Structural integrity and healing efficiency study of micro-capsule based composite materials via 1H NMR relaxometry.

In this work we present a novel approach utilizing nuclear magnetic resonance (NMR) relaxometry to assess the structural stability of microcapsules employed as self-healing agents in advanced aerospace composites both in ambient and harsh environmental conditions. We successfully correlate the amount of the encapsulated self-healing agent with the signal intensity and confirm non-destructively the quantity of the encapsulated self-healing agent mass for the first time in the literature using 1H NMR spin-spin relaxation techniques on urea-formaldehyde (UF) microcapsules of different diameters containing an epoxy healing agent. The amount of self-healing agent is shown to increase by reducing the capsule diameter; however, the reduced shell mass renders the capsules more fragile and prone to failure. Most notably, via NMR experiments conducted during thermal cycling simulating flight conditions, we demonstrate that the microcapsule integrity under thermal fatigue varies according to their size. Especially we experimentally verify that the microcapsules with the most sensitive shells are the 147 nm and 133 nm diameter microcapsules, which are the most commonly used in self-healing systems. Finally, we were able to retrieve the same results using a portable NMR spectrometer developed in-house for in situ microcapsule testing, thus demonstrating the potential of NMR relaxometry as a powerful non-destructive evaluation tool for the microcapsule production line.

The peculiar size and temperature dependence of water diffusion in carbon nanotubes studied with 2D NMR diffusion-relaxation D -T 2eff spectroscopy.

It is well known that water inside hydrophobic nano-channels diffuses faster than bulk water. Recent theoretical studies have shown that this enhancement depends on the size of the hydrophobic nanochannels. However, experimental evidence of this dependence is lacking. Here, by combining two-dimensional nuclear magnetic resonance diffusion-relaxation ( D - T 2 e f f ) spectroscopy in the stray field of a superconducting magnet and molecular dynamics simulations, we analyze the size dependence of water dynamics inside Carbon Nanotubes (CNTs) of different diameters ( 1.1 - 6.0 nm), in the temperature range of 265 - 305 K. Depending on the CNT diameter, the nanotube water is shown to resolve in two or more tubular components acquiring different self-diffusion coefficients. Most notably, a favorable CNT diameter range ( 3.0 - 4.5 nm) is experimentally verified for the first time, in which water molecule dynamics at the center of the CNTs exhibits distinctly non-Arrhenius behavior, characterized by ultrafast diffusion and extraordinary fragility, a result of significant importance in the efforts to understand water behavior in hydrophobic nanochannels.

Structural, static and dynamic magnetic properties of dextran coated γ-Fe(2)O(3) nanoparticles studied by (57)Fe NMR, Mössbauer, TEM and magnetization measurements.

The structural and magnetic properties and spin dynamics of dextran coated and uncoated γ-Fe(2)O(3) (maghemite) nanoparticles have been investigated using high resolution transmission electron microscopy (HRTEM), (57)Fe nuclear magnetic resonance (NMR), Mössbauer spectroscopy and dc magnetization measurements. The HRTEM observations indicated a well-crystallized system of ellipsoid-shaped nanoparticles, with an average size of 10 nm. The combined Mössbauer and magnetic study suggested the existence of significant interparticle interactions not only in the uncoated but also in the dextran coated nanoparticle assemblies. The zero-field NMR spectra of the nanoparticles at low temperatures are very similar to those of the bulk material, indicating the same hyperfine field values at saturation in accord with the performed Mössbauer measurements. The T(2) NMR spin-spin relaxation time of the nanoparticles has also been measured as a function of temperature and found to be two orders of magnitude shorter than that of the bulk material. It is shown that the thermal fluctuations in the longitudinal magnetization of the nanoparticles in the low temperature limit may account for the shortening and the temperature dependence of the T(2) relaxation time. Thus, the low temperature NMR results are in accord with the mechanism of collective magnetic excitations, due to the precession of the magnetization around the easy direction of the magnetization at an energy minimum, a mechanism originally proposed to interpret Mössbauer experiments in magnetic nanoparticles. The effect of the surface spins on the NMR relaxation mechanisms is also discussed.

