‘SAUVEUR‘1 st June 2006Fabian Käser BUA Lifetime prediction of solid materials using chemiluminescence to characterise oxidative reactions and model-free.

Slides:



Advertisements
Similar presentations
Atkins & de Paula: Atkins’ Physical Chemistry 9e
Advertisements

Aim: Creating the model of thermal decomposition of energetic material (tetryl). Data:4 results (data sets) of DSC experiment carried out in linear heating.
Kinetics Quick Review. Radioactive Decay and Kinetics.
Application of Bayesian Statistical Methods for the Analysis of DSMC Simulations of Hypersonic Shocks James S. Strand and David B. Goldstein The University.
Mathematical Modeling Overview on Mathematical Modeling in Chemical Engineering By Wiratni, PhD Chemical Engineering Gadjah Mada University Yogyakarta.
Chemical Kinetics © 2009, Prentice-Hall, Inc. Temperature and Rate Generally, as temperature increases, so does the reaction rate. This is because k is.
Chemiluminescence – a tool for determination of degree of oxidation of polymers + Residual service life Jozef Rychlý Polymer Institute Dúbravská cesta.
AA and Atomic Fluorescence Spectroscopy Chapter 9
“Cool Light”. Three types of “Cool Light” Fluorescence: Fluorescence: higher energy radiation is absorbed by a species and stored Phosphorescence: Phosphorescence:
Ahmad Aqel Ifseisi Assistant Professor of Analytical Chemistry College of Science, Department of Chemistry King Saud University P.O. Box 2455 Riyadh
Activation Energy and Catalyst. Temperature and Rate Generally, as temperature increases, so does the reaction rate. This is because k is temperature.
Kinetic Data for Polymers
The Thermodynamics and Kinetics of Explosives Thomas M. Jerant Cindy D. Spangler.
1 st Workshop on Photo-cathodes: nm Klaus Attenkofer, Karen Byrum, Henry Frisch, Oswald Siegmund July 20-21, 2009: University of Chicago.
Data Analysis Issues in Time-Resolved Fluorescence Anisotropy Bill Laws Department of Chemistry University of Montana Support from NSF EPSCoR, NIH, and.
Atkins’ Physical Chemistry Eighth Edition Chapter 22 – Lecture 2 The Rates of Chemical Reactions Copyright © 2006 by Peter Atkins and Julio de Paula Peter.
Electronic Excitation in Atomic Collision Cascades COSIRES 2004, Helsinki C. Staudt Andreas Duvenbeck Zdenek SroubekFilip Sroubek Andreas Wucher Barbara.
Lecture 11 Chemical Reaction Engineering (CRE) is the field that studies the rates and mechanisms of chemical reactions and the design of the reactors.
Photoelectron Spectroscopy Lecture 7 – instrumental details –Photon sources –Experimental resolution and sensitivity –Electron kinetic energy and resolution.
6-1 RFSS: Lecture 6 Gamma Decay Part 2 Readings: Modern Nuclear Chemistry, Chap. 9; Nuclear and Radiochemistry, Chapter 3 Energetics Decay Types Transition.
Fabrice Laturelle, Snecma Moteurs
What is a DSC? What is DSC? Differential: measurement of the difference in heat flow from sample and reference side Scanning: the common operation.
Organic Reactions Kinds of Reactions Mechanisms (polar, non-polar) Bond Dissociation Energy Reaction Profiles.
Chemiluminescence Producing light with chemicals Rachel Eisenbraun Chemistry Outreach, Chem 292.
Collision Rate Model Three conditions must be met at the nano- scale level if a reaction is to occur: the molecules must collide; they must be positioned.
Determination of fundamental constants using laser cooled molecular ions.
= rate = rate constant derived definition: Rate law can be written from molecularity Lowers the E a by making a new ______________ Why? Experimentally.
AOSC 634 Air Sampling and Analysis
The Experimental Program of the “FLASH” Experiment.
Kinetics The Study of Rates of Reaction. Rate of a Reaction The speed at which the reactants disappear and the products are formed determines the rate.
