Andy Cassez

Rate Coefficients for the Gas-Phase Reaction of Hydroxyl Radicals with 2-Methoxyphenol (Guaiacol) and Related Compounds

2-Methoxyphenol (guaiacol) and its derivatives are potential marker compounds for wood smoke emissions in the atmosphere. To investigate the atmospheric reactivity of this type of compounds, rate coefficients for their reactions with hydroxyl (OH) radicals have been determined at 294 ± 2 K and 1 atm using the relative rate method with gas chromatography for chemical analysis. The rate coefficients (in units of cm³ molecule⁻¹ s⁻¹) are: 2-methoxyphenol, (7.53 ± 0.41) × 10⁻¹¹; 3-methoxyphenol, (9.80 ± 0.46) × 10⁻¹¹; 4-methoxyphenol, (9.50 ± 0.55) × 10⁻¹¹; 2-methoxy-4-methylphenol, (9.45 ± 0.59) × 10⁻¹¹; and methoxybenzene, (2.20 ± 0.15) × 10⁻¹¹. The estimated atmospheric lifetime for 2-methoxyphenol is ~2 h, indicating that it is too reactive to be used as a tracer for wood smoke emissions. The reactivity of the methoxyphenols is compared with other substituted aromatics and interpreted in relation to the type, number, and positions of the different substituents on the aromatic ring. The atmospheric implications of the reactions are also discussed.

Rate Coefficients for the Gas-Phase Reaction of Chlorine Atoms with a Series of Methoxylated Aromatic Compounds

The reaction of a series of oxygenated aromatics (two methoxybenzene and six methoxyphenol isomers) with chlorine atoms has been studied in two simulation chambers with volumes of 1080 and 480 L at the University of Wuppertal. Experiments were performed at 295 ± 2 K and a total pressure of synthetic air of 1 bar using the relative kinetic method with in situ Fourier transform infrared spectroscopy for chemical analysis. The following rate coefficients (in units of cubic centimeter per molecule per second) were determined: (1.07 ± 0.24) × 10(-10) for methoxybenzene, (1.20 ± 0.24) × 10(-10) for 1-methoxy-2-methylbenzene, (2.97 ± 0.66) × 10(-10) for 2-methoxyphenol (guaiacol), (2.99 ± 0.62) × 10(-10) for 3-methoxyphenol, (2.86 ± 0.58) × 10(-10) for 4-methoxyphenol, (3.35 ± 0.68) × 10(-10) for 2-methoxy-4-methylphenol, (4.73 ± 1.06) × 10(-10) for 2,3-dimethoxyphenol, and (2.71 ± 0.61) × 10(-10) for 2,6-dimethoxyphenol (syringol). To the best of our knowledge, this work represents the first determination of the rate coefficients for the gas-phase reaction of the chlorine atoms with the methoxy-aromatic compounds investigated. The reactivity of the methoxylated aromatics toward Cl is compared with that of other substituted aromatic compounds, and the differences in the rate coefficients are interpreted in terms of the type, number, and position of the different substituents on the aromatic ring. The atmospheric implications of the studied reactions are also discussed.

Kinetic Study of the Gas-Phase Reactions of Nitrate Radicals with Methoxyphenol Compounds: Experimental and Theoretical Approaches.

The gas-phase reactions of five methoxyphenols (three disubstituted and two trisubstituted) with nitrate radicals were studied in an 8000 L atmospheric simulation chamber at atmospheric pressure and 294 ± 2 K. The NO3 rate constants were investigated with the relative kinetic method using PTR-ToF-MS and GC-FID to measure the concentrations of the organic compounds. The rate constants (in units of cm(3) molecule(-1) s(-1)) determined were: 2-methoxyphenol (guaiacol; 2-MP), k(2-MP) = (2.69 ± 0.57 × 10(-11); 3-methoxyphenol (3-MP), k(3-MP) = (1.15 ± 0.21) × 10(-11); 4-methoxyphenol (4-MP), k(4-MP) = (13.75 ± 7.97) × 10(-11); 2-methoxy-4-methylphenol, k(2-M-4-MeP) = (8.41 ± 5.58) × 10(-11) and 2,6-dimethoxyphenol (syringol; 2,6-DMP), k(2,6-DMP) = (15.84 ± 8.10) × 10(-11). The NO3 rate constants of the studied methoxyphenols are compared with those of other substituted aromatics, and the differences in the reactivity are construed regarding the substituents (type, number and position) on the aromatic ring. This study was also supplemented by a theoretical approach of the methoxyphenol reactions with nitrate radicals. The upper limits of the NO3 overall rate constants calculated were in the same order of magnitude than those experimentally determined. Theoretical calculations of the minimum energies of the adducts formed from the reaction of NO3 radicals with the methoxyphenols were also performed using a DFT approach (M06-2X/6-31G(d,p)). The results indicate that the NO3 addition reactions on the aromatic ring of the methoxyphenols are exothermic, with energy values ranging between -13 and -21 kcal mol(-1), depending on the environment of the carbon on which the oxygen atom of NO3 is attached. These energy values allowed identifying the most suitable carbon sites for the NO3 addition on the aromatic ring of the methoxyphenols: at the exception of the 3-MP, the NO3 ipso-addition to the hydroxyl group is one of the favored sites for all the studies compounds.

