Effect of Grinding and the Mill Type on Magnetic Properties of Carboxylated Multiwall Carbon Nanotubes

The influence of the grinding process on the magnetic properties of as prepared and functionalized multiwall carbon nanotubes (MWCNTs) is presented. We have observed that 3 h mechanical grinding at 400 rpm in contrast to functionalization does not remove the iron contamination from MWCNTs. However, it changes the Fe chemical states. The magnetic properties of iron nanoparticles (Fe-NPs) embedded in the carbon matrix of MWCNTs have been analyzed in detail. We have proven that single-domain non-interacting Fe(C,O)-NPs enriched in the Fe3C phase (~10 nm) enclosed inside these nanotubes are responsible for their magnetic properties. Mechanical grinding revealed a unique impact of -COOH groups (compared to -COONH4 groups) on the magnetism of functionalized MWCNTs. In MWCNT-COOH ground in a steel mill, the contribution of the Fe2O3 and α-Fe phases increased while the content of the magnetically harder Fe3C phase decreased. This resulted in a 2-fold coercivity (Hc) decrease and saturation magnetization (MS) increase. A 2-fold remanence (Mr) decrease in MWCNT-COOH ground in an agate mill is related to the modified Fe(C,O)-NP magnetization dynamics. Comparison of the magnetostatic exchange and effective anisotropy length estimated for Fe(C,O)-NPs allows concluding that the anisotropy energy barrier is higher than the magnetostatic energy barrier. The enhanced contribution of surface anisotropy to the effective anisotropy constant and the unique effect of the -COOH groups on the magnetic properties of MWCNTs are discussed. The procedure for grinding carboxylated MWCNTs with embedded iron nanoparticles using a steel mill has a potential application for producing Fe-C nanocomposites with desired magnetic properties

A UHV MOKE magnetometer complementing XMCD-PEEM at the Elettra Synchrotron

We report on a custom-built UHV-compatible Magneto-Optical Kerr Effect (MOKE) magnetometer for applications in surface and materials sciences, operating in tandem with the PhotoEmission Electron Microscope (PEEM) endstation at the Nanospectroscopy beamline of the Elettra synchrotron. The magnetometer features a liquid-nitrogen-cooled electromagnet that is fully compatible with UHV operation and produces magnetic fields up to about 140 mT at the sample. Longitudinal and polar MOKE measurement geometries are realized. The magneto-optical detection is based on polarization analysis using a photoelastic modulator. The sample manipulation system is fully compatible with that of the PEEM, making it possible to exchange samples with the beamline endstation, where complementary X-ray imaging and spectroscopy techniques are available. The magnetometer performance is illustrated by experiments on cobalt ultra-thin films, demonstrating close to monolayer sensitivity. The advantages of combining in situ growth, X-ray Magnetic Circular Dichroism imaging (XMCD-PEEM) and MOKE magnetometry into a versatile multitechnique facility are highlighted

The Valence and Spin State Tuning of Iron(II/III) Porphyrazines with Bulky Pyrrolyl Periphery in Solution and Solid State

Iron(III) porphyrazines containing peripheral 2,5-dimethyl-, 2-methyl-5-phenyl-, and 2,3,5-triphenyl-1H-pyrrol-1-yl substituents were synthesized and subjected to physicochemical characterization. This was accomplished by high-resolution mass spectrometry, nuclear magnetic resonance (as diamagnetic Fe(II) derivatives), HPLC purity analysis, and UV-Vis spectroscopy, accompanied by the solvation study in dichloromethane and pyridine. X-ray structure analysis was performed for a single crystal of the previously obtained 2,5-diphenyl-substituted derivative of porphyrazine complex (5d). The octahedral geometries of iron cation, present in the porphyrazine core, influenced the packing mode of molecules in the crystals. Mössbauer studies, performed for solid samples of iron porphyrazines, indicated that low-spin reduced iron states might occupy low- or high-symmetry binding sites. It was found that the hyperfine parameters and the subsequent contribution of the iron cations depend on the number of phenyl groups surrounding the pyrrolyl moiety. For iron(II) porphyrazine 2,3,5-triphenylpyrrol-1-yl substituents (5b), a high-spin ferrous state fraction was observed. Temperature-dependent measurements showed that the freed rotation of the peripheral porphyrazine ligands and the increased flexibility of the macrocycle ring result in the Fe2+ ion being stabilized in a diamagnetic state at a binding site of high symmetry at room temperature in the solid state. This process is most probably stimulated by the range of collective motions of the polymeric ribbons consisting of iron(II) porphyrazines observed in the X-ray