A (48.03% O, 34.01% Fe, 17.97% Co), expressed in atomic percents, is close to the theoretical composition of CoFe O (57.1% O, 28.6% Fe, 14.3% Co).
Fig. 4. FESEM Images of samples A1 and A4.
7
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
SC
RI PT
The hysteresis curves of the obtained powders are presented in Fig. 5. The saturation magnetization (M ), remanence magnetization (M^ ) and coercivity (H ) were summarized in Table 2. The saturation magnetization (M ) of CoFe O powders ranges between 31.6 and 83.7 emu/g. The coercivity (H ) of CoFe O powders ranges between 870 and 1667.8 O . With increasing SGH , the spin canting phenomenon is created due to the change in the position of the ions in the particle surface relative to the corresponding ions in the particle core. The spin canting phenomenon leads to the formation of a 1.69 nm dead surface layer on the surface of cobalt ferrite particles and reduces the saturation magnetization [10,25]. Difference in combustion and crystallizaton process could influence the distribution of Co ions at octahedral, Fe ions between octahedral and tetrahedral sites, and then more affect the super-exchange interaction between two sites [27]. By increasing the weight percentage of extra fuel and so T , the crystallite size and crystallinity of samples increased. Thus, the value M in samples A# (31.6 emu/g) to A (66.4 emu/g) and A (45.6 emu/g) to AI (83.7 emu/g) increased. The critical size of cobalt ferrite particles was reported at 70 nm with a blocking temperature of 235 ° K [3,10]. The particles smaller than the critical size, exhibit a super-paramagnetic behavior and the coercivity of super-paramagnetic particles is zero. The equivalent particle size (DGH ) in samples A# (20 nm), A (53 nm), and A (48 nm) is smaller than the critical size (70 nm), but the coercivity (H ) of samples A# (870 O ), A (957.5 O ), and A (877.7 O ) is not zero. This can be the result of particles that are agglomerated and the presence of ferrimagnetic particles in the wide particle size distribution. This fraction of ferrimagnetic particles increases coercivity and magnetization.The equivalent particle size (DGH ) in samples A (707 nm), A& (339 nm), and AI (80 nm) is larger than the critical size (70 nm), thus, these samples exhibit a ferrimagnetic behavior. By comparing DGH of the produced powders with critical size, it can be concluded that glycine-produced samples have ferrimagnetic behavior, while a part of the urea-produced samples have ferrimagnetic behavior and the other part of the urea-produced samples have superparamagnetic behavior. Therefore, by using urea and glycine fuels and adding extra fuel, the particle size, specific surface area and magnetic properties of the cobalt ferrite particles can be modified and optimized in a wide range.
8
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 5. Magnetic hysteresis curves of solution combustion synthesized CoFe O powders.
TE D
4. Conclusion
AC C
EP
In this study, cobalt ferrite nanoparticles (CoFe O NPs) were produced by solution combustion synthesis method using urea and glycine fuels. The major difference in combustion reaction with urea fuel that was carried out as bulk in 5 s with a large amount of gas exiting, than the glycine fuel that was done in the combustion front in 10 s, made SGH in the urea-produced sample (56.2 m /g) much larger than that of glycine (1.6 m /g). According to thermodynamic calculations, by increasing the weight percentage of extra fuel, T increased in the process of Solution combustion synthesis leading to the growth of crystallites in products and increase of crystallite size and crystallinity of the produced samples. As expected, the amounts of saturation magnetization of the samples increased by increasing the weight percentage of extra fuel. On the other hand, by increasing the weight percentage of extra fuel, the number of moles of gases produced, increased leading to the increase of SGH in produced samples. The superparamagnetic behavior of particle fraction in urea-produced samples reduced the amount of magnetization of these samples. In addition, the glycine-produced samples had a hard ferrimagnetic behavior. It can be concluded that urea fuel should be used to produce cobalt ferrite nanoparticles (with a particle size less than 100 nm) by using solution combustion synthesis and in case of using glycine, the minimum amount of this fuel should be 2 times the stoichiometric amount.
