Onion-like carbon-encapsulated Co,Ni, and Fe magnetic nanoparticles with low cytotoxicity synthesized by a pulsed plasma in a liquid

We synthesized onion-like carbon-encapsulated Co, Ni, and Fe (Co–C, Ni–C, and Fe–C) magnetic nanoparticles with low cytotoxicity using pulsed plasma in a liquid. The pulsed plasma is induced by a low-voltage spark discharge submerged in a dielectric liquid. The face-centered cubic Co and Ni, and body-centered cubic Fe core nanoparticles showed good crystalline structures with an average size between 20 and 30 nm were encapsulated in onion-like carbon coatings with a thickness of 2–10 nm. Vibrating-sample magnetometer measurements revealed the ferromagnetic properties of as-synthesized samples at room temperature (Co–C = 360 Oe, Fe–C = 380 Oe, and Ni–C = 211 Oe). Raman-spectroscopy analysis found onion-like carbon shells composed of well-organized graphitic structures. Thermal gravimetric analysis showed a high stability of the as-synthesized samples under thermal treatment and oxidation. Cytotoxicity measurements showed higher cancer cell viability than samples synthesized by different methods.     

One-step chemical vapor deposition synthesis of magnetic CNT–hercynite (FeAl2O4) hybrids with good aqueous colloidal stability

A multiwall carbon nanotube (MWCNT)/hercynite (FeAl₂O₄) hybrid nanomaterial was synthesized by one-step chemical vapor deposition (CVD) using acetylene as precursor and FeO_x–AlOOH xerogel as catalyst. The hybrid material was composing by hercynite nanoparticles (diameter 10–50 nm) intimately attached to the walls of the MWCNTs. The diameter of the MWCNTs was related to particle size of the catalyst. The hybrid nanomaterial exhibited a characteristic magnetic behavior that can be considered as a combination of superparamagnetism and ferromagnetism, with a saturation magnetization of 5.7 emu/g at an applied field of 18 kOe and a coercivity of 520 Oe. The hybrid displayed a relatively low pH_ZPC (approx. 3.2) and formed very stable aqueous suspensions at pH 5.5. Controlled oxidation of the hybrid generated oxidized functional groups, as –OH and –COOH, and promoted the transformation of hercynite to hematite. Due to the high dispersibility of the hybrid in water, it presents an interesting potential as nanofiller for hydrophilic polymers.     

Hydrothermal synthesis,magnetic properties and characterization of CoFe2O4 nanocrystals

Magnetic cobalt ferrite (CoFe₂O₄) nanocrystals were synthesized via the hydrothermal method and the crystallite size was measured using Sherrer's equation. Instrumental broadening was a significant parameter for determining crystallite size. The effect of annealing time and calcination on crystallite size and magnetic properties was discussed. It was found that the coercivity was highly dependent on the crystallite size. As the crystallite size increased from 61 to 68.2 nm, room temperature coercivity increased from 1488 Oe to 1700 Oe, while high coercivity (5.2 kOe) was achieved at lower temperature (80 K). It was found that the presence of hematite could affect the crystallite size after calcination.     

MnFe2O4 bulk,nanoparticles and film: A comparative study of structural and magnetic properties

MnFe₂O₄ bulk sample was synthesized by conventional solid state reaction method, at 1350 °C. Nanoparticles with mean size of 〈D〉_TEM=10.4(±1.1) nm were prepared by thermal decomposition of metal nitrates, at 350 °C. And a film sample was prepared by pulsed laser deposition of bulk ferrite on MgO(100) at substrate temperature of 600 °C. Then a comparative study of the structural and magnetic properties of the samples has been carried out using different measurements. X-ray diffraction pattern of bulk and nanoparticles samples confirmed formation of spinel phase. The film sample showed an epitaxial growth on MgO in (400) direction. Saturation magnetization of nanoparticles at 300 K, M_S=33 emu/g, was comparable with film sample, M_S=38 emu/g, both being ∼2.5 times smaller than that of bulk sample (M_S=82 emu/g). The results showed the importance of surface effects in the film sample and nanoparticles. The obtained zero coercivity of bulk sample at 300 K and the low value of 8 Oe at 5 K is attributed to soft magnetic behavior of the MnFe₂O₄. On the other hand, nanoparticles showed superparamagnetic behavior at 300 K; and blocked state with a large coercivity of 730 Oe at 5 K. The film sample showed non-zero corecivity at both 5 and 300 K which reveals higher magnetic anisotropy of film compared to the bulk ferrite.     

