The 9 International Conference on Material Sciences

9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France

The 9th International Conference on Material Sciences (CSM9) ENSIC, University of Lorraine, Nancy, France August 26 – 28, 2015

Chairman of the Conference and Editor Prof. Tayssir HAMIEH Volume IX 1


The 9th International Conference on Material Sciences (CSM9) August 26-28, 2015, ENSIC, Nancy, France The International Conference on Material Sciences (CSM) was created in 1996 by a strong French-Lebanese collaboration between the Lebanese University (LU), the University of Haute-Alsace (UHA) and the University of Nancy that became the University of Lorraine. Eight international conferences on materials sciences (CSM1 to CSM8) were organized in Beirut (Lebanon) by Lebanese University, Washington State University, Haute-Alsace University, University of Nancy, University of Lyon, University of Caen, University of Algiers, University of Tlemcen, and University of Annaba with the participation of many hundred researchers from more than 50 universities, research institutions and laboratories around the world (European, American, Arabic and Asian countries). The Order of Engineers in Beirut is continuing to support our international conference as a real and important partner for many times by sponsoring and helping the organization of this bigger scientific and research manifestation in the Mediterranean region. Many thanks go to Dr Khaled Chehab, the President of the Order of Engineers in Beirut for its permanent support. The help of French embassies and the University Agency of the Francophonie (AUF) were very appreciated in the realization of the success of this international conference on material sciences. The organizing committee of the Ninth International Conference on Material Sciences (CSM9) has decided this year to organize the ninth edition of our colloquium in Nancy (France). An important and strong academic and research collaboration exist through many years between the University of Lorraine and the Lebanese University, reason for which we had chosen the location of CSM9 and more particularly we are very honored to realize this CSM9 it in the Higher National School of Chemical Industries (ENSIC), the most famous French school in Advanced Study of the chemical engineering in Europe. By this occasion we have to congratulate the ENSIC and the 9 other engineering schools of Lorraine INP to obtain the third rank of 2015 ranking of the top 100 engineering schools (directed by "Usine Nouvelle"), just behind Grenoble INP and Polytechnic School (X). I would like to present my great and warmest thanks to Prof. Bernard Vitoux, the Director of the ENSIC, to Prof. Eric Gaffet, the Director of Jean Lamour Institute and to Prof. Laurent Falk the Director of LRGP for accepting to organize the conference in the ENSIC and provide us all the facilities for the success of the ninth international conference on materials sciences CSM9. Special thanks go also to Prof. Pierre Mutzenhardt, the President of the University of Lorraine and to Prof. Adnan El Sayed Hussein, the Rector of the Lebanese University for

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their permanent support to strengthen the French Lebanese collaboration between our institutions. Finally, my heartfelt thanks go to Prof. Thibault Roques-Carmes, the President of the Organization Committee of CSM9, to Dr. Halima Alem-Marchand, the Vice-President and to Prof. Joumana Toufaily, the Coordinator of CSM9 for their permanent efforts during the preparation of the conference activities. I would like to present my sincere thanks and my respect to Prof. Bachar Koubaissy and Prof. Houssam Obeid for all correspondences realized during the last months with the participants and for their spontaneities and availabilities. All of our thanks have to go to the Algerian researchers and colleagues that always continue to support the success of this conference and more particularly the colleagues of Tlemcen University represented by Prof. Boumédiène Benyoucef, the Director of the division of the renewable energies (URMER) in the Department of Physics in Tlemcen University. I cannot finsh this introduction without addressing my warmest thanks to our two colleagues that were always implicated in the strong Academic and research collaboration between French and Lebanese Universities: 1. Prof. Frédéric Villieras, the Vice-President for scientific research at the University of Lorraine and the Coordinator of the French-Lebanese agreement between the Lebanese University and the University of Lorraine. 2. Prof. Jean-Luc Bischoff, the Vice-President for scientific research at the University of Mulhouse and the Coordinator of the French-Lebanese agreement between the Lebanese University and the University of Mulhouse. Many topics in material sciences will be developed in this ninth edition with a particular attention given to the domain of nanomaterials and nanotechnologies. The research topics of the Ninth International Conference on Material Sciences (CSM9) will be divided into three symposia:

Symposium I: Materials, Nanomaterials and New Materials (Chairman: Prof. Jacques LALEVÉE) 1. Industrial Innovations in Material Engineering and New Materials 2. Nanomaterials and Nanotechnology 3. Multi-Materials and Composite Materials 4. Inorganic Porous Organized Materials 5. Inverse Gas Chromatography for characterization of materials 6. Materials for Catalysis 7. Properties of Surfaces and Interfaces, and Adhesion of Materials 8. Textiles Materials 9. Polymer and Organic Materials 10. Asphaltic Materials. 11. High Performance Materials. 3


Symposium II: Materials and Bio-Engineering, Chemical, and petrochemical engineering, Photocatalysis and Photodynamic Therapy, Colloids, Environment, Food technology (Chairman: Prof. Hussein ZBIB) 12. Biomedical Engineering, Bio-Materials, 13. Materials, Membranes and chemical and petrochemical engineering 14. Photocatalysis and Photodynamic Therapy 15. Colloidal dispersions and industrial applications 16. Materials and Environmental Chemistry and Pollution of Earth 17. Treatment of Waters and Solid Wastes and Recycling Materials 18. Geology and Material Sciences 19. Valorization of Industrial and Agricultural Wastes 20. Materials and Food Technology 21. Quality Controls of Materials 22. Smart Materials

Symposium III: Materials and Renewable Energies, Mechanical, Electrical, Optical Properties, Mathematical Modelling, Simulation, and Computational Methods (Chairmen: Prof. Boumédiène BENYOUCEF and Prof. Jean-François GANGHOFFER) 23. Materials, Solar Cells and Energy 24. Construction Materials and Civil Engineering 25. Optic, Electric and Magnetic Properties of Materials 26. Mechanical Properties of Materials, Durability and fatigue 27. Metallic Materials 28. Ceramics and applications 29. Mathematical Modelling in Materials 30. Numerical analysis and Simulation 31. Nondestructive Testing and Evaluation. 32. Theoretical aspects of materials. 33. Computational Methods. 34. Materials Education Finally, we hope a great success for the Ninth International Conference on Material Sciences (CSM9) and more collaboration between universities and research laboratories and institutions of the different countries represented in this conference. Nancy, August 26, 2015 The Chairman of CSM Conference

Prof. Tayssir Hamieh 4


9th International Conference on Material Sciences (CSM9) ENSIC, University of Lorraine, Nancy, France August 26 – 28, 2015 Chairman of the Conference: Prof. Tayssir HAMIEH, Lebanese University, Lebanon, Email: [email protected]; [email protected]; Coordinator of the Conference: Prof. Joumana Toufaily, Lebanese University, Lebanon, Email: [email protected]; [email protected]. Chairman of the symposium I (Materials, Nanomaterials and New Materials): Prof. Jacques LALEVÉE, IS2M, University of Mulhouse, France, Email: [email protected] Chairman of the symposium II (Materials and Bio-Engineering, Photocatalysis and Photodynamic Therapy, Colloids, Environment and Food technology) Prof. Jean Jacques Gaumet Université de Lorraine, LCP-A2MC, Jean Barriol Institute, Email : [email protected] Chairmen of the symposium III (Materials and Renewable Energies, Mechanical, Electrical, Optical Properties, Mathematical Modelling, Simulation and Computational Methods)

Prof. Boumédiène BENYOUCEF, University of Tlemcen, Algeria, [email protected] Prof. Jean-François GANGHOFFER, University of Lorraine, Nancy, France, [email protected]

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Scientific Committee and Review Board President: Prof. Frédéric VILLIERAS, [email protected] University of Lorraine, Nancy, France Vice-President: Prof. Jean-Luc BISCHOFF, [email protected] University of Mulhouse, UHA, France

