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Fabrication and characterization of Manganese–Zinc Ferrite nanoparticles produced utilizing heat treatment technique
Results in Physics 12 (2019) 1821–1825
Contents lists available at ScienceDirect
Results in Physics journal homepage: www.elsevier.com/locate/rinp
Fabrication and characterization of Manganese–Zinc Ferrite nanoparticles produced utilizing heat treatment technique ⁎
T
⁎
Naif Mohammed Al-Hada , Halimah Mohamed Kamari , Abdul H. Shaari, Elias Saion Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia
A R T I C LE I N FO
A B S T R A C T
Keywords: Calcination Polyvinyl pyrrolidine Manganese–Zinc Ferrite nanoparticle
In this research, the thermal treatment technique has been employed to produce Mn0.5Zn0.5Fe2O4 nanoparticles. Manganese, Zinc and iron nitrates have been mixed with capping agent of polyvinylpyrrolidone. Several techniques have been used to examine the structural, morphological and optical properties of the prepared product. X-ray diffraction (XRD) has demonstrated the prepared product and showed that the product contains tetragonal crystalline structures. Scanning electron microscopy (SEM) has showed that the sample grain size is increasing alongside temperature calcination. Energy dispersive X-ray (EDX) has showed that the presence of Mn, Zn, Fe and O in the product nanoparticle was confirmed as original from the precursor starting materials. Transmission electron microscopy (TEM) images have demonstrated that elevating the different of calcination temperature from 500 °C to 650 °C has resulted in an increase average nanoparticle size from 12 nm to 19 nm. Fourier Transform Infrared Spectroscopy (FT-IR) has been used to describe compounds of the samples prepared before and after calcination.
Introduction Nanomaterials with idiosyncratic physiochemical features have attracted many researchers and scientists due to a wide range of applications can utilize [1]. The imperative for nanostructures of Manganese Zinc Ferrite is that, they have unique properties such as high magnetic permeability, low core losses, high saturation magnetization and high resistivity. For aforementioned, there are many uses and applications from this product like noise filters, choke coils, data memory, storage devices and electromagnetic gadget [2]. Additionally, the Manganese Zinc Ferrite nanoparticles applications are utilized by screening a talented bid inside the biomedical turfs similar through healing, bioimaging, hyperthermia, directed medication distribution organization, biosensors, MRI, besides microelectronics, etc [3]. Numerous routes were formerly said that they were aimed to the nanoparticles production of the spinels Mn0.5Zn0.5Fe2O4, counting including hydrothermally produced [4], thermal decomposition method [5], co-precipitation and macroemulsions techniques [5,6], microwave route [7] and sol-gel process [8]. But, these routes had remained used toughly near being accepted to obtain Mn0.5Zn0.5Fe2O4 nanoparticles at a huge device development owing towards intricate processes trailed, lengthier response periods, tall response malaises, poisonous substances cast-off besides side-effects wastes complicated inside these mixtures procedures [9–11]. To overwhelm disadvantages of the earlier method ⁎
systems, a shallow thermal action way stayed used to intend manufacturing spinel Mn0.5Zn0.5Fe2O4 nanoparticles. The contribution of this research is that a thermal treatment technique offers a number of advantages such as control growth of the size of particles, particles agglomeration reduction, toxic production prevention, an inexpensive technique, and its processing time is short [12]. In this study, the production of Mn0.5Zn0.5Fe2O4 nanoparticles by thermal technique was attained for first time in high purity in powder form. The structural and morphological features of pure product prepared using PVP as capping agent and thermal treatment process have been successfully investigated in detail. Experimental Materials There are four main materials have been used in this technique without any purification. The first material is Manganese nitrate [Mn (NO3)2·4H2O], the second one is zinc nitrate [Zn(NO3)2·6H2O], and the third is iron nitrate [Fe(NO3)3·9H2O] metallic salts were used as metal precursors. The last one is polyvinyl pyrrolidone (PVP) where it has been used as capping agent to prevent nanoparticles aggregated. Deionized water also has been used as a solvent for all metallic salts and PVP. Sigma-Aldrich was the source for all materials which have been
Corresponding authors. E-mail addresses: [email protected] (N.M. Al-Hada), [email protected] (H.M. Kamari).
https://doi.org/10.1016/j.rinp.2019.02.019 Received 16 January 2019; Received in revised form 5 February 2019; Accepted 5 February 2019 Available online 07 February 2019 2211-3797/ © 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/BY/4.0/).
Results in Physics 12 (2019) 1821–1825
N.M. Al-Hada, et al.
used in this process.
100
0.0
89 oC 80
Wieght (%)
PVP solution has been successfully synthesis using 3 g of PVP dissolved in 100 ml deionized water at 70 °C for 2 h using stirrer. The metallic salts of 0.5 mmol of Mn(NO3)3·9H2O, 0.5 mmol of Zn (NO3)2·6H2O and 1 mmol of Fe(NO3)3·9H2O, have been mixed with PVP and continuous stirrer for 1 h until become homogeneous solution. Later on, the prepared solution emptied into a Petri dish and sent it to oven to dry for 24 h at 80 °C. The dried results have been crushed into fine powder and exposed 3 h for calcination temperatures at 500, 550, 600 and 650 °C. The product prepared has been examined using various characterization tools including powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR) and energy dispersive X-ray spectroscopy (EDX).
