Elsevier

Applied Surface Science

Volume 289, 15 January 2014, Pages 462-471
Applied Surface Science

Optical and magnetic properties of Fe2O3 nanoparticles synthesized by laser ablation/fragmentation technique in different liquid media

https://doi.org/10.1016/j.apsusc.2013.11.009Get rights and content

Highlights

  • Optical band gap of bulk iron oxide powder has been tailored using pulse laser ablation.

  • Crystalline size dependent optical and magnetic properties have been studied.

  • In the present study it is shown that strain depends on crystalline size and different phases of iron oxide NPs.

Abstract

Iron oxide (Fe2O3) bulk powder have been ablated/fragmented in different liquid medium by Nd:YAG laser beam using 1064 nm wavelength. Sodium dodecyl sulfate (SDS), cetyltrimethyl ammonium bromide (CTAB) and double distilled water (DDW) are used as liquid medium. Crystalline size, lattice strain, phase and structure of ablated particles have been investigated using synchrotron X-ray diffraction. Optical band gap energy of as purchased Fe2O3 found 1.92 eV that increased to 2.03 eV after ablation in CTAB determined by UV–vis absorption spectroscopy. Magnetic properties have been analyzed by hysteresis loops using vibrating sample magnetometer (VSM). Crystalline sizes have been found in the range of 29.23–16.54 nm and coercivity tailored in the range of 206.91–298.36 Oe using laser ablation. Saturation magnetization and remanence have been found in the range of 0.013–3.41 emu/g and 0.0023–.0.51 emu/g respectively. Particle shape and size have been examined by scanning electron microscopy (SEM). CTAB (cationic) and SDS (anionic) surfactants are used as capping agent. CTAB produces phase transformation in ablated iron oxide (Fe2O3). Crystallinity and crystalline size of ablated particles in DDW increased due to presence of rich oxygen in it due to oxidation. Ablated Fe2O3 nanoparticles have been widely used experimentally for numerous in vivo applications such as MRI contrast enhancement agent, tissue repair, immunoassay, detoxification of biological fluids, hyperthermia, drug delivery and cell separation.

Introduction

Laser induced ablation/fragmentation in liquid media is one of the powerful techniques used for synthesis of nanoparticles with special anisotropy which is otherwise difficult to produce by conventional methods [1], [2], [3]. The size and shape of the nanoparticles can be controlled by changing the laser wavelength [4], [5] laser fluence [6], [7] liquid environment [8], [9] and surfactants [10], [11], [12]. Iron can form several oxides of different stoichiometry and crystalline structure depending upon synthesis technique. These oxides are wustite (FeO), magnetite (γ-Fe3O4), hematite (α-Fe2O3), and magnetite (γ-Fe2O3). Hematite is thermodynamically most stable phase of Fe2O3, and is the subject of this work. Hematite (α-Fe2O3) has been considered as promising material since α-Fe2O3 is inexpensive, abundant, nontoxic, and stable in most alkaline electrolytes [13], [14], [15]. In order to prepare homogenous nano-particles of iron oxide, researchers have employed in different routes to facilitate single-phase iron oxide nano-particles such as sol–gel processes [16], microemulsion [17], combustion [18], solvothermal [19], hydrothermal [20] and precursor [21]. In the absence of any surface coating, magnetic iron oxide particles have hydrophobic surfaces with a large surface area to volume ratio. Due to hydrophobic interactions between the particles, these particles agglomerate and form large clusters, resulting in increased particle size. These clusters exhibit strong magnetic dipole–dipole attractions between them and show ferromagnetic behavior. When two large-particle clusters approach one another, each of them comes into the magnetic field of the neighbor. Besides the arousal of attractive forces between the particles, each particle is in the magnetic field of the neighbor and gets further magnetized. To avoid further agglomeration cationic and anionic surfactants are subject of present study used.

In the present communication we have studied optical as well as magnetic properties of as purchased iron oxide (Fe2O3) bulk powder and ablated NPs in different liquid medium using pulse laser ablation/fragmentation technique. Here it is shown that optical band gap and magnetic properties (coercivity, saturation magnetization, and remanence) and phase of as purchased iron oxide (Fe2O3) bulk powder has been tailored. Samples R2, R3, and R4 were prepared in DDW SDS, and CTAB, respectively, while R1 (Fe2O3) bulk powder purchased commercially. Liquid phase pulse laser ablation (LP-PLA) which involves the firing of laser pulses on the surface of solid/powder target immersed into liquid media. In laser pulses, front part of pulse creates vapors on the target surface, which are irradiated by tail part of same pulse. Zeng et al. has already reported the mechanism of laser ablation/irradiation in liquid media [22], [23]. This process causes photo ionization and the generation of dense high-temperature and high pressure laser plasma plume, which expands perpendicular to the target surface into the liquid. This expanding plume interacts with the surrounding liquid, creating cavitations bubbles, and collapse, give rise to very high temperature and pressure however; these conditions are much localized and exist in nanoscale range.

Section snippets

Experimental

The experimental setup of laser ablation/fragmentation is shown in Fig. 1. [24], [25], [26]. High purity (99.9%, Qualigens, India) powder of iron oxide (Fe2O3) (particle size 1–5 μm) was dispersed in a test tube containing 50 ml aqueous solution SDS and CTAB. The suspension was continuously stirred using magnetic stirrer. Nd:YAG laser (Spectra Physics, USA) operated at 1064 nm wavelength, 40 mJ/pulse energy, and 10 Hz repetition rate was focused to a spot size of 2 mm at the center of the glass tube

X-ray diffraction

Fig. 2(a) and (b) shows XRD pattern of samples R1 and R2 respectively. The peak positions at 2θ = 11.377°, 2θ = 15.543°, 2θ = 16.771°, 2θ = 19.042°, 2θ = 22.869°, 2θ = 24.877°, 2θ = 26.395°, 2θ = 28.434°, 2θ = 29.085°, 2θ = 32.328°, 2θ = 33.709°, 2θ = 35.749°, 2θ = 36.586°, 2θ = 37.717°, and 2θ = 38.637° correspond to the plane [0 1 2], [1 0 4], [1 1 0], [1 1 3], [0 2 4], [1 1 6], [0 1 8], [2 1 4], [3 0 0], [1 0 1 0], [2 2 0], [1 2 8], [0 2 1 0], [1 3 4], and [2 2 6] respectively with, Rhomb-centered, hexagonal lattice parameters, a = 5.035 = b, c = 13.74, α = β = γ

Conclusion

In present work optical band gap of as commercially purchased Fe2O3 powder is ablated by laser ablation technique in different liquid media. Williamson–Hall plot and Scherrer formula employed for effective particle size and strain calculation. It has been analyzed that double distilled water have enhanced the crystallinity and crystalline size of Fe2O3 due to oxidation in the presence of oxygen in it. While surfactant supports to reduce crystalline size due to its capping effect. Mix phases of

Acknowledgement

Authors are thankful to Dr. A.K. Sinha, RRCAT Indore for providing Synchrotron radiation source for X-ray diffraction and UGC for D. Phil. Fellowship.

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