Lipase-catalyzed kinetic resolution of (±)-mandelonitrile under conventional condition and microwave irradiation

The kinetic resolution of (±)-mandelonitrile was carried out using lipase from Candida antarctica under conventional condition (orbital shaker) and microwave irradiation in toluene, producing the (S)-mandelonitrile acetate with high selectivity (up to > 98% ee, enantiomeric excess). The unreacted (R)-mandelonitrile under microwave irradiation and conventional condition was partially converted into benzaldehyde by spontaneous chemical equilibrium. The (S)-mandelonitrile acetate under microwave irradiation was produced with 92% ee and 35% yield for 8 h of reaction. Conventional transesterification of (±)-mandelonitrile in an orbital shaker produced unreacted (R)-mandelonitrile (51% ee) and (S)-mandelonitrile acetate (98% ee) in accordance with Kazlauskas rule for 184 h of reaction.

Efficient 1535 nm light emission from an all-Si-based optical micro-cavity containing Er3+ and Yb3+ ions

This work reports on the construction and spectroscopic analyses of optical micro-cavities (OMCs) that efficiently emit at ~1535 nm. The emission wavelength matches the third transmission window of commercial optical fibers and the OMCs were entirely based on silicon. The sputtering deposition method was adopted in the preparation of the OMCs, which comprised two Bragg reflectors and one spacer layer made of either Er- or ErYb-doped amorphous silicon nitride. The luminescence signal extracted from the OMCs originated from the 4I13/2→4I15/2 transition (due to Er3+ ions) and its intensity showed to be highly dependent on the presence of Yb3+ ions.According to the results, the Er3+-related light emission was improved by a factor of 48 when combined with Yb3+ ions and inserted in the spacer layer of the OMC. The results also showed the effectiveness of the present experimental approach in producing Si-based light-emitting structures in which the main characteristics are: (a) compatibility with the actual microelectronics industry, (b) the deposition of optical quality layers with accurate composition control, and (c) no need of uncommon elements-compounds nor extensive thermal treatments. Along with the fundamental characteristics of the OMCs, this work also discusses the impact of the Er3+-Yb3+ ion interaction on the emission intensity as well as the potential of the present findings.

A simple-versatile approach to achieve all-Si-based optical micro-cavities

At present, solid thin films are recognized by their well established and mature processing technology that is able to produce components which, depending on their main characteristics, can perform either passive or active functions. Additionally, Si-based materials in the form of thin films perfectly match the concept of miniaturized and low-consumption devices-as required in various modern technological applications. Part of these aspects was considered in the present work that was concerned with the study of optical micro-cavities entirely based on silicon and silicon nitride thin films. The structures were prepared by the sputtering deposition method which, due to the adopted conditions (atmosphere and deposition rate) and arrangement of layers, provided cavities operating either in the visible (at ~ 670 nm) or in the near-infrared (at ~ 1560 nm) wavelength ranges. The main differential of the work relies on the construction of optical microcavities with a reduced number of periods whose main properties can be changed by thermal annealing treatments. The work also discusses the angle-dependent behavior of the optical transmission profiles as well as the use of the COMSOL software package to simulate the microcavities.

Sistemi multistrato per il miglioramento del comportamento tribologico dell'acciaio inossidabile AISI 316L: cementazione a bassa temperatura seguita da deposizione PACVD di carbonio amorfo (a-C:H)

