L. Chitu

Towards strain gauges based on a self-assembled nanoparticle monolayer--SAXS study.

An in situ small-angle x-ray scattering study of the nanoparticle displacement in a self-assembled monolayer as a function of a supporting membrane strain is presented. The average nanoparticle spacing is 6.7 nm in the unstrained state and increases in the applied force direction, following linearly the membrane strain which reaches the maximum value of 11%. The experimental results suggest a continuous mutual shift of the nanoparticles and their gradual separation with the growing stress rather than nanoparticle islands formation. No measurable shift of the nanoparticles was observed in the direction perpendicular to the applied stress.

Kinetics and mechanism of the biodegradation of PLA/clay nanocomposites during thermophilic phase of composting process

The degradation mechanism and kinetics of polylactic acid (PLA) nanocomposite films, containing various commercially available native or organo-modified montmorillonites (MMT) prepared by melt blending, were studied under composting conditions in thermophilic phase of process and during abiotic hydrolysis and compared to the pure polymer. Described first order kinetic models were applied on the data from individual experiments by using non-linear regression procedures to calculate parameters characterizing aerobic composting and abiotic hydrolysis, such as carbon mineralization, hydrolysis rate constants and the length of lag phase. The study showed that the addition of nanoclay enhanced the biodegradation of PLA nanocomposites under composting conditions, when compared with pure PLA, particularly by shortening the lag phase at the beginning of the process. Whereas the lag phase of pure PLA was observed within 27days, the onset of CO2 evolution for PLA with native MMT was detected after just 20days, and from 13 to 16days for PLA with organo-modified MMT. Similarly, the hydrolysis rate constants determined tended to be higher for PLA with organo-modified MMT, particularly for the sample PLA-10A with fastest degradation, in comparison with pure PLA. The acceleration of chain scission in PLA with nanoclays was confirmed by determining the resultant rate constants for the hydrolytical chain scission. The critical molecular weight for the hydrolysis of PLA was observed to be higher than the critical molecular weight for onset of PLA mineralization, suggesting that PLA chains must be further shortened so as to be assimilated by microorganisms. In conclusion, MMT fillers do not represent an obstacle to acceptance of the investigated materials in composting facilities.

Modified Langmuir-Blodgett deposition of nanoparticles - measurement of 2D to 3D ordered arrays

Modified Langmuir-Blodgett deposition of nanoparticles - measurement of 2D to 3D ordered arrays The ordered nanoparticle monolayers and multilayers over macroscopic areas were prepared by the modified Langmuir-Blodgett method. Using this approach, the nanoparticle monolayer is formed on the water surface by compression and subsequently it is transferred onto the substrate by a controlled removal of the water subphase. The ordering and homogeneity of the prepared mono- and multilayers was studied by scanning electron microscope (SEM), grazing-incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR) techniques. From the results it follows that an ordered nanoparticle monolayer was formed over a large area. For the multilayer, the layering and lateral ordering of each layer was confirmed by XRR and SEM performed after the deposition of each nanoparticle layer.

Kinetics of nanoparticle reassembly mediated by UV-photolysis of surfactant.

Real-time reassembly of an ordered nanoparticle monolayer due to UV-photolysis of the surfactant shell of nanoparticles was observed. The technique of grazing-incidence small-angle X-ray scattering provided the possibility to track in situ the nanoparticle pair correlation function of the sample processed in a UV-ozone reactor. The analysis revealed a total shift of approximately 1 nm of the nanoparticle nearest-neighbor distance. The temporal evolution of the interparticle distance proved to be the first-order process governed by the UV-photolysis and described by a single-exponential decay function. The nanoparticles tend to agglomerate into a labyrinth-like structure with a typical length scale of some 30 nm.

Real-time tracking of superparamagnetic nanoparticle self-assembly.

The spontaneous self-assembly process of superparamagnetic nanoparticles in a fast-drying colloidal drop is observed in real time. The grazing-incidence small-angle X-ray scattering (GISAXS) technique is employed for an in situ tracking of the reciprocal space, with a 3 ms delay time between subsequent frames delivered by a new generation of X-ray cameras. A focused synchrotron beam and sophisticated sample oscillations make it possible to relate the dynamic reciprocal to direct space features and to localize the self-assembly. In particular, no nanoparticle ordering is found inside the evaporating drop and near-surface region down to a drop thickness of 90 microm. Scanning through the shrinking drop-contact line indicates the start of self-assembly near the drop three-phase interface, in accord with theoretical predictions. The results obtained have direct implications for establishing the self-assembly process as a routine technological step in the preparation of new nanostructures.

Interface study of a high‐performance W/B4C X‐ray mirror

A high-performance W/B4C multilayer mirror with 80 periods of nominally 1.37 nm was measured by grazing-incidence small-angle X ray scattering (GISAXS) in order to analyse the lateral and vertical correlations of the interface roughness within the framework of a scaling concept of multilayer growth. A dynamic growth exponent z = 2.19 (7) was derived, which is close to the value predicted by the Edwards–Wilkinson growth model. The effective number of correlated periods indicates a partial replication of the low interface roughness frequencies. A simulation of the GISAXS pattern based on the Born approximation suggests a zero Hurst fractal parameter H and a logarithmic type of autocorrelation function. The as-deposited mirror layers are amorphous and exhibit excellent thermal stability up to 1248 K in a 120 s rapid thermal vacuum annealing process. At higher temperatures, the B4C layers decompose and poorly developed crystallites of a boron-rich W–B hexagonal phase are formed, and yet multilayer collapse is not complete even at 1273 K. Ozone treatment for 3000 s in a reactor with an ozone concentration of 150 mg m−3 results in the formation of an oxidized near-surface region of a thickness approaching ∼10% of the total multilayer thickness, with a tendency to saturation.

Correlation between x-ray reciprocal space maps and magnetic properties of current-induced magnetization switching pseudospin valve structures

A thorough study of x-ray diffuse scattering from the spin valve structures suitable for current induced magnetization switching is presented. We used complete reciprocal space maps of diffusely scattered x rays to show the effect of bottom Au electrode on the morphology of buried spin valve interfaces. The thickness and roughness of each layer, as well as vertical and lateral roughness correlation lengths, were obtained. The impact of interfaces morphology on the magnetic properties, especially on the increase of spin valve coercivity, was measured and simulated within the frame of Neel magnetostatic coupling model based on the parameters from the x-ray diffuse scattering data. Measurement of x-ray diffuse scattering presents a rapid and nondestructive technique for in-depth and self-contained analysis of spin valve layers and interfaces.

Chapter 107 - Time-resolved absorption spectroscopy of metal nanoparticles in colloidal solution

An intense femtosecond laser spectroscopy-based research focusing on the fast relaxation processes of excited electrons in nanoparticles has started in the past decade. The electron dynamics and non-linear optical properties of nanoparticles in colloidal solutions, thin films, and glasses have been studied in the femto- and picosecond time scales. Most work has been done with noble metal nanoparticles Au, Ag and Cu, providing information about the electron-electron and electron-phonon coupling or coherent phenomenon. A large surface-to-volume ratio of the particle gives a possibility to investigate the surface/interface processes. This chapter focusses on the comparison of the induced absorption dynamics of Ag and Fe 2 O 3 colloidal nanoparticles on the early picosecond time scale. A comparative study is performed using the same experimental conditions for both colloidal solutions with the mean particle diameter of 10 nm. The broadband single shot probe registration in spectral region of 430 - 650 nm enabled to examine the Fe 2 O 3 relaxation dynamics at shorter wavelengths than those reported in. The wavelength and power dependence of the induced absorption decay are analyzed.