321 oC
-0.2
60
-0.4
40
-0.6
dw/dt (g/min)
Procedure
o
498 C
20
437 oC
-0.8
0 0
200
400
600
800
1000
-1.0
Temperature (oC) Fig. 2. The TGA/DTA curves obtained for metal nitrate in the presence of PVP with temperature increasing at 10 °C/min.
Results and discussion reduce nanoparticle size. [9,13]. The nanoparticle size explanation or lesson is done with stopping metal ions from breaking on the nanoparticle’s surface. The hypothesis is that after the impact happens the nanoparticle will shrink [14–16].
Mechanism of nanoparticles The mechanism and growth of the nanoparticles during thermal treatment stage have demonstrated in Fig. 1. PVP’s primary function is employed and intended for complex metallic salts to be calmed down. Generally, it might remain accomplished by electrostatic stabilization in addition side steric that are for the amide groups aimed at pyrrolidone rings besides methylene groups. Throughout the mingling result procedure, metallic ions would consume being suppressed over towards trapping through the amine group done and communication course of ionic-dipole in polymeric chains. Later, when the ventilation development is forming up, the metallic cations converted into stationary inside polymer cavity since H2O needed to stay deducted. Afterwards, the calcination progression, carbon-based resources were disintegrated to vapors like N2, NO, CO, or CO2. PVP gives changes to the creation of the nuclei for the Manganese–Zinc Ferrite nanoparticles in the calcining method. Throughout the procedure, if PVP didn’t exist, the Ostwald seasoning development could increase the growth of the nanoparticle’s size by surged connected dynamism heights on their shallow. Now, PVP had represented to neutralize the steric hindrance with which the nanoparticles converted to uncollected nanoparticles. PVP can help to
Thermogravimetric analysis Significant result relating to the choice of a suitable calcination temperature is obtained by thermal analysis of the metal nitrate and the PVP. Fig. 2 presents the thermogram obtained by TGA-DTG analysis of the un-calcined sample. This indicates two episodes of weight loss – the first taking place due to loss of water at around 89 °C, and the second (more substantial) weight loss taking place at approximately 437 °C due to the organic (PVP) decomposition [17]. At 321 °C, the weight loss starts, this losses as a result of NOx compounds decomposition. The resulting sample nanoparticles were pure and stable at 498 °C. These results indicate that the optimum annealing temperature for the generation of sample nanoparticles is above 498 °C. XRD analysis XRD patterns of Mn0.5Zn0.5Fe2O4 product have been showed in Fig. 3. Fig. 3a showed abroad peak in the sample before calcination due to the samples are still in an amorphous stage. The samples which have been calcined at 500 °C and above revealed sharper and narrower peaks due to that the Mn0.5Zn0.5Fe2O4 nanoparticles has been formed. Furthermore, increasing in intensity value was observed alongside calcination temperatures and resulted to enhance the crystallinity of the Mn0.5Zn0.5Fe2O4 nanoparticles. Also, the crystalline volume to surface ratio has been increased alongside calcination, as evinced in results of TEM, which occurred due to particle size expansion. The crystallite sizes of product have been calculated using Scherrer’s equation (1) and found to be between 12 and 17 nm at calcination temperatures 500 and 650 °C.
D = 0.9λ/βcosθ
(1)
where D is the crystalline size (nm), β is the full width of the diffraction line at half of the maximum intensity measured in radians, λ is the Xray wavelength of Cu Kα = 0.154 nm, and θ is the Bragg angle [18]. From the Scherrer formula, it has found that the sizes of crystal have been found to be increase alongside calcination temperature from 12 nm at 500 °C to 17 nm at 650 °C as showed in Table 1. TEM analysis Fig. 1. Schematic proposed of nanoparticles growth mechanism.
The calcined of Mn0.5Zn0.5Fe2O4 nanoparticles at 500 °C and above 1822
Results in Physics 12 (2019) 1821–1825
N.M. Al-Hada, et al.
Fig. 3. XRD patterns for Mn0.5Zn0.5Fe2O4 nanoparticles calcined at temperatures of (a) room temperature, (b) 500, (c) 550, (d) 600 and (e) 650 °C.
has been investigated using TEM as shown in Fig. 4. The prepared product using heat treatment has been demonstrated and observed that the particle is in uniform shape. The particle size of product has been increased alongside heat treatment whereas found between 14 and 19 nm at temperatures of 500 and 650 °C respectively as shown in Table 1, which has agreed with XRD results. The increment in particle size of the product alongside calcination temperatures is due to many neighboring particles have been fused to each other to become larger size [19,20]. The homogeneously morphology in the product is due to advantage of heat treatment technique. The controlling growth of particle size in product is due to the presence of PVP which has play important role in prevent particles agglomeration [17,21–27].
Table 1 Briefing of the structural and morphological properties of synthesized Mn0.5Zn0.5Fe2O4 nanoparticles at various calcination. Temperature °C
DXRD nm
DTEM nm
500 550 600 650
12.6 14 15 17
14 15 17 19
Fig. 4. TEM image of samples calcined at (a) 500, (b) 550, (c) 600 and (d) 650 °C. 1823
Results in Physics 12 (2019) 1821–1825
N.M. Al-Hada, et al.
(e)
Transmittance (%)
533
(d)
370
538
(c)
393 372 544
(b)
553
(a) 839 3414.47
4500
382
4000
3500
2945
3000
1646
2500
2000
14281277
1500
409 388 420 395
639
1000
582
500
Wave number (cm-1) Fig. 5. FTIR spectra of sample nanoparticles calcined at temperatures of (a) room temperature, (b) 500, (c) 550, (d) 600 and (e) 650 °C.