Gli acciai inossidabili austenitici presentano ottime caratteristiche che li rendono ideali in tutti quei settori in cui è richiesta un’elevata resistenza alla corrosione associata a caratteristiche estetiche e funzionali. L’acciaio AISI 316L risulta essere uno dei più studiati ed utilizzati, specie nell’industria alimentare e farmaceutica, dove leapparecchiature debbono poter essere sottoposte ad aggressive procedure di sanificazione. Tuttavia, la modesta resistenza meccanica e la bassa durezza superficiale di questo acciaio determinano un comportamento non soddisfacente dal punto di vista dell’usura da strisciamento in assenza di lubrificanti, situazione che si verifica sovente in molti macchinari dedicati a queste industrie. Tra le varie soluzioni, studiate per migliorare il suo comportamento tribologico, la cementazione a bassa temperatura (LowTemperature Carburizing, LTC) seguita dalla deposizione PE-CVD (Plasma-Enhanced Chemical Vapour Deposition) di un rivestimento di carbonio amorfo idrogenato (a-C:H), sembra essere molto promettente. In questo lavoro vengono analizzate le caratteristiche tribologiche dell’acciaio AISI 316L cementato a bassa temperatura e rivestito di carbonio amorfo idrogenato, tramite prove tribologiche di strisciamento non lubrificato in geometria di contatto pattino su cilindro. Sono state verificate, inoltre, le caratteristiche microstrutturali e meccaniche superficiali del rivestimento multistrato LTC/a-C:H tramite osservazioni morfologiche/topografiche, analisi in spettroscopia micro-Raman e misure di indentazione strumentata sulle superfici rivestite, seguite da analisi metallografia e misura dei profili di microdurezza Vickers in sezione trasversale. I risultati ottenuti dimostrano che, ai fini di contenere l’effetto negativo legato all’aumento di rugosità dovuto al trattamento LTC, è opportuno effettuare una lucidatura precedente al trattamento stesso, poiché effettuandola successivamente si rischierebbe dicomprometterne lo strato efficace. Inoltre, si osserva come il trattamento LTC incrementi le capacità del substrato di supportare il rivestimento a-C:H, portando ad un miglioramento delle prestazioni tribologiche, nelle prove di strisciamento non lubrificato. Infine, si dimostra come l’utilizzo di un rivestimento a base di carbonio amorfo idrogenato adeguatamente supportato permetta una riduzione dell’attrito (di oltre cinque volte) e dell’usura (di circa dieci ordini di grandezza) rispetto ai corrispondenti materiali non rivestiti.

Abscheidung und Charakterisierung von Plasmapolymerschichten auf Fluorkohlenstoff- und Siloxan-Basis

In dieser Arbeit wurden Fluorkohlenstoff-basierte und siliziumorganische Plasmapolymerfilme hergestellt und hinsichtlich ihrer strukturellen und funktionalen Eigenschaften untersucht. Beide untersuchten Materialsysteme sind in der Beschichtungstechnologie von großem wissenschaftlichen und anwendungstechnischen Interesse. Die Schichtabscheidung erfolgte mittels plasmachemischer Gasphasenabscheidung (PECVD) an Parallelplattenreaktoren. Bei den Untersuchungen zur Fluorkohlenstoff-Plasmapolymerisation stand die Herstellung ultra-dünner, d. h. weniger als 5 nm dicker Schichten im Vordergrund. Dies wurde durch gepulste Plasmaanregung und Verwendung eines Gasgemisches aus Trifluormethan (CHF3) und Argon realisiert. Die Bindungsstruktur der Schichten wurden in Abhängigkeit der eingespeisten Leistung, die den Fragmentationsgrad der Monomere im Plasma bestimmt, analysiert. Hierzu wurden die Röntgen-Photoelektronenspektroskopie (XPS), Rasterkraftmikroskopie (AFM), Flugzeit-Sekundärionenmassenspektrometrie (ToF-SIMS) und Röntgenreflektometrie (XRR) eingesetzt. Es zeigte sich, dass die abgeschiedenen Schichten ein homogenes Wachstumsverhalten und keine ausgeprägten Interfacebereiche zum Substrat und zur Oberfläche hin aufweisen. Die XPS-Analysen deuten darauf hin, dass Verkettungsreaktionen von CF2-Radikalen im Plasma eine wichtige Rolle für den Schichtbildungsprozess spielen. Weiterhin konnte gezeigt werden, dass der gewählte Beschichtungsprozess eine gezielte Reduzierung der Benetzbarkeit verschiedener Substrate ermöglicht. Dabei genügen Schichtdicken von weniger als 3 nm zur Erreichung eines teflonartigen Oberflächencharakters mit Oberflächenenergien um 20 mN/m. Damit erschließen sich neue Applikationsmöglichkeiten ultra-dünner Fluorkohlenstoffschichten, was anhand eines Beispiels aus dem Bereich der Nanooptik demonstriert wird. Für die siliziumorganischen Schichten unter Verwendung des Monomers Hexamethyldisiloxan (HMDSO) galt es zunächst, diejenigen Prozessparameter zu identifizieren, die ihren organischen bzw. glasartigen Charakter bestimmen. Hierzu wurde der Einfluss von Leistungseintrag und Zugabe von Sauerstoff als Reaktivgas auf die Elementzusammensetzung der Schichten untersucht. Bei niedrigen Plasmaleistungen und Sauerstoffflüssen werden vor allem kohlenstoffreiche Schichten abgeschieden, was auf eine geringere Fragmentierung der Kohlenwasserstoffgruppen zurückgeführt wurde. Es zeigte sich, dass die Variation des Sauerstoffanteils im Prozessgas eine sehr genaue Steuerbarkeit der Schichteigenschaften ermöglicht. Mittels Sekundär-Neutralteilchen-Massenspektrometrie (SNMS) konnte die prozesstechnische Realisierbarkeit und analytische Quantifizierbarkeit von Wechselschichtsystemen aus polymerartigen und glasartigen Lagen demonstriert werden. Aus dem Intensitätsverhältnis von Si:H-Molekülen zu Si-Atomen im SNMS-Spektrum ließ sich der Wasserstoffgehalt bestimmen. Weiterhin konnte gezeigt werden, dass durch Abscheidung von HMDSO-basierten Gradientenschichten eine deutliche Reduzierung von Reibung und Verschleiß bei Elastomerbauteilen erzielt werden kann.

