www.mtmml.gr

Laboratory Director: Dr. Ioannis G. Economou

2008 Activities Report

I. Research work

Research work in the Molecular Thermodynamics and Modeling of Materials Laboratory (MTMML) focuses on the development and implementation of novel hierarchical methods and algorithms for the computer modelling and calculation of advanced material properties at the molecular, mesoscopic and macroscopic levels. Through this work, quantitative links are established between chemical constitution, processing conditions, and physical (thermal, mechanical, rheological, transport, interfacial, optical, dielectric) properties, which are critical for the optimal design of industrial processes and also govern the end-use performance of commercial products. In parallel, the molecular mechanisms underlying structure - property - processing - performance relations are elucidated with the objective of designing new, tailor-made materials.

The hierarchical approaches developed and implemented at MTMML start with atomistic simulations addressing length scales on the order of tens of nanometers and time scales on the order of tens of nanoseconds (e.g., Monte Carlo, molecular dynamics, transition-state theory analysis of infrequent events) and proceed with mesoscopic methods (e.g., entanglement network modelling, kinetic Monte Carlo simulation, self-consistent field theory of inhomogeneous systems) to address longer time- and length scale phenomena. Finally, for the efficient design of novel processes mainly for the chemical, polymer and pharmaceutical industry, accurate macroscopic models, mostly in the form of equations of state (eos), are developed for phase equilibria and other thermodynamic properties of multicomponent mixtures. These eos are rooted to statistical mechanics and can be safely extrapolated to conditions where limited or no experimental data exist.

Research work in 2008 focused on:

(a) Molecular simulation of elastomeric and glassy polymers,

(b) Polymer solutions and blends,

(c) Sorption and diffusion of small molecules in silicon-containing polymers,

(d) Molecular simulation of polar homo- and co-polymers,

(e) Mesoscopic simulation of polydisperse colloids,

(f) Thermodynamic properties of polar fluids in pure and in mixture,

(g) Ionic liquids in pure and in mixture with supercritical carbon dioxide or water,

(h) Development of a new EoS based on lattice theory for pharmaceutical solutions (new activity initiated in 2008),

(i) Development of a new molecular model for the prediction of solubility of pharmaceuticals in water and other solvents (new activity initiated in 2008).

In order to strengthen the collaboration with industry, a new project dedicated to research services was formed entitled Molecular Simulation and Thermodynamics of Fluids and Advanced Materials co-ordinated by Dr, I. Economou. Within less than a year, the project has signed three research contracts with industry with a total budget of € 53,700.

More information about MTMML can be found at: www.mtmml.gr.

II. Personnel

Researchers: Dr. Ioannis G. Economou, Researcher A’, Laboratory Director

Research Scientist: Dr. Niki Vergadou

Collaborating Researcher: Dr. Nikolas Zacharopoulos (faculty under contract, University of the Aegean)

Post-doctoral scientists in projects:

• Dr. Theodora Spyriouni (EU-STREP until 28/2/2008 and then on industrial research contracts)

• Dr. Stelios Karanikas (GSRT – ENTER until 30/5/2008)

PhD students:

• Zoi Makrodimitri (GSRT – PENED)

• Marianna Yiannourakou

• Eleni Androulaki (Demokritos PhD fellow)

Senior undergraduate students:

• Vassilios Niotis (School of Chemical Engineering, NTUA)

Visiting researchers:

• Δρ. Stanislav Burov (1 / 10 – 21 / 12 / 2008, from Department of Chemistry, State University of Saint Petersburg, Russia)

• Nuno M.F. Garrido (1 / 9 – 20 / 12 / 2008, PhD student, Department of Chemical Engineering, University of Porto, Portugal)

Collaborating faculty:

• Professor Doros N. Theodorou, School of Chemical Engineering, NTUA.

III. Publications in peer-reviewed journals

1. Z. Kechagia, C. Kiparissides and I.G. Economou, “Determination of Liquid – Gas Partition Coefficients of BuA and MMA by Headspace-Gas Chromatography Utilizing the Phase Ratio Variation Method”, Fluid Phase Equil., 266, 21 – 30 (2008).

