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Effect of calcination on the microstructural and magnetic properties of PVA, PVP and PEG assisted zinc ferrite nanoparticles
Journal Pre-proof Effect of calcination on the microstructural and magnetic properties of PVA, PVP and PEG assisted zinc ferrite nanoparticles Samson O. Aisida, Ishaq Ahmad, Fabian I. Ezema PII:
S0921-4526(19)30786-0
DOI:
https://doi.org/10.1016/j.physb.2019.411907
Reference:
PHYSB 411907
To appear in:
Physica B: Physics of Condensed Matter
Received Date: 20 October 2019 Revised Date:
21 November 2019
Accepted Date: 22 November 2019
Please cite this article as: S.O. Aisida, I. Ahmad, F.I. Ezema, Effect of calcination on the microstructural and magnetic properties of PVA, PVP and PEG assisted zinc ferrite nanoparticles, Physica B: Physics of Condensed Matter (2019), doi: https://doi.org/10.1016/j.physb.2019.411907. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. 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. © 2019 Published by Elsevier B.V.
Effect of calcination on the microstructural and magnetic properties of PVA, PVP and PEG assisted zinc ferrite nanoparticles Samson O. Aisida1, 2*, Ishaq Ahmad2, 3, 4 and Fabian I. Ezema1, 4, 5** 1
2
3
Department of Physics and Astronomy, University of Nigeria, Nsukka, Nigeria
National Centre for Physics, Quaid-i-Azam University campus, Islamabad 44000, Pakistan
NPU-NCP Joint International Research Center on Advanced Nanomaterials and Defects Engineering, Northwestern Polytechnical University, Xi'an 710072, China 4
5
Nanosciences African Network (NANOAFNET), iThemba LABS-National Research
Department of Physics, Faculty of Natural and Applied Sciences, Coal City University, Enugu, Nigeria.
Corresponding authors:*[email protected]; (+234 8063957679) **[email protected] ; (+234 8036239214)
Abstract The
effects
of
calcination
on
the
synthesis
of
polymer
(P)
assisted
zinc
ferrite (Ζn. Ϝ Ο ) (0.00 ≤ ≤ 0.10) nanoparticles by the biological thermal method were investigated. The zinc ferrite synthesized was doped with 0.1g in situ by polyvinyl alcohol (PVA), Polyvinyl Pyrrolidone (PVP) and Polyethylene glycol (PEG) respectively. The properties of the formulated nanoparticles were determined by various characterization techniques. The XRD confirmed the formation of a single-phase spinel with intense crystallinity for samples calcined at 500 oC. SEM revealed the spherical morphology of the calcined samples. FTIR analysis shows the existence of the spinel ferrite phases with a slight variation in the two main bands. The VSM showed a transformation from ferromagnetic to superparamagnetic behavior.
1
Thus, the calcined sample yields favorable structure, low crystallite size, uniform morphology and good magnetic properties. These controllable and improved properties obtained by calcination help the nanoparticles to attain its maximum functionality for various applications Keywords: Zinc ferrite; nanoparticles; polyvinyl alcohol; Polyethylene glycol; Polyvinyl Pyrrolidone; calcination
Highlight: Biopolymers serve as a substitute to chemical reagents The polymers play the role of capping and reducing agent Single-phase cubic ZFNPs was described after calcination Calcined prepared samples showed small particles size and good magnetic properties
1.0
Introduction
Nanoparticles (NPs) are basically nanometer-scale materials in various dimensions with special interfacial layers in the form of organic, inorganic or ions. The study of NPs has gained more scientific interest in the last decade owing to its effectiveness serving as a bridge between the molecules and the bulk materials [1-7]. This uniqueness enhanced their properties for myriad applications. NPs are broadly categorized as magnetic metals, transition metals, noble metals, metal oxides and semiconductor materials. Among these materials, magnetic nanoparticles (MNPs) has copious application that spans through industries and biomedicine such as targeted drug delivery for cancer therapy [8, 9], thermal ablation via Hyperthermia for cancer therapy [8], antibacterial/antimicrobial activity [10-15] and magnetic storage devices [16, 17]. Among the various applications of MNPs, magnetic ferrofluid for Hyperthermia and drug delivery using
2
MNPs have been potent in therapeutic purposes where various cancer cells are killed as a result of an increase in temperature around the tumor cell between 42 – 46 oC and specific site drug delivery with minimal side effect respectively. For these applications to be optimized, the MNPs required some requisite properties such as biocompatibility, congenial chemical stability, reasonable particle size, appropriate magnetic properties, minimal systemic side effects and nontoxicity [18, 19].
Great effort has been emplaced in the development of MNPs to enhance their performance. Spinel ferrite magnetic nanoparticles (SFMNPs) with the general molecular formula XY2O4 where X is the tetrahedral cation sites with either of Zinc, Manganese, Cobalt, Nickel, or Magnesium, Y is Fe and O indicate the oxygen (anion site) with the face-centered-cubic (fcc) close packing structure. In the family of SFMNPs, zinc ferrite nanoparticles (ZFNPs) have been receiving tremendous attention owing to their excellent physical, chemical and magnetic properties [20, 21, 22-24]. The uniqueness in these properties enhanced ZFNPs with a unique spherical and diameter range of 10 ≤ 100 for biomedical applications such as drug delivery and hyperthermia [18, 19, 25-27]. ZFNPs have the capacity to improve the solubility and stability of encapsulated drugs with less or no side effects after cell uptake [28-31]. The synthesis of ZFNPs with a size range of ≈ 8 nm and ≈ 100 nm find special biomedical applications for the renal clearance threshold and the cancer blood vessel respectively [28, 29]. For the ZFNPs to function optimally for the desired applications, the processing protocols, functionalization and the calcination/sintering played a substantial role which can significantly affect the size and shape of the formulated particles. The thermal treatment (calcination) is done to enhance its crystalline spinel structure to function optimally [32-36]. Various synthesis routes
3
have been used by researchers via co-precipitation [35], sol-gel [21], ball-milling method, microemulsion [37], thermal decomposition [38], solvothermal [39] and reverse micelles process. Among these methods, only few authors pay attention to the effect of calcination to enhance the formulated NPs. The effect of calcination is paramount for the optimal functionalization of ZFNPs. It has been observed that the particle crystallite size, morphology, structure and magnetic properties of ZFNPs are strongly temperature-dependent [20, 21, 32-36].
To circumvent these challenges, we employ a biological thermal synthesis procedure without any chemical reagents as an alternative to the chemical and physical route of synthesis. PVA, PVP, and PEG were used differently for the encapsulation of ZFNPs to enhance the colloidal stability, narrow size distribution and reduce agglomeration due to their hydrophilicity potency, ecofriendly, nontoxicity and biocompatible as an organic passivating agent on ZFNPs [40]. For the enhancement of the properties, the obtained polymer assisted ZFNPs were calcined up to 600 oC to enhanced their properties for biomedical applications. This work aimed to study the effect of calcination on the properties of polymer assisted ZFNPs via their size distribution, structural, magnetic properties, morphological and crystallite size. It was observed that the calcination improves the qualities of the particles considerably by altering the cationic site location of the polymer assisted ZFNPs. 2.
Experimental materials and method
2.1
Materials and instruments
Ferric nitrate nonahydrate (Fe(NO3)3.9H2O) (99.5%), zinc (II) nitrate hexahydrate (Zn(NO3)2.6H2O) (99%), polyvinyl alcohol (PVA) (Mw = 30,000 -70,000), Polyethylene glycol (PEG) (MW = 4000) and Polyvinyl Pyrrolidone (PVP) (Mw = 40,000) were all analytical grade
4
of Sigma-Aldrich product procured commercially and used without further purifications. Distilled water (DW) was used for all the reaction mixture. The crystalline structures of all the samples were investigated by powder X-rays diffractometer technique, a Shimadzu-7000 diffractometer model using Cu-Kα radiation (λ = 1.5406 Å) and a lattice parameter (a = 4.08620 Å) at room temperature in the continuous scanning mode and a scanning 2θ range of 10o to 80°. The calcination effect of the microstructures of the ZFNPs as-prepared and PVA, PVP and PEG assisted were imaged by scanning electron microscopy (SEM) JEOL 6400 microscope. The EDX attached to the SEM was used to determine the elemental compositions of the samples.
The
spectral analysis of the functional groups was determined using a Fourier transform infrared spectroscopy (FTIR) (PerkinElmer FT-IR spectra 1650) model. The magnetic properties of the samples were measured using a vibrating sample magnetometer (VSM) Lake Shore 4700 model at room temperature in the magnetic field range of 15KOe. 2.2
Synthesis of polymers assisted Zinc ferrites
The stoichiometric amount of zinc nitrate and ferric nitrate in the molar ratio 1:2 were dissolved in DW separately and stirred for 1 h at 800 rpm to obtain a homogeneous solution. 100 ml solution of 0.1 g of PVA, PVP and PEG was prepared in a separate beaker at 80 oC under vigorous stirring for 2 h. The mixed solution of iron and zinc nitrate was poured gently in dropwise into the solution of PVA, PVP and PEG separately and stirred for another 1h each. The homogeneous solution was placed in a hot air oven at 100 oC for 24 h for drying. The obtained residues of the ZFNPs as-prepared labeled (A) and polymer assisted ZFNPs labeled (PVA_B, PVP_B and PEG_B) were crushed into a powder with the aid of pestle and mortar followed by washing with DW three times and later transferred to the oven and left to dry for 3 h at 80 oC.