Caratterizzazione tribologica e microstrutturale di acciai sottoposti a trattamenti duplex (trattamenti termochimici di diffusione seguiti da deposizione di rivestimenti in carbonio amorfo DLC)

Lo studio condotto in questa tesi ha lo scopo di esplorare possibili soluzioni alternative per aumentare la vita in esercizio di componenti per un contatto tribologico da strisciamento in motori idraulici. In particolare, per limitare l’usura e ridurre l’attrito fra i corpi a contatto, è stata presa in considerazione la deposizione di rivestimenti in carbonio amorfo idrogenato, appartenenti alla famiglia dei rivestimenti DLC (Diamond-Like Carbon), prodotti con tecnologia PACVD (Plasma Assisted Chemical Vapour Deposition), grazie alla collaborazione con la ditta STS srl presso la quale sono state prodotte ed in parte caratterizzate diverse tipologie di strati sottili a base carbonio-carbonio. Questa scelta è stata motivata dal fatto che i rivestimenti DLC combinano basso attrito ed alta resistenza ad usura, dato che l’elevata durezza (e resistenza ad usura) è data dalla presenza di un’elevata frazione di C ibridati sp3 (con struttura simil-diamante) fra loro interconnessi, mentre la tendenza al basso attrito contro la maggior parte degli antagonisti deriva dalla struttura lamellare (quindi a basso sforzo di taglio), tipica del C sp2 (simil-grafite), che permette lo scorrimento fra i piani basali. Nel corso del presente lavoro sono quindi stati presi in esame due gruppi di rivestimenti DLC, differenziati in base alla tipologia di interstrato impiegato per moderare le tensioni residue e migliorare l’adesione (CrN singolo strato o WC/C multistrato), depositati su acciaio 20MnV6 sottoposto preliminarmente a cementazione gassosa per ottenere una adeguata capacità di supporto del carico. Gli strati in esame sono stati caratterizzati dal punto di vista microstrutturale e meccanico (con prove sia di adesione e con prove di nanoindentazione). Successivamente, i materiali rivestiti sono stati sottoposti a prove tribologiche di laboratorio (block-on-ring) in condizioni di strisciamento non lubrificato, per effettuare una valutazione comparativa fra i rivestimenti ed identificare i meccanismi di usura prevalenti nelle diverse coppie tribologiche.