Direct NMR evidence of phase solitons in the spin ground state of overdoped manganites.

Charge ordering phenomena in overdoped La1-xCaxMnO3 (LCMO) manganites with x>or=0.5 are generally believed to be associated with the formation of charge stripes composed of alternating Mn3+ and Mn4+ charges. However, a number of recent experiments indicate that instead of stripes the charge in these systems is spatially organized in a uniform charge density wave. At the same time theory predicts that the ground state is modulated by an incommensurate (IC) orbital and charge soliton lattice. Here, by using nuclear magnetic resonance we provide the first direct evidence that the spin ground state in overdoped LCMO manganites is IC modulated with phase solitons. At higher temperatures the solitonic superstructure is replaced by a uniform spin-density wave, subjected to coherent slow fluctuations, showing a striking similarity with slow fluctuations in the striped phase of high T{c} cuprates and nickelates.

In vitro studies on ultrasmall superparamagnetic iron oxide nanoparticles coated with gummic acid for T2 MRI contrast agent.

Ultrasmall superparamagnetic iron oxide nanoparticles coated with gummic acid have been investigated as possible constituents of aqueous ferrofluids for biomedical applications and especially for MRI contrast agent. The structural characteristics and the size of the nanoparticles have been analyzed as well as the magnetic properties. In order to evaluate any possible capabilities as a contrast agent, the relaxation time, T2, of hydrogen protons in the colloidal solutions of nanoparticles have been measured in order to gain information on the relaxation behavior compared to other MRI contrast agents. The in vitro cytotoxicity of the obtained magnetic nanoparticles of iron oxide coated with gummic acid was investigated by two separate methods (MTT and FACS analysis) and by using three different normal and transformed cell lines. Our results showed that the synthesized nanoparticles had no toxic effect on any of the cell lines used.

Low temperature charge and orbital textures in La0.875Sr0.125MnO3.

By using nuclear magnetic resonance techniques we show that for T<30 K the La0.875Sr0.125MnO3 compound displays a nonuniform charge distribution, comprised of two interconnected Mn ion subsystems with different spin, orbital, and charge couplings. The NMR results agree very well with the two spin wave stiffness constants observed at small q values in the spin wave dispersion curves [Phys. Rev. B 67, 214430 (2003)]. This picture is probably related to a yet undetermined charge and orbital superstructure occurring in the ferromagnetic insulating state of the La0.875Sr0.125MnO3 compound.

Morphology, ionic diffusion and applicability of novel polymer gel electrolytes with LiI/I2.

Novel polymer gel electrolytes have been prepared by incorporating LiI-I(2) solutions into a polyethylene oxide matrix supported by a TiO(2) filler. The gel electrolytes, based on either acetonitrile or propylene carbonate solvents are compared with liquid standard ones and are examined by (7)Li solid state nuclear magnetic resonance relaxometry and diffusion measurements. In parallel, the triiodide apparent diffusion coefficient has been determined by linear sweep voltammetry. The results are correlated with atomic force microscopic images of the electrolytes and give insight of the dynamic properties of the ions in the constrained polymer medium. Furthermore, the dissociation of the ions is estimated by relating the ionic conductivity to the ionic diffusion. As a prime application, the polymer gel electrolytes were incorporated in dye sensitized solar cells and the measured energy conversion efficiencies were successfully correlated with their morphological, diffusive and conducting properties.

Orbital domain state and finite size scaling in ferromagnetic insulating manganites.

55Mn and 139La NMR measurements on a high quality single crystal of ferromagnetic (FM) La0.80Ca0.20MnO3 demonstrate the formation of localized Mn(3+,4+) states below 70 K, accompanied by a strong cooling-rate dependent increase of certain FM neutron Bragg peaks. (55,139)(1/T(1)) spin-lattice and (139)(1/T(2)) spin-spin relaxation rates are strongly enhanced on approaching this temperature from below, signaling a genuine phase transition at T(tr) approximately 70 K. The disappearance of the FM metallic signal by applying a weak external magnetic field, the different NMR radio-frequency enhancement of the FM metallic and insulating states, and the observed finite size scaling of T(tr) with Ca (hole) doping, as observed in powder La(1-x)CaxMnO3 samples, are suggestive of freezing into an inhomogeneous FM insulating and orbitally ordered state embodying "metallic" hole-rich walls.