5
The polymer assisted ZFNPs were calcined in a vacuum oven at 500 oC and labeled as (PVA_C, PVP_C and PEG_C) after calcination. 3.0
Results and discussion
3.1
Morphological results analysis
The surface morphology and the particle size distribution of the samples were obtained from SEM analysis as depicted in (Fig. 1- 4). It can be seen that the morphology is homogeneous and the particle size of the PVA_B, PVP_B and PEG_B are 8.8 ± 65, 8.5 ± 9.6, 6.3 ± 5.7 respectively. Calcination enhances the coalescence of the grains and the particle size decreases to 8.5 ± 0.4, 7.8 ± 5.8, 7.2 ± 5.0 for PVA_C, PVP_C and PEG_C after calcination respectively, except for PEG which may be attributed to the preparation method and grain growth due to the particles and the neighboring particles coalesce together in the molecules of PEG [41]. This shows that the morphologies of the materials are highly influenced by the calcination temperature which is in agreement with the previous observation by the following authors [42, 43]. The EDX analysis as shown in Fig. 1b confirmed the presence of iron, Zinc and Oxygen chemical composition in the prepared sample within the host lattice. The peaks at 6.48 Kev and 1.2 Kev give the highest peak for iron and zinc which dovetail the stoichiometric concentration of iron and zinc in the prepared sample [41].
6
Fig.1. (a) SEM and (b) EDX images of sample A
7
Fig.2. SEM images and particle size distributions images of PVA_B (a,c,) and PVA_C (b, d)
Fig.3. SEM images and particle size distributions images of PVP_B (a,c) and PVP_C (b, d)
8
Fig.4. SEM images and particle size distributions images of PEG_B (a,c) and PEG_C ( b,d) 3.2 XRD results analysis
The structural analysis by XRD of all the samples was analyzed as shown in Fig. (5 a-c). The diffraction peaks of the calcined polymers assisted samples became narrower, intense and stronger due to the calcination effect, at this moment, revealing the characteristics of a singlephase and cubic symmetry of sample A with an inverse spinel lattice structure and JCPD file NO. 22-1012 [44]. The intensity in the crystallinity may be attributed to the calcination as observed by Abbas et al. [45]. The average crystallite size (ACS) as analyzed by the Debye– Scherer’s formula (equ. 1) decreases after calcination from 26.90 to 26.46 nm, 26.46 to 25.47 nm 9
and 25.62 to 24.98 nm for PVA_C, PVP_C and PEG_C respectively (as shown in Table 1). The decrease may be owing to the ionic properties in the polymer that binds the molecules together [32, 33, 35].
#=
.%&
(1)
' ()* +
where D , λ, β and θ are the crystallite size (nm), X-ray wavelength (λ = 1.5406 nm), full width at half maximum (FWHM) in radians and the Bragg diffraction angle respectively [46]. The plane spacing ( ,-. ) of the ZFNPs is obtained using the Bragg’s law (equ. 2) for each plane while the lattice parameter (a) is calculated by the relation in (equ. 3) ,-. =
/ (2) 2012
= × 4ℎ + 7 + 8 (3) Where h, k, 8 are the Miller indices, and d is the plane spacing Table 1. Different parameters obtained from XRD data of sample A, Bs and Cs Samples
9:;< =Å?
a (Å)
Plane
ACS (nm)
A
2.6494
8.7871
(220, 311, 400, 511, 440)
18.2
PVA _B
2.6061
8.6435
(220, 311, 400, 511, 440)
26.90
PVA _C
2.6061
8.6435
(220, 311, 400, 511, 440)
26.46
PVP_B
2.6265
8.7111
(220, 311, 400, 511, 440)
26.46
PVP_C
2.6265
8.7111
(220, 311, 400, 511, 440)
25.47
PEG_B
2.6265
8.7111
(220, 311, 400, 511, 440)
25.62
PEG_C
2.6265
8.7111
(220, 311, 400, 511, 440)
24.98
,-. is the plane space; a is the lattice parameter, ACS is the average crystallite size, 10
ZnO Fe2O3
(533)
(440)
(400)
(422) (511)
(311)
Intensity (a.u)
(220)
(a)
ZnFe2O4
PVA_C
PVA_B
A
(422) (511)
2θ θ (Degree)
60
70
80
ZnFe O 2 4 ZnO Fe O 2 3
(533)
50
(440)
40
(400)
Intensity (a.u)
(b)
30
(311)
20
(220)
10
PVP_C
PVP_B
A 10
20
30
40
50
2θ θ (Degree) 11
60
70
80
(440)
Fe2O3
(533)
(400)
(422) (511)
(311) (220)
Intensity (a.u)
(c)
ZnFe O 2 4 ZnO
PEG_C
PEG_B A 10
20
30
40
50
2θ θ (Degree)
60
70
80
Fig. 5. XRD patterns of sample As, Bs and Cs for (a) PVA (b) PVP and (c) PEG.
3.3
Functional group analysis
The functional analysis determined by FTIR spectra as shown in Figure 6 (a-c) revealed the stretching and bending vibrations in the wavelength range of 4000 – 500 cm-1 of the formulated sample. The bands around 430 - 480 cm-1 and 550 - 580 cm-1 are assigned to the Fe – O(octahedral) and Zn – O- (tetrahedral) stretching vibration bond respectively [41]. The band between 3000 - 3487 cm-1 is assigned to (O = H stretching), the band between 1600 - 1750 cm-1 is assigned to (C = O stretching), also the band between 1300 - 1480 cm-1 is (C-N stretching) vibration of aromatic amines, while the band between 1200 - 1350 cm-1 is assigned to (C-O- C bending) which helped in the interaction with the surface ions [46-49]. The presence of these 12
organic functional groups on the surface of the synthesized samples indicates the interaction between the ZF and the Polymers. The aforementioned bands in (Fig. 6 (a, b and c)) belong to the functional groups of PVA, PVP and PEG complexes which help in the interaction with the surface ions of the samples respectively. This is owing to the strong affinity of the bioactive compounds in the polymers towards the ZF ion. After calcination, there was a drastic shift in the O-H stretching and bending. The peaks remain unchanged when the calcination temperature was increased to 600oC. The absorption bands in the samples connote the characteristic features of single-phase spinel ferrite [50].
(a)
o
PVA_C @ 600 C o
Transmittance (%)
PVA_C @ 500 C PVA_B
A
Wavenumber (cm-1)
13
1000
Fe - O
2000
Zn - O
C-N
3000
C-O-C
C=O
O-H
4000
(b)
o
Transmittance (%)
PVP_C @ 600 C o
PVP_C @ 500 C PVP_B
A 1047
1629
430 592
1332
3497
4000
3000
2000
1000
Wavenumber (cm-1)
(c)
o
PEG_C @ 600 C o
Transmittance (%)
PEG_C @ 500 C PEG_B
A
1332
3000
2000
Wavenumber (cm-1)
14
440 598
1047
1649
3191
4000
1000
Fig. 6. FTIR spectra of sample As, Bs and Cs for (a) PVA (b) PVP and (c) PEG. 3.4
Magnetic properties
The VSM studied the magnetic properties via hysteresis loops (Fig. 7) of all samples at room with the applied field of ± 5 ΚΟ . Sample Bs exhibit ferromagnetic behavior while sample Cs show superparamagnetic behavior (as shown in fig. 7b) the magnification of the inset. After calcination, the magnetic behavior of sample Bs was altered by the thermal forces altering the degree of ferromagnetic loops to form a single domain with each dopant to superparamagnetic behavior. It was observed from the M-H loops that, after calcination, the saturation magnetization (Ms) of sample PVA_B, PVP_B and PEG_B decreased. This is in agreement with the previous studies reported with a decrease in the magnetization of polymer doped MgFe2O3 and ZnFe2O3 [41, 51-54]. This decrease in Ms after calcination is thought to be due to the distribution of cation inversion among the X-Y interstitial sites which yields the X-O-Y magnetic exchange interaction as a result of thermal treatment which made some of the Fe+3 cations moves from Y sites to the X sites in the sample Cs [55-57]. However, sample Cs show smaller Ms than the bulk counterpart 80.8 and 93.9 emu/g as observed by Ahangar et al., and Kombaiah et al. [58, 59]. The crystallite size also plays a significant role in the saturation magnetization of sample Cs as a result of the thermal agitation in the molecules [59].
