Studies of water penetration into LDPE--calcium lactate composite

Penetration of water into low-density polyethylene-calcium lactate composite is studied with NMR techniques. The presence of filler speeds up the water uptake by the polymer matrix and facilitates polyethylene degradation. Spatial distribution of absorbed water molecules within the composite visualised with MRI corroborates differences in dynamical behaviour of the absorbed water molecules revealed by T2 measurements.     

Molecular dynamics of tert-butyl chloride confined in CPG studied by NMR

The molecular dynamics of tert-butyl chloride (TBC) confined to Controlled Pore Glass matrices of 25 and 7.5 nm were investigated by measuring NMR linewidths, lineshapes, and 1H and 2H spin--lattice relaxation times. The behaviour of confined TBC can be explained assuming that the guest molecules form two distinct phases; the surface-affected phase, composed of molecules located at the pore surface, and the bulk-like phase located at the centre of the pores. The bulk-like component of confined TBC, at the temperatures corresponding to the phase III, is characterized by two dynamically different subphases.     

Proton relaxation NMR study of polycrystalline progesterone.

Polycrystalline progesterone (4-pregnene-3,20-dione, C21H30O2) has been investigated by proton NMR methods between 80 and 350 K. A reduction in dipolar second moment is ascribed to methyl group reorientation. Minima in the spin-lattice relaxation time found in measurements at five frequencies from 7 to 200 MHz are attributed to reorientation of two of the three methyl groups in each molecule, characterized by activation energy Ea = 10.9 +/- 0.8 kJ/mol and tau o = (2.3 +/- 0.2) x 10(-13) s. Additional relaxation at lower temperatures is attributed to reorientation of the third methyl group with Ea approximately 3.4 kJ/mol. Measurements were also made of relaxation in the rotating frame.     

Superconducting properties of an NbN–SiO2 disordered system obtained by ammonolysis of NbN–SiO2 sol–gel derived coatings

Studies in superconducting properties of NbN–SiO₂ films are reported. The films were obtained through nitridation of sol–gel derived Nb₂O₅–SiO₂ coatings at 1200 °C, a process leading to the formation of disordered structures with NbN metallic grains dispersed in the insulating SiO₂ matrix. Electrical resistivity was measured with the conventional four-terminal method in the temperature range from 5 to 280 K. The samples’ superconducting properties, examined with magnetically modulated microwave absorption (MMMA), depend on the NbN/SiO₂ molar ratio and the film’s thickness.     

Novel method to determine the actual surface area of a laser-nanotextured sensor

The actual surface area of a gold-coated conductive layer over the laser nano-textured surface of sapphire is determined using an electrochemical cyclic voltammetry. The method is down scaled to measure the sensing surface area of 200 × 200 μm² on a laser-ablated ripple sensor used for surface-enhanced Raman spectroscopy/scattering (SERS). Ripple SERS sensors made on different substrates of high refractive index materials such as GaP, diamond, SiC, and Al₂O₃ make a versatile sensing platform with the detection of analyte (here a thiophenol) down to 10 nM concentrations. Direct measurement of the surface area provides a powerful tool to investigate roughness, porosity, and morphology of coatings used for SERS or other light harvesting surfaces such as solar cells. Novelty of the proposed method is in the use of cathodic peak of surface passivation–activation cycle for calculation of surface charge. The method enables high-accuracy surface area measurements from as small as 0.01 mm² pads up to functional solar cells.     

High homogeneity B(1) 30.2 MHz Nuclear Magnetic Resonance Probe for off-resonance relaxation times measurements

This paper reports on design and construction of a double coil high-homogeneity ensuring Nuclear Magnetic Resonance Probe for off-resonance relaxation time measurements. NMR off-resonance experiments pose unique technical problems. Long irradiation can overheat the sample, dephase the spins because of B(1) field inhomogeneity and degrade the signal received by requiring the receiver bandwidth to be broader than that needed for normal experiment. The probe proposed solves these problems by introducing a separate off-resonance irradiation coil which is larger than the receiver coil and is wound up on the dewar tube that separates it from the receiver coil thus also thermally protects the sample from overheating. Large size of the irradiation coil also improves the field homogeneity because as a ratio of the sample diameter to the magnet (coil) diameter increases, the field inhomogeneity also increases (Blümich et al., 2008) [1]. The small receiver coil offers maximization of the filling factor and a high signal to the noise ratio.     

Molecular dynamics in solid pyridoxine as studied by 1H NMR

Spin-lattice relaxation times T1 and T1d as well as NMR second moment were employed to study molecular dynamics of pyridoxine (vitamin B6) in the temperature range 10-350 K. The T1 minimum observed at low temperatures at 200 MHz is attributed to a motion of methyl group. The motion is interpreted in terms of Haupt's theory, which takes into account the tunneling assisted relaxation. At low temperatures, where T1 is temperature independent, occupation of the ground state only is assumed. A motion of proton of the hydroxyl groups or CH2OH groups probably provides additional mechanism of relaxation, in the high-temperature region.     

Molecular dynamics in stiff ionene below glass transition

Temperature dependences of proton and fluorine second moments and spin-lattice relaxation time T₁ below glass transition were measured in glassy “I-Do,Pip-Me-BF₄” ionene. The existence of motions of methyl groups and segments linking the cationic centers, namely piperidinium rings and trimethylene groups, for the polymeric part of ionene were established. Isotropic rotation of the counter-ion was evidenced and its limited diffusion suggested. To interpret the proton and fluorine relaxation data, a Davidson-Cole distribution of correlation times was assumed.     

Study of nucleation induced structure modification in isotactic polypropylene by DMTA and solid state NMR

Isotactic polypropylene (iPP) modified by heterogeneous nucleation and molten state drawing was investigated using the DMTA and NMR methods. The nucleation was realized by specific α and β nucleating agents, 1,3,2,4-bis(3,4-dimetylobenzylideno) sorbitol (Millad 3988, Miliken) leading to the creation of the α phase, and N,N′-dicyklohexylo-2,6-naftaleno dikarboxy amid (NJ100) as the β phase promoter. The processing induced modification was performed by molten state drawing during an extrusion in the range between the die exit and the calibration unit. An increase of the glass transition temperature of iPP was found to be drawing independent for the β-nucleated samples, and dependent in the case of the α-iPP. Changes in the macromolecular mobility, depending on the α/β iPP structure and molten state drawing, was found by NMR lineshape and second moment measurements.