Members of the Scientific Committee and Review Board Prof. Girolamo GIORDANO, University of Calabria, Italy Prof. Jean-Marie BASSET, KAUST, Saudi Arabia Prof. Fawaz ELOMAR, Dean, EDST, Lebanese University, Lebanon Prof. Tayssir HAMIEH, LU, Beirut, Lebanon Prof. Omar YAGHI, UCLA, California, USA Prof. Jean-Luc BISCHOFF, University of Mulhouse, UHA, France Prof. Frédéric VILLIERAS, University of Lorraine, France Prof. Augusto MONTISCI, Calgiari University, Italy Prof. Jean-francois GANGHOFFER, University of Lorraine, Nancy, France Prof. Hussein ZBIB, School of Mechanical and Materials Engineering, WSU, USA Prof. Thibault ROQUES-CARMES, (University of Lorraine, Nancy, France Dr. Halima ALEM-MARCHAND, University of Lorraine, Nancy France Prof. David F. BAHR, School of Mechanical and Materials Engineering, WSU, USA Prof. Jean Jacques GAUMET, University of Lorraine, Metz, France Prof. Renaud BACHELOT, UTT, Troyes, France, Prof. Pierre Michel ADAM, UTT, Troyes, France Prof. Nehal ABU-LAIL, Washington State University, Pullman, USA. Prof. Mohammad AHAMAD, Department of Mechanical Engineering, AUB, Beirut, Lebanon Prof. Vladimir ZAITSEV, Taras Shevchenko National University, Kiev, Ukraine Prof. Meisam TABATAABAEI, ABRII, Team Leader of Biofuel Research Team, Karaj, Iran Prof. Bénédicte LE BEAU (UHA, Mulhouse, France) Prof. Jacques NOUDEM, LUSAC Laboratory, Caen university, France Prof. Mohammed Essaid ACHOUR, Ibn Tofail University, Morocco Prof. Tahar BENDEIKHA (Dean, University of Batna. Algeria Prof. Nadine ESSAYEM, IRCE Lyon, France Prof. Boumédiène BENYOUCEF, University of Tlemcen, Algeria Prof. Rafik ITANI, Expert in structural materials, WSU, USA Prof. Stéphane DANIELE, IRCE Lyon, France Prof . Bao-Lian SU, Director, FUNDP, Namur, Belgium Prof. Joumana TOUFAILY, Lebanese University, Lebanon Prof Yannick POUILLOUX, Directeur adjoint de l’IC2MP, University of Poitiers Prof. Ludovic PINARD, IC2MP, UMR CNRS 7285, University of Poitiers Prof. David CORNU, ENSC, Montpellier, France Prof. Abdelhamid SAYARI, University of Ottawa, Canada Prof. Hamidou HAIDARA, University of Mulhouse, UHA, France Prof. Christine LANCELOT, Université des Sciences et Technologies de Lille, France Prof. Khaled BERRADA, SIAM, Faculty of Sciences, Semlalia, Marrakech, Morocco Prof. Jean DAOU, University of Mulhouse, UHA, France Prof. Henri BALARD, UHA, Mulhouse, France 6


Dr. Anne DAVIDSON, Université Pierre et Marie Curie, Paris, France Dr. Hassan LAKISS, Faculty of Engineering, Lebanese University, Lebanon Dr. Maria Laura FODDIS, Calgiari University, Italy Dr. Safi JRADI, UTT, Troyes, France, Dr. Suzanna Akil, University of Lorraine, Metz, France Dr. Karine MOUGIN, University of Mulhouse, UHA, France Dr. Mohamed CHEHIMI, Université Paris 7, Paris, France Dr Ali TRABOLSI, New York University Abu Dhabi (NYUAD), Saadiyat Island, Abu Dhabi, UAE

Organization Committee President: Prof. Thibault ROQUES-CARMES, University of Lorraine, Nancy, France, [email protected]

Vice-President: Dr. Halima ALEM-MARCHAND, University of Lorraine, Nancy, France, [email protected]

Members of the Organization Committee Prof. Celine FROCHOT, University of Lorraine, Nancy, France Prof. Salah HAMIEH, Faculty of Sciences, Lebanese University, Lebanon Prof. Houssam OBEID, Lebanese University, Beirut, Lebanon Prof. Ali KAROUT, Lebanese University, Beirut, Lebanon Prof. Khalil CHERRI, Lebanese University, Beirut, Lebanon Prof. Bachar KOBEISSI, , Lebanese University, Beirut, Lebanon Dr. Raphaël SCHNEIDER, University of Lorraine, Nancy, France Dr. Hassan LAKISS, Faculty of Engineering, Lebanese University, Lebanon Dr. Philippe ARNOUX, University of Lorraine, Nancy, France Dr. Mohamad HAMADEH, AUB, Lebanon Dr. Houssein MORTADA, Lebanese University, Beirut, Lebanon Dr. Ali MCHEIK, Lebanese University, Beirut, Lebanon Dr. Mostafa HAMIEH, Lebanese University, Beirut, Lebanon Dr. Nada NEHME, Faculty of Agricultural Engineering, LU, Lebanon Dr. Akram HIJAZI, Lebanese University, Beirut, Lebanon Dr. Ahmad KASSAS, Lebanese University, Beirut, Lebanon Dr. Mohamad RAJAB, Lebanese University, Beirut, Lebanon Dr. Mounir KASSIR, Lebanese University, Beirut, Lebanon Dr. Mohamad KHAYWA, UTT, Troyes, France Dr. Nabil TABAJA, UPMC, Paris, France and Lebanese University, Beirut, Lebanon Mme Batoul HAMIE, University of Lorraine, Nancy, France and LU, Beirut, Lebanon Miss Zahraa YOUSSEF, University of Lorraine, Nancy, France and LU, Beirut, Lebanon Miss Hawraa AYOUB, University of Lorraine, Nancy, France and LU, Beirut, Lebanon 7


Secretariat of the Conference: [email protected] Dr. Halima Alem-Marchand, ENSIC, University of Lorraine, Nancy, France [email protected],

Prof. Bachar Koubaissy, Lebanese University, Beirut, Lebanon [email protected];

Prof. Houssam Obeid, Lebanese University, Beirut, Lebanon [email protected];

Prizes of CSM9 Conference: We will discern during this Conference three prizes for the best oral presentations and three prizes for the best posters: 1. Prize of the best poster for Symposium I. 2. Prize of the best poster for Symposium II. 3. Prize of the best paper for Symposium III.

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List of plenary sessions

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Jérémie D. A. Pelletier and Jean-Marie Basset Catalysis by design: well-defined single-site heterogeneous catalysts via surface organometallic chemistry P.23 David Quéré On a few functions of water-repellent materials.

P.26

Jacques Lalevée, Haifaa Mokbel, Tayssir Hamieh2, Joumana Toufaily Radical photoinitiators for polymer synthesis P.27 Jean Jacques Gaumet, Raphaël Schneider Soft Ionization Mass Spectrometry and Nanometrology: Access to the Size and the Stability of Quantum Dots P.29 Thibault Roques-Carmes, Mounir Kassir, Haytham Alloul, Angelina Razafitianamaharavo , Tayssir Hamieh, Joumana Toufaily, Frédéric Villiéras New insight into organosilane grafting onto titania and silica nanoparticles using volumetric techniques based on molecular probing P.32 Jean-François Ganghoffer, Ibrahim Goda, Khaled El Nady, Yosra Rahali Consideration of size effects of architectured materials based on micropolar anisotropic media obtained by homogenization techniques P.34 Tayssir Hamieh New progresses in the development of a scientific methodology to characterize materials by Inverse Gaz Chromatography at infinite dilution P.37 Enaam Jamal Al Dine, Thibault Roques-Carmes, Alexandra Schejn, Tayssir Hamieh, Joumana Toufaily, Eric Gaffet, Raphaël Schneider, Halima Alem Thermoswitchable Fluorescent Nanoparticles: Preparation, Properties and Applications P.38 Boumédiène BENYOUCEF Approche de la globalisation et de la stratégie des Energies Renouvelables et les énergies nouvelles dans les pays développés et ceux en développement P. 40

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List of oral communications, Symposium I Materials, Nanomaterials and New Materials Chairman of the Symposium I: Prof. Jacques LALEVÉE M.-A. Tehfe, S. Elkoun, M. Robert Starch Nanocrystals as Initiator and additive for Thermal Cationic Polymerization at Room Temperature with In Situ Formation of Silver Nanoparticles P.43 E. Jamal Al Dine, J. Toufaily, A. Schejn, T. Roques-Carmes, M. Kassir, H. Obeid, T. Hamieh, E. Gaffet, S. Marchal, R. Schneider, H. Alem Three steps synthesis process to obtain core/shell nanoparticles serving as capsules for effective drug delivery P.47 M. Belhadji and M. Heireche Effect of Sb in Se90X10 (X = In, Zn) thermal properties

P.49

A. Issa, J. Toufaily, M. Khanafer, S. Akil, T. Hamieh, P. M. Adam, S. Jradi Organized metallic nanostructures via polymer self-assembly P.50 Y. Peng, S. Jradi, S. Akil, R. Bachelot Fabrication of true 3D polymer nanostructures with sub-100 nm feature sizes via femtosecond direct laser writing based on two- photon polymerization P.52 H. Mokbel, J. Toufaily, F. Dumur, D. Campolo, Didier Gigmes, J.P. Fouassier, J. Ortyl, T. Hamieh, J. Lalevée Specific Cationic Photoinitiators for Near UV and visible LEDs: Iodonium vs. Ferrocenium Structures P.53 Safi Jradi, Lama Zaarour, Suzanna Akil1, Irene Izquierdo-Lorenzo1, Pierre Michel Adam, Jérôme Plain, Renaud Bachelot P.56 Metallic nanoparticles: new strategies of nanofabrication and characterization of their near-field thermal properties by nanoscale polymerization R. Omar, J. Toufaily 1, T. Hamieh, S. Jradi, H. Mortada, A. En-Naciri , S. Akil P.58 New Approach for the Synthesis of Uniform Gold Nanoparticles 11