15
16
Fig.7.VSM analysis of samples As, Bs & Cs. The inset reveals the overlapping superparamagnetic behavior of sample Cs
4.0
Conclusion
Polyvinyl alcohol, polyvinyl-pyrrolidone, and polyethylene glycol assisted ZFNPs were synthesized by the biological thermal method. The effect of calcination was observed with towering leverage on the properties of polymer assisted ZFNPs for various applications. The SEM micrograph showed fine spherical morphology with less aggregation and reasonable particle sizes after calcination. The XRD confirmed the cubic nanocrystalline spinel phase structure that is calcination dependent. The VSM gave varied magnetic properties from ferromagnetic to superparamagnetic behavior after calcination with decrease in saturation magnetization due to the thermal influence on the magnetic moment by the calcination. Therefore, this innocuous and benign method with the help of calcination produced a favorable structural, morphological and magnetic properties of the formulated ZFNPs which in turn serve as an impetus to attain its optimal functionality for various applications such as contrasted enhancement magnetic resonance imaging, hyperthermia and drug delivery.
Acknowledgments Samson O. Aisida (NCP-CAAD/TWAS_Fellow8408) acknowledges the NCP-TWAS Postdoc Fellowship award. FIE (90407830) cordially acknowledge UNISA for VRSP Fellowship award. We thank Engr. Emeka Okwuosa for the generous sponsorship of April 2014, July 2016 and July 2018 Conference/Workshops on Applications of Nanotechnology to Energy, Health &.Environment conference
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Conflict of interest: The authors declare no conflict of interest References [1] Abraham, A. G., Manikandan, A., Manikandan, E., Jaganathan, S. K., Baykal, A., & Renganathan, P. S. (2017). Enhanced Opto-Magneto Properties of Ni x Mg1–x Fe2O4 (0.0 ≤ x ≤ 1.0) Ferrites Nano-Catalysts. Journal of Nanoelectronics and Optoelectronics, 12, 1326-1333. [2] Abraham, A. G., Manikandan, A., Manikandan, E., Vadivel, S., Jaganathan, S. K., Baykal, A., & SriRenganathana, P. (2018). Enhanced magneto-optical and photo-catalytic properties of transition metal cobalt (Co2+ ions) doped spinel MgFe2O4 ferrite nanocomposites. Journal of Magnetism and Magnetic Materials, 452, 380-388. [3] Arul, K. T., Manikandan, E., Ladchumananandasivam, R., & Maaza, M. (2016). Novel polyvinyl alcohol polymer based nanostructure with ferrites co‐doped with nickel and cobalt ions for magneto‐sensor application. Polymer International, 65, 1482-1485. [4] Arul, K. T., Manikandan, E., Murmu, P. P., Kennedy, J., & Henini, M. (2017). Enhanced magnetic properties of polymer-magnetic nanostructures synthesized by ultrasonication. Journal of Alloys and Compounds, 720, 395-400. [5] Diallo, A., Doyle, T. B., Mothudi, B. M., Manikandan, E., Rajendran, V., & Maazaa, M. (2017). Magnetic behavior of biosynthesized Co3O4 nanoparticles. Journal of Magnetism and Magnetic Materials, 424, 251255. [6] Sasikala, C., Durairaj, N., Baskaran, I., Sathyaseelan, B., Heninie, M., & Manikandan, E. (2017). Transition metal titanium (Ti) doped LaFeO3 nanoparticles for enhanced optical structural and magnetic properties. Journal of Alloys and Compounds, 712, 870-877. [7] Siva, T., Muralidharan, S., Sathiyanarayanan, S., Manikandan, E., & Jayachandran, M. (2015). Enhanced Polymer Induced Precipitation of Polymorphous in Calcium Carbonate: Calcite Aragonite Vaterite Phases. Journal of Inorganic and Organometallic Polymers and Materials, 27, 770-778.
18
[8] Sharma, R., Thakur, P., Kumar, M., Thakur, N., Negi, N. S., Sharma, P., & Sharma, V. (2016). Improvement in the magnetic behavior of cobalt-doped magnesium zinc nano-ferrites via co-precipitation route. Journal of Alloys and Compounds, 684, 569-581. [9] Aisida, S. O., Paul A. Akpa, Ishaq Ahmad, Ting-kai, Zhao, Maaza, M., & Ezema, F. I. (2019). Bio-inspired encapsulation and functionalization of iron oxide nanoparticles for biomedical applications. European Polymer Journal. https://doi.org/10.1016/j.eurpolymj.2019.109371 [10] Samavati, A., & Ismail, A. F. (2017). Antibacterial properties of copper-substituted cobalt ferrite nanoparticles synthesized by co-precipitation method, Particuology, 30, 158-163. [11] Elayakumar, K., Dinesh, A., Manikandan, A., Palanivelu, M., Kavith, G., Prakash, S., . . . Baykal, A. (2019). Structural, morphological, enhanced magnetic properties and antibacterial bio-medical activity of rare earth element (REE) Cerium (Ce3+) doped CoFe2O4 nanoparticles. Journal of Magnetism and Magnetic Materials, 476, 157-165. [12] Manikandan, A., Manikandan, E., Meenatchi, B., Vadivel, S., Jaganathan, S. K., Ladchumananandasivam, R., . . . Aananda, J. S. (2017). Rare earth element (REE) lanthanum doped zinc oxide (La: ZnO) nanomaterials: Synthesis structural optical and antibacterial studies. Journal of Alloys and Compounds, 723, 1155-1161. [13] Aisida, S. O., Madubuonu, N., Alnasir, M. H., Ahmad, I., Botha, S., Maaza, M., & Ezema, F. I. (2019). Biogenic synthesis of iron oxide nanorods using Moringa oleifera leaf extract for antibacterial applications. Appl Nanosci. Retrieved from https://doi.org/10.1007/s13204-019-01099-x [14] Aisida, S. O., Ugwu, K., Akpa, P. A., Nwanya, A. C., Ejikeme, P. M., Botha, S. S., . . . Ezema, F. I. (2019b). Biogenic synthesis and antibacterial activity of controlled silver nanoparticles using an extract of Gongronema Latifolium. Materials Chemistry and Physics, 237, 121859. [15] Aisida, S. O., Ugwu, K., Akpa, P. A., Nwanya, A. C., Nwankwo, U., Botha, S. S., . . . Ezema, F. I. (2019 a). Biosynthesis of silver nanoparticles using bitter leave (Veronica amygdalina) for antibacterial activities. Surfaces and Interfaces, 17, 100359.
19
[16]Dantas, J., Leal, E., Mapossa, A. B., & Costa, A. (2017). Magnetic nanocatalysts of Ni 0.5 Zn 0.5 Fe 2O4 doped with Cu and performance evaluation in transesterification reaction for biodiesel production. Fuel, 191, 463–471. [17] Swamy, P. P., S, B., Arunkumar, L., Srinivas, N. R., & Nijagunappa, R. V. (2011). Synthesis and characterization of zinc ferrite nanoparticles obtained by self-propagating low-temperature combustion method. Bull. Mater. Sci., 34, 1325–1330. [18] Mahmoud, G. N., Mohammad, H. M., Elias, B. S., & Abdul, H. S. (2014). Superparamagnetic magnesium ferrite nanoparticles fabricated by a simple, thermal-treatment method. Journal of Magnetism and Magnetic Materials 350 (2014) 141–147, 350, 141-147. [19] Gangopadhyay, P., Kesavmoorthy, R., Bera, S. M., Nair, K., Panigrahi, B., & Narasimhan, S. (2005).Optical absorption and photoluminescence spectroscopy of the growth of silver nanoparticles. Rev. Lett., 94, 47403–47404. [20] Ramakrishna K S, Srinivasb C, Prajapat C L, Meena S S, Mehar M V K, Potukuchf D M and Sastry D L (2018). Structural and magnetic investigations: Study of magnetocrystalline anisotropy and magnetic behavior of 0.1% Cu2+ substituted Ni–Zn ferrite nanoparticles. Ceramics International 44 1193 1200 [21] Tirupanyam B V, Srinivas C, Meena S S, Yusuf S M, Satish Kumar A, Sastry D L and Seshubai V (2017). Investigation of cation distribution and magnetocrystalline anisotropy of NixCu0.1Zn0.9−xFe2O4 nanoferrites: Role of constant mole percent of Cu2+ dopant in place of Zn2+. Ceramics International 43 7984-7991 [22] Subramanian, A. P., Jaganathan, S. K., Manikandan, A., Pandiaraj, K. N., N, G., & Supriyantoa, E. (2016). Recent trends in nano-based drug delivery systems for efficient delivery of phytochemicals in chemotherapy. RSC Advances, 6, 48294-48314. [23] Vellayappan, M. V., Jaganathan, S. K., & Manikandan, A. (2016). Nanomaterials as a game changer in the management and treatment of diabetic foot ulcers. RSC Advances, 6, 114859-114878.
