Available online at https://ijcpe.edu.iq and www.iasj.net Iraqi Journal of Chemical and Petroleum Engineering Vol.19 No.2 (June 2018) 27 – 31 ISSN: 1997-4884 Corresponding Authors: Najwa Saber Majeed, Email: dr.najwa_saber@yahoo.com, Duaa Mahammed Naji, Email: duaa_mohammed92@yahoo.com IJCPE is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License Synthesis and Characterization of Iron Oxide Nanoparticles by Open Vessel Ageing Process Najwa Saber Majeed and Duaa Mahammed Naji Chemical Engineering Department, College of Engineering, University of Baghdad Abstract Nano-crystalline iron oxide nanoparticles (magnetite) was synthesized by open vessel ageing process. The iron chloride solution was prepared by mixing deionized water and iron chloride tetrahydrate. The product was characterized by X-Ray, Surface area and pore volume by Brunauer-Emmet-Teller, Atomic Force Microscope (AFM) and Fourier Transform Infrared Spectroscopy(FTIR) . The results showed that the XRD in compatibility of the prepared iron oxide (magnetite) with the general structure of standard iron oxide, and in Fourier Transform Infrared Spectroscopy, it is strong crests in 586 bands, because of the expansion vibration manner related to the metal oxygen absorption band (Fe–O bonds in the crystals of iron oxide). The results show that the prepared nano iron oxide is with average crystal size 75.92 nm, surface area was 85.97 m 2 /g and the pore volume was found equal to 0.1566 cm 3 /g. Keywords: Nanomaterial; Magnetite; Iron oxide; (characterization; Iron (II) chloride) tetrahydrate. Accepted on 12/3/2018 1- Introduction Nano-technology has been considered as one of the most important recent advancements in science and technology. Nano-particles are one of the important building blocks in the fabrication and development of nano-materials ‎[1]. As a consequence, the nanoparticle has drawn a huge interest from researchers globally due to specific characteristics such as shape, size, and distribution, which could be utilized in a distinct field of applications. Nanoparticles iron oxide has an essential role in many chemical, physical and materials science ‎[2]. Among nanoparticles, iron magnetic nanoparticles have gained more interest due to their abundance, rapid reaction, superparamagnetic , high competence , non- toxic, enhanced stability and efficiency in chemical and physical adsorption of organic and inorganic pollutants including heavy metals from polluted waters ‎[3]. These unique properties allow Fe3O4-NPs to be widely used in different areas of applications, such as catalysis ‎[4], magnetic storage media ‎[5], environmental treatment ‎[6], magnetic resonance imaging (MRI)‎[7] , and targeted drug delivery ‎[8]. Magnetic properties of nanoparticles magnetic can be fitted by their size distributions and particle sizes. The particle sizes and size distributions of nanoparticles magnetic are successively, affected by the synthesis path. For these points, different synthesis methods have been advanced to make iron oxide nanoparticles in order to obtain desired properties ‎[9],which have been reported in other papers, gas-phase deposition and mechanical techniques (Physical methods ) ‎[10] ,green synthesis (biological method) ‎[11], co-precipitation method ‎[12], microwave assisted synthesis ‎[13], (chemical methods). The chemical method is the most common for preparing Fe3O4 nanoparticles. Chemical preparation methods, relatively less energy were consumed compared with that of physical methods. The size and morphology of the nanoparticles can be controlled by selectively choosing the reaction media, the physical parameters of the reaction, such as precursors, reactant concentration, base (NaOH and ammonium hydroxide), temperature, pH . Biological method represents an advantageous manufacturing technology with respect to high yield, good, as well as low costs and low energy input, but the fermentation process is rather time-consuming ‎[14]. In other work presents the synthesis of multi shapes of Fe3O4 nanoparticles like spherical , plate, and nano flowers by chemical method by solve thermal method assisted by microwave radiation, by using FeSO4⋅(NH4)2SO4⋅6H2O as iron precursor, , ethanol and NaOH ‎[15]. This work presents the synthesis and characterization of Fe3O4 nanoparticles from raw materials, cheap and available by iron (II) chloride tetrahydrate and sodium hydroxide by open vessel ageing process. 2- Experimental Work 2.1. Materials Every component used for the preparation of Fe3O4 were analytical grade and used without further purification. Iron (II) chloride tetrahydrate(98%), sodium hydroxide [NaOH](98%) were purchased from Sigma, Germany. N. S. Majeed and D. M. Naji / Iraqi Journal of Chemical and Petroleum Engineering91,2 (2018) 27-31 82 2.2. The Procedure of Fe3O4 Synthesis The preparation process of Fe3O4 including the following steps: a. 1L of a 30 mM solution of FeCl2 was prepared from deionized water and FeCl2.4H2O. b. The solution was then titrated with sodium hydroxide solution at a rate about 1mL/min. The solution kept on constant mixing to attain a well-mixed blend. c. Then the Fe(OH)x was put in the Teflon container and heated in a programmable electrical furnace with maximum temperature. d. The particles were heated at constant temperature of 100ºC for 60 min and consequently cooled to room temperature. e. The product obtained was filtered using Buckner funnel with the aid of a vacuum pump and washed twice with deionized water and then dried in an electrical oven for 24 hours at 100 °C. FeCl2+2NaOH Fe(OH)2+2NaCl 3Fe(OH)2 Fe3O4+2H2O+H2 Fig. 1 shows schematic diagram of preparation procedure of magnetite. On the other hand Fig. 1. The schematic diagram of preparation method Fig. 2. Photographs of a solution in the absence and presence of a magnet Fig. 2 the magnetic response of Fe3O4 MNPs was test by placing a magnet near the glass bottle. The particles were attracted toward the magnet; so, the Fe3O4 MNPs can be separated under an external magnetic field. 