Nano-scale morphological and electrical characterization of nc-SiOxNy thin layers for photovoltaic applications

Il presente lavoro di tesi propone uno studio approfondito di proprietà morfologiche e di trasporto di carica di film sottili di SiOxNy amorfi (a-SiOxNy) e nanocristallini (nc-SiOxNy), che trovano importanti applicazioni in celle fotovoltaiche ad eterogiunzione in silicio, ad alta efficienza. Lo studio è condotto mediante caratterizzazione elettrica e morfologica attraverso tecniche di microscopia a forza atomica (AFM). Sono stati studiati campioni di a-SiOxNy cresciuti con tecnica PECVD (Plasma Enhanced Chemical Vapor Deposition), in cui è stata variata unicamente la distanza tra gli elettrodi durante la deposizione. Sono stati inoltre studiati campioni di nc-SiOxNy, cresciuti con PECVD con una differente percentuale di N2O come gas precursore e un differente tempo di annealing. In entrambi i casi si tratta di un materiale innovativo, le cui proprietà fisiche di base, nonostante le numerose applicazioni, sono ancora poco studiate. L'analisi morfologica, condotta mediante AFM e successiva analisi statistica delle immagini, ha permesso di determinare alcune proprietà morfologiche dei campioni. L’analisi statistica delle immagini è stata validata, dimostrandosi stabile e consistente per lo studio di queste strutture. Lo studio delle proprietà di trasporto è stato condotto mediante acquisizione di mappe di corrente con tecnica conductive-AFM. In questo modo si è ottenuta una mappa di conducibilità locale nanometrica, che permette di comprendere come avviene il trasporto nel materiale. L'analisi di questo materiale mediante tecniche AFM ha permesso di evidenziare che l'annealing produce nei materiali nanocristallini sia un clustering della struttura, sia un significativo aumento della conducibilità locale del materiale. Inoltre la distanza tra gli elettrodi in fase di deposizione ha un leggero effetto sulle dimensioni dei grani. È da notare inoltre che su questi campioni si sono osservate variazioni locali della conducibilità alla nanoscala. L’analisi delle proprietà dei materiali alla nanoscala ha contribuito alla comprensione più approfondita della morfologia e dei meccanismi di trasporto elettronico.

Development of a multifunctional platform for extra- and intracellular ionic activities recording

We present the development of a multifunctional platform equipped with an array of silicon nitride micropipettes with dimensions allowing the implementation of extra- and intracellular operations. Micropipettes with outer diameter that ranges from 6 mum down to 300 nm and with walls thicknesses of 500 down to 150 nm are presented. The generic technology developed to fabricate these micropipettes has a number of advantages, including the ability to be implemented as ion-selective electrodes for (A) intracellular and (B) extracellular recordings and as (C) local drug microdispensers.