Extreme large mode area in single-mode pixelated Bragg fiber

This paper reports the design and the fabrication of an all-solid photonic bandgap fiber with core diameter larger than 100 µm, a record effective mode area of about 3700 µm2 at 1035 nm and robust single-mode behavior on propagation length as short as 90 cm. These properties are obtained by using a pixelated Bragg fiber geometry together with an heterostructuration of the cladding and the appropriated generalized half wave stack condition applied to the first three higher order modes. We detail the numerical study that permitted to select the most efficient cladding geometry and present the experimental results that validate our approach.

Solitonization of a dispersive wave

We report the observation of a nonlinear propagation scenario in which a dispersive wave is transformed into a fundamental soliton in an axially varying optical fiber. The dispersive wave is initially emitted in the normal dispersion region and the fiber properties change longitudinally so that the dispersion becomes anomalous at the dispersive wave wavelength, which allows it to be transformed into a soliton. The solitonic nature of the field is demonstrated by solving the direct Zakharov-Shabat scattering problem. Experimental characterization performed in spectral and temporal domains show evidence of the solitonization process in an axially varying photonic crystal fiber.

Polarization maintaining single-mode fiber delivering a flat top intensity profile

We report, through numerical simulations and experimental data, the first successful fabrication of a polarization maintaining single-mode fiber delivering a flat top intensity profile at 1.05 µm. A high quality flat mode was obtained and single-mode behavior was checked by shifting the injection and by S² imaging method. Numerical investigations were performed to show that it would be possible to increase further the 0.6x10⁻⁴ experimental group birefringence.

F/Yb-codoped sol-gel silica glasses: toward tailoring the refractive index for the achievement of high-power fiber lasers

Accurate control of both the doping distribution inside the fiber core and the low refractive index contrast between the fiber core and cladding materials is essential for the development of high-power fiber lasers based on the use of single-mode large-mode-area (LMA) optical fibers. Herein, sol-gel monolithic F/Yb3+-codoped silica glasses were prepared from porous large silica xerogels doped with ytterbium salt solution, which had been subjected to fluorination with hexafluoroethane gas, before subsequent sintering. The fluorine content inside the doped glass has been varied by adjusting the fluorination duration. The space homogeneity of fluorine and ytterbium concentrations in the cylindrical preforms has been checked by chemical analysis and Raman spectroscopy. Moreover, the glass with the lowest fluorine content has been successfully integrated as a core material in a microstructured optical fiber made using the stack-and-draw method. This fiber was tested in an all-fiber cavity laser architecture to evaluate potential lasing performances of the F/Yb3+-codoped silica glass. It presents a maximum efficiency of 70.4%, achieved at 1031 nm from a 1.16 m length fiber. These results confirm the potentialities of the obtained F/Yb3+-codoped glasses for the fabrication of LMA optical fiber lasers.

Ultra large mode area pixelated Bragg fiber

We report on the design and the fabrication of a new design of an all-solid Bragg fiber based on the pixelization and heterostructuration of a cladding made of only two high index rings. The thickness of the low index ring as well as the geometry of the heterostructuration (its symmetry and the number of removed pixels) have been chosen to maximize the confinement losses of the Higher Order Modes (HOM) (above 10 dB/m) while keeping the Fundamental Mode (FM) losses low (below 0.1 dB/m). The proposed geometry allows having access to different Mode Field Diameter (MFD) from 54 μm to 60 μm at 1 μm wavelength by drawing the same stack to different fiber (and hence, core) diameters. As a result, a record MFD of 60 μm is reported for a Solid Core Photonic Bandgap Fiber (SC-PBGF) and single-mode behavior is obtained experimentally even for a short fiber length (few tens centimeters) maintained straight.

Design and characterization of a 10-mode few-mode erbium-doped fiber with multicore pedestal core

A new few-mode fiber design taking advantage of a micro-structured core consisting of 19 secondary cores embedded in a pedestal geometry is presented. This design offers the possibility of precisely tailoring the rare earth ion distribution in the core in order to manage the differential modal gain. An optimized configuration of an erbium-doped few-mode fiber supporting 10 modes in the C-band with a theoretical low gain excursion is designed and realized. Preliminary optical characterizations of this fiber are presented.

Top hat single-mode polarization maintaining fiber and polarizing numerical design

Compactness, long term stability and no free-space alignment are important advantages of fiber lasers over bulky systems. These fiber lasers have also demonstrated their capability to deliver high-power pulses and are thus suitable for numerous applications. Nevertheless the intensity profile delivered usually has a Gaussian-like shape, which most of the time is sufficient, but it could be interesting, for many applications (laser-biological tissues interactions, heat treatment, industrial laser processing or for seeding large-scale laser facilities like Laser MegaJoule) to obtain a homogeneous intensity profile at the fiber laser output. Moreover several of these applications required a linearly polarized output beam. In order to achieve all these requirements we have developed and realized a new fiber design. This fiber is the first polarization maintaining single-mode fiber delivering a flat top intensity. A high quality flat mode was obtained at 1.05μm through the use of a well-tailored index profile and single-mode behavior was verified by shifting the injection and using the S² imaging. Moreover, boron Stress Applying Parts (SAPs) including in the cladding led to a birefringence of 0.6x10-4 and a measured PER better than 20dB even for a long fiber length (~20 m). Alongside the fabrication, we developed a simulation code, using Comsol Multiphysics®, to take into account the stress dependency induced by the SAPs. Further modeling allows us to present an effectively single-mode fiber design, delivering a top-hat mode profile and exhibiting a polarizing behavior.