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Giant faraday rotation through ultra-small Fe0n clusters in superparamagnetic FeO-SiO2 vitreous films
Magnetooptical (MO) glasses and, in particular, Faraday rotators are becoming key components in lasers and optical information processing, light switching, coding, filtering, and sensing. The common design of such Faraday rotator materials follows a simple path: high Faraday rotation is achieved by maximizing the concentration of paramagnetic ion species in a given matrix material. However, this approach has reached its limits in terms of MO performance; hence, glass‐based materials can presently not be used efficiently in thin film MO applications. Here, a novel strategy which overcomes this limitation is demonstrated. Using vitreous films of xFeO·(100 − x)SiO2, unusually large Faraday rotation has been obtained, beating the performance of any other glassy material by up to two orders of magnitude. It is shown that this is due to the incorporation of small, ferromagnetic clusters of atomic iron which are generated in line during laser deposition and rapid condensation of the thin film, generating superparamagnetism. The size of these clusters underbids the present record of metallic Fe incorporation and experimental verification in glass matrices.
Controlling Growth of Poly (Triethylene Glycol Acrylate-Co-Spiropyran Acrylate) Copolymer Liquid Films on a Hydrophilic Surface by Light and Temperature
A quartz crystal microbalance with dissipation monitoring (QCM-D) was employed for in situ investigations of the effect of temperature and light on the conformational changes of a poly (triethylene glycol acrylate-co-spiropyran acrylate) (P (TEGA-co-SPA)) copolymer containing 12–14% of spiropyran at the silica–water interface. By monitoring shifts in resonance frequency and in acoustic dissipation as a function of temperature and illumination conditions, we investigated the evolution of viscoelastic properties of the P (TEGA-co-SPA)-rich wetting layer growing on the sensor, from which we deduced the characteristic coil-to-globule transition temperature, corresponding to the lower critical solution temperature (LCST) of the PTEGA part. We show that the coil-to-globule transition of the adsorbed copolymer being exposed to visible or UV light shifts to lower LCST as compared to the bulk solution: the transition temperature determined acoustically on the surface is 4 to 8 K lower than the cloud point temperature reported by UV/VIS spectroscopy in aqueous solution. We attribute our findings to non-equilibrium effects caused by confinement of the copolymer chains on the surface. Thermal stimuli and light can be used to manipulate the film formation process and the film’s conformational state, which affects its subsequent response behavior.
Mid-infrared laser absorption spectroscopy for process and emission control in the glass melting industry : Part 1. Potentials
Laser spectroscopic diagnostics of combustion species at elevated temperature has shown considerable progress during the last years and decades. Particularly, techniques of mid-infrared absorption spectroscopy using fundamental rotational/vibrational transitions offer potentially great sensitivity and selectivity for combustion control. However, applications are still limited to mostly laboratoryscale investigations, which is mainly due to drawbacks of light sources and beam guidance materials. On the other band, many efforts are made to facilitate industrial application. In this context, the relevance of mid-infrared absorption spectroscopy for in situ monitoring of minor species in glass melting furnaces is obvious, too. The present paper gives a general review of available techniques and their impact on emission diagnostics in the glass industry, considering conventional as well as emerging light sources, detectors, peripheral devices and spectroscopic techniques.
Biomimetic light dilution using side-emitting optical fiber for enhancing the productivity of microalgae reactors
Photoautotrophic microbes present vast opportunities for sustainable lipid production, CO2 storage and green chemistry, for example, using microalgae beds to generate biofuels. A major challenge of microalgae cultivation and other photochemical reactors is the efficiency of light delivery. In order to break even on large scale, dedicated photon management will be required across all levels of reactor hierarchy – from the harvesting of light and its efficient injection and distribution inside of the reactor to the design of optical antenna and pathways of energy transfer on molecular scale. Here, we discuss a biomimetic approach for light dilution which enables homogeneous illumination of large reactor volumes with high optical density. We show that the immersion of side-emitting optical fiber within the reactor can enhance the fraction of illuminated volume by more than two orders of magnitude already at cell densities as low as ~5 104ml−1. Using the green algae Haematococcus pluvialis as a model system, we demonstrate an increase in the rate of reproduction by up to 93%. Beyond micoralgae, the versatile properties of side-emitting fiber enable the injection and dilution of light with tailored spectral and temporal characteristics into virtually any reactor containment.
Mid-infrared laser absorption spectroscopy for process and emission control in the glass melting industry : Part 2. Difference frequency generation based MIR laser spectrometer for glass melting furnaces
Emerging techniques of mid-infrared absorption spectroscopy offer potentially great sensitivity and selectivity for combustion control and emission monitoring. Beeause of that, a differenee frequency based mid-infrared absorption spectrometer has been considered for application in the glass industry. Based on preliminary tests within laboratory conditions, a spectrometer which operates at wavelengths around 5 μm was applied to online monitoring of the atmosphere of a gas fired glass melting furnace. The CO concentration was measured in order to demonstrate the feasibility of a mid-infrared absorption spectrometer for process control in the glass industry. Α series of measurements was performed in situ as well as crossing the recuperator entry, resulting in general advice on the construction of a prototype device.