9
ACCEPTED MANUSCRIPT References
AC C
EP
TE D
M AN U
SC
RI PT
[1] Mathew, D. Shin Juang, R, ’An overview of the structure and magnetism of spinel ferrite nanoparticles and their synthesis in microemulsions’, Chemical Engineering Journal, No. 129, pp. 51-65, 2007. [2] Ianos, R. Bosca, M. Lazau, R,’ Fine tuning of CoFe O properties prepared by solution combustion synthesis’, Ceramics International, No. 40, pp. 10223-10229, 2014. [3] Naik, S.R. Salker, A.V. Yusuf, S.M. Meena, S.S, ’Influence of Co distribution and spin–orbit coupling on the resultant magnetic properties of spinel cobalt ferrite nanocrystals’, Journal of Alloys and Compounds, No. 566, pp. 54-61, 2013. [4] Toksha, B.G. Shirsath, S.E. Patange, S.M. Jadhav, K.M, ’Structural investigations and magnetic properties of cobalt ferrite nanoparticles prepared by sol–gel auto combustion method’, Solid State Communications, No. 147, pp. 479-483, 2008. [5] Hajarpour, S. Gheisari, Kh. Honarbakhsh Raouf, A, ’Characterization of nanocrystalline Mg J.I ZnJ. Fe O soft ferrites synthesized by glycine-nitrate combustion process ’, Journal of Magnetism and Magnetic Materials, No. 329, pp. 165-169, 2013. [6] Wan, C. Li, J, ’Synthesis of well-dispersed magnetic Cofe O nanoparticles in cellulose aerogels via a facile oxidative co-precipitation method ’, Carbohydrate Polymers, No. 134, pp. 144-150, 2015. [7] Zhang, R. Sun, L. Wang, Z. Hao, W. Cao, E. Zhang, Y, ’ Dielectric and magnetic properties of CoFe2O4 prepared by sol-gel auto-combustion method’, Materials Research Bulletin, No. 98, pp. 133-138, 2018. [8] Amiri, S. Shokrollahi, H, ’ The role of cobalt ferrite magnetic nanoparticles in medical science’, Materials Science and Engineering C, No. 33, pp. 1-8, 2013. [9] Chakrabarty, S. Dutta, A. Pal, M, ’Enhanced magnetic properties of doped cobalt ferrite nanoparticles by virtue of cation distribution’, Journal of Alloys and Compounds, No. 625, pp. 216-223, 2015. [10] Bensebaa, F. Zavaliche, F. L’Ecuyer, P. Cochrane, R.W. Veres, T, ’Microwave synthesis and characterization of Co–ferrite nanoparticles’, Journal of Colloid and Interface Science, No. 277, pp. 104-110, 2004. [11] Tan, X. Wang, X. Liu, Q. Zhou, J. Zhang, P. Zheng, S. Miao, S, ’ Bio-gel template synthesis of CoFe O nano-catalysts and application in aerobic oxidation of cyclohexane’, Journal of Hydrogen Energy, No. 42, pp. 19001-19009, 2017. [12] Waje, S.B. Hashim, M. Yusoff, W.D. Abbas, Z, ’X-ray diffraction studies on crystallite size evolution of Cofe O nanoparticles prepared using mechanical alloying and sintering’, Applied Surface Science, No. 256, pp. 3122-3127, 2010. [13] Shi, Y. Ding, J. Yin, H, ’ CoFe O nanoparticles prepared by the mechanochemical method’, Journal of Alloys and Compounds, No. 308, pp. 290-295, 2000. [14] Shobana, M.K. Rajendran, V. Jeyasubramanian, K. Kumar N.S, ’Preparation and characterisation of NiCo ferrite nanoparticles’, Materials Letters, No. 61, pp. 2616-2619, 2007. [15] Thorat, N.D. Shinde, K.P. Pawar, S.H. Barick, K.C. Betty, C.A. Ningthoujam, R.S, ’ Polyvinyl alcohol: an efficient fuel for synthesis of superparamagnetic LSMO nanoparticles for biomedical application’, Dalton Transactions, No. 10, pp. 3060-3071, 2012. [16] Vojisavljevic, K. Wicker, S. Can, I. Bencan, A. Barsan, N. Malic, B, ’ Nanocrystalline cobalt-oxide powders by solution-combustion synthesis and their application in chemical sensors’, Advanced Powder Technology, No. 28, pp. 1118-1128, 2017. [17] Zhou, Q. Xue, L, Wang, Y. Li, H. Chikada, T. Oya, Y. Yan, Y, ’ Preparation of Li TiO ceramic with nano-sized pores by ultrasonic-assisted solution combustion’, Journal of the European Ceramic Society, No. 37, pp. 3595-3602, 2017. [18] Sherikar, P. Sherikar, B, ’Synthesis Of Yttrium Ferrite (YFeO ) By Solution Combustion Synthesis Using Alanine As A Fuel’, Materials Today: Proceedings, No. 4, pp. 10792-10797, 2017. [19] Patil, K.C. Hegde, M.S. Rattan, T. Aruna, S.T ,Chemistry of Nanocrystalline Oxide Materials Combustion Synthesis Properties and Applications, World Scientific Publishing Co, Singapore, 2008. [20] Borisov, A.A. Luca, L. Merzhanov, A , Self-Propagating High-Temperature Synthesis of Materials , Vo. 5 ,Taylor & Francis, New York, 2002. [21] kasapoglu, N. Baykal, A. Koseoglu, Y. Toprak, M.S, ’ Microwave-assisted combustion synthesis of CoFe O with urea and its magnetic characterization’, Scripta Materialia, No. 57, pp. 441-444, 2007. [22] Franco Jr, A. Zapf, V, ’ Temperature dependence of magnetic anisotropy in nanoparticles of CoP Fe( $P) O ’, Journal of Magnetism and Magnetic Materials, No. 320, pp. 709-713, 2008.