Fig. 7. EDX pattern of Mn0.5Zn0.5Fe2O4 nanoparticles for sample calcined at 650 °C.
Functional analysis
bending vibration created from methylene group; while 1277 cm−1 had associated with c-n stretching vibration. Furthermore, 839 and 639 cm−1 correspond to the vibrations that occurred due to C–C ring and CeN]O bending and 553, 420 and 395 cm−1 to Fe–O, Mn–O and Zn–O respectively [29–32]. The single absorption peak is thought to be due to the production of remarkably pure Manganese–Zinc Ferrite nanoparticles also indicated by a move in the wave number for the product nanoparticles spectra associated with increasing heating temperatures. This calcination effect is corroborated by the crystallinity enhancement of the Manganese–Zinc Ferrite nanoparticles generated. Therefore, an increasing in sample calcination has enhancement the crystalline which has been observed that the sample had sharper peaks at higher calcination.
FTIR spectroscopy assistances analysing multi-component systems and provides necessary information pertaining the material's phase composition and types of interactions existing amongst various kinds of polymers. In the present study, FTIR measurement was employed to determine the appropriate calcination temperature at which pure crystal nanoparticles conform with no organic agent trace being detected. The obtained FTIR spectrum at 280–4000 cm−1 for the product prepared using thermal process is shown in Fig. 5. The organic compounds and sample nanoparticles have been observed in Fig. 5a. Fig. 5a shown the sample before heating whereas the absorption peaks at wave numbers of 3414, 2945 and 1646 cm−1 have been assigned to N–H, C–H and C]O stretching vibrations, respectively [28]. Additionally, the absorption peak existed at 1428 cm−1 had attributed to C–H
Fig. 6. SEM image calcined at (a) 500, (b) 550, (c) 600 and (d) 650 °C. 1824
Results in Physics 12 (2019) 1821–1825
N.M. Al-Hada, et al.
SEM analysis
[9] Al-Hada NM, Saion E, Kamari HM, Flaifel MH, Shaari AH, Talib ZA, et al. morphological and optical behaviour of PVP capped binary (ZnO)0.4(CdO)0.6 nanoparticles synthesised by a facile thermal route. Mater Sci Semicond Process 2016;53:56–65. [10] Salem A, Saion E, Al-Hada NM, Kamari HM, Shaari AH, Radiman S. Simple synthesis of ZnSe nanoparticles by thermal treatment and their characterization. Results Phys 2017;7:1175–80. [11] Baqer AA, Matori KA, Al-Hada NM, Kamari HM, Shaari AH, Saion E, et al. Copper oxide nanoparticles synthesized by a heat treatment approach with structural, morphological and optical characteristics. J Mater Sci: Mater Electron 2018;29:1025–33. [12] Al-Hada NM, Saion E, Shaari A, Kamarudin M, Gene SA. The influence of calcination temperature on the formation of zinc oxide nanoparticles by thermal-treatment. Appl Mech Mater 2014;446:181–4. [13] Izu N, Uchida T, Matsubara I, Itoh T, Shin W, Nishibori M. Formation mechanism of monodispersed spherical core–shell ceria/polymer hybrid nanoparticles. Mater Res Bull 2011;46:1168–76. [14] Koczkur KM, Mourdikoudis S, Polavarapu L, Skrabalak SE. Polyvinylpyrrolidone (PVP) in nanoparticle synthesis. Dalton Trans 2015;44:17883–905. [15] Thanh NT, Maclean N, Mahiddine S. Mechanisms of nucleation and growth of nanoparticles in solution. Chem Rev 2014;114:7610–30. [16] Visaveliya N, Köhler JM. Control of shape and size of polymer nanoparticles aggregates in a single-step microcontinuous flow process: a case of flower and spherical shapes. Langmuir 2014;30:12180–9. [17] Baqer AA, Matori KA, Al-Hada NM, Shaari AH, Saion E, Chyi JLY. Effect of polyvinylpyrrolidone on cerium oxide nanoparticle characteristics prepared by a facile heat treatment technique. Results Phys 2017;7:611–9. [18] Cullity BD. Elements of X-ray diffraction. BiblioBazaar 2011. [19] Kamari HM, Al-Hada NM, Saion E, Shaari AH, Talib ZA, Flaifel MH, et al. Calcined solution-based PVP influence on ZnO semiconductor nanoparticle properties. Crystals 2017;7:2. [20] Al-Hada NM, Saion EB, Shaari AH, Kamarudeen MA, Flaifel MH, Gene SA, et al. Structural and morphological properties of cadmium oxide nanoparticles prepared by thermal treatment method. Adva Mater Res Trans Tech Publ 2015:291–4. [21] Al-Hada NM, Saion EB, Shaari AH, Kamarudin MA, Flaifel MH, Ahmad SH, et al. A facile thermal-treatment route to synthesize the semiconductor CdO nanoparticles and effect of calcination. Mater Sci Semicond Process 2014;26:460–6. [22] Al-Hada NM, Saion E, Talib ZA, Shaari AH. The impact of polyvinylpyrrolidone on properties of cadmium oxide semiconductor nanoparticles manufactured by heat treatment technique. Polymers 2016;8:113. [23] Hashem M, Saion E, Al-Hada NM, Kamari HM, Shaari AH, Talib ZA, et al. Fabrication and characterization of semiconductor nickel oxide (NiO) nanoparticles manufactured using a facile thermal treatment. Results Phys 2016;6:1024–30. [24] Al-Hada NM, Kamari HM, Baqer