Transport of 234U in the Opalinus Clay on centimetre to decimetre scales

The Opalinus Clay formation in North Switzerland is a potential host rock for a deep underground radioactive waste repository. The distribution of U-238, U-234 and Th-230 was studied in rock samples of the Opalinus Clay from an exploratory borehole at Benken (Canton of Zurich) using MC-ICP-MS. The aim of U-234 was to assess the in situ, long-term migration behaviour in this rock. Very low hydraulic conductivities of the Opalinus Clay, reducing potential of the pore water and its chemical equilibrium with the host rock are expected to render both U-238 and Th-230 immobile. If U is heterogeneously distributed in the Opalinus Clay, gradients in the supply of U-234 from the rock matrix to the pore water by the decay of U-238 will be established. Diffusive redistribution separates U-234 from its immobile parent U-238 resulting in bulk rock U-234/U-238 activity disequilibria. These may provide a means of estimating the mobility of U-234 in the rock if the diffusion rate of U-234 is significant compared to its decay rate. Sampling was carried out on two scales. Drilling of cm-spaced samples from the drill-core was done to study mobility over short distances and elucidate possible small-scale lithological control. Homogenized 25-cm-long portions of a 2-m-long drill-core section were prepared to provide information on transport over a longer distance. Variations in U and/or Th content on the cm-scale between clays and carbonate-sandy layers are revealed by beta-scanning, which shows that the (dominant) clay is richer in both elements. Samples were digested using aqua regia followed by total HF dissolution, yielding two fractions. in all studied samples U was found to be concentrated in the HF digestion fraction. It has a high U/Th ratio and a study by SEM-EDS points to sub-mu m up to several mu m in size zircon grains as the main U-rich phase. This fraction consistently has U-234/U-238 activity ratios below unity. The minute zircon grains constitute the major reservoir of U in the rock and act as constant rate suppliers of U-234 into the rock matrix and the pore water. The aqua regia leach fraction was found to be enriched in Th, and complementary to the HF fraction, having U-234/U-238 activity ratios above unity. It is believed that these U activity ratios reflect the surplus of having U-234 delivered from the zircon grains. Some cm-spaced samples show bulk rock U-234/U-238 activity ratios that are markedly out of equilibrium. In most of them a striking negative correlation between the total U content and the bulk rock U-234/U-238 activity ratios is observed. This is interpreted to indicate net U-234 transfer from regions of higher supply of U-234 towards those of lower supply which is, in most cases, equivalent to transfer from clayey towards carbonate/sandy portions of the rock. In contrast, the 25 cm averaged samples all have uniform bulk rock U-234/U-238 activity ratios in equilibrium, indicating U immobility in the last 1-1.5 Ma on this spatial scale. It is concluded that the small-scale lithological variations which govern U spatial distribution in the Opalinus Clay are the major factor determining U-234 in situ supply rates, regulating its diffusive fluxes and controlling the observed bulk rock U-234/U-238 activity ratios. A simple box-model is presented to simulate the measured bulk rock U-234/U-238 activity ratios and to give an additional insight into the studied system. (C) 2008 Elsevier Ltd. All rights reserved.

Gravitational wave background from Standard Model physics: qualitative features

Because of physical processes ranging from microscopic particle collisions to macroscopic hydrodynamic fluctuations, any plasma in thermal equilibrium emits gravitational waves. For the largest wavelengths the emission rate is proportional to the shear viscosity of the plasma. In the Standard Model at 0T > 16 GeV, the shear viscosity is dominated by the most weakly interacting particles, right-handed leptons, and is relatively large. We estimate the order of magnitude of the corresponding spectrum of gravitational waves. Even though at small frequencies (corresponding to the sub-Hz range relevant for planned observatories such as eLISA) this background is tiny compared with that from non-equilibrium sources, the total energy carried by the high-frequency part of the spectrum is non-negligible if the production continues for a long time. We suggest that this may constrain (weakly) the highest temperature of the radiation epoch. Observing the high-frequency part directly sets a very ambitious goal for future generations of GHz-range detectors.

Nd and Mn concentration in planktonic foraminifera

Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ~20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

Strontium and neodymium concentrations and isotope compositions in fossil fish teeth and pore waters at ODP Sites 130-807 and 125-786

We analyzed Nd and Sr isotopic compositions of Neogene fossil fish teeth from two sites in the Pacific in order to determine the effect of cleaning protocols and burial diagenesis on the preservation of seawater isotopic values. Sr is incorporated into the teeth at the time of growth; thus Sr isotopes are potentially valuable for chemostratigraphy. Nd isotopes are potential conservative tracers of paleocirculation; however, Nd is incorporated post-mortem, and may record diagenetic pore waters rather than seawater. We evaluated samples from two sites (Site 807A, Ontong Java Plateau and Site 786A, Izu-Bonin Arc) that were exposed to similar bottom waters, but have distinct lithologies and pore water chemistries. The Sr isotopic values of the fish teeth appear to accurately reflect contemporaneous seawater at both sites. The excellent correlation between the Nd isotopic values of teeth from the two sites suggests that the Nd is incorporated while the teeth are in chemical equilibrium with seawater, and that the signal is preserved over geologic timescales and subsequent burial. These data also corroborate paleoseawater Nd isotopic compositions derived from Pacific ferromanganese crusts that were recovered from similar water depths (Ling et al., 1997; doi:10.1016/S0012-821X(96)00224-5). This corroboration strongly suggests that both materials preserve seawater Nd isotope values. Variations in Pacific deepwater e-Nd values are consistent with predictions for the shoaling of the Isthmus of Panama and the subsequent initiation of nonradiogenic North Atlantic Deep Water that entered the Pacific via the Antarctic Circumpolar Current.