Lecture 5 Intermolecular electronic energy transfer
Experimental and computational studies of elementary reactions involving small radicals Combustion chemistry Planetary and interstellar chemistry The kinetics.
Chapter 15 Molecular Luminescence Spectrometry Three types of Luminescence methods are: (i) molecular fluorescence (ii) phosphorescence (iii) chemiluminescence.
13-1 CHEM 102, Spring 2012, LA TECH CTH 328 9:30-10:45 am Instructor: Dr. Upali Siriwardane Office: CTH 311 Phone Office.
© 2014 Carl Lund, all rights reserved A First Course on Kinetics and Reaction Engineering Class 13.
The LBNL submission Fabian Wagner (joint work with Jayant Sathaye, LBNL)
Possible calibration methods for the final LXe calorimeter A. Papa 01/20/2004.
Reaction Mechanisms in Inorganic Chemistry. Elementary Reaction Kinetics: A Review of the Fundamentals.
Reaction Rates AP chapter Reaction Rates Describe how quickly concentration of reactants or products are changing Units typically  M/  t for aqueous.
Thermal Analysis Techniques
The Arrhenius Equation AP Chemistry Unit 8 Kinetics.
A.P. Exam Review Regular Review Day 4. Big Idea #4 Rates of chemical reactions are determined by details of the molecular collisions.
Status of AIRFLY fluorescence yield measurements Paolo Privitera Università di Roma Tor Vergata, INFN Prague, May 19, 2006.
© 2014 Carl Lund, all rights reserved A First Course on Kinetics and Reaction Engineering Class 13.
Single photon counting detector for THz radioastronomy. D.Morozov 1,2, M.Tarkhov 1, P.Mauskopf 2, N.Kaurova 1, O.Minaeva 1, V.Seleznev 1, B.Voronov 1 and.
The first law of Thermodynamics. Conservation of energy 2.
Chemical Kinetics Chapter 14. Reminders Assignment 1 due today (end of class) Assignment 2 up on ACME, due Jan. 29 (in class) Assignment 3 will be up.
1 B. Roduit (1), P. Guillaume (2), S. Wilker (3), P. Folly (4), A. Sarbach (4), B. Berger (4), J. Mathieu (4), M. Ramin (5), B. Vogelsanger (5) (1) AKTS.
13-1 CHEM 102, Spring 2015, LA TECH Instructor: Dr. Upali Siriwardane Office: CTH 311 Phone Office Hours: M,W 8:00-9:30.
Instability of optical speckle patterns in cold atomic gases ? S.E. Skipetrov CNRS/Grenoble (Part of this.
Kinetic analysis of Temperature Programmed Reduction R. Jude vimal Michael National Centre for Catalysis Research 31 January 2009.
Chemical Kinetics How quickly does that chemical reaction occur?
DESCRIPTION OF PIXIRAD  The PIXIRAD Imaging Counter is an INFN-Pisa Spin-off  It works in photon counting  Pulse discrimination with two thresholds.
THERMAL ANALYSIS FOR PREFORMULATION TRIALS
Luminescence.
Combustion Control based on Flame Ionization Application in Condensing Heating Appliances by: Martin Kiefer 07 June 2012 Venue: EF5.B: WOC5 Gas Quality.
T 1/2 : Half Life Chemical Kinetics-6. Can be derived from integrated rate law.
Željko V. Despotović, Miloš.D. Jovanović Mihajlo Pupin Institute, University of Belgrade, Serbia
Fred Hartjes 1 RD51 mini week, CERN, June 14, 2012 Implementing GridPix in a Darwin detector Matteo Alfonsi, Niels van Bakel, Patrick Decowski, Harry van.
Electronic Structure Determination of CuRh 1-x Mg x O 2 using Soft X-Ray Spectroscopies.
7th International DOAS Workshop Brussels 2015
Recycling of APC fly ash in a pilot-scale road subbase
Ultrafast Spectroscopy
Y. Mongbanziama, S. Aeby, S. Roth and P. Brodard
Really Basic Optics Instrument Sample Sample Prep Instrument Out put
CHEM 312: Lecture 6 Part 2 Gamma Decay
Progress on whole atmosphere lidar
TGA and DSC. Thermal analysis ○Thermal analysis is a branch of materials science where the properties of materials are studied as they change with temperature.
Diameter Control of Single-Walled Metal Oxide Nanotubes
GRAPHICAL DETERMINATION OF ΔHº AND ΔSº
Presentation transcript:

‘SAUVEUR‘1 st June 2006Fabian Käser BUA Lifetime prediction of solid materials using chemiluminescence to characterise oxidative reactions and model-free simulation based on experimental data Fabian Käser Berne University of the Arts - BUA

‘SAUVEUR‘1 st June 2006Fabian Käser BUA Oxidation -the major cause of degradation of most organic materials! -even occurs under ambient environmental conditions => Aim: prediction of lifetime expectancy under given, realistic conditions

‘SAUVEUR‘1 st June 2006Fabian Käser BUA Aim: Lifetime prediction

‘SAUVEUR‘1 st June 2006Fabian Käser BUA Abstract New approach of lifetime prediction: -experimental data acquisition using Chemiluminescence method -full kinetic analysis -lifetime prediction  conclusion

‘SAUVEUR‘1 st June 2006Fabian Käser BUA Experimental data acquisition Testing stability by high temperature methods (conventional thermal analysis) Disadvantage: -very high temperature profiles -high possibility of phase transitions => doubtful correlation to long-term stability (different kinetic behaviour)

1 st June 2006Fabian Käser BUA ‘SAUVEUR‘ Chemiluminescence CL method -light emission resulting from chemical energy -relaxation of excited electrons -especially during oxidation: 3 R=O* -mechanism not yet clarified entirely

1 st June 2006Fabian Käser BUA ‘SAUVEUR‘ Advances of CL method very high sensitivity moderate experimental conditions: T exp close to RT CL-signal is not overlapped by other thermal effects excellent baseline stability differentiation of ROOH-decay and mechanism of oxidation acquisition of inhomogeneous character of oxidation reactions implementation of rH% as oxidative factor below 95°C acquisition of oxidationkinetics of most organic materials => numerous applications

1 st June 2006Fabian Käser BUA ‘SAUVEUR‘ CL instrumentation oven: precise controll of T gas exchange facility optical path: as short as possible shutter system detector: PMT photon counting mode thermoelectrically cooled spectral range of CL

1 st June 2006Fabian Käser BUA ‘SAUVEUR‘ Fields of application 120°C 110°C 100°C 90°C 80°C unstabilised stabilised

‘SAUVEUR‘1 st June 2006Fabian Käser BUA Advanced kinetic analysis 1. baseline optimisation of experimental data 2. isoconversional kinetic analysis: -ln (dα / dt) vs. T -1 (Arrhenius based) -E A = slope of ln (dα / dt) vs. T -1 -  (α) is constant for every state of reaction α i = isoconversional analysis

‘SAUVEUR‘1 st June 2006Fabian Käser BUA Prediction of reaction progress Description of reaction rate dependent of reaction progress alpha at any given temperature profile -isothermal -non-isothermal -modulated -customised climate conditions

‘SAUVEUR‘1 st June 2006Fabian Käser BUA °C °C °C °C °C °C °C °C Prediction: isothermal conditions

‘SAUVEUR‘1 st June 2006Fabian Käser BUA Prediction: modulated conditions

‘SAUVEUR‘1 st June 2006Fabian Käser BUA Conclusion Useful approach to predict lifetime and to assess treatment effects in context of conservation-restoration. Procedure consists of: -data acquisition using CL -full kinetic analysis -prediction of oxidation reaction progress

1 st June 2006Fabian Käser BUA ‘SAUVEUR‘ „… Chemiluminescence which has developed as the most sensitive method for detection of oxidation …“ Popíšil, J. et al., Polymer Degradation and Stability., 82 (2003), 155.