AA, Shaari AH, Saion E. Thermal calcination-based production of SnO2 nanopowder: an analysis of SnO2 nanoparticle characteristics and antibacterial activities. Nanomaterials 2018;8:250. [25] Al-Hada NM, Kamari HM, Abdullah CAC, Saion E, Shaari AH, Talib ZA, et al. Downtop nanofabrication of binary (CdO)x(ZnO)1–x nanoparticles and their antibacterial activity. Int J Nanomed 2017;12:8309. [26] Salem A, Saion E, Al-Hada NM, Kamari HM, Shaari AH, Abdullah CAC, et al. Synthesis and characterization of CdSe nanoparticles via thermal treatment technique. Results Phys 2017;7:1556–62. [27] Baqer AA, Matori KA, Al-Hada NM, Shaari AH, Saion E, Chyi JLY, et al. Structural and optical properties of cerium oxide nanoparticles prepared by thermal treatment method. Solid State Phenomena Trans Tech Publ 2017:132–7. [28] Al-Hada NM, Saion EB, Shaari AH, Kamarudin MA, Flaifel MH, Ahmad SH, et al. A facile thermal-treatment route to synthesize ZnO nanosheets and effect of calcination temperature. PLoS ONE 2014;9:e103134. [29] Gene SA, Saion E, Shaari AH, Kamarudin MA, Al-Hada NM, Kharazmi A. Structural, optical, and magnetic characterization of spinel zinc chromite nanocrystallines synthesised by thermal treatment method. J Nanomater 2014;2014:7. [30] Zakiyah LB, Saion E, Al-Hada NM, Gharibshahi E, Salem A, Soltani N, et al. Upscalable synthesis of size-controlled copper ferrite nanocrystals by thermal treatment method. Mater Sci Semicond Process 2015;40:564–9. [31] Gene SA, Saion EB, Shaari AH, Kamarudeen MA, Al-Hada NM. Fabrication and characterization of nanospinel ZnCr2O4 using thermal treatment method. Adv Mater Res 2015;1107:301. [32] Lee PJ, Saion E, Al-Hada NM, Soltani N. A simple up-scalable thermal treatment method for synthesis of ZnO nanoparticles. Metals 2015;5:2383–92.
SEM have been used to examine the surface morphologies of prepared product which has been calcined at various temperatures. The SEM results of product and the impact of calcination have been shown in Fig. 6(a–d). At 500 °C and above calcination, the grain size of product was observed that its growth alongside calcination temperatures as shown in Fig. 6(c–d). EDX spectrum analysis EDX has been used to investigate the atomic composition of the product prepared using calcination technique. Fig. 7 exhibits the EDX spectrum and the compounds which still in the product after calcination. The matching peaks of Mn, Zn, Fe and O have been detected in the sputtered product and thus approve the Mn0.5Zn0.5Fe2O4 nanoparticles formation. The presence peaks of Au have been detected in the sample because of the sputtering procedure that used during the preparation of sample for EDX test. The EDX results determines the Mn0.5Zn0.5Fe2O4 nanoparticles formation with spinel phase and also highlights on the point that the heat treatment technique implemented in the present research is very active, because no loss any elements during the process. Conclusion The product of Mn0.5Zn0.5Fe2O4 nanoparticles has been successfully prepared using calcination technique. Characteristics of the product nanoparticles have been tested using XRD and TEM analyses which revealed that the crystal sizes and particle size have been increased alongside calcination to be found 12 nm at 500 °C and 17 nm at 650 °C. EDX analysis revealed the peaks of Mn, Zn, Fe and O have been detected with the atomic composition and confirmed that the prepared product has high purity. This confirms that the nanoparticle has formed and also proves that this technique which used in this study is very successful and able to produce product with high purity. References [1] Pardavi-Horvath M. Microwave applications of soft ferrites. J Magn Magn Mater 2000;215:171–83. [2] Huang A, He H, Feng Z, Wang S. Study on electromagnetic properties of MnZn ferrites with Fe-poor composition. Mater Chem Phys 2007;105:303–7. [3] Yoo D, Lee J-H, Shin T-H, Cheon J. Theranostic magnetic nanoparticles. Acc Chem Res 2011;44:863–74. [4] Nalbandian L, Delimitis A, Zaspalis VT, Deliyanni EA, Bakoyannakis DN, Peleka EN. Hydrothermally prepared nanocrystalline Mn–Zn ferrites: synthesis and characterization. Microporous Mesoporous Mater 2008;114:465–73. [5] Szczygieł I, Winiarska K. Synthesis and characterization of manganese–zinc ferrite obtained by thermal decomposition from organic precursors. J Therm Anal Calorim 2014;115:471–7. [6] Makovec D, Kodre A, Arčon I, Drofenik M. Structure of manganese zinc ferrite spinel nanoparticles prepared with co-precipitation in reversed microemulsions. J Nanopart Res 2009;11:1145–58. [7] Komarneni S, D'Arrigo MC, Leonelli C, Pellacani GC, Katsuki H. Microwave-hydrothermal synthesis of nanophase ferrites. J Am Ceram Soc 1998;81:3041–3. [8] Azadmanjiri J. Preparation of Mn–Zn ferrite nanoparticles from chemical sol–gel combustion method and the magnetic properties after sintering. J Non-Cryst Solids 2007;353:4170–3.