2. I.G. Economou, E.K. Karakatsani, G.-E. Logotheti, J. Ramos and A. Vanin, “Multi-scale Modeling of Structure, Dynamic and Thermodynamic Properties of Imidazolium-Based Ionic Liquids: Ab initio DFT Calculations, Molecular Simulation and Equation of State Predictions”, Oil & Gas Sci. Tech., 63(3), 283 – 293 (2008).

3. A. Grenner, I. Tsivintzelis, G.M. Kontogeorgis, I.G. Economou and C. Panayiotou, “Evaluation of the Non-Random Hydrogen Bonding (NRHB) Theory and the simplified Perturbed Chain-Statistical Associating Fluid Theory (sPC-SAFT). I. Vapor – Liquid Equilibria”, Ind. Eng. Chem. Res., 47(15), 5636 – 5650 (2008).

4. I. Tsivintzelis, A. Grenner, I.G. Economou and G.M. Kontogeorgis, “Evaluation of the Non-Random Hydrogen Bonding (NRHB) Theory and the simplified Perturbed Chain-Statistical Associating Fluid Theory (sPC-SAFT). II. Liquid – Liquid Equilibria and Prediction of Monomer Fraction in Hydrogen Bonding Systems”, Ind. Eng. Chem. Res., 47(15), 5651 – 5659 (2008).

5. Z.A. Makrodimitri and I.G. Economou, “Atomistic Simulation of Poly(dimethysiloxane) Permeability Properties to Gases and n-Alkanes”, Macromolecules, 41(15), 5899 – 5907 (2008).

6. G. Tsolou, V.G. Mavrantzas, Z.A. Makrodimitri, I.G. Economou and R. Gani, “Atomistic Simulation of the Sorption of Small Gas Molecules in Polyisobutylene”, Macromolecules, 41(16), 6228 – 6238 (2008).

7. E.K. Karakatsani, I.G. Economou, M.C. Kroon, M.D. Bermejo, C.J. Peters and G.-J. Witkamp, “Equation of State Modeling of the Phase Equilibria of Ionic Liquid Mixtures at Low and High Pressure”, Phys. Chem. Chem. Phys., 10(40), 6160 – 6168 (2008).

8. T. Spyriouni, G.C. Boulougouris and D.N. Theodorou, “Prediction of Sorption of CO₂ in Glassy Atactic Polystyrene at Elevated Pressures Through a New Computational Scheme”, Macromolecules, in press (2008)

9. I. Tsivintzelis, I.G. Economou and G.M. Kontogeorgis, “Modeling the Solid – Liquid Equilibrium in Pharmaceutical – Solvent Mixtures: Systems with Complex Hydrogen Bonding Behavior”, AIChE J., in press (2008).

10. I. Tsivintzelis, I.G. Economou and G.M. Kontogeorgis, “Modeling the Phase Behavior in Mixtures of Pharmaceuticals with Liquid or Supercritical Solvents”, J. Phys. Chem. B, in press (2008).

11. G.E. Logotheti, J. Ramos, I.G. Economou, “Molecular Modeling of Imidazolium-Based [Tf₂N^-] Ionic Liquids: Microscopic Structure, Thermodynamic Properties and Segmental Dynamics”, J. Phys. Chem. B, in press (2008).

12. M. Yiannourakou, I.G. Economou and I.A. Bitsanis, “Phase Equilibrium of Colloidal Suspensions with Particle Size Dispersity: A Monte Carlo Study”, J. Chem. Phys., in press (2008).

13. P. Ahlström, K. Aim, R. Dohrn, J.R. Elliott, G. Jackson, J.-N. Jaubert, M.E.R.A. Macedo, J.-P. Pokki, K. Reczey, A. Victorov, L. Fele Žilnik, and I.G. Economou, “A Survey of the Role of Thermodynamics and Transport Properties in Chemical Engineering University Education in Europe and the USA”, Chem. Eng. Ed., in press (2008).