20
[24] Vellayappan, M. V., Venugopal, J. R., Ramakrishna, S., Ray, S., Ismail, A. F., Mandal, M., . . . Jaganathan, S. K. (2016). Electrospinning applications from diagnosis to treatment of diabetes. RSC Advances, 6, 8363883655. [25] Shaban, I. H., Ashraf, S. E., Rashad, M. M., & Megahid, R. (2015). Structural and magnetic properties of magnesium ferrite nanoparticles prepared via EDTA-based sol-gel reaction. Journal of Magnetism and Magnetic Materials, 379, 9-15. [26] Zachary, R. S., Forrest, M. K., & Miqin, Z. (2011). Magnetite Nanoparticles for Medical MR Imaging. Mater. Today, 14(7-8), 330. [27] Krishnan, K. M. (2010). Biomedical Nanomagnetics: A Spin Through Possibilities in Imaging, Diagnostics, and Therapy. IEEE Trans. Magn., 46(7), 36. [28] Gao, J., Gu, H., & Xu, B. (2009). Multifunctional magnetic nanoparticles: design, synthesis, and biomedical applications. Acc Chem Res., 42, 1097-107. [29] Schlorf, T., Meincke, M., Kossel, E., Gluer, C., Jansen, O., & Mentlein, R. (2010). Biological properties of iron oxide nanoparticles for cellular and molecular magnetic resonance imaging. Int J Mol Sci., 12, 12-23. [30] Gang, H., Huabing, C., Ying, D., Xiuquan, L., Haijun, Y., Zachary, M., . . . Gao, J. (2013). Superparamagnetic Iron Oxide Nanoparticles: Amplifying ROS Stress to Improve Anticancer Drug Efficacy. Theranostics, 3(2), 116-126. [31] Verma, R. K., & Garg, S. (2001.). Current status of drug delivery technologies and future directions. Pharmaceutical Technology, 25, 1-14. [32] Aisida S. O., Paul, A., Ishaq, A., Maaza, M. and Fabian, I. E. (2019). Influence of PVA, PVP and PEG doping on the optical, structural, morphological and magnetic properties of zinc ferrite nanoparticles produced by thermal method. Physica B: Condensed Matter, 571, 130–136, 2019. [33] Okoroh, D. O., Ozuomba, J. O., Aisida, S. O. and Asogwa, P. U., (2019 a). Properties of Zinc
21
Ferrite Nanoparticles Due to PVP Mediation and Annealing at 500˚C," Advances in Nanoparticles, 8, 3645. [34] Aisida, S. O., Ugwoke, E., Ali Uwais, Iroegbu, C., Botha, S, Ahmad, I., Maaza, M., Ezema, F. I. (2019). Incubation period induced biogenic synthesis of PEG enhanced Moringa Oleifera silver nanocapsules and its antibacterial activity [35] Okoro, D. O., Ozuomba, J., Aisida, S. O., and Asogwa, P (2019b). Thermal treated sysnthesis and characterization of polyethylene glycol (PEG) mediated Zinc ferrite nanoparticles, Surface and Interface, 16, 127-131. [36] Ranjith Kumar E, Arunkumar T and Prakash T (2015). Heat treatment effects on structural and dielectric properties of Mn substituted CuFe2O4 and ZnFe2O4 nanoparticles. Superlattices and Microstructures 85 530 -535 [37] Mahmoud, G. N., Elias, B. S., Mansor, H., Abdul, H. S., & Hossein, A. A. (2011). Synthesis and characterization of zinc ferrite nanoparticles by a thermal treatment method. Solid State Communications, 151, 1031-1035. [38] Yan ˜ez-Vilara, S., Sanchez-And´ujara, M., G´omez-Aguirre, C., Mira, J., Sen˜ar´ıs-Rodr´ıguez, M., & CastroGarc´ıa, S. (2009). A simple solvothermal synthesis of MFe2O4 (M ¼ Mn, Co, and Ni) nanoparticles. Journal of Solid State Chemistry, 182, 2685–2690. [39] Ismail, M. I. M. (2018). Role of calcination on structural, morphology and magnetic properties of zinc substituted Mn-Ni nanoferrites. Mater. Res. Express 5, 095004 [40] Kane, S., & Satalkar, M. (2017). Correlation between magnetic properties and cationic distribution of Zn 0.85−xNi xMg 0.05 Cu 0.1 Fe 2O4 nano spinel ferrite: effect of Ni doping. J Mater Sci., 52, 3467. [41] Kombaiah K., Judith, J. Vijaya, John, L. Kennedy, Bououdina, M., Hamad A. Al-Lohedan, Jothi, R. Ramalingam. (2017). Studies on Opuntia dilenii haw mediated multifunctional ZnFe2O4 nanoparticles: Optical, magnetic and catalytic. Materials Chemistry and Physics 194 153-164
22
[42] Jaberolansar, E., Kameli, P., Ahmadvand, H., & Salamati, H. (2016). Synthesis and characterization of PVPcoated Co Zn Fe O 0.3 0.7 2 4 ferrite nanoparticles. Journal of Magnetism and Magnetic Materials, 404, 21-28. [43] Rahimi, M., Kameli, P., Ranjbar, M., & Salamati, H. (2013). The effect of polyvinyl alcohol (PVA) coating on structural, magnetic properties and spin dynamics of Ni0.3Zn0.7Fe2O4 ferrite nanoparticles. J. Magn. Magn. Mater., 347, 139–145. [44] Zulfiqar, M., Rahman, M. U., Hasanain, S., Rahman, Z., Ullah, A., & Kim, W. (2014, ). Structural, optical, dielectric and magnetic properties of PVP coated magnetite (Fe3O4) nanoparticles. J. Korean Phys. Soc., 65, 1925–1929. doi:https://doi.org/10.1007/s10854-018-0134-6 [45] Abbas, F., Jan, T. I., Ahmad, I., & Naqvi, M. M. (2015). Facile synthesis of ferromagnetic Ni-doped CeO2 nanoparticles with enhanced anticancer activity. Applied Surface Science. Retrieved from http://dx.doi.org/10.1016/j.apsusc.2015.08.229 [46] Cullity, B. (1978). The element of X-ray Diffraction (2nd ed ed.). Addison-Wesley, London. [47] Arsalani, N., Fattahi, H., & Nazarpoor, M. (2010).Arsalani, N., Fattahi, H., & Nazarpoor, M. (2010). Synthesis and characterization of PVP-functionalized superparamagnetic Fe3O4 nanoparticles as an MRI contrast agent. Express Polym. Lett., 4, 329-338. [48] Sharma, R.K., Ghose, R. (2015). Synthesis of zinc oxide nanoparticles by homogeneous precipitation method and its application in antifungal activity against Candida albicans, Ceram. Int. 41 967. [49] Thangaraj, P., Rajan, X., Durai, S. Kumar, S., Phani, A.R., Neri, G. (2011). The role of albumen (egg white) in controlled particle size and electrical conductivity behavior of zinc oxide nanoparticles, Vacuum 86 140. [50] Meidanchi, A. Akhavan, O., Khoei, S., Shokri, A.A., Hajikarimi, Z, Khansari, N. (2015). ZnFe2O4 nanoparticles as radiosensitizers in radiotherapy of human prostate cancer cells, Mater. Sci. Eng. C 46 394. [51] Mahmoud, G. N., Halimah, M. K., Arash, D., Ahmad, K., Elias, B. S., & Burhanuddin, Y. M. (2014). A comprehensive overview of the structure and comparison of magnetic properties of nanocrystalline synthesized by a thermal treatment method. Journal of Physics and Chemistry of Solids, 75, 315-327.
23
[52] Thanigai, K. A, Manikandan, E., Murmu, P.P., Kennedy, J., Henini, M. (2017). Enhanced magnetic properties of polymer-magnetic nanostructures synthesized by ultrasonication. Journal of Alloys and Compounds. 720, 395400 [53] Williams, GVM, Kennedy, J. Murmu, PP, Rubanov, S. Chong, S. V. The effect of different Fe concentrations on the structural and magnetic properties of near-surface superparamagnetic Ni1− xFex nanoparticles in SiO2 made by dual low energy. Journal of Magnetism and Magnetic Materials 473, 125-130 [54] Murmu, P.P, Kennedy, J., Ruck, B. J., Williams, G.V.M., Markwitz, A., Rubanov, S. (2012). Effect of annealing on the structural, electrical and magnetic properties of Gd-implanted ZnO thin films. Journal of Materials Science 47 (3), 1119-1126 [55] Da Dalt, S., Takimi, A., Volkmer, T. M., Sousa, V., & Bergmann, C. (2011). Magnetic and Mössbauer behavior of the nanostructured MgFe2O4 spinel obtained at low temperature. Powder Technology, 210, 103-108. [56] Holec, P., Plocek, J., Nižňansky´, D., & Poltierova´ Vejpravov, J. (2009). Preparation of MgFe2O4 nanoparticles by microemulsion method and their characterization. Journal oSol-Gelel Science and Technology, 51, 301-305. [57] Grant, V.M. Williams, Tushara, P., John, Kennedy, Shen V. C., Sergey R. (2018). Spindependent tunnelling in magnetite nanoparticles. Journal of Magnetism and Magnetic Materials 460, 229– 233 [58] Ahangar, M. Hashim, A.H. Shaari, Synthesis and characterization of manganese ferrite nanoparticles by thermal treatment method, J. Magn. Magn. Mater. 323 (2011), 1745-1749. [59] Kombaiah, K., Judith Vijaya J., John, Kennedy, L., Bououdina, M. Jothi, Ramalingam, R., Hamad, A. Al-Lohedan. (2018). Okra extract-assisted green synthesis of CoFe2O4 nanoparticles and their optical, magnetic and antimicrobial properties. Materials Chemistry and Physics 204, 410-419
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The idea was conceive and the experiment was conducted by S.O Aisida. The write-up was done by S.O Aisida. The characterization and general editing were done by S.O Aisida, F. I Ezema and Ishaq Ahmed
The authors declared no conflict of interest
S0921-4526(19)30786-0
DOI:
https://doi.org/10.1016/j.physb.2019.411907
Reference:
PHYSB 411907
To appear in:
Physica B: Physics of Condensed Matter
Received Date: 20 October 2019 Revised Date:
21 November 2019
Accepted Date: 22 November 2019
Please cite this article as: S.O. Aisida, I. Ahmad, F.I. Ezema, Effect of calcination on the microstructural and magnetic properties of PVA, PVP and PEG assisted zinc ferrite nanoparticles, Physica B: Physics of Condensed Matter (2019), doi: https://doi.org/10.1016/j.physb.2019.411907. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. 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. © 2019 Published by Elsevier B.V.