M. Ghamnia, N. Hamzaoui P.60 A simple method for synthesizing zinc oxide (ZnO) nanostructured thin films H. Boutefnouchet , C. Curfs P.61 Etude in-situ de la synthèse de matériaux composites base céramique Seell A. Ramanaiah P.64 The Role of Inverse Gas Chromatography in the Characterization of Pharmaceutical Materials I. Rekkab-Hammoumraoui, A. Dali, A. Choukchou-Braham and R. Bachir Allylic oxidation of cyclohexene over ruthenium-doped titanium-pillared clay P.66 Z. Chehadi , J. Toufaily, S. Zaid, J.-S. Girardon, M. Capron, F. Dumeignil, T. Hamieh, R. Bachelot , S. Jradi P.68 Plasmon induced oxidation of glycerol: Highly efficient and selective oxidation by supported gold nanoparticles using visible light at ambient temperature H. Ayoub, J. Toufaily, M. Kassir, H. Obeid, T. Roques-Carmes, F. Villieras, T. Hamieh P.71 Modification of TiO2 nanoparticules «Study of the selectivity in photocatalysis » N. Tabaja, J. Toufaily, S. Casale, D. Brouri, A. Davidson, T. Hamieh Dépollution des eaux avec des nanoparticules d’oxydes de fer et de ferrites P.73 Z. Youssef, R. Hamiye, Ch. Lancelot, J. Toufaily, T. Hamieh Oxidative Desulfurization Catalysts, an Alternative to Hydro Desulfurization; Study of the Support Structure P.75 F. Haidar, J. Toufaily, Y. Chen, A. Pradel, M. Ribes, M.-Ch. Record, A. Elmoll, T. Hamieh Electrodeposition of Sb2Se3thin films via the route of Electro-Chemical Atomic Layer Epitaxy (EC-ALE) P.78 A. Said, J. Toufaily, L. Limousy, J. Halawani, T. Hamieh, J. Daou P.79 Design of new tubular ceramic membranes using a double layered MFI thin film

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M. Rajab, J. Toufaily, K. Mougin, A. Airoudj, K. Hariri, T. Hamieh Polystyrene-b-Poly(4-vinylpyridine): Synthesis by ATRP and Characterization by Inverse GC P.80 I. Kabalan, B. Lebeau, M.-B. Fadlallah, J. Toufaily, T. Hamieh, J.P. Bellat, J. Daou P.83 Synthesis of nanoporous materials for molecular decontamination Ahmed Wasfi, Hammad Humud, Mohammed Ismael Synthesis of Nanostructure Carbon Thin Films by Microwave Plasma-Enhanced Chemical Vapor Deposition P.85

List of oral communications, Symposium II Materials and Bio-Engineering, Chemical, and petrochemical engineering, Photocatalysis and Photodynamic Therapy, Colloids, Environment, Food technology A. Dandach, J. Toufaily, T. Hamieh, M. Karaki, A. Karout, N. Essayem Liquefaction of cellulose into bioproducts in the presence of zirconia doped with W, Mo, Ta and Nb P.87 R. Hamiye, J. Toufaily, C. Lamonier, Ch. Lancelot, P. Blanchard, T. Hamieh Influence de la modification des catalyseurs sur leurs performances en HDS des gazoles P.90 R. Secci, M.-L. Foddis, G. Uras P.94 Weight of Evidence method for landslide susceptibility assessment W. Diab, J. Toufaily, F. Villieras, H. Lakiss, T. Roques-Carmes, T. Hamieh P.97 Total and Extractable Trace Elements in Upper Litani River Sediments, Lebanon R. Omar, M. De Biase, F. Chidichimo, J. Toufaily, T. Hamieh, S. Straface Unsaturated soil characterization using water retention curves measured by means of TDR. A case study P.99

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Z. Makhloufi, M. Hadjoudja, T. Bouziani, M. Bederina Effect of activation of addition minerals of quaternary binders on compressive strength of limestone mortars P.101 B. S. Ebahi, L. Zeghichi, D. Benamara Etude de la porosité capillaire et la résistance des mortiers à base de la poudre de verre P.104 M. Tarzout, M.T. Abadlia, B. Bezzazi P.105 Etude de l’usinabilité de bois de pin d’Alep (Pinus halepensis Mild ) et d’Eucalyptus Camaldulensis Dehn algériens sous l’effet D. Benamara, B. S. Ebahi,, L. Zeghichi, B. Mezghiche P.107 Possibilité d’utilisation des granulats recyclés dans la fabrication des nouveaux bétons H. Medlej, H. Awada, M. Abbas, G. Wantz, K. Hariri, J. Toufaily, T. Hamieh, R. C. Hiorns, C. Dagron-Lartigau P.108 A comparison between benzothiadiazole and dithienylbenzothiadiazole donoracceptor type copolymers for organic bulk heterojunction photovoltaic devices

List of oral communications, Symposium III Materials and Renewable Energies, Mechanical, Electrical, Optical Properties, Mathematical Modelling, Simulation, and Computational Methods Chairmen of the Symposium III: Prof. Boumédiène BENYOUCEF and Prof. Jean-François GANGHOFFER Halima Kazdaba P.111 Experimental study of an indirect water heating system with forced-circulation in real conditions in Morocco (Rabat). Youssef Hamze Concrete analysis for petrographic examination in old concrete structures and its corresponding photomicrographs P.112

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A. Benaceur , A. Bah, O. Ansari Solar drying of foodstuff: a prototype of a direct banana solar dryer for domestic use P.113 R. Mehaddener, S. Nechaf P.114 Comportement en compression des éléments en béton incorporant de la poudre de verre M. Chadli, M. Mellas P.115 Formulation et comportement d’un béton à poudre réactive fibré Z. Belamri, Dj. Hamana P.117 Study of the effect of the substitution of Ge atoms on the properties of Fe-Al alloys A. Alimi, J. Fajoui, M. Kchaou, R. Elleuch, F. Jacquemin Analyse multi-échelle de l’endommagent des outillages de matriçage P.118 M.Sellami, A. Sellami, S. Berrah P.120 A Neural Network Model of Practical SARG04 Quantum Key Distribution Dj. Rechem, Ch. Azizi, A. Khial, F. Lagraf and S. Benzitouni Analysis of the threshold voltage and its temperature dependence in shortchannel CNTFETs P.121 Z. El-Moussawi, H. Medlej, A. Nourdine, J. Toufaily, T. Hamieh, L. Flandin New Pyridylthiadiazole-Based Donor-Acceptor Copolymer Semiconductors for Efficient Polymer Solar Cells P.122

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List of Poster communications

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List of Poster communications, Symposium I Materials, Nanomaterials and New Materials

Kahina Issaadi, Abderrahmane Habi, Yves Grohens, Isabelle Pillin Maleic anhydride grafted poly (lactic acid) to improve rheological and barrier properties of poly (lactic acid)/graphene oxide nanocomposites Johnny Moughames, Aurélien Bruyant, Suzanna Akil, Ziad Herro, Safi Jradi New formulation for 2D photolithography with ultra-high resolution for photonic applications Enaam Jamal Al Dine, Joumana Toufaily, Alexandra Schejn, Thibault Roques-Carmes, Mounir Kassir, Houssam Obeid, Tayssir Hamieh, Eric Gaffet, Sophie Marchal, Raphaël Schneider, Halima Alem Synthesis and characterization of smart nanomaterials for cancer treatment Fatima Zohra Rahou, A. Guen Bouazza, B. Bouazza , Effects Of High-K Dielectric With Metal Gate for Electrical Characteristics Of Nanostructure SOITri Gate FinFET Izzat M. Al-Essa, Ameer F. Abdulameer , Mahdi Hasan Suhail Fabrication and Study of Nickel(II) Phthalocyanine - Tetrasulfonic Acid Tetrasodum Salt based Surface Type Capacitive-Resistive Humidity Sensors A. Benhamou, J.P. Basly, M. Baudu, Z. Derriche, R. Hamacha Amino-functionalized MCM-41 and MCM-48 for the removal of chromate and arsenate Z. Fares, W. Aliaouat, I. Hamma, Y. Saidi, C. Azizi Effect of temperature on (IV) statistics characteristics of GaAs MESFET Smail MERABET, Zarfa BENDJEDOU, Abdelkrim BOUZAZA Optimisation du procédé de dégradation photocatalytique des polluants organiques en phase aqueuse en présence TiO2 fixé sur support Abir Swaidan, Joumana Toufaily, Mira Jaafar, and Tayssir Hamieh Titania and Ag-doped Titania nanoparticles for photocatalysis of pesticides in water