Fluoride-Sulfophosphate/Silica Hybrid Fiber as a Platform for Optically Active Materials
Pressure-assisted melt filling (PAMF) of pre-fabricated micro-capillaries has been proven an effective way of fabricating hybrid optical fiber (HOF) from unusual combinations of materials. Here, we extend the applicability of PAMF to multi-anionic fluoride-sulfophosphate (FPS) glasses. FPS glasses provide extended transmission windows and high solubility for various transition metal (TM) and rare earth (RE) ion species. Using PAMF for fabricating FPS/silica HOFs can therefore act as a platform for a broad variety of optically active fiber devices. For the present demonstration purposes, we selected Cr3+- and Mn2+-doped FPS. For both glasses, we demonstrate how the spectral characteristics of the bulk material persist also in the HOF. Using a double-core fiber structure in which waveguiding is conducted in a primary GeO2-SiO2 core, mode coupling to the secondary FPS-filled core allows one to exploit the optical activity of the doped FPS glass even when the intrinsic optical loss is high.Pressure-assisted melt filling (PAMF) of pre-fabricated micro-capillaries has been proven an effective way of fabricating hybrid optical fiber (HOF) from unusual combinations of materials. Here, we extend the applicability of PAMF to multi-anionic fluoride-sulfophosphate (FPS) glasses. FPS glasses provide extended transmission windows and high solubility for various transition metal (TM) and rare earth (RE) ion species. Using PAMF for fabricating FPS/silica HOFs can therefore act as a platform for a broad variety of optically active fiber devices. For the present demonstration purposes, we selected Cr3+- and Mn2+-doped FPS. For both glasses, we demonstrate how the spectral characteristics of the bulk material persist also in the HOF. Using a double-core fiber structure in which waveguiding is conducted in a primary GeO2-SiO2 core, mode coupling to the secondary FPS-filled core allows one to exploit the optical activity of the doped FPS glass even when the intrinsic optical loss is high.
Boson peak, heterogeneity and intermediate-range order in binary SiO2-Al2O3 glasses
In binary aluminosilicate liquids and glasses, heterogeneity on intermediate length scale is a crucial factor for optical fiber performance, determining the lower limit of optical attenuation and Rayleigh scattering, but also clustering and precipitation of optically active dopants, for example, in the fabrication of high-power laser gain media. Here, we consider the low-frequency vibrational modes of such materials for assessing structural heterogeneity on molecular scale. We determine the vibrational density of states VDoS g(ω) using low-temperature heat capacity data. From correlation with low-frequency Raman spectroscopy, we obtain the Raman coupling coefficient. Both experiments allow for the extraction of the average dynamic correlation length as a function of alumina content. We find that this value decreases from about 3.9 nm to 3.3 nm when mildly increasing the alumina content from zero (vitreous silica) to 7 mol%. At the same time, the average inter-particle distance increases slightly due to the presence of oxygen tricluster species. In accordance with Loewensteinian dynamics, this proves that mild alumina doping increases structural homogeneity on molecular scale.
Plasma-based VAD process for multiply doped glass powders and high-performance fiber preforms with outstanding homogeneity
An innovative approach using the vapor axial deposition (VAD), for the preparation of silica-based high-power fiber laser preforms, is described in this study. The VAD uses a plasma deposition system operating at atmospheric pressure, fed by a single, chemically adapted solution containing precursors of laser-active dopants (e.g., Yb2O3), glass-modifier species (e.g., Al2O3), and the silica matrix. The approach enables simultaneous doping with multiple optically active species and overcomes some of the current technological limitations encountered with well-established fiber preform technologies in terms of dopant distribution, doping levels, and achievable active core diameter. The deposition of co-doped silica with outstanding homogeneity is proven by Raman spectroscopy and electron probe microanalysis. Yb2O3 concentrations are realized up to 0.3 mol% in SiO2, with simultaneous doping of 3 mol% of Al2O3.
Simulation of thermally induced stresses in glass-polymer composites
Due to differenees in thermal expansion, crazing and delamination effects are observed in multiphase materials such as glasspolymer composites. For a composite consisting of spherical particles homogeneously embedded in a matrix phase, the radial and tangential stresses occurring have been simulated. Two-dimensional calculations were used as a basis for optimizing the optical transparency of the material which was found to be strongly affected by the mechanical properties of the constituents of the composite and the resulting stresses. Further, the influence of the shape and the size distribution of the particles on the emergence of scattering surfaces inside the material is described. With the Christiansen-Shelyubskii method the maximum transparency of a potential material depending on whether it is a gradient material or not can be predicted.
Structural relaxation phenomena in silicate glasses modified by irradiation with femtosecond laser pulses
Structural relaxation phenomena in binary and multicomponent lithium silicate glasses were studied upon irradiation with femtosecond (fs) laser pulses (800 nm central wavelength, 130 fs pulse duration) and subsequent thermal annealing experiments. Depending on the annealing temperature, micro-Raman spectroscopy analyses evidenced different relaxation behaviours, associated to bridging and non-bridging oxygen structures present in the glass network. The results indicate that the mobility of lithium ions is an important factor during the glass modification with fs-laser pulses. Quantitative phase contrast imaging (spatial light interference microscopy) revealed that these fs-laser induced structural modifications are closely related to local changes in the refractive index of the material. The results establish a promising strategy for tailoring fs-laser sensitivity of glasses through structural mobility.