Effect of calcination on the microstructural and magnetic properties of PVA, PVP and PEG assisted zinc ferrite nanoparticles Samson O. Aisida1, 2*, Ishaq Ahmad2, 3, 4 and Fabian I. Ezema1, 4, 5** 1
2
3
Department of Physics and Astronomy, University of Nigeria, Nsukka, Nigeria
National Centre for Physics, Quaid-i-Azam University campus, Islamabad 44000, Pakistan
NPU-NCP Joint International Research Center on Advanced Nanomaterials and Defects Engineering, Northwestern Polytechnical University, Xi'an 710072, China 4
5
Nanosciences African Network (NANOAFNET), iThemba LABS-National Research
Department of Physics, Faculty of Natural and Applied Sciences, Coal City University, Enugu, Nigeria.
Corresponding authors:*[email protected]; (+234 8063957679) **[email protected] ; (+234 8036239214)
Abstract The
effects
of
calcination
on
the
synthesis
of
polymer
(P)
assisted
zinc
ferrite (Ζn. Ϝ Ο ) (0.00 ≤ ≤ 0.10) nanoparticles by the biological thermal method were investigated. The zinc ferrite synthesized was doped with 0.1g in situ by polyvinyl alcohol (PVA), Polyvinyl Pyrrolidone (PVP) and Polyethylene glycol (PEG) respectively. The properties of the formulated nanoparticles were determined by various characterization techniques. The XRD confirmed the formation of a single-phase spinel with intense crystallinity for samples calcined at 500 oC. SEM revealed the spherical morphology of the calcined samples. FTIR analysis shows the existence of the spinel ferrite phases with a slight variation in the two main bands. The VSM showed a transformation from ferromagnetic to superparamagnetic behavior.
1
Thus, the calcined sample yields favorable structure, low crystallite size, uniform morphology and good magnetic properties. These controllable and improved properties obtained by calcination help the nanoparticles to attain its maximum functionality for various applications Keywords: Zinc ferrite; nanoparticles; polyvinyl alcohol; Polyethylene glycol; Polyvinyl Pyrrolidone; calcination
Highlight: Biopolymers serve as a substitute to chemical reagents The polymers play the role of capping and reducing agent Single-phase cubic ZFNPs was described after calcination Calcined prepared samples showed small particles size and good magnetic properties
1.0
Introduction
Nanoparticles (NPs) are basically nanometer-scale materials in various dimensions with special interfacial layers in the form of organic, inorganic or ions. The study of NPs has gained more scientific interest in the last decade owing to its effectiveness serving as a bridge between the molecules and the bulk materials [1-7]. This uniqueness enhanced their properties for myriad applications. NPs are broadly categorized as magnetic metals, transition metals, noble metals, metal oxides and semiconductor materials. Among these materials, magnetic nanoparticles (MNPs) has copious application that spans through industries and biomedicine such as targeted drug delivery for cancer therapy [8, 9], thermal ablation via Hyperthermia for cancer therapy [8], antibacterial/antimicrobial activity [10-15] and magnetic storage devices [16, 17]. Among the various applications of MNPs, magnetic ferrofluid for Hyperthermia and drug delivery using
2
MNPs have been potent in therapeutic purposes where various cancer cells are killed as a result of an increase in temperature around the tumor cell between 42 – 46 oC and specific site drug delivery with minimal side effect respectively. For these applications to be optimized, the MNPs required some requisite properties such as biocompatibility, congenial chemical stability, reasonable particle size, appropriate magnetic properties, minimal systemic side effects and nontoxicity [18, 19].
Great effort has been emplaced in the development of MNPs to enhance their performance. Spinel ferrite magnetic nanoparticles (SFMNPs) with the general molecular formula XY2O4 where X is the tetrahedral cation sites with either of Zinc, Manganese, Cobalt, Nickel, or Magnesium, Y is Fe and O indicate the oxygen (anion site) with the face-centered-cubic (fcc) close packing structure. In the family of SFMNPs, zinc ferrite nanoparticles (ZFNPs) have been receiving tremendous attention owing to their excellent physical, chemical and magnetic properties [20, 21, 22-24]. The uniqueness in these properties enhanced ZFNPs with a unique spherical and diameter range of 10 ≤ 100 for biomedical applications such as drug delivery and hyperthermia [18, 19, 25-27]. ZFNPs have the capacity to improve the solubility and stability of encapsulated drugs with less or no side effects after cell uptake [28-31]. The synthesis of ZFNPs with a size range of ≈ 8 nm and ≈ 100 nm find special biomedical applications for the renal clearance threshold and the cancer blood vessel respectively [28, 29]. For the ZFNPs to function optimally for the desired applications, the processing protocols, functionalization and the calcination/sintering played a substantial role which can significantly affect the size and shape of the formulated particles. The thermal treatment (calcination) is done to enhance its crystalline spinel structure to function optimally [32-36]. Various synthesis routes
3
have been used by researchers via co-precipitation [35], sol-gel [21], ball-milling method, microemulsion [37], thermal decomposition [38], solvothermal [39] and reverse micelles process. Among these methods, only few authors pay attention to the effect of calcination to enhance the formulated NPs. The effect of calcination is paramount for the optimal functionalization of ZFNPs. It has been observed that the particle crystallite size, morphology, structure and magnetic properties of ZFNPs are strongly temperature-dependent [20, 21, 32-36].
To circumvent these challenges, we employ a biological thermal synthesis procedure without any chemical reagents as an alternative to the chemical and physical route of synthesis. PVA, PVP, and PEG were used differently for the encapsulation of ZFNPs to enhance the colloidal stability, narrow size distribution and reduce agglomeration due to their hydrophilicity potency, ecofriendly, nontoxicity and biocompatible as an organic passivating agent on ZFNPs [40]. For the enhancement of the properties, the obtained polymer assisted ZFNPs were calcined up to 600 oC to enhanced their properties for biomedical applications. This work aimed to study the effect of calcination on the properties of polymer assisted ZFNPs via their size distribution, structural, magnetic properties, morphological and crystallite size. It was observed that the calcination improves the qualities of the particles considerably by altering the cationic site location of the polymer assisted ZFNPs. 2.
Experimental materials and method
2.1
Materials and instruments
Ferric nitrate nonahydrate (Fe(NO3)3.9H2O) (99.5%), zinc (II) nitrate hexahydrate (Zn(NO3)2.6H2O) (99%), polyvinyl alcohol (PVA) (Mw = 30,000 -70,000), Polyethylene glycol (PEG) (MW = 4000) and Polyvinyl Pyrrolidone (PVP) (Mw = 40,000) were all analytical grade
4
of Sigma-Aldrich product procured commercially and used without further purifications. Distilled water (DW) was used for all the reaction mixture. The crystalline structures of all the samples were investigated by powder X-rays diffractometer technique, a Shimadzu-7000 diffractometer model using Cu-Kα radiation (λ = 1.5406 Å) and a lattice parameter (a = 4.08620 Å) at room temperature in the continuous scanning mode and a scanning 2θ range of 10o to 80°. The calcination effect of the microstructures of the ZFNPs as-prepared and PVA, PVP and PEG assisted were imaged by scanning electron microscopy (SEM) JEOL 6400 microscope. The EDX attached to the SEM was used to determine the elemental compositions of the samples.
The
spectral analysis of the functional groups was determined using a Fourier transform infrared spectroscopy (FTIR) (PerkinElmer FT-IR spectra 1650) model. The magnetic properties of the samples were measured using a vibrating sample magnetometer (VSM) Lake Shore 4700 model at room temperature in the magnetic field range of 15KOe. 2.2
Synthesis of polymers assisted Zinc ferrites
The stoichiometric amount of zinc nitrate and ferric nitrate in the molar ratio 1:2 were dissolved in DW separately and stirred for 1 h at 800 rpm to obtain a homogeneous solution. 100 ml solution of 0.1 g of PVA, PVP and PEG was prepared in a separate beaker at 80 oC under vigorous stirring for 2 h. The mixed solution of iron and zinc nitrate was poured gently in dropwise into the solution of PVA, PVP and PEG separately and stirred for another 1h each. The homogeneous solution was placed in a hot air oven at 100 oC for 24 h for drying. The obtained residues of the ZFNPs as-prepared labeled (A) and polymer assisted ZFNPs labeled (PVA_B, PVP_B and PEG_B) were crushed into a powder with the aid of pestle and mortar followed by washing with DW three times and later transferred to the oven and left to dry for 3 h at 80 oC.