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List of Poster communications, Symposium II

Materials and Bio-Engineering, Chemical, and petrochemical engineering, Photocatalysis and Photodynamic Therapy, Colloids, Environment, Food technology

L. Osmani, L. Salik, N. Benouattas, Failure of sputtered Ta-Si diffusion barrier between Cu and Si Walaa Diab, Joumana Toufaily, Frédéric Villieras, Hassan Lakiss, Thibault Roques-Carmes, Tayssir Hamieh Qualitative Analysis of Clay Minerals in Sediments of the Litani River by X-ray Diffraction Method Z. SKANDERI, I. R. KRIBA; A. DJEBAILI1, J.P. CHOPART Study of the isomeric ratio of oriented polyacetylene isomerization reaction by laser beam Bachar Koubaissy, Joumana Toufaily, Zainab Yaseen , Tayssir Hamieh Application of Zeolites in the Treatment of Uremia Malak Missilmani, Joumana Toufaily, Rasha Hamdan, William T. Cooper, Tayssir Hamieh Studying the effect of fire-induced black carbon on peat accumulation by using advanced analytical techniques M. Taleb, R. Chaib, Y. Chetouani Evaluation des accidents de travail au niveau de l’unité Anabib de Tébessa Bachar Koubaissy, Joumana Toufaily, Sawsan Banjak, Rimal Obeid, Tayssir Hamieh Preparation of ZSM5 zeolites encapsulating redox species and its application in photocatalysis Bachar Koubaissy, Joumana Toufaily, Zahraa Moustafa, Tayssir Hamieh Adsorption behavior of nicotine from aqueous solutions on different types of adsorbents

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Nadjib BENOSMANE1, Baya BOUTEMEUR, Maamar HAMDI, Safouane. M. HAMDI Application of cellulose acetate PIMs material for toxic metals ions removal from wastewater Bachir Meghzili, Michel Soulard, Medjram Mohamed Salah Risk of residual aluminum in treated water with aluminum sulfate: the case of the treatment plant of the city of Skikda (Algeria) F. Naitali and H. Ghoualem. Dégradation biologique d’un medicament antihistaminique. Chaib Rachid, Aib Abdelatif , Akni Ahcene Contribution à la Gestion des risques dans l’industrie pétrolière Etude de cas : sphère de stockage GPL T002 Bachar Koubaissy, Joumana Toufaily, Safaa Cheikh, Tayssir Hamieh Valorization of agricultural waste into activated carbons and its adsorption characteristics for heavy metals Rania Msayleb, Joumana Toufaily, Mariam Karaki, Tayssir Hamieh Sulfonic Periodic Mesoporous organosilicas for the hydrolysis of the biomass Elissa Naim, Chadi Hosri Fat substitution by whey protein and gum tragacanth in Halloumi production Amal ZEAITER, Amira HADDARAH, Tayssir HAMIEH, Karim ALLAF Caractérisation de la graine de caroube et facteurs affectant les propriétés fonctionnelles

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List of Poster communications, Symposium III Materials and Renewable Energies, Mechanical, Electrical, Optical Properties, Mathematical Modelling, Simulation, and Computational Methods E. Barakat, N. Sinno Design of an intelligent energy harvesting road using solar panels and piezoelectric harvesters L. MERAD, K. CHERIFI et B. BENYOUCEF Optimisation d’un système de réfrigération solaire à absorption à usage domestique S. Bensmaine, B. Benyoucef Simulation d’une couche mince de CuInSe2 par SCAPS-1D pour une application photovoltaïque S. Zargou, S. M Chabane Sari, M.S. Aida, N. Attaf Spray pyrolytic growth of nanocrystalline ZnO thin films: effect of solution spray rate F. Z. Bedia, A. Bedia, M. Aillerie, N. Maloufi and B. Benyoucef Synthesis and Characterization of Al-doped ZnO Nanostructures by Spray Pyrolysis method A. Bedia, F. Z. Bedia, M. Aillerie, N. Maloufi and B. Benyoucef Structural and optical properties of Cu-doped ZnO thin film growth on glass substrate A. Chabane, S. Bensebti, A. Boukezzoula, R. Lassoued, A. Aggoun Contribution à la prédiction du fluage des BAP en flexion « Application des modèles réglementaires » Ilhem R. Kriba; K. Benoumesaad; A. Djebaili Solidification dynamics of two molten droplets in plasma spray forming process F. Aouadja, F. Bouzerara, A. Boudjada, H. Merazig, S. Benayache, H. Meradi, K. Boubendira, K. Labiod Caractérisation de la diatomite algérienne par DRX, FTIR et XRF pour l'utilisation dans la filtration des eaux

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K. Benoumsaad; Ilhem. R. Kriba; A. Djebaili The prediction of coating microstructure

in

plasma

spray

process

Fayçal Mili, Toufik Achour, Noureddine Benseddiq Optimisation Mécanique des Techniques de Réparation de Structures Endommagées par des Patchs Composites N. Karkar, A. Megradi, and K. Benmhammed Q-learning application for navigation of mobile robot Boudjelal Samia, Fourar Ali, Benoumessad Kamel, Fawaz Massouh Two Dimensions Numerical Modeling of Transient free Surface Flow Downstream of a Spillway Farida Merrouchi, Ali Fourar, Benoumessad Kamel, Fawaz Massouh, Djamel haddad Modelling of turbulent, incompressible and unsteady free surface flows in the presence of macro-roughness in a channel with complex geometry N. Guenifi, I. Rahmani and R. Mahamdi Study of Heavily Boron Doped Polysilicon Thin Films Using Finite Difference Method and SILVACO Samir Khamel Diagnostic de l’usure d’un outil de coupe en tournage dur via un système expert Lahcene Ziet Improving image binarization techniques using specific pretreatment, according the document degradation level B. Lezzar, O. Hardouin Duparc, O. Khalfallah1 and V. Paidar Numerical Study of polyatomic segregation in binary metallic systems D. TAHARCHAOUCHE; A. LAKHZOUM; Z. SKANDERI; A. DJEBAILI Ab-initio and DFT study of the isomerisation kinetics of substituted decapentaene Z. SKANDERI; I. R. KRIBA; A. DJEBAILI; J.P. CHOPART Quantum study of different structures of the cis-trans transition of substituted polyacetylene by different methods: semi empirical AM1+PM6, HF (Ab-initio) and DFT (B3LYP)

21


Plenary Sessions

22


Catalysis by design: well-defined single-site heterogeneous catalysts via surface organometallic chemistry* Jérémie D. A. Pelletier† and Jean-Marie Basset*† † KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia. Email: [email protected]

Abstract Heterogeneous catalysis, a field important industrially and scientificatlly, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally very low, their “acid strengths” or “ redox properties” is not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution passes by generating single-site catalysts in which most of, if not all, the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be welldefined, that is elucidated to reach a molecular understanding. It is then feasible to understand structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using Surface Organometallic Chemistry. This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metals nano particles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all the elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity). Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposition and the rules of molecular chemistry (organometallic, organic, supramolecular) associated to concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selecting metal and its ligand set (or support taken as a X, L, Z ligands in the Green formalism), the catalyst can be designed and generated by grafting organometallic precursors with functional groups suitable 23


to targeted transformation. Subtles transformations are necessary to go from a precatalyst stage to the real catalytic intermediates.

The coordination sphere necessary for any catalytic reaction involving paraffins, olefis, alkynes aso can now be predicted. This catalysis occurs via successive elementary steps occuring on surface organometallic intermediates. Only their most complete understanding can allow to develop catalytic reactions with the highest possible selectivity, activity and lifetime.In this lecture we will examine the results of SOMC for hydrocarbon transformations on oxide surfaces bearing metals of group IV - VIII. The silica-supported catalyst are exhibiting remarkable performances for Ziegler Natta polymerization and depolymerization, low temperature hydrogenolysis of alkanes, waxes, metathesis of alkanes, cycloalkanes, metathesis alkenes, …. References [1].

Hamieh, A.; Chen, Y.; Abdel-Azeim, S.; Abou-hamad, E.; Goh, S.; Samantaray, M.; Dey, R.; Cavallo, L.; Basset, J. M. Well-Defined Surface Species [( Si-O)W(=O)Me-3) Prepared by Direct Methylation of [( Si-O-)W(=O)Cl-3), a Catalyst for Cycloalkane Metathesis and Transformation of Ethylene to Propylene. Acs Catal 2015, 5, 2164-2171. 24

9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France [2].

[3].

[4].

[5].

[6].

[7].

[8].

[9].

[10].

[11].

[12].

[13].