Novel method for synthesis of Fe core and C shell magnetic nanoparticles

Using a newly developed method, carbon-encapsulated iron (Fe) nanoparticles were synthesized by plasma due to ultrasonication in toluene. Fe core with carbon shell nanoparticles were characterized using Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM). Fe nanoparticles of diameter 7–115 nm are encapsulated by 7–8 nm thick carbon layers. There was no iron carbide formation observed between the Fe core and the carbon shell. The Fe nanoparticles have body centered cubic (bcc) crystal structure. Synthesized nanoparticles showed a saturation magnetization of 9 A m²/kg at room temperature. After thermal treatment crystalline order of the nanoparticles improved and saturation magnetization increased to 24 A m²/kg. We foresee that the carbon-encapsulated Fe nanoparticles are biologically friendly and could have potential applications in Magnetic Resonance Imaging (MRI) and photothermal cancer therapy.     

Formation of bamboo-like conducting carbon nanotubes decorated with Au nanoparticles by the thermal decomposition of sucrose in an AAO template

An easy method is reported for the preparation of bamboo-like conducting carbon nanotubes decorated with Au nanoparticles (Au-CNT), by carbonization of sucrose inside of anodic aluminum oxide (AAO) nanochannels (～80 nm and ～30 μm in diameter and length, respectively). First, the AAO membrane nanochannels were coated with Au nanoparticles (～10 nm in diameter) and the carbon nanotubes were then formed in the same channels below 973 K. Electron microscopy shows long bamboo-like carbon nanotubes, ～30 μm in length, decorated with crystalline gold nanoparticles, ～50 nm in diameter. The coalescence of the precoated small Au nanoparticles inside the channel results in the attached large Au nanoparticles. The apparent resistivity of the Au-CNT prepared at 973 K, was ～16.8 Ω cm. The electrical conductivity of the structure is discussed with relation to electrochemical and micro Raman experiments.     

The effect of ceramic nanoparticles on tribological properties of alumina sol–gel thin coatings

Thin alumina coatings containing zirconia or alumina nanoparticles having diameter of ～20–30 nm were deposited by the sol–gel dip-coating process on silicon wafers. The mass content of nanoparticles in the alumina coating was fixed at 15% in relation to the theoretical mass of alumina matrix resulted from the amount of the applied precursor. Atomic force microscopy (AFM) was used to image the surface topography of as-made coatings and find out the wear level after frictional tests. Tribological tests were performed with the use of a microtribometer operating in the load range of 30–100 mN. It was found that the presence of α-alumina (corundum) or zirconia nanoparticles enhances the tribological performance of alumina layers annealed at 100 °C by decreasing the average wear rate by 20% and 63% for zirconia and corundum nanoparticles, respectively. No wear was observed for samples containing both types of nanoparticles annealed at 500 °C.     

Halloysite nanotubes coated with magnetic nanoparticles

Co nanoparticles were assembled on the surface of halloysite nanotubes (HNTs) to prepare one-dimensional magnetic Co-HNTs via electroless deposition. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDXS) and vibrating sample magnetometer (VSM). The cobalt nanoparticles of 3–7 nm in size were uniformly deposited on the surface of the nanotubes. The remanent magnetization (M_r), saturation magnetization (M_s) and coercivity (H_c) values of the Co-HNTs were 13.9 emu/g, 27.05 emu/g and 1659 O_e, respectively, larger than that of the pure Co nanoparticles (580.72 O_e). A mechanism of the deposition of the magnetic nanoparticles on the surface of the halloysite nanotubes is suggested. Co-HNTs showed an interesting potential in the field of magnetic devices.     

Sonochemical synthesis of CoFe2O4 nanoparticles and their application in magnetic polystyrene nanocomposites

CoFe₂O₄ (CoFe) nanoparticles were synthesized via a facile surfactant-free sonochemical reaction. For preparation of magnetic polymeric films, CoFe₂O₄ nanoparticles were added to polystyrene (PS). Nanoparticles were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Magnetic properties of the samples were investigated using an alternating gradient force magnetometer (AGFM). CoFe₂O₄ nanoparticles exhibit a ferromagnetic behaviour with a saturation magnetization of 62 emu/g and a coercivity of 640 Oe at room temperature. By preparing magnetic films the coercivity is increased. The coercivity of PS/CoFe₂O₄ (10%) nanocomposites is higher than that obtained for PS/CoFe₂O₄ (30%).     