5
The polymer assisted ZFNPs were calcined in a vacuum oven at 500 oC and labeled as (PVA_C, PVP_C and PEG_C) after calcination. 3.0
Results and discussion
3.1
Morphological results analysis
The surface morphology and the particle size distribution of the samples were obtained from SEM analysis as depicted in (Fig. 1- 4). It can be seen that the morphology is homogeneous and the particle size of the PVA_B, PVP_B and PEG_B are 8.8 ± 65, 8.5 ± 9.6, 6.3 ± 5.7 respectively. Calcination enhances the coalescence of the grains and the particle size decreases to 8.5 ± 0.4, 7.8 ± 5.8, 7.2 ± 5.0 for PVA_C, PVP_C and PEG_C after calcination respectively, except for PEG which may be attributed to the preparation method and grain growth due to the particles and the neighboring particles coalesce together in the molecules of PEG [41]. This shows that the morphologies of the materials are highly influenced by the calcination temperature which is in agreement with the previous observation by the following authors [42, 43]. The EDX analysis as shown in Fig. 1b confirmed the presence of iron, Zinc and Oxygen chemical composition in the prepared sample within the host lattice. The peaks at 6.48 Kev and 1.2 Kev give the highest peak for iron and zinc which dovetail the stoichiometric concentration of iron and zinc in the prepared sample [41].
6
Fig.1. (a) SEM and (b) EDX images of sample A
7
Fig.2. SEM images and particle size distributions images of PVA_B (a,c,) and PVA_C (b, d)
Fig.3. SEM images and particle size distributions images of PVP_B (a,c) and PVP_C (b, d)
8
Fig.4. SEM images and particle size distributions images of PEG_B (a,c) and PEG_C ( b,d) 3.2 XRD results analysis
The structural analysis by XRD of all the samples was analyzed as shown in Fig. (5 a-c). The diffraction peaks of the calcined polymers assisted samples became narrower, intense and stronger due to the calcination effect, at this moment, revealing the characteristics of a singlephase and cubic symmetry of sample A with an inverse spinel lattice structure and JCPD file NO. 22-1012 [44]. The intensity in the crystallinity may be attributed to the calcination as observed by Abbas et al. [45]. The average crystallite size (ACS) as analyzed by the Debye– Scherer’s formula (equ. 1) decreases after calcination from 26.90 to 26.46 nm, 26.46 to 25.47 nm 9
and 25.62 to 24.98 nm for PVA_C, PVP_C and PEG_C respectively (as shown in Table 1). The decrease may be owing to the ionic properties in the polymer that binds the molecules together [32, 33, 35].
#=
.%&
(1)
' ()* +
where D , λ, β and θ are the crystallite size (nm), X-ray wavelength (λ = 1.5406 nm), full width at half maximum (FWHM) in radians and the Bragg diffraction angle respectively [46]. The plane spacing ( ,-. ) of the ZFNPs is obtained using the Bragg’s law (equ. 2) for each plane while the lattice parameter (a) is calculated by the relation in (equ. 3) ,-. =
/ (2) 2012
= × 4ℎ + 7 + 8 (3) Where h, k, 8 are the Miller indices, and d is the plane spacing Table 1. Different parameters obtained from XRD data of sample A, Bs and Cs Samples
9:;< =Å?
a (Å)
Plane
ACS (nm)
A
2.6494
8.7871
(220, 311, 400, 511, 440)
18.2
PVA _B
2.6061
8.6435
(220, 311, 400, 511, 440)
26.90
PVA _C
2.6061
8.6435
(220, 311, 400, 511, 440)
26.46
PVP_B
2.6265
8.7111
(220, 311, 400, 511, 440)
26.46
PVP_C
2.6265
8.7111
(220, 311, 400, 511, 440)
25.47
PEG_B
2.6265
8.7111
(220, 311, 400, 511, 440)
25.62
PEG_C
2.6265
8.7111
(220, 311, 400, 511, 440)
24.98
,-. is the plane space; a is the lattice parameter, ACS is the average crystallite size, 10
ZnO Fe2O3
(533)
(440)
(400)
(422) (511)
(311)
Intensity (a.u)
(220)
(a)
ZnFe2O4
PVA_C
PVA_B
A
(422) (511)
2θ θ (Degree)
60
70
80
ZnFe O 2 4 ZnO Fe O 2 3
(533)
50
(440)
40
(400)
Intensity (a.u)
(b)
30
(311)
20
(220)
10
PVP_C
PVP_B
A 10
20
30
40
50
2θ θ (Degree) 11
60
70
80
(440)
Fe2O3
(533)
(400)
(422) (511)
(311) (220)
Intensity (a.u)
(c)
ZnFe O 2 4 ZnO
PEG_C
PEG_B A 10
20
30
40
50
2θ θ (Degree)
60
70
80
Fig. 5. XRD patterns of sample As, Bs and Cs for (a) PVA (b) PVP and (c) PEG.
3.3
Functional group analysis
The functional analysis determined by FTIR spectra as shown in Figure 6 (a-c) revealed the stretching and bending vibrations in the wavelength range of 4000 – 500 cm-1 of the formulated sample. The bands around 430 - 480 cm-1 and 550 - 580 cm-1 are assigned to the Fe – O(octahedral) and Zn – O- (tetrahedral) stretching vibration bond respectively [41]. The band between 3000 - 3487 cm-1 is assigned to (O = H stretching), the band between 1600 - 1750 cm-1 is assigned to (C = O stretching), also the band between 1300 - 1480 cm-1 is (C-N stretching) vibration of aromatic amines, while the band between 1200 - 1350 cm-1 is assigned to (C-O- C bending) which helped in the interaction with the surface ions [46-49]. The presence of these 12
organic functional groups on the surface of the synthesized samples indicates the interaction between the ZF and the Polymers. The aforementioned bands in (Fig. 6 (a, b and c)) belong to the functional groups of PVA, PVP and PEG complexes which help in the interaction with the surface ions of the samples respectively. This is owing to the strong affinity of the bioactive compounds in the polymers towards the ZF ion. After calcination, there was a drastic shift in the O-H stretching and bending. The peaks remain unchanged when the calcination temperature was increased to 600oC. The absorption bands in the samples connote the characteristic features of single-phase spinel ferrite [50].
(a)
o
PVA_C @ 600 C o
Transmittance (%)
PVA_C @ 500 C PVA_B
A
Wavenumber (cm-1)
13
1000
Fe - O
2000
Zn - O
C-N
3000
C-O-C
C=O
O-H
4000
(b)
o
Transmittance (%)
PVP_C @ 600 C o
PVP_C @ 500 C PVP_B
A 1047
1629
430 592
1332
3497
4000
3000
2000
1000
Wavenumber (cm-1)
(c)
o
PEG_C @ 600 C o
Transmittance (%)
PEG_C @ 500 C PEG_B
A
1332
3000
2000
Wavenumber (cm-1)
14
440 598
1047
1649
3191
4000
1000
Fig. 6. FTIR spectra of sample As, Bs and Cs for (a) PVA (b) PVP and (c) PEG. 3.4
Magnetic properties
The VSM studied the magnetic properties via hysteresis loops (Fig. 7) of all samples at room with the applied field of ± 5 ΚΟ . Sample Bs exhibit ferromagnetic behavior while sample Cs show superparamagnetic behavior (as shown in fig. 7b) the magnification of the inset. After calcination, the magnetic behavior of sample Bs was altered by the thermal forces altering the degree of ferromagnetic loops to form a single domain with each dopant to superparamagnetic behavior. It was observed from the M-H loops that, after calcination, the saturation magnetization (Ms) of sample PVA_B, PVP_B and PEG_B decreased. This is in agreement with the previous studies reported with a decrease in the magnetization of polymer doped MgFe2O3 and ZnFe2O3 [41, 51-54]. This decrease in Ms after calcination is thought to be due to the distribution of cation inversion among the X-Y interstitial sites which yields the X-O-Y magnetic exchange interaction as a result of thermal treatment which made some of the Fe+3 cations moves from Y sites to the X sites in the sample Cs [55-57]. However, sample Cs show smaller Ms than the bulk counterpart 80.8 and 93.9 emu/g as observed by Ahangar et al., and Kombaiah et al. [58, 59]. The crystallite size also plays a significant role in the saturation magnetization of sample Cs as a result of the thermal agitation in the molecules [59].
15
16
Fig.7.VSM analysis of samples As, Bs & Cs. The inset reveals the overlapping superparamagnetic behavior of sample Cs
4.0
Conclusion
Polyvinyl alcohol, polyvinyl-pyrrolidone, and polyethylene glycol assisted ZFNPs were synthesized by the biological thermal method. The effect of calcination was observed with towering leverage on the properties of polymer assisted ZFNPs for various applications. The SEM micrograph showed fine spherical morphology with less aggregation and reasonable particle sizes after calcination. The XRD confirmed the cubic nanocrystalline spinel phase structure that is calcination dependent. The VSM gave varied magnetic properties from ferromagnetic to superparamagnetic behavior after calcination with decrease in saturation magnetization due to the thermal influence on the magnetic moment by the calcination. Therefore, this innocuous and benign method with the help of calcination produced a favorable structural, morphological and magnetic properties of the formulated ZFNPs which in turn serve as an impetus to attain its optimal functionality for various applications such as contrasted enhancement magnetic resonance imaging, hyperthermia and drug delivery.