Riache, N.; Dery, A.; Callens, E.; Poater, A.; Samantaray, M.; Dey, R.; Hong, J. H.; Lo, K.; Cavallo, L.; Basset, J. M. Silica-Supported Tungsten Carbynes ( SiO)(x)W( CH)(Me)(y) (x=1, y=2; x=2, y=1): New Efficient Catalysts for Alkyne Cyclotrimerization. Organometallics 2015, 34, 690-695. Riache, N.; Callens, E.; Espinas, J.; Dery, A.; Samantaray, M. K.; Dey, R.; Basset, J. M. Striking difference between alkane and olefin metathesis using the well-defined precursor [ Si-O-WMe5]: indirect evidence in favour of a bifunctional catalyst W alkylidene-hydride. Catal Sci Technol 2015, 5, 280-285. Callens, E.; Abou-Hamad, E.; Riache, N.; Basset, J. M. Direct observation of supported W bis-methylidene from supported W-methyl/methylidyne species. Chem Commun 2014, 50, 3982-3985. Riache, N.; Callens, E.; Samantaray, M. K.; Kharbatia, N. M.; Atiqullah, M.; Basset, J. M. Cyclooctane Metathesis Catalyzed by Silica-Supported Tungsten Pentamethyl [( SiO)W(Me)(5)]: Distribution of Macrocyclic Alkanes. Chem-Eur J 2014, 20, 1508915094. Chen, Y.; Abou-hamad, E.; Hamieh, A.; Hamzaoui, B.; Emsley, L.; Basset, J. M. Alkane Metathesis with the Tantalum Methylidene [( SiO)Ta(=CH2)Me-2]/[( SiO)(2)Ta(=CH2)Me] Generated from Well-Defined Surface Organometallic Complex [( SiO)(TaMe4)-Me-V]. J Am Chem Soc 2015, 137, 588-591. Chen, Y.; Callens, E.; Abou-Hamad, E.; Merle, N.; White, A. J. P.; Taoufik, M.; Coperet, C.; Le Roux, E.; Basset, J. M. [( SiO)(TaCl2Me2)-Cl-V]: A Well-Defined Silica-Supported Tantalum(V) Surface Complex as Catalyst Precursor for the Selective Cocatalyst-Free Trimerization of Ethylene. Angew Chem Int Edit 2012, 51, 11886-11889. Chen, Y.; Credendino, R.; Callens, E.; Atiqullah, M.; Al-Harthi, M. A.; Cavallo, L.; Basset, J. M. Understanding Tantalum-Catalyzed Ethylene Trimerization: When Things Go Wrong. Acs Catal 2013, 3, 1360-1364. Samantaray, M. K.; Callens, E.; Abou-Hamad, E.; Rossini, A. J.; Widdifield, C. M.; Dey, R.; Emsley, L.; Basset, J. M. WMe6 Tamed by Silica: Si-O-WMe5 as an Efficient, WellDefined Species for Alkane Metathesis, Leading to the Observation of a Supported WMethyl/Methylidyne Species. J Am Chem Soc 2014, 136, 1054-1061. Mazoyer, E.; Szeto, K. C.; Merle, N.; Norsic, S.; Boyron, O.; Basset, J. M.; Taoufik, M.; Nicholas, C. P. Study of ethylene/2-butene cross-metathesis over W-H/Al2O3 for propylene production: Effect of the temperature and reactant ratios on the productivity and deactivation. J Catal 2013, 301, 1-7. Szeto, K. C.; Hardou, L.; Merle, N.; Basset, J. M.; Thivolle-Cazat, J.; Papaioannou, C.; Taoufik, M. Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts. Catal Sci Technol 2012, 2, 1336-1339. El Eter, M.; Hamzaoui, B.; Abou-Hamad, E.; Pelletier, J. D. A.; Basset, J. M. Well-defined azazirconacyclopropane complexes supported on silica structurally determined by 2D NMR comparative elucidation. Chem Commun 2013, 49, 4616-4618. Polshettiwar, V.; Thivolle-Cazat, J.; Taoufik, M.; Stoffelbach, F.; Norsic, S.; Basset, J. M. "Hydro-metathesis" of Olefins: A Catalytic Reaction Using a Bifunctional Single-Site Tantalum Hydride Catalyst Supported on Fibrous Silica (KCC-1) Nanospheres. Angew Chem Int Edit 2011, 50, 2747-2751.

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On a few functions of water-repellent materials.

David Quéré PMMH, ESPCI, Paris, and École polytechnique, Paris, France

Abstract We discuss three functions of water-repellent materials, and how to duplicate them from the natural world. (i) Anti-rain function: we describe the rebounds of impacting drops on repellent materials, and show how and why adding macrotextures decreases significantly the bouncing time, allowing us to maximize even further the water-repellency. (ii) Anti-fogging function: we present nanotextured materials that repel water at the scale of a dew (that is, around 10 micrometers), instead of repelling it at the millimetric scale of rain. (iii) Super-aerophilic function: we show how films and bubbles of air can be entrapped by hydrophobic solids immersed in a bath, and how to control the volume of these bubbles. In each case, examples from Nature are described, and shown to inspire novel artificial materials.

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Radical photoinitiators for polymer synthesis Jacques Lalevée1, Haifaa Mokbel1, 2, Tayssir Hamieh2, Joumana Toufaily2 1. Institut de Science des Matériaux de Mulhouse – UMR 7361 CNRS - UHA. 2. Laboratory of Materials, Catalysis, Environment and Analytical Methods (MCEMACHAMSI), EDST and Faculty of Sciences I, Lebanese University, Campus Rafic Hariri, Beirut, Lebanon

Abstract Although there have been many reports on photoinitiating systems adapted to visible lights for radical photopolymerization, the challenge for the design and development of photoinitiating systems

for

cationic

photopolymerization

or

concomitant

radical/cationic

photopolymerization (for interpenetrating polymer network IPN synthesis) with visible lights still remains open.[1-3] Particularly, the recent development of cheap and easily accessible LEDs operating upon soft visible light irradiations has opened new fields for polymer synthesis. New radical initiators were proposed recently (Figure 1); they are able to initiate radical, cationic, thiol-ene and interpenetrated polymer networks synthesis upon soft irradiation (e.g. household LED bulb). Since 2011, many novel photoinitiating systems based on organic and organometallic compounds with excellent visible light absorption have emerged and exhibited outstanding photoinitiating abilities especially for cationic photopolymerization. In this presentation, recent progress (mainly from 2011 to early 2014) in applications of photoinitiators and sensitive photoinitiating systems under visible lights will be reported. In addition, their relative efficiencies in the photopolymerization of different monomers will be exemplified and discussed.

27


Figure 1. Photoinitiators for polymer synthesis in soft conditions (LED irradiation).

References [1] Xiao, P. ; Zhang, Jing, Lalevée, J. ; Progress in Polymer Science, 2014, under press. [2] Lalevée, J.; Tehfe, M.A.; Zein-Fakih, A.; Ball, B.; Telitel, S.; Morlet-Savary, F.; Graff, B.; Fouassier, J.P. ACS Macro Lett. 2012, 1, 802-806. [3] Tehfe, M.-A.; Dumur, F.; Graff, B.; Morlet-Savary, F.; Fouassier, J.-P.; Gigmes, D.; Lalevée, J. Macromolecules 2013, 46, 3761-3770.

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Soft Ionization Mass Spectrometry and Nanometrology: Access to the Size and the Stability of Quantum Dots Jean Jacques Gaumet1, Raphaël Schneider2 1. Université de Lorraine, LCP-A2MC, Jean Barriol Institute, 1 Bd Arago, 57078 Metz Cedex 03, France. 2. Université de Lorraine, LRGP, CNRS, UMR 7274, 1 rue Grandville, 54001 Nancy, France

Abstract

Nanomaterials are used every day in various domains such as energy, transport, communications, food, packaging, cosmetics and medicine. With the developments in material sciences, systematic characterization of nanomaterials has become a key issue in managing their fascinating size-dependent physical and chemical properties. Controlling these properties from the synthesis to the application phase, and consequently to their fate as a worldwide environmental and societal concern, is becoming more and more crucial [1-3]. The principal techniques currently used to achieve the characterization of nanoparticles are physical and physico-chemical methods, such as Transmission Electron Microscopy (TEM), X-ray diffraction, UV-visible absorption and photoluminescence spectroscopy. All these analytical tools are of high interest for the global analyses of clusters and nanomaterials. Soft ionization mass spectrometry methods (MS) are especially useful in producing molecular or pseudo-molecular ions from large molecular systems (polymers, peptides, bio-molecules...) because they overcome these molecules propensity to fragment when severely ionized. Consequently, MS is also a very promising method to analyze nanoparticles with sizes close to the previously mentionned macromolecular systems. To that extent, both Nanospray MS for very small quantum dots (QDs) (up to 1.5 nm) [4] and Matrix Assisted Laser Desorption Ionization coupled with Time of Flight MS (MALDI-TOFMS) have already proven high interest as tools in the nanometrology of II-VI QDs such as CdS, CdSe, ZnS and ZnSe. Results obtained by Nanospray MS and MALDI-TOFMS were found to be consistent with TEM and optical spectroscopy measurements [5-7]. 29