1825
Contents lists available at ScienceDirect
Results in Physics journal homepage: www.elsevier.com/locate/rinp
Fabrication and characterization of Manganese–Zinc Ferrite nanoparticles produced utilizing heat treatment technique ⁎
T
⁎
Naif Mohammed Al-Hada , Halimah Mohamed Kamari , Abdul H. Shaari, Elias Saion Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia
A R T I C LE I N FO
A B S T R A C T
Keywords: Calcination Polyvinyl pyrrolidine Manganese–Zinc Ferrite nanoparticle
In this research, the thermal treatment technique has been employed to produce Mn0.5Zn0.5Fe2O4 nanoparticles. Manganese, Zinc and iron nitrates have been mixed with capping agent of polyvinylpyrrolidone. Several techniques have been used to examine the structural, morphological and optical properties of the prepared product. X-ray diffraction (XRD) has demonstrated the prepared product and showed that the product contains tetragonal crystalline structures. Scanning electron microscopy (SEM) has showed that the sample grain size is increasing alongside temperature calcination. Energy dispersive X-ray (EDX) has showed that the presence of Mn, Zn, Fe and O in the product nanoparticle was confirmed as original from the precursor starting materials. Transmission electron microscopy (TEM) images have demonstrated that elevating the different of calcination temperature from 500 °C to 650 °C has resulted in an increase average nanoparticle size from 12 nm to 19 nm. Fourier Transform Infrared Spectroscopy (FT-IR) has been used to describe compounds of the samples prepared before and after calcination.
Introduction Nanomaterials with idiosyncratic physiochemical features have attracted many researchers and scientists due to a wide range of applications can utilize [1]. The imperative for nanostructures of Manganese Zinc Ferrite is that, they have unique properties such as high magnetic permeability, low core losses, high saturation magnetization and high resistivity. For aforementioned, there are many uses and applications from this product like noise filters, choke coils, data memory, storage devices and electromagnetic gadget [2]. Additionally, the Manganese Zinc Ferrite nanoparticles applications are utilized by screening a talented bid inside the biomedical turfs similar through healing, bioimaging, hyperthermia, directed medication distribution organization, biosensors, MRI, besides microelectronics, etc [3]. Numerous routes were formerly said that they were aimed to the nanoparticles production of the spinels Mn0.5Zn0.5Fe2O4, counting including hydrothermally produced [4], thermal decomposition method [5], co-precipitation and macroemulsions techniques [5,6], microwave route [7] and sol-gel process [8]. But, these routes had remained used toughly near being accepted to obtain Mn0.5Zn0.5Fe2O4 nanoparticles at a huge device development owing towards intricate processes trailed, lengthier response periods, tall response malaises, poisonous substances cast-off besides side-effects wastes complicated inside these mixtures procedures [9–11]. To overwhelm disadvantages of the earlier method ⁎
systems, a shallow thermal action way stayed used to intend manufacturing spinel Mn0.5Zn0.5Fe2O4 nanoparticles. The contribution of this research is that a thermal treatment technique offers a number of advantages such as control growth of the size of particles, particles agglomeration reduction, toxic production prevention, an inexpensive technique, and its processing time is short [12]. In this study, the production of Mn0.5Zn0.5Fe2O4 nanoparticles by thermal technique was attained for first time in high purity in powder form. The structural and morphological features of pure product prepared using PVP as capping agent and thermal treatment process have been successfully investigated in detail. Experimental Materials There are four main materials have been used in this technique without any purification. The first material is Manganese nitrate [Mn (NO3)2·4H2O], the second one is zinc nitrate [Zn(NO3)2·6H2O], and the third is iron nitrate [Fe(NO3)3·9H2O] metallic salts were used as metal precursors. The last one is polyvinyl pyrrolidone (PVP) where it has been used as capping agent to prevent nanoparticles aggregated. Deionized water also has been used as a solvent for all metallic salts and PVP. Sigma-Aldrich was the source for all materials which have been
Corresponding authors. E-mail addresses: [email protected] (N.M. Al-Hada), [email protected] (H.M. Kamari).
https://doi.org/10.1016/j.rinp.2019.02.019 Received 16 January 2019; Received in revised form 5 February 2019; Accepted 5 February 2019 Available online 07 February 2019 2211-3797/ © 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/BY/4.0/).
Results in Physics 12 (2019) 1821–1825
N.M. Al-Hada, et al.
used in this process.
100
0.0
89 oC 80
Wieght (%)
PVP solution has been successfully synthesis using 3 g of PVP dissolved in 100 ml deionized water at 70 °C for 2 h using stirrer. The metallic salts of 0.5 mmol of Mn(NO3)3·9H2O, 0.5 mmol of Zn (NO3)2·6H2O and 1 mmol of Fe(NO3)3·9H2O, have been mixed with PVP and continuous stirrer for 1 h until become homogeneous solution. Later on, the prepared solution emptied into a Petri dish and sent it to oven to dry for 24 h at 80 °C. The dried results have been crushed into fine powder and exposed 3 h for calcination temperatures at 500, 550, 600 and 650 °C. The product prepared has been examined using various characterization tools including powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR) and energy dispersive X-ray spectroscopy (EDX).