14. H. Leontiadou, I.G. Economou, “Microscopic Structure and Thermodynamic Properties of Aqueous Glycol Mixtures”, Molec. Simul., in press (2008).

IV. Presentations in international conferences

1. I.G. Economou, “Molecular Design of Rubbery Polymers for Membrane Applications”, International Workshop on Molecular Modeling and Simulation in Applied Material Science, Frankfurt am Main, Germany (2008). Invited talk.

2. I.G. Economou, “Multi-Scale Modeling of Structure, Dynamic and Thermodynamic Properties of Ionic Liquids: Ab initio DFT Calculations, Molecular Simulation and Equation of State Predictions“, 11^th European Meeting on Supercritical Fluids, Barcelona, Spain (2008). Invited talk.

3. I.G. Economou, “Molecular Simulation of Rubbery Polymer Membranes”, 23^hd European Symposium on Applied Thermodynamics, Cannes, France (2008). Invited talk.

4. I.G. Economou, “Thermodynamic Properties and Phase Equilibria of Complex Fluid Mixtures: Equation of State Modeling”, Thermodynamic Colloquium, Erlangen, Germany (2008).

5. I.G. Economou and Z.A. Makrodimitri, “Atomistic Simulation of Poly(dimethylsiloxane) Permeability Properties to Gases and n-Alkanes”, 7^th Greek Polymer Conference, Ioannina, Greece (2008).

6. I.A. Bitsanis, A.N. Rissanou, M. Yannourakou, I.G. Economou and D.Vlassopoulos, “Simulations of Temperature Induced Ageing and Crystallization in Dense Suspensions of Ultrasoft Colloids”, 7^th Greek Polymer Conference, Ioannina, Greece (2008).

7. G. Tsolou, V.G. Mavrantzas, Z.A. Makrodimitri, I.G. Economou and R. Gani, “Atomistic Simulation of the Sorption of Small Gas Molecules in Poly(isobutylene)”, 7^th Greek Polymer Conference, Ioannina, Greece (2008). Award for best poster of the conference.

8. I.G. Economou and Z.A. Makrodimitri, “Atomistic Simulation of Poly(dimethyl siloxane): Structure, Thermodynamic and Diffusion Properties to Gases and n-Alkanes”, Centennial AIChE Annual Meeting, Session No 519, Philadelphia, Pennsylvania, USA (2008).

9. I.G. Economou, G.-E. Logotheti, J. Ramos and A. Vanin, “Ab Initio Calculations and Molecular Dynamics Simulations for [Imidazolium][Tf₂N] Ionic Liquids: Microscopic Structure and Thermodynamic Properties”, Centennial AIChE Annual Meeting, Session No 182, Philadelphia, Pennsylvania, USA (2008).

10. P. Ahlström, K. Aim, R. Dohrn, R. Elliott, L. Fele-Žilnik, G. Jackson, J.-N. Jaubert, M.E. Rebello de A. Macedo, J. Pekka Pokki, K. Reczey, A. Victorov and I.G. Economou, “A Survey of Thermodynamics and Transport Properties in Chemical Engineering Education in Europe and the USA”, Centennial AIChE Annual Meeting, Session No 62, Philadelphia, Pennsylvania, USA (2008).

V. Invited lectures

1. Ioannis G. Economou, “Energy, Environment and Business: A Global Challenge”, School of Business, Bifröst University, Iceland, July 2008.

2. Ioannis G. Economou, “Molecular Simulation Prediction of Physical Properties of Complex Fluids”, Shell Global Solutions International BV, Amsterdam, The Netherlands, October 2008.

VI. Educational work

Teaching

Α. Undergraduate courses

1. Ioannis G. Economou, "Physical Chemistry", 2^nd year course in Studies in Natural Sciences, Open University of Greece,, 2007 – 08, 2008 - 09.