10
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
SC
RI PT
[23] Gabal, M.A. Juaid, A.A. Rashed, S. Hussein, M.A, ’ Synthesis and characterization of nano-sized Cofe O via facile methods: A comparative study’, Materials Research Bulletin, No. 89, pp. 68-78, 2017. [24] Prabhakaran, T. Hemalatha, J, ’ Combustion synthesis and characterization of cobalt ferrite nanoparticles’, Ceramics International, No. 42, pp. 14113-14120, 2016. [25] Wahba, A.M. Mohamed, M.B,’Structural and magnetic characterization and cation distribution of nanocrystalline CoP Fe( $P) O ferrites ’, Journal of Magnetism and Magnetic Materials, No. 378, pp. 246-252, 2015. [26] Salunkhe, A.B. Khot. V.M. Thorat, N.D. Phadatare, M.R. Sathish, C.I. Dhawale, D.S. Pawar, S.H,’ Polyvinyl alcohol functionalized cobalt ferrite nanoparticles for biomedical applications’, Applied Surface Science, No. 264, pp. 598-604, 2013. [27] Salunkhe, A.B. Khot, V.M. Phadatare, M.R. Pawar, S.H,’ Combustion synthesis of cobalt ferrite nanoparticles-Influence of fuel to oxidizer ratio’, Journal of Alloys and Compounds, No. 514, pp. 91-96, 2012. [28] Pourgolmohammad, B. Masoudpanah, S.M. Aboutalebi, M.R, ’ Synthesis of CoFe O powders with high surface area by solution combustion method: Effect of fuel content and cobalt precursor’, Ceramics International, No. 43, pp. 3797-3803, 2017. [29] Ianos, R,’ Highly sinterable cobalt ferrite particles prepared by a modified solution combustion synthesis’, Materials Letters, No. 135, pp. 24-26, 2014. [30] Anazi, A. Abdelraheem, H.W. Han, C. Nadagouda, M.N. Sygellou, L. Arfanis, M.K. Falaras, P. Sharma, V.K. Dionysiou, D.D,’ Cobalt ferrite nanoparticles with controlled composition-peroxymonosulfate mediated degradation of 2-phenylbenzimidazole-5-sulfonic acid’, Applied Catalysis B: Environmental, No. 221, pp. 266279, 2018. [31] Khandekar, M.S. Kambale, R.C. Latthe, S.S. Patil, J.Y. Shaikh, P.A. Hur, N. Suryavanshi, S.S,’ Role of fuels on intrinsic and extrinsic properties of CoFe O synthesized by combustion method’, Materials Letters, No. 65, pp. 2972-2974, 2011. [32] Sundararajan, M. Kennedy, L.J. Aruldoss, U. Pasha, S.K. Vijaya, J.J. Dunn, S,’ Microwave combustion synthesis of zinc substituted nanocrystalline spinel cobalt ferrite: Structural and magnetic studies’, Materials Science in Semiconductor Processing, No. 40, pp. 1-10, 2015. [33] Dean, J.A , lange's handbook of chemistry, McGRAW-HILL, USA, 1999.
11
ACCEPTED MANUSCRIPT
Highlights:
RI PT
Cobalt ferrite nano powders are prepared by solution combustion synthesis using urea and glycine as fuels. The magnetic and structural properties of cobalt ferrite particles produced by the use of urea and glycine fuels are compared.
SC
The specific surface of the urea-produced sample (56.2 m /g) is much larger than that of glycine (1.6 m /g).
AC C
EP
TE D
M AN U
Urea fuel should be used to produce cobalt ferrite nanoparticles by using solution combustion synthesis and in case of using glycine, the minimum amount of this fuel should be 2 times the stoichiometric amount.