321 oC
-0.2
60
-0.4
40
-0.6
dw/dt (g/min)
Procedure
o
498 C
20
437 oC
-0.8
0 0
200
400
600
800
1000
-1.0
Temperature (oC) Fig. 2. The TGA/DTA curves obtained for metal nitrate in the presence of PVP with temperature increasing at 10 °C/min.
Results and discussion reduce nanoparticle size. [9,13]. The nanoparticle size explanation or lesson is done with stopping metal ions from breaking on the nanoparticle’s surface. The hypothesis is that after the impact happens the nanoparticle will shrink [14–16].
Mechanism of nanoparticles The mechanism and growth of the nanoparticles during thermal treatment stage have demonstrated in Fig. 1. PVP’s primary function is employed and intended for complex metallic salts to be calmed down. Generally, it might remain accomplished by electrostatic stabilization in addition side steric that are for the amide groups aimed at pyrrolidone rings besides methylene groups. Throughout the mingling result procedure, metallic ions would consume being suppressed over towards trapping through the amine group done and communication course of ionic-dipole in polymeric chains. Later, when the ventilation development is forming up, the metallic cations converted into stationary inside polymer cavity since H2O needed to stay deducted. Afterwards, the calcination progression, carbon-based resources were disintegrated to vapors like N2, NO, CO, or CO2. PVP gives changes to the creation of the nuclei for the Manganese–Zinc Ferrite nanoparticles in the calcining method. Throughout the procedure, if PVP didn’t exist, the Ostwald seasoning development could increase the growth of the nanoparticle’s size by surged connected dynamism heights on their shallow. Now, PVP had represented to neutralize the steric hindrance with which the nanoparticles converted to uncollected nanoparticles. PVP can help to
Thermogravimetric analysis Significant result relating to the choice of a suitable calcination temperature is obtained by thermal analysis of the metal nitrate and the PVP. Fig. 2 presents the thermogram obtained by TGA-DTG analysis of the un-calcined sample. This indicates two episodes of weight loss – the first taking place due to loss of water at around 89 °C, and the second (more substantial) weight loss taking place at approximately 437 °C due to the organic (PVP) decomposition [17]. At 321 °C, the weight loss starts, this losses as a result of NOx compounds decomposition. The resulting sample nanoparticles were pure and stable at 498 °C. These results indicate that the optimum annealing temperature for the generation of sample nanoparticles is above 498 °C. XRD analysis XRD patterns of Mn0.5Zn0.5Fe2O4 product have been showed in Fig. 3. Fig. 3a showed abroad peak in the sample before calcination due to the samples are still in an amorphous stage. The samples which have been calcined at 500 °C and above revealed sharper and narrower peaks due to that the Mn0.5Zn0.5Fe2O4 nanoparticles has been formed. Furthermore, increasing in intensity value was observed alongside calcination temperatures and resulted to enhance the crystallinity of the Mn0.5Zn0.5Fe2O4 nanoparticles. Also, the crystalline volume to surface ratio has been increased alongside calcination, as evinced in results of TEM, which occurred due to particle size expansion. The crystallite sizes of product have been calculated using Scherrer’s equation (1) and found to be between 12 and 17 nm at calcination temperatures 500 and 650 °C.
D = 0.9λ/βcosθ
(1)
where D is the crystalline size (nm), β is the full width of the diffraction line at half of the maximum intensity measured in radians, λ is the Xray wavelength of Cu Kα = 0.154 nm, and θ is the Bragg angle [18]. From the Scherrer formula, it has found that the sizes of crystal have been found to be increase alongside calcination temperature from 12 nm at 500 °C to 17 nm at 650 °C as showed in Table 1. TEM analysis Fig. 1. Schematic proposed of nanoparticles growth mechanism.
The calcined of Mn0.5Zn0.5Fe2O4 nanoparticles at 500 °C and above 1822
Results in Physics 12 (2019) 1821–1825
N.M. Al-Hada, et al.
Fig. 3. XRD patterns for Mn0.5Zn0.5Fe2O4 nanoparticles calcined at temperatures of (a) room temperature, (b) 500, (c) 550, (d) 600 and (e) 650 °C.
has been investigated using TEM as shown in Fig. 4. The prepared product using heat treatment has been demonstrated and observed that the particle is in uniform shape. The particle size of product has been increased alongside heat treatment whereas found between 14 and 19 nm at temperatures of 500 and 650 °C respectively as shown in Table 1, which has agreed with XRD results. The increment in particle size of the product alongside calcination temperatures is due to many neighboring particles have been fused to each other to become larger size [19,20]. The homogeneously morphology in the product is due to advantage of heat treatment technique. The controlling growth of particle size in product is due to the presence of PVP which has play important role in prevent particles agglomeration [17,21–27].
Table 1 Briefing of the structural and morphological properties of synthesized Mn0.5Zn0.5Fe2O4 nanoparticles at various calcination. Temperature °C
DXRD nm
DTEM nm
500 550 600 650
12.6 14 15 17
14 15 17 19
Fig. 4. TEM image of samples calcined at (a) 500, (b) 550, (c) 600 and (d) 650 °C. 1823
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(e)
Transmittance (%)
533
(d)
370
538
(c)
393 372 544
(b)
553
(a) 839 3414.47
4500
382
4000
3500
2945
3000
1646
2500
2000
14281277
1500
409 388 420 395
639
1000
582
500
Wave number (cm-1) Fig. 5. FTIR spectra of sample nanoparticles calcined at temperatures of (a) room temperature, (b) 500, (c) 550, (d) 600 and (e) 650 °C.