During this presentation, we will first discuss some of these results for various smallsized QDs less than 10 nm in diameter and synthesized either by thermal growth processes or by microwave irradiation using organometallic precursors. MALDI-TOFMS enabled us to estimate the number of II-VI units in the QDs and therefore evaluate their size and size dispersities. Evaluating the potential toxicity of nanoparticles is also critical for the responsible development of applications. One such example is the now commonplace use of zinc oxide (ZnO) QDs as antibacterial, anti-corrosive, antifungal and UV filtering powders and dispersions. In the second part of the discussion, we will show some results obtained by MALDI-TOFMS on small-sized ZnO QDs (with diameters varying from 2.8 to 3.1 nm) synthesized by sol-gel chemistry and stabilized through an aminosilane coating [8]. Having a better understanding about the stability of ZnO QDs aged in biological solutions is fundamental in evaluating the two toxicity forms of these nanocrystals: i) Zn2+ leakage during dissolution of QDs, and ii) nanotoxicity related to size, shape, surface chemistry and aggregation of nanoparticles. A careful investigation of the stability of ZnO QDs was initiated once these dots were dispersed in different media (water, biological buffer) for a period up to 3 weeks. Positive ion mode mass spectra MALDI-TOF-MS combined with optical spectrometry were used to monitor the stability of ZnO QDs during aging. Results obtained indicate that ZnO QDs did not lose their integrity after three weeks even if an aggregation process occurred as observed jointly by TEM and MALDI-TOFMS. Such a high stability makes ZnO QDs useful nanocrystals for studying the nanoparticles toxicity in media containing microorganisms like bacteria. In conclusion, the unique combination of MALDI-TOF-MS and physico-chemical techniques is a highly valuable approach in nanometrology to better understand the structure, the stability and the potential toxicity of nanomaterials.

References 1. K. Thomas, P. Aguar, H. Kawasaki, J. Morris, J. Nakanishi and N. Savage, Toxicol. Sci. 92(1), 23-32 (2006). 2. J.E Hutchinson, ACS Nano, 2(3) 395-403 (2008). 3. A. Kumar, P. Kumar, A. Anandan, T. F. Fernandes, G.A. Ayoko and G. Biskos, J. Nanomater. 2014 Article ID 130198, 16 pp (2014). 30

9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France 4. J.J. Gaumet and G. Strouse, Mater. Sci. Eng. C, 19, 299-304 (2002). 5. M. Fregnaux, S. Dalmasso, P. Durand, Y. Zhang, J.J. Gaumet and J.P. Laurenti, Mater. Chem. Phys, 142, 52-60 (2013). 6. M. Fregnaux, J.J. Gaumet, S. Dalmasso, J.P. Laurenti and R. Schneider, Microelectron. Eng. 108, 187-191(2013). 7. G.A. Khitrov and G.F. Strouse, J. Am. Chem. Soc., 125, 10465-10469 (2003). 8. R.O. Moussodia, L. Balan, C. Merlin, C. Mustin and R. Schneider, J. Mater. Chem, 20, 11471155 (2010).

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New insight into organosilane grafting onto titania and silica nanoparticles using volumetric techniques based on molecular probing Thibault Roques-Carmes 1,*, Mounir Kassir 2,3, Haytham Alloul 2,3, Angelina Razafitianamaharavo 2, Tayssir Hamieh 3, Joumana Toufaily 3, Frédéric Villiéras 2 1. Université de Lorraine, Laboratoire Réactions et Génie des Procédés, UMR 7274 CNRS, 1 rue Grandville, 54001 Nancy Cedex, France 2. Université de Lorraine, Laboratoire Interdisciplinaire des Environnements Continentaux, UMR 7360 CNRS, 15 avenue du Charmois, 54500 Vandœuvre-lès-Nancy, France

3. Laboratory of Materials, Catalysis, Environment and Analytical Methods, Faculty of Sciences I, Lebanese University, Campus Rafic Hariri, Beyrouth, Lebanon Email: [email protected],

Abstract This paper addresses the surface modification of oxide nanoparticles using organosilane molecules. To this aim, the surface of TiO2 nanoparticles is modified with n-(6-aminohexyl) aminopropyltrimethoxysilane (AHAPS) while hexadecyltrichlorosilane (HTS) is applied as surface modifier of Aerosil OX50 silica particles. A detailed study is conducted to obtain new insights into the grafting process using volumetric techniques based on molecular probing. More precisely, the evolution of the surface energy heterogeneity during the grafting of the organosilane molecules have been investigated by quasi-equilibrium low-pressure approaches using argon and nitrogen as probe molecules. DIS modeling of the distribution functions of condensation give access to follow the evolution of the different energy sites when grafting organic molecules. Very few studies have directly addressed the contribution of physisorbed aminosilane molecules during the organosilane grafting process on titania. The main objective of this work is to show experimentally the importance of the physisorption during the grafting process of an aminosilane coupling agent n-(6-aminohexyl) aminopropyltrimethoxysilane (AHAPS) on TiO2 nanoparticles. The distinction between chemisorbed and physisorbed aminosilane molecules on TiO2 is thoroughly analyzed. The surface of bare and modified TiO2 particles has been characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) to gain a better understanding of the adsorption mechanism of AHAPS on TiO2. Quantitative information on surface energy of TiO2, in terms of adsorption energy sites and heterogeneity, has been investigated by quasi– equilibrium low–pressure adsorption technique using nitrogen and argon as probe molecules. The FTIR and XPS data are combined to estimate and discuss the chemisorbed and physisorbed contribution. The results demonstrate that both physisorption and chemisorption occurs but they

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9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France display a different behavior. The physisorbed amounts are much higher than the chemisorbed amounts. This shows that the main part of the adsorbed layer is composed of physisorbed molecules. The physisorbed uptake depends highly on the AHAPS concentration while the chemisorbed amount remains constant. Quasi-equilibrium Ar derivative adsorption isotherms reveal that the AHAPS molecules are mostly located on the {101} and {001} faces of titania and that the 2 faces display the same reactivity toward AHAPS sorption. Nitrogen adsorption experiments show that the sorption takes place on the 3 polar surface sites of high energy. The molecules are chemisorbed onto the site displaying the highest energy while they are physisorbed on the 2 lower energy sites. Although many works were conducted with the aim of preparing hydrophobic silica surfaces, the thorough analysis of the change of the silica surface properties which occurs during the chemical modification was never reported in the literature. The surface heterogeneity of a hydrophilic silica OX 50 is studied before and after hydrophobic chemical modification. This fumed silica is chemically modified using the hydrophobic organosilane hexadecyltrichlorosilane (HTS). The modifications of surface heterogeneity due to HTS adsorption was analyzed using low-pressure adsorption techniques. For bare silica, the shape of the derivative experimental curve obtained with argon can be described by five local adsorption domains or local isotherms. This assesses that the silica surface is energetically heterogeneous due to the heterogeneity in the distribution of the adsorption sites. Conversely, for the totally covered silica (QHTS = 2.1 µmol/m2), only one local derivative isotherm is needed to represent the experimental data. The experimental curves corresponding to the partial HTS surface coverages (QHTS = 0.35-2.0 µmol/m2) can be represented by a linear combination of the different local models corresponding to bare silica and full HTS-covered silica, without any change of the local energy parameters. This suggests that the HTS grafting can be view as being patchwise with the formation of HTS aggregates on the surface leaving free patches of silica surface. Nitrogen is a Lewis base, and can be used to attest the polar−apolar nature of the solid surfaces. The shift of all the peaks at a high and medium energy from argon to nitrogen highlights the presence of polar surface sites on the surface of the silica since the HTS molecules are covalently linked to the surface polar hydroxyl groups through the Ti-O-Si bond. The information obtained from the low-pressure gas adsorption are used to reproduce the HTS grafted amount along its adsorption isotherm from cyclohexane. The data are compared to experimental data obtained using carbon mass measurements. The data derived from volumetry analysis compare well with those of TOC measurements. Consequently, the grafting content can be accurately reproduced through the DIS modelling.