2.3. Characterization Many characterization techniques were used to measure specification and properties of nanoFe3o4. XRD analyses were carried out at room temperature using a Shimadzu 6000 (Japan) using CuKα radiation Nickel filter (λ= 1.5418A). ata ere o e ted ithin the 2 range of 2 and 50 ith a 2θ step size of 0.02 and a step time of 0.24s per step (40kv and 30mA). The surface area of prepared catalyst was measured by nitrogen adsorption at liquid nitrogen temperature at -196 C using the BET method, Pore volume is a measure the void space in the catalyst. The chemical composition of the prepared Fe3O4 was analyzed using XRF technique. Conducted the test for a device of the type SPECTRO XEROS, Germany by weight of sample is 3g in powder state, put in plastic cup 30mm diameter. Test conducted in inert atmosphere (Helium). Atomic Force Microscope (AFM) is a powerful technique for surface investigation by providing material topology in high resolution. The test was performed by Device (type Angstrom, Scanning Probe Microscope, Advanced Inc, AA 3000, USA), performed for samples by ethanol dispersion to conducted the surface morphology and the particles size. And FT-IR spectroscopy analysis of Fe3O4 was carried out to study the features their structural by the chemical bonds (functional group) between molecules. This test was determined using a Shimadzu FTIR 8400S (Japan) with wave number range (400-4000 cm -1 ). 3- Results and Discussion 3.1. X-Ray Diffraction (XRD) X-ray diffraction was implemented to check the required pattern of Fe3O4 and its crystalline. From Fig. 3 X-ray diffraction pattern of the prepared nanoFe3O4 is approximately comparable with the standard and Table1 comparison of lattice spacing and angle, between prepared nanoFe3O4 and standard. Fig. 3. XRD pattern of prepared nano Fe3O4 N. S. Majeed and D. M. Naji / Iraqi Journal of Chemical and Petroleum Engineering91,2 (2018) 27-31 82 Table 1. Comparison of lattice spacing and angle, between prepared Fe3O4 and standard Prepared catalyst Standard of catalyst Angle(2Theta)deg d, spacing(Å) Angle(2Theta)deg d, spacing(Å) 30.22 2.954 30.094 2.967 35.601 2.519 35.422 2.532 43.246 2.09 43.051 2.099 53.59 1.708 53.390 1.714 57.225 1.608 56.942 1.615 62.873 1.476 62.514 1.484 71.310 1.321 70.923 1.327 3.2. Surface Area and Pore Volume The surface area of magnetite range from 4-100m 2 /g .The obtained value of surface area of prepared nanomagnetite =85.97m 2 /g, this value is in agreement with standard ‎[16]. The pore volume for nanomagnetite (Fe3O4) was found equal to 0.1566cm 3 /g. 3.3. Atomic Force Microscope (AFM) The surface uniformity of the prepared nanoFe3O4 was studied using Atomic Force Microscope with 408 pixel density. Fig. 4 shows AFM on two-dimensional surface profile while Fig. 5 shows AFM for two dimensional surface profiles. The two dimensional image showed hexagonal structure and three dimensional image of the Fe3O4 crystal obtained by AFM indicated hexagonal layers. The particle size distribution for prepared nano Fe3O4 was obtained as shown in Fig. 6 From Fig. 6 show that the most volume percentage 12.98% of particle size distribution was at 90 nm and the lowest volume percentage 0.38 % was at 35nm and also show the prepared nano Fe3O4 consisted of particles with diameters ranged between 35 - 100 nm this means that the particles of prepared nanoFe3O4 are nanometer-sizes and the average particles diameter of nanoFe3O4was 75.92nm. Fig. 4. AFM two-dimensional surface profiles for Fe3O4 Fig. 5. AFM three-dimensional surface profiles for Fe3O4 Fig. 6. Granularity cumulation distribution for prepared Fe3O4 3.4. X- Ray Florescence (XRF) The chemical composition of the prepared Fe3O4 was analyzed using XRF technique. Table 2 represents the chemical composition of the prepared nano Fe3O4 expressing in weight percent. Fe and O elemental composition 69% and 28.24% respectively this value is not far from the value 71.58% for Fe and 28.4% for O. Table 2. The chemical composition for the prepared Fe3O4 Oxides, wt. % Fe2O3 P2O5 CaO TiO2 MgO Fe3O4 77.8 0.5 0.25 0.45 0.37 N. S. Majeed and D. M. Naji / Iraqi Journal of Chemical and Petroleum Engineering91,2 (2018) 27-31 03 3.5. Fourier Transform Infrared Spectroscopy (FTIR) Fig. 7 illustrates the FTIR spectra of prepared nano Fe3O4. From this figure it can be observed that, the bands 586 is assigned to characteristic Fe–O vibrations of Fe3O4.The band O–H vibrations occur from 3160 to 3430 cm -1 . Slight differences occur in the peaks at 3414 cm -1 representing–OH functions .The band at 1616 cm -1 is due to bending modes of the water molecules adsorbed on magnetite surfaces ‎[17]. Fig. 7. FTIR of synthesized nano Fe3O4 4- Conclusion According to the results obtained from this study, nanomagnetite can be synthesized successfully by using iron (II) chloride tetrahydrate and Sodium Hydroxide by open vessel ageing process. The X-Ray diffraction patterns of synthesized nanomagnetite show very good agreements with standard magnetite. The value of surface area of prepared nanomagnetite was 85.97m 2 /g and the pore volume was find equal to 0.1566 cm3/g. 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