Fig. 7. EDX pattern of Mn0.5Zn0.5Fe2O4 nanoparticles for sample calcined at 650 °C.
Functional analysis
bending vibration created from methylene group; while 1277 cm−1 had associated with c-n stretching vibration. Furthermore, 839 and 639 cm−1 correspond to the vibrations that occurred due to C–C ring and CeN]O bending and 553, 420 and 395 cm−1 to Fe–O, Mn–O and Zn–O respectively [29–32]. The single absorption peak is thought to be due to the production of remarkably pure Manganese–Zinc Ferrite nanoparticles also indicated by a move in the wave number for the product nanoparticles spectra associated with increasing heating temperatures. This calcination effect is corroborated by the crystallinity enhancement of the Manganese–Zinc Ferrite nanoparticles generated. Therefore, an increasing in sample calcination has enhancement the crystalline which has been observed that the sample had sharper peaks at higher calcination.
FTIR spectroscopy assistances analysing multi-component systems and provides necessary information pertaining the material's phase composition and types of interactions existing amongst various kinds of polymers. In the present study, FTIR measurement was employed to determine the appropriate calcination temperature at which pure crystal nanoparticles conform with no organic agent trace being detected. The obtained FTIR spectrum at 280–4000 cm−1 for the product prepared using thermal process is shown in Fig. 5. The organic compounds and sample nanoparticles have been observed in Fig. 5a. Fig. 5a shown the sample before heating whereas the absorption peaks at wave numbers of 3414, 2945 and 1646 cm−1 have been assigned to N–H, C–H and C]O stretching vibrations, respectively [28]. Additionally, the absorption peak existed at 1428 cm−1 had attributed to C–H
Fig. 6. SEM image calcined at (a) 500, (b) 550, (c) 600 and (d) 650 °C. 1824
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SEM analysis
[9] Al-Hada NM, Saion E, Kamari HM, Flaifel MH, Shaari AH, Talib ZA, et al. morphological and optical behaviour of PVP capped binary (ZnO)0.4(CdO)0.6 nanoparticles synthesised by a facile thermal route. Mater Sci Semicond Process 2016;53:56–65. [10] Salem A, Saion E, Al-Hada NM, Kamari HM, Shaari AH, Radiman S. Simple synthesis of ZnSe nanoparticles by thermal treatment and their characterization. Results Phys 2017;7:1175–80. [11] Baqer AA, Matori KA, Al-Hada NM, Kamari HM, Shaari AH, Saion E, et al. Copper oxide nanoparticles synthesized by a heat treatment approach with structural, morphological and optical characteristics. J Mater Sci: Mater Electron 2018;29:1025–33. [12] Al-Hada NM, Saion E, Shaari A, Kamarudin M, Gene SA. The influence of calcination temperature on the formation of zinc oxide nanoparticles by thermal-treatment. Appl Mech Mater 2014;446:181–4. [13] Izu N, Uchida T, Matsubara I, Itoh T, Shin W, Nishibori M. Formation mechanism of monodispersed spherical core–shell ceria/polymer hybrid nanoparticles. Mater Res Bull 2011;46:1168–76. [14] Koczkur KM, Mourdikoudis S, Polavarapu L, Skrabalak SE. Polyvinylpyrrolidone (PVP) in nanoparticle synthesis. Dalton Trans 2015;44:17883–905. [15] Thanh NT, Maclean N, Mahiddine S. Mechanisms of nucleation and growth of nanoparticles in solution. Chem Rev 2014;114:7610–30. [16] Visaveliya N, Köhler JM. Control of shape and size of polymer nanoparticles aggregates in a single-step microcontinuous flow process: a case of flower and spherical shapes. Langmuir 2014;30:12180–9. [17] Baqer AA, Matori KA, Al-Hada NM, Shaari AH, Saion E, Chyi JLY. Effect of polyvinylpyrrolidone on cerium oxide nanoparticle characteristics prepared by a facile heat treatment technique. Results Phys 2017;7:611–9. [18] Cullity BD. Elements of X-ray diffraction. BiblioBazaar 2011. [19] Kamari HM, Al-Hada NM, Saion E, Shaari AH, Talib ZA, Flaifel MH, et al. Calcined solution-based PVP influence on ZnO semiconductor nanoparticle properties. Crystals 2017;7:2. [20] Al-Hada NM, Saion EB, Shaari AH, Kamarudeen MA, Flaifel MH, Gene SA, et al. Structural and morphological properties of cadmium oxide nanoparticles prepared by thermal treatment method. Adva Mater Res Trans Tech Publ 2015:291–4. [21] Al-Hada NM, Saion EB, Shaari AH, Kamarudin MA, Flaifel MH, Ahmad SH, et al. A facile thermal-treatment route to synthesize the semiconductor CdO nanoparticles and effect of calcination. Mater Sci Semicond Process 2014;26:460–6. [22] Al-Hada NM, Saion E, Talib ZA, Shaari AH. The impact of polyvinylpyrrolidone on properties of cadmium oxide semiconductor nanoparticles manufactured by heat treatment technique. Polymers 2016;8:113. [23] Hashem M, Saion E, Al-Hada NM, Kamari HM, Shaari AH, Talib ZA, et al. Fabrication and characterization of semiconductor nickel oxide (NiO) nanoparticles manufactured using a facile thermal treatment. Results Phys 2016;6:1024–30. [24] Al-Hada NM, Kamari HM, Baqer AA, Shaari AH, Saion E. Thermal