Acknowledgments Samson O. Aisida (NCP-CAAD/TWAS_Fellow8408) acknowledges the NCP-TWAS Postdoc Fellowship award. FIE (90407830) cordially acknowledge UNISA for VRSP Fellowship award. We thank Engr. Emeka Okwuosa for the generous sponsorship of April 2014, July 2016 and July 2018 Conference/Workshops on Applications of Nanotechnology to Energy, Health &.Environment conference
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Conflict of interest: The authors declare no conflict of interest References [1] Abraham, A. G., Manikandan, A., Manikandan, E., Jaganathan, S. K., Baykal, A., & Renganathan, P. S. (2017). Enhanced Opto-Magneto Properties of Ni x Mg1–x Fe2O4 (0.0 ≤ x ≤ 1.0) Ferrites Nano-Catalysts. Journal of Nanoelectronics and Optoelectronics, 12, 1326-1333. [2] Abraham, A. G., Manikandan, A., Manikandan, E., Vadivel, S., Jaganathan, S. K., Baykal, A., & SriRenganathana, P. (2018). Enhanced magneto-optical and photo-catalytic properties of transition metal cobalt (Co2+ ions) doped spinel MgFe2O4 ferrite nanocomposites. Journal of Magnetism and Magnetic Materials, 452, 380-388. [3] Arul, K. T., Manikandan, E., Ladchumananandasivam, R., & Maaza, M. (2016). Novel polyvinyl alcohol polymer based nanostructure with ferrites co‐doped with nickel and cobalt ions for magneto‐sensor application. Polymer International, 65, 1482-1485. [4] Arul, K. T., Manikandan, E., Murmu, P. P., Kennedy, J., & Henini, M. (2017). Enhanced magnetic properties of polymer-magnetic nanostructures synthesized by ultrasonication. Journal of Alloys and Compounds, 720, 395-400. [5] Diallo, A., Doyle, T. B., Mothudi, B. M., Manikandan, E., Rajendran, V., & Maazaa, M. (2017). Magnetic behavior of biosynthesized Co3O4 nanoparticles. Journal of Magnetism and Magnetic Materials, 424, 251255. [6] Sasikala, C., Durairaj, N., Baskaran, I., Sathyaseelan, B., Heninie, M., & Manikandan, E. (2017). Transition metal titanium (Ti) doped LaFeO3 nanoparticles for enhanced optical structural and magnetic properties. Journal of Alloys and Compounds, 712, 870-877. [7] Siva, T., Muralidharan, S., Sathiyanarayanan, S., Manikandan, E., & Jayachandran, M. (2015). Enhanced Polymer Induced Precipitation of Polymorphous in Calcium Carbonate: Calcite Aragonite Vaterite Phases. Journal of Inorganic and Organometallic Polymers and Materials, 27, 770-778.
18
[8] Sharma, R., Thakur, P., Kumar, M., Thakur, N., Negi, N. S., Sharma, P., & Sharma, V. (2016). Improvement in the magnetic behavior of cobalt-doped magnesium zinc nano-ferrites via co-precipitation route. Journal of Alloys and Compounds, 684, 569-581. [9] Aisida, S. O., Paul A. Akpa, Ishaq Ahmad, Ting-kai, Zhao, Maaza, M., & Ezema, F. I. (2019). Bio-inspired encapsulation and functionalization of iron oxide nanoparticles for biomedical applications. European Polymer Journal. https://doi.org/10.1016/j.eurpolymj.2019.109371 [10] Samavati, A., & Ismail, A. F. (2017). Antibacterial properties of copper-substituted cobalt ferrite nanoparticles synthesized by co-precipitation method, Particuology, 30, 158-163. [11] Elayakumar, K., Dinesh, A., Manikandan, A., Palanivelu, M., Kavith, G., Prakash, S., . . . Baykal, A. (2019). Structural, morphological, enhanced magnetic properties and antibacterial bio-medical activity of rare earth element (REE) Cerium (Ce3+) doped CoFe2O4 nanoparticles. Journal of Magnetism and Magnetic Materials, 476, 157-165. [12] Manikandan, A., Manikandan, E., Meenatchi, B., Vadivel, S., Jaganathan, S. K., Ladchumananandasivam, R., . . . Aananda, J. S. (2017). Rare earth element (REE) lanthanum doped zinc oxide (La: ZnO) nanomaterials: Synthesis structural optical and antibacterial studies. Journal of Alloys and Compounds, 723, 1155-1161. [13] Aisida, S. O., Madubuonu, N., Alnasir, M. H., Ahmad, I., Botha, S., Maaza, M., & Ezema, F. I. (2019). Biogenic synthesis of iron oxide nanorods using Moringa oleifera leaf extract for antibacterial applications. Appl Nanosci. Retrieved from https://doi.org/10.1007/s13204-019-01099-x [14] Aisida, S. O., Ugwu, K., Akpa, P. A., Nwanya, A. C., Ejikeme, P. M., Botha, S. S., . . . Ezema, F. I. (2019b). Biogenic synthesis and antibacterial activity of controlled silver nanoparticles using an extract of Gongronema Latifolium. Materials Chemistry and Physics, 237, 121859. [15] Aisida, S. O., Ugwu, K., Akpa, P. A., Nwanya, A. C., Nwankwo, U., Botha, S. S., . . . Ezema, F. I. (2019 a). Biosynthesis of silver nanoparticles using bitter leave (Veronica amygdalina) for antibacterial activities. Surfaces and Interfaces, 17, 100359.
19
[16]Dantas, J., Leal, E., Mapossa, A. B., & Costa, A. (2017). Magnetic nanocatalysts of Ni 0.5 Zn 0.5 Fe 2O4 doped with Cu and performance evaluation in transesterification reaction for biodiesel production. Fuel, 191, 463–471. [17] Swamy, P. P., S, B., Arunkumar, L., Srinivas, N. R., & Nijagunappa, R. V. (2011). Synthesis and characterization of zinc ferrite nanoparticles obtained by self-propagating low-temperature combustion method. Bull. Mater. Sci., 34, 1325–1330. [18] Mahmoud, G. N., Mohammad, H. M., Elias, B. S., & Abdul, H. S. (2014). Superparamagnetic magnesium ferrite nanoparticles fabricated by a simple, thermal-treatment method. Journal of Magnetism and Magnetic Materials 350 (2014) 141–147, 350, 141-147. [19] Gangopadhyay, P., Kesavmoorthy, R., Bera, S. M., Nair, K., Panigrahi, B., & Narasimhan, S. (2005).Optical absorption and photoluminescence spectroscopy of the growth of silver nanoparticles. Rev. Lett., 94, 47403–47404. [20] Ramakrishna K S, Srinivasb C, Prajapat C L, Meena S S, Mehar M V K, Potukuchf D M and Sastry D L (2018). Structural and magnetic investigations: Study of magnetocrystalline anisotropy and magnetic behavior of 0.1% Cu2+ substituted Ni–Zn ferrite nanoparticles. Ceramics International 44 1193 1200 [21] Tirupanyam B V, Srinivas C, Meena S S, Yusuf S M, Satish Kumar A, Sastry D L and Seshubai V (2017). Investigation of cation distribution and magnetocrystalline anisotropy of NixCu0.1Zn0.9−xFe2O4 nanoferrites: Role of constant mole percent of Cu2+ dopant in place of Zn2+. Ceramics International 43 7984-7991 [22] Subramanian, A. P., Jaganathan, S. K., Manikandan, A., Pandiaraj, K. N., N, G., & Supriyantoa, E. (2016). Recent trends in nano-based drug delivery systems for efficient delivery of phytochemicals in chemotherapy. RSC Advances, 6, 48294-48314. [23] Vellayappan, M. V., Jaganathan, S. K., & Manikandan, A. (2016). Nanomaterials as a game changer in the management and treatment of diabetic foot ulcers. RSC Advances, 6, 114859-114878.