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Consideration of size effects of architectured materials based on micropolar anisotropic media obtained by homogenization techniques Jean-François Ganghoffer1, Ibrahim Goda1, Khaled El Nady1, Yosra Rahali2 1. LEMTA – ENSEM, 2, Avenue de la Foret de Hay, TSA 60604 - 54504 Université de Lorraine, Vandoeuvre les Nancy Cedex , France, 2. ESSTT, Tunis, Tunisia Email: [email protected]

Abstract 3D architectured materials require a proper methodology for the computation of their effective mechanical response, accounting for their complex internal architecture and for possible size effects. A general micromechanical approach based on the discrete asymptotic homogenization method (Dos Reis, 2012; Goda, 2013) has been developed to compute the overall effective anisotropic mechanical properties of periodical architectured materials. Additional microrotations are incorporated into the kinematics of the homogenized continuum, leading to micropolar continua at the mesoscopic level, including bending and torsional lengths reflecting the size effects. The effective mechanical response of trabecular bone, auxetic materials, 3D textiles, braided biomaterials, and biological membranes is computed in this framework, considering successively the small and large strains regimes. Anisotropic micropolar continuum model of trabecular bone 3D anisotropic micropolar continuum models of trabecular bone are developed, accounting for the influence of microstructure-related scale effects on the effective properties (DosReis, 2012; Goda, 2012, Goda, 2013). Trabecular bone is modeled as a cellular material with an idealized periodic structure made of open 3-D cells (fig. 1); the kinematics at the microlevel incorporates nodal microrotations and translations. The effective elastic properties of 3-D lattices made of articulated beams accounting for both axial, transverse shearing, flexural and torsional deformations of the cell struts are evaluated versus the geometrical and mechanical microparameters; the effective constitutive law relates the stress and couple stress tensors σ, m respectively to the strain and curvature tensors ε, κ respectively. The classical and micropolar moduli are incorporated into the constitutive matrices E, K there above respectively. The internal bending and torsion length inherent to the micropolar model are computed from the effective classical and micropolar moduli. 34


Fig. 1: internal architecture of trabecular bone (left) Scaling laws of effective shear moduli with density (middle) - Variation of bending and torsion length with inclination angle (right).

Scaling laws of the effective moduli versus density are determined (fig. 1); the internal flexural and torsional lengths are identified versus the microparameters of the unit cell of bone, and their evolution with microstructural parameters are pictured in fig. 1. Homogenized response accounting for geometrical nonlinearities The computational scheme of the effective mechanical response of periodical architectured materials is next extended to the geometrically nonlinear setting; an incremental scheme is constructed whereby the structure topology is actualized at each loading step. We evaluate as an application the homogenized mechanical response of biomembranes represented as quasi periodical 2D lattices of elastic filaments building a planar network (Dos Reis, 2011; ElNady, 2015). Both the in-plane and bending effective mechanical properties are evaluated versus the microstructural network parameters.

Fig. 2: Perturbed lattice topology (left), peptidoglycan network (middle) Uniaxial tensile response (right) 35


Computations done for disordered initial configurations (fig. 2, left) show a weak impact on the effective moduli in comparison to perfectly periodic networks. Non affine deformations and large rotations of the filaments lead to generalized continua, such as micropolar media or second order grade continua. The homogenized moduli (fig. 2, right) accurately predict measurements from the literature at the network scale (Boal, 2012), as exemplified for the peptidoglycan and erythrocyte networks. Finally, considering the more general context of tissue engineering, a modeling and computational framework for the evaluation of the mechanical response of biodegradable scaffolds for the Anterior Cruciate Ligament is exposed (fig. 3).

Fig. 3: multilayer scaffold subjected to combined tension-torsion loadings References [1]. Dos Reis, F., Ganghoffer, J.F. Construction of micropolar models from lattice homogenization. Computers and Structures, 112-113, 354-363: 2012. [2]. Goda, I. Assidi, M., Ganghoffer, J.F. A micropolar constitutive model of cancellous bone from discrete homogenization. Computer Methods in Biomechanics and Biomedical Engineering, 16:87-108, 2012. [3]. Goda, I. Assidi, M., Ganghoffer, J.F. Equivalent mechanical properties of textile monolayers from discrete asymptotic homogenization. J. Mech. Phys. Solids., 61, 12: 2537-2565, 2013. [4]. Boal, D. Mechanics of the cell, Cambridge University Press, Second Edition, 2012. [5]. Dos Reis, F., Assidi, M., Ganghoffer, J.F. Equivalent mechanical properties of biological membranes from lattice homogenization. J. Mech. Behav. Biomed. Mat., 4, 1833-1845:2011. [6]. El Nady, K., Ganghoffer, J.F., Computation of the effective mechanical response of biological networks accounting for large configuration changes. J. Mech. Behav. Biomed. Mat., 2015. In print.

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New progresses in the development of a scientific methodology to characterize materials by Inverse Gaz Chromatography at infinite dilution Tayssir Hamieh Laboratory of Materials, Catalysis, Environment and Analytical Methods, EDST, Faculty of Sciences , Lebanese University, Campus Rafic Hariri, Beirut, Lebanon

Abstract The physicochemical properties of materials previously determined by inverse gaz chromatography at infinite dilution were contested by many authors during the last ten years. In our approach, we proved that the surface area of molecule adsorbed on solid surfaces extremely depended on the thermal agitation and then depend in general on the temperature. The two dimensionnel equations of state were reformulated and the model of perfet two dimensionnel gaz cannot be used in such case. The specific interactions have to be recalculated based on the new values of the surface areas. The acid base constants in Lewis terms of solid substrates have to be corrected using new models of equations. The second transition phenomena of polymers were determined by our new approach with an excellent accuracy. Many results were obtained by using several solid substrates as polymers, metals, oxides or polymers adsorbed on oxides or metals.

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Thermoswitchable Fluorescent Nanoparticles: Preparation, Properties and Applications Enaam Jamal Al Dine1, 3, Thibault Roques-Carmes2, Alexandra Schejn2, Tayssir Hamieh3, Joumana Toufaily3, Eric Gaffet1, Raphaël Schneider2 , Halima Alem1*

1. Institut Jean Lamour (IJL), UMR CNRS 7198, Université de Lorraine, Department N2EV, Parc de Saurupt CS50840 54011 Nancy, France. 2. Laboratoire Réaction et Génie des Procédés (LRGP), UMR CNRS 7274, Université de Lorraine, 1 rue Grandville 54001 Nancy, France. 3. Laboratory of Materials, Catalysis, Environment and Analytical Methods, Faculty of Sciences I, Lebanese University, Campus Rafic Hariri, Beirut, Lebanon Email: [email protected]

Abstract

In this work, we developed a new process to covalently graft a thermo-responsive polymer on the surface of fluorescent nanocrystals in order to synthesize hybrid materials that combine both responsive and fluorescent properties. Nontoxic ZnO quantum dots (QDs) formed the core because usually QDs shows excellent fluorescence properties. These dots were synthesized by a sol-gel method followed by stabilization with organosilane. For the first time, poly(N-isopropylacrylamide) (PNIPAM) and poly(ether oxide) derivatives copolymers were grown by Activator ReGenerated by Electron Transfer-Atom Transfer Radical Polymerization (ARGET-ATRP) from ZnO quantum dots by surface-initiated polymerization. This process allowed the formation of fluorescent and responsive ZnO/PNIPAM core/shell QDs and ZnO/(co-)polymer while only requiring the use of ppm amount of copper for the synthesis. Each step of the synthesis process was monitored by the combination of various techniques such as UV measurements, fluorescence spectroscopy, dynamic light scattering and transmission electron microscopy. More particularly, thermo-responsive polymers are generally characterized by either lower critical solution temperature (LCST) or upper critical 38


solution temperature (UCST). The LCST represents the temperature above which the polymer phase is separated from water, and below the LCST this polymer is miscible in water.

We demonstrated that aqueous dispersible core/shell ZnO@PNIPAM QDs could be prepared by growing PNIPAM chains by ARGET-ATRP from silanized ZnO surfaces. The influence of the nature of the silanized layer and the PNIPAM polymerization time on the properties of the final nanomaterials were investigated. Results clearly evidence that the nanomaterial displays temperature-dependent optical properties and sizes. Both the PNIPAM layer thickness and the temperature affected the luminescence properties of the core/shell nanoparticles. In addition, the PNIPAM layer, when it is thick enough, could stabilize the QDs optical properties. Copolymer with different length chain and proportions of 2-(2-methoxyethoxy) ethyl methacrylate (MEO2MA) and hydroxyl-terminated oligo (ethylene glycol) methacrylate (HOEGMA) were also used as thermoswitchable copolymers. The nanomaterials exhibit temperature-dependent optical and sizes properties which depend mainly on the content of each monomer. By tuning the amount of each monomer, LCST ranging from 20 to 50°C can be obtained. Then, drug loading and release capacity of ZnO/(co-)polymer as well as their cytotoxicity towards cancer cells were evaluated. Results demonstrate the impact of the copolymer structure on quantum dots properties in view of the application in cancer therapy.