calcination-based production of SnO2 nanopowder: an analysis of SnO2 nanoparticle characteristics and antibacterial activities. Nanomaterials 2018;8:250. [25] Al-Hada NM, Kamari HM, Abdullah CAC, Saion E, Shaari AH, Talib ZA, et al. Downtop nanofabrication of binary (CdO)x(ZnO)1–x nanoparticles and their antibacterial activity. Int J Nanomed 2017;12:8309. [26] Salem A, Saion E, Al-Hada NM, Kamari HM, Shaari AH, Abdullah CAC, et al. Synthesis and characterization of CdSe nanoparticles via thermal treatment technique. Results Phys 2017;7:1556–62. [27] Baqer AA, Matori KA, Al-Hada NM, Shaari AH, Saion E, Chyi JLY, et al. Structural and optical properties of cerium oxide nanoparticles prepared by thermal treatment method. Solid State Phenomena Trans Tech Publ 2017:132–7. [28] Al-Hada NM, Saion EB, Shaari AH, Kamarudin MA, Flaifel MH, Ahmad SH, et al. A facile thermal-treatment route to synthesize ZnO nanosheets and effect of calcination temperature. PLoS ONE 2014;9:e103134. [29] Gene SA, Saion E, Shaari AH, Kamarudin MA, Al-Hada NM, Kharazmi A. Structural, optical, and magnetic characterization of spinel zinc chromite nanocrystallines synthesised by thermal treatment method. J Nanomater 2014;2014:7. [30] Zakiyah LB, Saion E, Al-Hada NM, Gharibshahi E, Salem A, Soltani N, et al. Upscalable synthesis of size-controlled copper ferrite nanocrystals by thermal treatment method. Mater Sci Semicond Process 2015;40:564–9. [31] Gene SA, Saion EB, Shaari AH, Kamarudeen MA, Al-Hada NM. Fabrication and characterization of nanospinel ZnCr2O4 using thermal treatment method. Adv Mater Res 2015;1107:301. [32] Lee PJ, Saion E, Al-Hada NM, Soltani N. A simple up-scalable thermal treatment method for synthesis of ZnO nanoparticles. Metals 2015;5:2383–92.
SEM have been used to examine the surface morphologies of prepared product which has been calcined at various temperatures. The SEM results of product and the impact of calcination have been shown in Fig. 6(a–d). At 500 °C and above calcination, the grain size of product was observed that its growth alongside calcination temperatures as shown in Fig. 6(c–d). EDX spectrum analysis EDX has been used to investigate the atomic composition of the product prepared using calcination technique. Fig. 7 exhibits the EDX spectrum and the compounds which still in the product after calcination. The matching peaks of Mn, Zn, Fe and O have been detected in the sputtered product and thus approve the Mn0.5Zn0.5Fe2O4 nanoparticles formation. The presence peaks of Au have been detected in the sample because of the sputtering procedure that used during the preparation of sample for EDX test. The EDX results determines the Mn0.5Zn0.5Fe2O4 nanoparticles formation with spinel phase and also highlights on the point that the heat treatment technique implemented in the present research is very active, because no loss any elements during the process. Conclusion The product of Mn0.5Zn0.5Fe2O4 nanoparticles has been successfully prepared using calcination technique. Characteristics of the product nanoparticles have been tested using XRD and TEM analyses which revealed that the crystal sizes and particle size have been increased alongside calcination to be found 12 nm at 500 °C and 17 nm at 650 °C. EDX analysis revealed the peaks of Mn, Zn, Fe and O have been detected with the atomic composition and confirmed that the prepared product has high purity. This confirms that the nanoparticle has formed and also proves that this technique which used in this study is very successful and able to produce product with high purity. References [1] Pardavi-Horvath M. Microwave applications of soft ferrites. J Magn Magn Mater 2000;215:171–83. [2] Huang A, He H, Feng Z, Wang S. Study on electromagnetic properties of MnZn ferrites with Fe-poor composition. Mater Chem Phys 2007;105:303–7. [3] Yoo D, Lee J-H, Shin T-H, Cheon J. Theranostic magnetic nanoparticles. Acc Chem Res 2011;44:863–74. [4] Nalbandian L, Delimitis A, Zaspalis VT, Deliyanni EA, Bakoyannakis DN, Peleka EN. Hydrothermally prepared nanocrystalline Mn–Zn ferrites: synthesis and characterization. Microporous Mesoporous Mater 2008;114:465–73. [5] Szczygieł I, Winiarska K. Synthesis and characterization of manganese–zinc ferrite obtained by thermal decomposition from organic precursors. J Therm Anal Calorim 2014;115:471–7. [6] Makovec D, Kodre A, Arčon I, Drofenik M. Structure of manganese zinc ferrite spinel nanoparticles prepared with co-precipitation in reversed microemulsions. J Nanopart Res 2009;11:1145–58. [7] Komarneni S, D'Arrigo MC, Leonelli C, Pellacani GC, Katsuki H. Microwave-hydrothermal synthesis of nanophase ferrites. J Am Ceram Soc 1998;81:3041–3. [8] Azadmanjiri J. Preparation of Mn–Zn ferrite nanoparticles from chemical sol–gel combustion method and the magnetic properties after sintering. J Non-Cryst Solids 2007;353:4170–3.
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