(139)La NMR investigation of quasistatic orbital ordering in La(1-x)Ca(x)MnO(3).

We report (139)La nuclear magnetic resonance in ferromagnetic and insulating (FMI) La(1-x)Ca(x)MnO(3), 0.10< or =x< or =0.20, which at low temperatures shows the formation of Mn octants with enhanced Mn-O wave function overlapping and electron-spin alignment. The rapid increase of the relaxation rates and the "wipeout" of the (139)La NMR signal intensity on heating, imply a quasistatic character for the Mn octant cells in the FMI phase, which freeze below a transition temperature T(f).

55Mn NMR investigation of electronic phase separation in La1-xCaxMnO3 for 0.2 < or = x < or = 0.5.

55Mn NMR line shape measurements in La1-xCaxMnO3 for 0.20< or =x< or =0.50 provide experimental evidence about the existence of two distinct regions in the T-x magnetic phase diagram, where the homogeneous ferromagnetic (FM) metallic state is separated into FM metallic and FM insulating regions. These results are in agreement with recent theoretical predictions, which reveal a novel electronic phase separation in two FM states, providing orbital ordering and Jahn-Teller phonons are taken into consideration.

NMR in porous materials.

Nuclear magnetic resonance (NMR) was used to determine the pore size distribution of hardened Portland cement pastes. The method is based on the well-known freezing point depression of water when confined inside the pore matrix of a material. It is demonstrated how this technique can be applied in cementitious materials to probe the microstructure of the main hydration product: the cement gel.

Diagnostic impression cytology: a simple technique for the diagnosis of external eye disease.

The technique of impression cytology was used for cytologic examination of conjunctival samples from 128 patients with a variety of external eye diseases. The method of sample collection and the staining procedure are described. Microscopic examination showed 62 cases with allergic conjunctivitis, 23 with bacterial or viral infection, 26 cases with changes typical of dry eye and 17 cases with non-specific chronic inflammation. The cytologic features and numerous applications of impression cytology are discussed.

Assessment of liver iron overload by T2-quantitative magnetic resonance imaging: correlation of T2-QMRI measurements with serum ferritin concentration and histologic grading of siderosis.

PURPOSE: To correlate hepatic 1/T2 values obtained by means of a T2-Quantitative MRI (T2-QMRI) technique with three widely applied methods for the evaluation of hemosiderosis, i.e., (a) liver iron concentrations (LFeC) (b) serum ferritin (SF), and (c) histologic grading of siderosis. The impact of coexisting hepatitis was also considered. T2-QMRI measurements were compared with signal intensity (SI) ratio measurements on conventional SE images. MATERIALS AND METHODS: Liver T2 relaxation times were calculated in 40 thalassemic patients, on a 0.5 T magnetic resonance imaging system using a multiple spin-echo sequence with parameters: TR = 2500 ms, TE = 12 ms in 20 symmetrically repeatable echoes. RESULTS: (a) 1/T2 values were well correlated (r = 0.97) with liver iron concentrations, which ranged from 2.32 to 18.0 mg/g dry weight (normal < 1.6 mg/g). (b) 1/T2 values were also correlated with serum ferritin levels (r = 0.84). At various 1/T2 values, serum ferritin levels were higher for the anti-HCV(+) patients than the anti-HCV(-) ones. (c) T2 values corresponding to successive grades of siderosis presented statistically significant differences. (d) SI ratio measurement assigned less statistically significant results, as compared to T2 values. CONCLUSION: T2-QMRI measurement of T2 relaxation time is more accurate than SI ratios in evaluating liver iron overload. It is particularly useful for hemosiderotic patients with coexisting hepatitis since, in this case, serum ferritin is not considered a reliable index of hemosiderosis.