Plasma-assisted synthesis of carbon encapsulated magnetic nanoparticles with controlled sizes correlated to smooth variation of magnetic properties

This paper reports rapid, continuous and carbon-nanotube free synthesis of carbon encapsulated magnetic nanoparticles by thermal-plasma expansion technique, which combines the typical advantages of high-temperature plasma assisted synthesis method with efficient particle-size control. Core nanocrystals were encapsulated with few layers of graphitized carbon, which could provide protection against both oxidation and intense chemical treatment. The average iron/iron-carbide nanoparticle diameter (7.7, 9 and 10 nm) and the width of the size distribution increased with pressure in the sample collection chamber, as a result of the decreasing quenching rate of the plasma jet. This also resulted in the smaller particles remaining frozen predominantly in the high-temperature γ-Fe phases, part of which was oxidized subsequently and eliminated preferentially during the purification process. All samples could be correlated with smooth variation of magnetic properties; saturation magnetization, remnant magnetization and coercive-field enhancing with increasing chamber pressure or average particle size. The low pressure synthesized sample with smallest average particle size approached super-paramagnetic behavior (saturation magnetization = 51.8 emu/g, ratio of remnant to saturation magnetization = 4.9 and coercive field = 52 Oe), which may be ideal for biomedical applications. High-pressure samples on the other hand have a higher saturation magnetization (76.3 emu/g) and coercive fields (123 Oe).     

Diameter dependence of interwall separation and strain in multiwalled carbon nanotubes probed by X-ray diffraction and Raman scattering studies

We have made a systematic study on the diameter dependent spectral features in X-ray diffraction (XRD) and Raman scattering studies of multiwalled carbon nanotubes (MWCNTs) of various diameters in the range 5?100 nm. High resolution transmission electron microscopy (HRTEM) imaging reveals a systematic decrease in the interwall separation from 3.8 Å down to 3.2 Å as the diameter of nanotubes increases from 5.8 nm to 63.2 nm. Analysis of the XRD patterns shows an exponential decrease in d₀₀₂ interlayer spacing with increasing tube diameter, in close agreement with the HRTEM results. Further, XRD profile line width shows inverse diameter dependence and exponential increase in intensity as the diameter of the MWCNTs increases. Raman spectra of different diameter nanotubes show different evolutions of metallic and semiconducting components in the G-band, as found from spectral deconvolution. The frequency and full width at half maximum (FWHM) of the semiconducting component of the G^? band gradually decreases as the tube diameter increases. Ratio of intensities of G^? band to D-band first shows a sharp fall as the tube diameter increases from 7 nm to 15 nm and then slowly increases with increasing diameter. On the other hand, G′ mode frequency shows large up shift when average diameter is increased from 7 nm to 15 nm and then saturates for higher diameter tubes. Analysis of Raman and XRD data reveals that the lowest diameter (7 nm) MWCNTs have features similar to those of the single walled nanotubes, while the spectral features are distinctly different for higher diameter MWCNTs due to the interaction among tube walls that is very significant for large diameter MWCNTs. Observed diameter dependence of the spectral features is explained in terms of nanotube curvature and atomic vibrations involving interaction among the walls in MWCNTs. The present study demonstrates the power of XRD for nondestructive evaluation of diameter distribution and interwall separation in MWCNTs with wide range of diameters.     

Upscaling potential of the CVD stacking growth method to produce dimensionally-controlled and catalyst-free multi-walled carbon nanotubes

Multi-walled CNTs (MWCNTs) with structural characteristics optimised for bio-applications have been produced using a catalyst-supported chemical vapour deposition (CVD) method. The upscale potential of the process was demonstrated by combining classical semi-continuous and stacked-growth modes. The vertically aligned MWCNT films thus obtained were multi-layered with five continuous strata of well-structured nanotubes. Following gentle disentanglement, the stacks were converted to individual MWCNTs with short dimensions (a final length and diameter of ～1.2 μm and ～12 nm) and almost catalyst-free (<0.04%). Overall, our process produces dispersed, bio-tailored MWCNTs with an output growth-yield 20 times higher than a standard CVD setup and exempt of complex or destructive post-growth steps of purification and separation. These constitute key steps towards the mass production of MWCNTs with low toxicological risks, an essential prerequisite for biomedical applications.     