20
[24] Vellayappan, M. V., Venugopal, J. R., Ramakrishna, S., Ray, S., Ismail, A. F., Mandal, M., . . . Jaganathan, S. K. (2016). Electrospinning applications from diagnosis to treatment of diabetes. RSC Advances, 6, 8363883655. [25] Shaban, I. H., Ashraf, S. E., Rashad, M. M., & Megahid, R. (2015). Structural and magnetic properties of magnesium ferrite nanoparticles prepared via EDTA-based sol-gel reaction. Journal of Magnetism and Magnetic Materials, 379, 9-15. [26] Zachary, R. S., Forrest, M. K., & Miqin, Z. (2011). Magnetite Nanoparticles for Medical MR Imaging. Mater. Today, 14(7-8), 330. [27] Krishnan, K. M. (2010). Biomedical Nanomagnetics: A Spin Through Possibilities in Imaging, Diagnostics, and Therapy. IEEE Trans. Magn., 46(7), 36. [28] Gao, J., Gu, H., & Xu, B. (2009). Multifunctional magnetic nanoparticles: design, synthesis, and biomedical applications. Acc Chem Res., 42, 1097-107. [29] Schlorf, T., Meincke, M., Kossel, E., Gluer, C., Jansen, O., & Mentlein, R. (2010). Biological properties of iron oxide nanoparticles for cellular and molecular magnetic resonance imaging. Int J Mol Sci., 12, 12-23. [30] Gang, H., Huabing, C., Ying, D., Xiuquan, L., Haijun, Y., Zachary, M., . . . Gao, J. (2013). Superparamagnetic Iron Oxide Nanoparticles: Amplifying ROS Stress to Improve Anticancer Drug Efficacy. Theranostics, 3(2), 116-126. [31] Verma, R. K., & Garg, S. (2001.). Current status of drug delivery technologies and future directions. Pharmaceutical Technology, 25, 1-14. [32] Aisida S. O., Paul, A., Ishaq, A., Maaza, M. and Fabian, I. E. (2019). Influence of PVA, PVP and PEG doping on the optical, structural, morphological and magnetic properties of zinc ferrite nanoparticles produced by thermal method. Physica B: Condensed Matter, 571, 130–136, 2019. [33] Okoroh, D. O., Ozuomba, J. O., Aisida, S. O. and Asogwa, P. U., (2019 a). Properties of Zinc
21
Ferrite Nanoparticles Due to PVP Mediation and Annealing at 500˚C," Advances in Nanoparticles, 8, 3645. [34] Aisida, S. O., Ugwoke, E., Ali Uwais, Iroegbu, C., Botha, S, Ahmad, I., Maaza, M., Ezema, F. I. (2019). Incubation period induced biogenic synthesis of PEG enhanced Moringa Oleifera silver nanocapsules and its antibacterial activity [35] Okoro, D. O., Ozuomba, J., Aisida, S. O., and Asogwa, P (2019b). Thermal treated sysnthesis and characterization of polyethylene glycol (PEG) mediated Zinc ferrite nanoparticles, Surface and Interface, 16, 127-131. [36] Ranjith Kumar E, Arunkumar T and Prakash T (2015). Heat treatment effects on structural and dielectric properties of Mn substituted CuFe2O4 and ZnFe2O4 nanoparticles. Superlattices and Microstructures 85 530 -535 [37] Mahmoud, G. N., Elias, B. S., Mansor, H., Abdul, H. S., & Hossein, A. A. (2011). Synthesis and characterization of zinc ferrite nanoparticles by a thermal treatment method. Solid State Communications, 151, 1031-1035. [38] Yan ˜ez-Vilara, S., Sanchez-And´ujara, M., G´omez-Aguirre, C., Mira, J., Sen˜ar´ıs-Rodr´ıguez, M., & CastroGarc´ıa, S. (2009). A simple solvothermal synthesis of MFe2O4 (M ¼ Mn, Co, and Ni) nanoparticles. Journal of Solid State Chemistry, 182, 2685–2690. [39] Ismail, M. I. M. (2018). Role of calcination on structural, morphology and magnetic properties of zinc substituted Mn-Ni nanoferrites. Mater. Res. Express 5, 095004 [40] Kane, S., & Satalkar, M. (2017). Correlation between magnetic properties and cationic distribution of Zn 0.85−xNi xMg 0.05 Cu 0.1 Fe 2O4 nano spinel ferrite: effect of Ni doping. J Mater Sci., 52, 3467. [41] Kombaiah K., Judith, J. Vijaya, John, L. Kennedy, Bououdina, M., Hamad A. Al-Lohedan, Jothi, R. Ramalingam. (2017). Studies on Opuntia dilenii haw mediated multifunctional ZnFe2O4 nanoparticles: Optical, magnetic and catalytic. Materials Chemistry and Physics 194 153-164
22
[42] Jaberolansar, E., Kameli, P., Ahmadvand, H., & Salamati, H. (2016). Synthesis and characterization of PVPcoated Co Zn Fe O 0.3 0.7 2 4 ferrite nanoparticles. Journal of Magnetism and Magnetic Materials, 404, 21-28. [43] Rahimi, M., Kameli, P., Ranjbar, M., & Salamati, H. (2013). The effect of polyvinyl alcohol (PVA) coating on structural, magnetic properties and spin dynamics of Ni0.3Zn0.7Fe2O4 ferrite nanoparticles. J. Magn. Magn. Mater., 347, 139–145. [44] Zulfiqar, M., Rahman, M. U., Hasanain, S., Rahman, Z., Ullah, A., & Kim, W. (2014, ). Structural, optical, dielectric and magnetic properties of PVP coated magnetite (Fe3O4) nanoparticles. J. Korean Phys. Soc., 65, 1925–1929. doi:https://doi.org/10.1007/s10854-018-0134-6 [45] Abbas, F., Jan, T. I., Ahmad, I., & Naqvi, M. M. (2015). Facile synthesis of ferromagnetic Ni-doped CeO2 nanoparticles with enhanced anticancer activity. Applied Surface Science. Retrieved from http://dx.doi.org/10.1016/j.apsusc.2015.08.229 [46] Cullity, B. (1978). The element of X-ray Diffraction (2nd ed ed.). Addison-Wesley, London. [47] Arsalani, N., Fattahi, H., & Nazarpoor, M. (2010).Arsalani, N., Fattahi, H., & Nazarpoor, M. (2010). Synthesis and characterization of PVP-functionalized superparamagnetic Fe3O4 nanoparticles as an MRI contrast agent. Express Polym. Lett., 4, 329-338. [48] Sharma, R.K., Ghose, R. (2015). Synthesis of zinc oxide nanoparticles by homogeneous precipitation method and its application in antifungal activity against Candida albicans, Ceram. Int. 41 967. [49] Thangaraj, P., Rajan, X., Durai, S. Kumar, S., Phani, A.R., Neri, G. (2011). The role of albumen (egg white) in controlled particle size and electrical conductivity behavior of zinc oxide nanoparticles, Vacuum 86 140. [50] Meidanchi, A. Akhavan, O., Khoei, S., Shokri, A.A., Hajikarimi, Z, Khansari, N. (2015). ZnFe2O4 nanoparticles as radiosensitizers in radiotherapy of human prostate cancer cells, Mater. Sci. Eng. C 46 394. [51] Mahmoud, G. N., Halimah, M. K., Arash, D., Ahmad, K., Elias, B. S., & Burhanuddin, Y. M. (2014). A comprehensive overview of the structure and comparison of magnetic properties of nanocrystalline synthesized by a thermal treatment method. Journal of Physics and Chemistry of Solids, 75, 315-327.
23
[52] Thanigai, K. A, Manikandan, E., Murmu, P.P., Kennedy, J., Henini, M. (2017). Enhanced magnetic properties of polymer-magnetic nanostructures synthesized by ultrasonication. Journal of Alloys and Compounds. 720, 395400 [53] Williams, GVM, Kennedy, J. Murmu, PP, Rubanov, S. Chong, S. V. The effect of different Fe concentrations on the structural and magnetic properties of near-surface superparamagnetic Ni1− xFex nanoparticles in SiO2 made by dual low energy. Journal of Magnetism and Magnetic Materials 473, 125-130 [54] Murmu, P.P, Kennedy, J., Ruck, B. J., Williams, G.V.M., Markwitz, A., Rubanov, S. (2012). Effect of annealing on the structural, electrical and magnetic properties of Gd-implanted ZnO thin films. Journal of Materials Science 47 (3), 1119-1126 [55] Da Dalt, S., Takimi, A., Volkmer, T. M., Sousa, V., & Bergmann, C. (2011). Magnetic and Mössbauer behavior of the nanostructured MgFe2O4 spinel obtained at low temperature. Powder Technology, 210, 103-108. [56] Holec, P., Plocek, J., Nižňansky´, D., & Poltierova´ Vejpravov, J. (2009). Preparation of MgFe2O4 nanoparticles by microemulsion method and their characterization. Journal oSol-Gelel Science and Technology, 51, 301-305. [57] Grant, V.M. Williams, Tushara, P., John, Kennedy, Shen V. C., Sergey R. (2018). Spindependent tunnelling in magnetite nanoparticles. Journal of Magnetism and Magnetic Materials 460, 229– 233 [58] Ahangar, M. Hashim, A.H. Shaari, Synthesis and characterization of manganese ferrite nanoparticles by thermal treatment method, J. Magn. Magn. Mater. 323 (2011), 1745-1749. [59] Kombaiah, K., Judith Vijaya J., John, Kennedy, L., Bououdina, M. Jothi, Ramalingam, R., Hamad, A. Al-Lohedan. (2018). Okra extract-assisted green synthesis of CoFe2O4 nanoparticles and their optical, magnetic and antimicrobial properties. Materials Chemistry and Physics 204, 410-419
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The idea was conceive and the experiment was conducted by S.O Aisida. The write-up was done by S.O Aisida. The characterization and general editing were done by S.O Aisida, F. I Ezema and Ishaq Ahmed
The authors declared no conflict of interest