2. Nikolas Zacharopoulos, "Simulation", 7^th Semester, Department of Product and Systems Design, University of the Aegean, 2008 – 2009.

3. Nikolas Zacharopoulos, "Materials", 4^th Semester, Department of Product and Systems Design, University of the Aegean, 2007 – 2008.

4. Nikolas Zacharopoulos, "New Materials", 7^th Semester, Department of Product and Systems Design, University of the Aegean, 2008 – 2009.

5. Nikolas Zacharopoulos, "Material Selection for Design", 9^th Semester, Department of Product and Systems Design, University of the Aegean, 2008 – 2009.

Β. Post-graduate courses

1. Ioannis G. Economou, “Environmental Management”, MBA Program, Graduate School, American College of Greece, January – April 2008.

2. Ioannis G. Economou, “Technology and Innovation Management”, MBA Program, Graduate School, American College of Greece, April – June 2008.

3. Ioannis G. Economou and Niki Vergadou, “Molecular Simulation of Complex Chemical Systems with Emphasis to Practical Applications”, PhD Program in Chemical Engineering, Technical University of Denmark, Lyngby, Denmark, June 2008.

4. Nikolas Zacharopoulos, "Materials", 2^nd Semester, Graduate program on Design of functional and industrial products and systems, Department of Product and Systems Design, University of the Aegean, 2007 – 2008.

Undergraduate Diploma Thesis

Eleni Androulaki, “Thermodynamic Analysis Based on Statistical Mechanics and Knot Theory”, School of Applied Mathematics and Physical Sciences, National Technical University of Athens, March 2008.

VII. Current External Funding

Basic Research Projects

1. “Computer Αided Μolecular Design of Multifunctional Materials with Controlled Permeability Properties” [MULTIMAT], European Union, STREP FP6, Priority 3, NMP. Scientific director: Doros N. Theodorou. Duration: March 1, 2005 – February 28, 2008.

2. “Development of New Molecular Simulation Methods and Macroscopic Models for the Calculation of Microscopic Structure and of Thermodynamic Properties of Complex Polymer Systems”, Greek Secretariat of Research and Technology, Program for Research Support (PENED). Scientific director: Ioannis G. Economou. Duration: December 1, 2005 – November 30, 2008.

3. “Development of Sustainable Industrial Processes: Experimental, Theoretical and Computational Investigation of Thermodynamic Properties and Phase Equilibria of Ionic Liquid Mixtures”, INTAS. Scientific director: Ioannis G. Economou. Duration: September 1, 2006 – May 30, 2009.

4. “Investigation of Structure, Thermodynamic and Transport Properties of Poly(styrene-co-acrylonitrile) in High Temperatures”, Greek Secretariat of Research and Technology, ENTER 2003 Program. Scientific director: Ioannis G. Economou. Duration: October 1, 2006 – October 30, 2008.

5. “Polymer Surfaces Responsive to Thermal and Chemical Stimuli: Towards the Micro-design of ‘Intelligent’ Materials”, Greek Secretariat of Research and Technology, Greece – USA Research and Technology Cooperation in Materials Research. Scientific director: Ioannis G. Economou. Duration: June 1, 2006 – September 30, 2008.

Applied Research Projects

6. “Implementation of SAFT / PC-SAFT Computer Codes for Polymer and Non-Polymer Systems into MAPS”, Contract Research Services, Scienomics SARL, Paris, France. Scientific director: Ioannis G. Economou. Duration: March 1 – August 30, 2008.

7. “Implementation of Computer Codes for Physical Properties of Polymer and Non-Polymer Systems into MAPS – Phase II”, Contract Research Services, Scienomics SARL, Paris, France. Scientific director: Ioannis G. Economou. Duration: September 1, 2008 – February 28, 2009.

8. “Molecular Simulation of Diffusion of Hydrogen, Carbon Monoxide and Water in Heavy n-Alkanes at High Temperatures and Pressures”, Contract Research Services, Shell Global Solutions, Amsterdam, The Netherlands. Scientific director: Ioannis G. Economou. Duration: December 15, 2008 – April 15, 2009.