A sonochemical method for synthesis of Fe3O4 nanoparticles and thermal stable PVA-based magnetic nanocomposite

Fe₃O₄ nanoparticles were synthesized via a simple surfactant-free sonochemical reaction. Room temperature synthesis without using inert atmosphere is the novelty of this work. The effect of different parameters on the morphology of the products was investigated. The magnetic properties of the samples were also investigated using an alternating gradient force magnetometer. Fe₃O₄ nanoparticles exhibit a ferromagnetic behavior with a saturation magnetization of 66 emu/g and a coercivity of 39 Oe at room temperature. For preparation magnetic nanocomposite, Fe₃O₄ nanoparticles were added to the polyvinyl alcohol (PVA). Nanoparticles can enhance the thermal stability and flame retardant property of the PVA matrix.     

PZT-cobalt ferrite particulate composites: Densification and lead loss controlled by quite-fast sintering

During densification at 1100–1200 °C of particulate lead zirconate titanate (PZT)/cobalt ferrite (CF, 26–81  mol%) composites, side reactions do occur that are detrimental to the properties of the so-obtained material. Such reactions are promoted by initial PbO loss, the extent of which can be determined by means of XRD analysis of the densified samples taking into account the amount of ZrO₂ and the variations of the perovskite’s tetragonality. In this process, titania is produced which reacts with CF to form cobalt titanate. Microstructural characterization showed that CF grain size distribution can be mono- or bi-modal, and CF overgrowth was found to affect the coercivity of the material. In the case of the PZT:CF 74:26 composites, full densification and prevention of unwanted side reactions were achieved by designing a quite-fast sintering process. The high coercivity (789 Oe) displayed by these composites is related to the good dispersion of 250 nm euhedral CF grains in the PZT matrix and limited PZT grain growth (240 nm).     

Size dependence of optical and magnetic properties of nickel oxide nanoparticles fabricated by electric arc discharge method

Nickel oxide nanoparticles with an average size of between 28 and 62 nm were fabricated by electric arc discharge method. The electric currents of 10, 100, 200, 300 and 400 A and oxygen pressures of 1, 2 and 3 atm. were tested. High yield production was observed for the samples prepared at low arc current. The samples were characterized using XRD and FESEM measurements. XRD results showed that the samples were pure and single phase of nickel oxide with cubic structure. The produced nanoparticles were cubic shaped and the average particle sizes increased by increasing the arc pressure, but decreased by increasing the arc current and their size distributions were uniform. The magnetic measurements confirmed a soft ferromagnetic behavior for the nickel oxide nanoparticles at low field region but the hysteresis loop tended to be antiferromagnetic like for the higher fields. By decreasing the particle size from 62 nm, the coercivity (H_c) increased but decreased when the particle size was less than about 57 nm. Such magnetic behavior which can be common for antiferromagnetic nanoparticles was interpreted based on a core-shell model.     

Microstructural evolution of multi-walled carbon nanotubes in the presence of mixture of silicon and silica powders at high temperatures

Microstructural evolution of multi-walled carbon nanotubes (MWCNTs) in the presence of mixture of silicon and silica powders in a coke bed is studied in the temperature range of 1000–1500 °C by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and thermogravimetry–differential scanning calorimetry (TG–DSC). The results showed that a thin amorphous SiO₂ coating was formed on the surface of MWCNTs at the temperature below 1300 °C. With the increase of the treated temperature, the coating became thicker, 3–7 nm in thickness at 1400 °C and a maximum of 10 nm at 1500 °C. Meanwhile, SiC nanowires and SiC nanocrystals around Ni catalyst at the tip of MWCNTs were formed at 1400 °C and 1500 °C, which were related to the vapor–vapor (V–V) and vapor–liquid–solid (V–L–S) reactions between SiO (g) and CO (g) or C (s), respectively. The oxidation resistance of all the treated MWCNTs was better than that of as-received ones. The oxidation peak temperature reached 804.2 °C for the treated MWCNTs, much higher than 652.2 °C for as-received ones.     