Laser-fired contact optimization in c-Si solar cells

In this work we study the optimization of laser-fired contact (LFC) processing parameters, namely laser power and number of pulses, based on the electrical resistance measurement of an aluminum single LFC point. LFC process has been made through four passivation layers that are typically used in c-Si and mc-Si solar cell fabrication: thermally grown silicon oxide (SiO2), deposited phosphorus-doped amorphous silicon carbide (a-SiCx/H(n)), aluminum oxide (Al2O3) and silicon nitride (SiNx/H) films. Values for the LFC resistance normalized by the laser spot area in the range of 0.65–3 mΩ cm2 have been obtained

Growth of AlN oriented films on insulating substrates.

This work describes the structural and piezoelectric assessment of aluminum nitride (AlN) thin films deposited by pulsed-DC reactive sputtering on insulating substrates. We investigate the effect of different insulating seed layers on AlN properties (crystallinity, residual stress and piezoelectric activity). The seed layers investigated, silicon nitride (Si3N4), silicon dioxide (SiO2), amorphous tantalum oxide (Ta2O5), and amorphous or nano-crystalline titanium oxide (TiO2) are deposited on glass plates to a thickness lower than 100 nm. Before AlN films deposition, their surface is pre-treated with a soft ionic cleaning, either with argon or nitrogen ions. Only AlN films grown of TiO2 seed layers exhibit a significant piezoelectric activity to be used in acoustic device applications. Pure c-axis oriented films, with FWHM of rocking curve of 6º, stress below 500 MPa, and electromechanical coupling factors measured in SAW devices of 1.25% are obtained. The best AlN films are achieved on amorphous TiO2 seed layers deposited at high target power and low sputtering pressure. On the other hand, AlN films deposited on Si3N4, SiO2 and TaOx exhibit a mixed orientation, high stress and very low piezoelectric activity, which invalidate their use in acoustic devices.

The internal structure of hydrogen-air difussion flames

The Internal Structure of Hydrogen-Air Diffusion Flames. Tho purpose of this paper is to study finite rate chemistry effects in diffusion controlled hydrogenair flames undor conditions appearing in some cases in a supersonic combustor. Since for large reaction rates the flame is close to chemical equilibrium, the reaction takes place in a very thin region, so thata "singular perturbation "treatment" of the problem seems appropriate. It has been shown previously that, within the inner or reaction zone, convection effects may be neglocted, the temperature is constant across the flame, and tho mass fraction distributions are given by ordinary differential equations, whore tho only independent variable involved is tho coordinate normal to the flame surface. Tho solution of the outer problom, which is a pure mixing problem with the additional condition that fuol and oxidizer do not coexist in any zone, provides t h e following information: tho flame position, rates of fuel consumption, temperature, concentrators of species, fluid velocity outside of tho flame, and the boundary conditions required to solve the "inner problem." The main contribution of this paper consists in the introduction of a fairly complicated chemical kinetic scheme representing hydrogen-oxygen reaction. The nonlinear equations expressing the conservation of chemical species are approximately integrated by means of an integral method. It has boen found that, in the case considered of a near-equilibrium diffusion flame, tho role played by the dissociation-recombination reactions is purely marginal, and that somo of the second order "shuffling" reactions are close to equilibrium. The method shown here may be applied to compute the distanco from the injector corresponding to a given separation from equilibrium, say ten to twenty percent. For the casos whore this length is a small fraction of the combustion zone length, the equilibrium treatment describes properly tho flame behavior.