Development Program for NCSR “Demokritos”

9. “Reorganization of the Liaison Office of NCSR “Demokritos””, Greek Secretariat of Research and Technology, Program for Support of Liaison Offices in Universities and Research Centers. Scientific director: Ioannis G. Economou. Duration: January 1, 2005 – July 30, 2008.

VIII. Current Collaborations

1. Professor Georgios Kontogeorgis, Department of Chemical Engineering, Technical University of Denmark. Development of thermodynamic models for pharmaceuticals.

2. Dr. Xenophon Krokidis, Scienomics SARL, France. Development of scientific software for prediction of material properties kai design of chemical processes.

3. Professor Sofia Lampropoulou, School of Applied Mathematics and Physical Sciences, National Technical University of Athens, Statistical Mechanics Theory

4. Professor Maria Eugénia Rebello de A. Macedo, Department of Chemical Engineering, University of Porto, Portugal. Molecular simulation of the solubility of pharmaceuticals in water.

5. Professor Vlasis Mavrantzas, Department of Chemical Engineering, University of Patras. Molecular simulation of polymers.

6. Dr. Ioannis Bitsanis, Institute of Electronic Structure and Laser, Foundation of Research and Technology, Hellas, Heraklion, Crete, Greece. Mesoscopic simulation of colloids and polymers.

7. Professor Costas Panayiotou. Department of Chemical Engineering, Aristotle University of Thessaloniki, Greece. Development of a lattice equation of state for non-ideal fluids.

8. Professor Cor Peters, Department of Chemical Engineering, Delft University of Technology, The Netherlands. Modeling thermodynamic properties of ionic liquids.

9. Dr. J. Ramos-Díaz, Department of Macromolecular Physics, Instituto de Estructura de la Materia  - CSIC, Madrid, Spain. Quantum-mechanics calculations for ionic liquids.

IX. Other activities

Ioannis Economou

1. Scientific Director of Technology Transfer Office, NCSR “Demokritos” (up to 7 / 2008).

2. Member of Research Council, NCSR “Demokritos”.

3. Visiting Professor, Department of Chemical and Biochemical Engineering, Technical University of Denmark, Lyngby, Denmark.

4. Visiting Professor, American College of Greece, Graduate School, Aghia Paraskevi Attikis.

5. Adjunct Professor, Open University of Greece.

6. Collaborating researcher, Centre for Management and International Business, Bifröst University, Iceland.

7. Chairman, Working Group on Thermodynamics and Transport Properties, European Federation of Chemical Engineering.

8. Member of the Editorial Board, Scientific Bulletin of University Politehnica of Bucharest, Series B: Chemistry and Materials Science.

9. Referee for the following international scientific journals: AIChE Journal, Canadian Journal of Chemical Engineering, Chemical Engineering Research and Design, Chemical Physics Letters, Colloid and Polymer Science, Computers in Chemical Engineering, Energy & Fuels, Environmental Science and Technology, European Polymer Journal, Fluid Phase Equilibria, Industrial and Engineering Chemistry Research, International Journal of Refrigeration, Journal of the American Chemical Society, Journal of Chemical and Engineering Data, Journal of Chemical Physics, Journal of Computational Chemistry, Journal of Physical Chemistry, Macromolecular Rapid Communications, Macromolecules, Polymer, Theoretical Chemistry Accounts.

10. Member of International Scientific Review Committee of the Directorate of Applied Chemistry and Physical Chemistry, Institut Français du Pétrole, Paris, France, June 2008.

11. External examiner for PhD thesis at:

• Department of Material Science, University of Ioannina, February 2008.

• Department of Process Engineering, Université Paris XIII (Paris-Nord), Villetaneuse, France, September 2008.

12. Consultant, Scienomics SARL, Paris, France.

Nikolas Zacharopoulos

Non-tenure teacher 407/80, Department of Product and Systems Design, University of the Aegean.