New LiNi0.5PrxFe2−xO4 nanocrystallites: Synthesis via low cost route for fabrication of smart advanced technological devices

Praseodymium substituted nano-crystalline Li-Ni spinel ferrites with different Pr³⁺ contents were synthesized by micro-emulsion method. X-ray diffraction (XRD), scanning electron spectroscopy (SEM) and vibrating sample magnetometery (VSM) techniques were employed to study the impact of substitution of the Pr³⁺ on the structure, surface morphology and magnetic parameters. XRD confirmed the formation of the single phase spinel ferrites of all compositions of LiNi_0.5Pr_xFe_2−xO₄ nanocrystallites. The crystallite size determined from XRD data by Scherrer formula was calculated in range from 40 nm to 70 nm. However the nanoparticles size estimated by SEM was found 35–115 nm. The room temperature VSM measurements were carried out in the applied field range from “−10,000 Oe” to “10000” Oe. Saturation magnetization (M_S) (41 emu/g) and coercivity (H_C) values (156.9 Oe) of LiNi_0.5Fe₂O₄ were improved by the addition of rare earth Pr³⁺ cations. The value of Hc is low, which is a strong indication of soft ferrites. The synthesized LiNi_0.5Pr_xFe_2−xO₄ ferrites may be utilized for low core losses on transformers.     

Effect of Ni2+ substitution on structural,magnetic, dielectric and optical properties of mixed spinel CoFe2O4 nanoparticles

Nanoparticles of Co_1−xNi_xFe₂O₄ with x=0.0, 0.10, 0.20, 0.30, 0.40 and 0.50 were synthesized by co-precipitation method. The structural analysis reveals the formation of single phase cubic spinel structure with a narrow size distribution between 13–17 nm. Transmission electron microscope images are in agreement with size of nanoparticles calculated from XRD. The field emission scanning electron microscope images confirmed the presence of nano-sized grains with porous morphology. The X-ray photoelectron spectroscopy analysis confirmed the presence of Fe²⁺ ions with Fe³⁺. Room temperature magnetic measurements showed the strong influence of Ni²⁺ doping on saturation magnetization and coercivity. The saturation magnetization decreases from 91 emu/gm to 44 emu/gm for x=0.0–0.50 samples. Lower magnetic moment of Ni²⁺ (2 µ_B) ions in comparison to that of Co²⁺ (3 µ_B) ions is responsible for this reduction. Similarly, overall coercivity decreased from 1010 Oe to 832 Oe for x=0.0–0.50 samples and depends on crystallite size. Cation distribution has been proposed from XRD analysis and magnetization data. Electron spin resonance spectra suggested the dominancy of superexchange interactions in Co_1−xNi_xFe₂O₄ samples. The optical analysis indicates that Co_1−xNi_xFe₂O₄ is an indirect band gap material and band gap increases with increasing Ni²⁺ concentration. Dispersion behavior with increasing frequency is observed for both dielectric constant and loss tangent. The conduction process predominantly takes place through grain boundary volume. Grain boundary resistance increases with Ni²⁺ ion concentration.     

Synthesis of carbon nanofibers with a polygonal cross section by the catalytic decomposition of C2H2 over bi-metal catalysts

Carbon nanofibers with a polygonal cross section were synthesized using catalytic chemical vapor deposition over Fe–Sn, Ni–Sn or Co–Sn catalysts. Their morphologies were characterized by scanning and transmission electron microscopy. Edges connecting of two walls can be clearly observed and some adjacent walls have a V-shape. The lengths of the sides of the polygonal cross sections range from 150 to 500 nm over Fe–Sn or Co–Sn nanoparticles, increasing to 700–900 nm over Ni–Sn nanoparticles. Polygonal catalyst particles can be seen at the ends of the fibers.     

Catalytic hydrogen transfer of ketones over atomic layer deposited highly-dispersed platinum nanoparticles supported on multi-walled carbon nanotubes

Hydrogen transfer of ketones, catalyzed by highly-dispersed platinum nanoparticles supported on multi-walled carbon nanotubes (MWCNTs), was studied. Pt nanoparticles were deposited on gram quantities of non-functionalized MWCNTs by atomic layer deposition (ALD) at 300 °C, using (methylcyclopentadienyl) trimethylplatinum and oxygen as precursors. TEM analysis showed that ~ 1.4 nm Pt nanoparticles were highly dispersed on MWCNTs. The heterogeneous hydrogen-transfer reactions of acetophenone indicated that an acetophenone conversion of 100% and a 1-phenylethanol selectivity of 99.0% could be obtained with a ketone to Pt mass ratio of 24,690 and a ketone to KOH mass ratio of 22 at 150 °C for 5 h. The selectivity of the Pt/MWCNT catalyst was higher than that of the commercial Pt/C catalyst, due to the highly-dispersed, uniform Pt nanoparticles and the unique porous structures of the Pt/MWCNT catalyst. The high stability of the Pt/MWCNT catalyst was demonstrated by reutilization of the catalyst. The high reactivity and selectivity of this catalyst for hydrogen transfer reduction were also demonstrated for other ketones.