Shape and Size-Dependent Magnetic Properties of Fe3O4 Nanoparticles Synthesized Using Piperidine
© The Author(s). 2017
Received: 15 February 2017
Accepted: 29 March 2017
Published: 26 April 2017
In this article, we proposed a facile one-step synthesis of Fe3O4 nanoparticles of different shapes and sizes by co-precipitation of FeCl2 with piperidine. A careful investigation of TEM micrographs shows that the shape and size of nanoparticles can be tuned by varying the molarity of piperidine. XRD patterns match the standard phase of the spinal structure of Fe3O4 which confirms the formation of Fe3O4 nanoparticles. Transmission electron microscopy reveals that molar concentration of FeCl2 solution plays a significant role in determining the shape and size of Fe3O4 nanoparticles. Changes in the shape and sizes of Fe3O4 nanoparticles which are influenced by the molar concentration of FeCl2 can easily be explained with the help of surface free energy minimization principle. Further, to study the magnetic behavior of synthesized Fe3O4 nanoparticles, magnetization vs. magnetic field (M-H) and magnetization vs. temperature (M-T) measurements were carried out by using Physical Property Measurement System (PPMS). These results show systematic changes in various magnetic parameters like remanent magnetization (Mr), saturation magnetization (Ms), coercivity (Hc), and blocking temperature (T B) with shapes and sizes of Fe3O4. These variations of magnetic properties of different shaped Fe3O4 nanoparticles can be explained with surface effect and finite size effect.
Nano-sized materials on account of their surface and quantum size effect not only are known to possess better physical and chemical properties but also have enhanced biocompatibility and bioefficacy [1, 2]. In this context, magnetic nanoparticles for their unique magnetic behavior have gained much attention in recent years, whereby they are known to have promising potential for various medical applications such as targeted drug delivery systems, MRI, diagnostics, radiofrequency hyperthermia, and cancer therapy [3–7]. Besides, magnetic nanoparticles are also being utilized as a key material for magnetic ferrofluid , catalysis , data storage , and environmental remediation . Fe3O4, a magnetic nanoparticle, has the cubic inverse spinal structure (two Fe3+ with one Fe2+) in which oxygen forms an fcc closed-pack structure . It is an important class of half-metallic materials, as electrons hop between Fe2+ and Fe3+. However, their utilization for practical application still requires rectification of several parameters, broadly categorized into two main class: (a) their tendency to get aggregate in order to reduce their surface energy and (b) their ability to get oxidize easily. The aforementioned parameters can hamper their interfacial area, thereby hindering their magnetism and dispersibility. Henceforth, it becomes essentially important to overcome such parameters which possibly can be achieved by developing potential synthesis methods which overrule such problems. With the advent of several wet chemical methods for the synthesis of nanoparticles in the recent past, the magnetic nanoparticles have been synthesized by different methods such as solvothermal , sol-gel , co-precipitation , thermal decomposition , and sonochemical reaction . Here in this work, we have designed a new and facile one-step synthesis of Fe3O4 nanoparticles by using a new chemical piperidine (C5H11N) by hydrolysis method. Amongst several chemicals such as ether (CH3OCH3) and formaldehyde (HCHO), piperidine was found most effective for the synthesis of Fe3O4 nanoparticles.
Chemicals: FeCl2·4H2O (anhydrous) was procured from Sigma-Aldrich, while piperidine (C6H5N) was procured from Merck. All chemicals were used as received. Double-distilled water was used in reaction as a medium.
Preparation of Fe3O4 Nanoparticles
Synthesis of Fe3O4 nanoparticles was made in four different sets (by varying the molarity of FeCl2 solution) to study the influence of the reaction parameters on the size and shape of Fe3O4 nanoparticles. A solution of piperidine (50 ml, 0.25 M) was prepared by mixing 1.24 ml piperidine (C5H11N) homogeneously into 50 ml double-distilled water. This was used as stock solution throughout the experiments. The solutions of FeCl2 (10 ml) with varying molarity (0.025, 0.05, 0.075, and 0.1 M) was prepared by dissolving 0.0497, 0.0994, 0.1491, and 0.1988 g FeCl2 in double-distilled water, respectively. These samples were designated as S1, S2, S3, and S4, respectively. Now, 5 ml of prepared piperidine solution was mixed with FeCl2 solution of different molarities as in above, under stirring. An instant change in color indicated the formation of Fe3O4 nanoparticles. The reaction mixture was then centrifuged at 10,000 rpm for 10 min. Particles were collected and resuspended in 5 ml double-distilled water for further characterizations.
The XRD analyses of resulting samples were carried out with an X-Pert Pro X-ray diffractometer (PAN analyst BV the Netherlands with a build in graphite monochromator meter) with Cu Kα radiation (λ = 1.54056 A°). Sample preparation for XRD was done by placing one drop of the reaction mixture on a circular disk (5 mm diameter) and allowing it to dry. Transmission electron microscopic (TEM) studies were done by employing TECHNI 20 G2 microscope at an accelerating voltage 200 KeV. Samples for TEM were prepared by suspending powder in double-distilled water and ultrasonicated it for 1 h. The suspension obtained was placed on a formvar-coated Cu grid. Magnetic measurements were performed on 14 T Physical Properties Measurement System, Cryogenics Limited, USA.
The XRD pattern can be matched to the series of Bragg reflections corresponding to the standard phase of the spinal structure of Fe3O4 with a lattice constant of a = 8.41A° (ICSD82-1533). Six peaks at 30.16°, 35.49°, 43.01°, 53.78°, 57.21°, and 62.73° can be indexed as (220), (311), (400), (422), (511), and (440) of the cubic structure (Fd3m space group) of Fe3O4 nanoparticles.
Magnetic Properties of Nano-sized Fe3O4
Some useful parameters of M-T and M-H measurements
Mr (emu/g) at 300 K
Ms (emu/g) at 300 K
Hc (Oe) at 300 K
Mr (emu/g) at 5 K
Ms (emu/g) at 5 K
Hc (Oe) at 5 K
T B (K)
Mechanism of Formation of Fe3O4 Nanoparticles
Fe3O4 nanoparticles are indeed synthesized using piperidine, which is confirmed by XRD characterization of as-synthesized samples.
TEM images give some useful information related to the shape and sizes of the particles. Our investigation shows that shape and size of the particles can be changed from rods to spheres by varying the molar concentration of FeCl2 solutions (from 0.025 to 0.1 M).
Measurement of magnetic properties found after deep analysis shows that these magnetic parameters like Ms, Mr, Hc, and T B have shown improved values than reported earlier.
These synthesized Fe3O4 nanoparticles of different shapes and sizes will further be used for their applications like EMI shielding. Some primitive experiments are going on and very soon will be followed by respective publications.
Authors are thankful to AIRF for the various measurements. AKS is especially thankful to UGC for the DSK PDF and UPE-II which have provided the financial support for the research. Further support from DST-FIST is gratefully acknowledged.
This study was funded by UPE-II/(172) and UGC/(BSR/14-15/0078).
AKS performed the experiments and characterizations. KS has done the magnetic measurements and its explanetion. ONS has drafted the paper. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
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