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Approche de la globalisation et de la stratégie des Energies Renouvelables et les énergies nouvelles dans les pays développés et ceux en développement Boumédiène BENYOUCEF Directeur de la Division Energies Renouvelables (URMER) Université de Tlemcen, Faculté des Sciences, Département de Physique, BP : 119, Tlemcen, 13000, Algérie Email : [email protected]

Résumé

En Algérie, nous affichons un intérêt certain sur la nécessité d’opérer par un champ multidisciplinaire vers l’alternative de la substitution des énergies hydrocarbures par les énergies nouvelles dont essentiellement la partie photo-solaire. La problématique et la stratégie associée résident dans le fait de rendre compétitif cette dernière forme d’énergie par une optimisation des matériaux et systèmes de photo-conversion et d’opérer par des normes d’efficacité énergétique. Des résultats appréciables à l’échelle nationale et internationale ont été valorisés par un riche potentiel humain formé dans nos institutions de recherche sur le domaine de la prédiction de nouveaux matériaux, les thématiques de l’élaboration et de la caractérisation des matériaux ainsi que le développement des énergies photo- solaires et photovoltaïques. Le Centre de Développement des Energies Renouvelables « CDER » en collaboration avec les Unités de Recherche ainsi que l’Unité de Recherche Matériaux et Energies Renouvelables (URMER) contribuent efficacement à la mise en œuvre d’une panoplie de solutions apportées au développement des Energies Renouvelables, et ce dans le cadre d’un développement harmonieux et constructif par rapport aux Energies Conventionnelles ou Nouvelles (hydrocarbures et nucléaires) , répondant à la fois aux exigences d’un environnement propre, d’une efficacité énergétique maîtrisée d’une part et au défi planétaire d’un développement durable d’autre part.

Ainsi les programmes affichés par l’URMER s’intègrent dans une vision multi disciplinaire et multisectorielle dans les domaines de la formation par et pour la recherche. De ce fait nous avons pu

40

9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France mettre en œuvre la création de l’Ecole Doctorale « Energies Renouvelables », intégrant un réseau national à plusieurs établissements nationaux et internationaux.

L’URMER, le CDER et l’URMER (Algérie), en collaboration avec l’Université de Beyrouth (Liban) et l’Université de la Lorraine (LMOPS de Metz, et de Nancy) lancent le challenge de s’intégrer avec les institutions nationales et internationales du monde socio-économique. Des perspectives fort appréciables sont

projetées

dans la construction d’actions valorisantes de notre recherche et

formation. Ils s’intègrent dans une stratégie nationale, globale et mondiale de promotion et de maîtrise des Energies Renouvelables pour un développement durable et un respect d’un environnement propre.

41


Oral Communications Symposium I: Materials, Nanomaterials and New Materials 1. Industrial Innovations in Material Engineering and New Materials 2. Nanomaterials and Nanotechnology 3. Multi-Materials and Composite Materials 4. Inorganic Porous Organized Materials 5. Inverse Gas Chromatography for characterization of materials 6. Materials for Catalysis 7. Properties of Surfaces and Interfaces, and Adhesion of Materials 8. Textiles Materials 9. Polymer and Organic Materials 10. Asphaltic Materials. 11. High Performance Materials.

42


Starch Nanocrystals as Initiator and additive for Thermal Cationic Polymerization at Room Temperature with In Situ Formation of Silver Nanoparticles *Mohamad-Ali Tehfe, Saïd Elkoun, Mathieu Robert Carrefour of Innovative Technology and Ecodesign (CITE), Faculty of Engineering, University of Sherbrooke; 2500 blvd Université, Sherbrooke, Quebec J1K 2C3, Canada. Author E-mail address: *[email protected]

Abstract Nanocomposite materials containing noble metal and dispersed nanoparticles in a polymer matrix may exhibit peculiar physical and chemical properties that are of high scientific and technological importance [1]. In particular, silver nanoparticles are very important for their excellent electrical conductivity [2], anti-microbial effect [3] and optical properties [4]. In recent years, a whole bunch of synthetic methods for the preparation of metal nanoparticules have been developed: chemical, photochemical and thermal. Cationic polymerization (CP) reactions are very attractive [5-9]. The cationic ring opening polymerization (ROP) of ɛ-caprolactone (ɛ-CL) or α-pinene oxide (α-PO) has received less attention than the other modes of activation [10-14]. The development of new and efficient cationic initiating systems for the polymerization of ɛ-CL or α-PO at room temperature (RT) and under air is still valuable due to the wide range of applications of biodegradable polycaprolactone (PCL) and/or biodegradable and bio-renewable polypinene oxide (PPO) in packaging, medicine and tissue engeenering. For instance, PCL can be used as an additive to improve the processing of resins and/or their end use properties (e.g. impact resistance). Incorporating nanoparticles (NP) to PCL could give extra properties, such as bactericide property due to the presence of Ag [15-19]. The incorporation of Ag(0) through photopolymerization processes has been elegantly presented in [17,18]. In the present work, we propose to use a redox system based on an organosilane, such as diphenylsilane

(DPSi)

or

1,1,3,3-tetramethyldisiloxane

(TMDSi)/starch

nanocrystals

(StN)/silver salts couple for thermal cationic polymerization of ɛ-CL and/or α-PO (Scheme 1). Our system should open up a new way for i) the cationic ROP of ɛ-CL or α-PO initiated by a 43


true redox process at RT and under air, ii) the in-situ incorporation of nanoparticles into PCL or PPO and iii) using a vegetal source, such as starch nanocrystals (StN) to improve the polymerization efficiency. On the other hand, starch is a cheap, abundant, renewable and biodegradable semi-crystalline raw material from which nano crystalline particles can be extracted. These starch nanoparticles/nanocrystals have many potential applications, such as plastic fillers, food additives, drug carriers, implant materials, fillers in biodegradable composites, coating binders, adhesives, etc [20]. Alternatively, the purpose of using starch nanocrystals as additive is i) to improve the efficiency of polymerization, ii) to reinforce agent of the polymer (improvement of mechanical property). Finally, the overall polymerization process has been investigated and the cured films characterized. HO HO

DPSi

TMDSi

ε-CL

α-PO

HO HO

R-OH

Scheme 1.

Starch nanocrystals (StN) is proposed as initiator and additive for epoxy thermal ring opening polymerization (ROP) at room temperature and under air. The two- and three-component new initiating systems based on starch nanocrystals (or silane)/silver salts and silane/starch nanocrystals/silver salt interaction lead to excellent polymerization profiles. The effects of the starch nanocrystals, silane, silver salt and monomer structures are investigated. Interestingly, silver nanoparticles Ag(0) are formed in situ. The as-synthetized nanocomposite materials contained spherical nanoparticles homogenously dispersed in the polymer matrices. Polymers and nanoparticles were characterized by gel permeation chromatography (GPC), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-vis spectroscopy. A coherent picture of the involved chemical mechanisms is presented.

44

9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France HO HO

HO HO

4

Ag (0)

60 sec

3

O.D.

+ Silver Salt

or ɛ-CL

Keywords:

α-PO

Starch

20 sec

10 sec

1

5 sec

0 sec

Thermal cationic polymerization at Ag(0) RT and under air

Nanocrystals,

30 sec

2

0 350

400

450

500

550

600

650

700

l (nm)

silver nanoparticles/polymer nanocomposite materials

Silver

Nanoparticles,

Silane,

Thermal

Cationic

Polymerization.

References [1]. Carotenuto G, Martorana B, Perlo PB, Nicolais L. A universal method for the synthesis of metal and metal sulfide clusters embedded in polymer matrices. J. Mater. Chem. 2003; 13 (1): 2927–2930. [2]. Chang LT., Yen CC. Studies on the Preparation and Properties of Conductive Polymers. VIII. Use of Heat Treatment to Prepare Metallized Films from Silver Chelate of PVA and PAN. Journal of Applied Polymer Science 1995; 55 (2): 371-374. [3]. Shanmugam S., Viswanathan B., Varadarajan TK. A novel single step chemical route for noble metal nanoparticles embedded organic-inorganic composite films. Materials Chemistry and Physics 2006; 95 (1): 51-55. [4]. Lin WC., Yang MC. Novel Silver/Poly(vinyl alcohol) Nanocomposites for Surface-Enhanced Raman Scattering-Active Substrates. Macromolecular Rapid Communications 2005; 26 (24): 1942-1947. [5]. Matyjaszewski K, Gnanou Y, Leibler L. Macromolecular engineering: from precise macromolecular synthesis to macroscopic materials properties and applications Eds, WileyVCH, Weinheim 2007. [6]. Crivello J.V. Photoinitiators for Free Radical, Cationic and Anionic Photopolymerization, 2nd Ed.; Bradley, G., Ed.; New York 1998. [7]. Crivello J.V. Ring-Opening Polymerization, Brunelle, D.J. Ed.; Hanser: Munich 1993. [8]. Fouassier, J.P. Photoinitiation, Photopolymerization and Photocuring: Fundamental and Applications Hanser Publishers: New York 1995. [9]. Fouassier J.P., Rabek, J.F. Radiation Curing in Polymer Science and Technology Eds. Elsevier Science Publishers Ltd.: London 1993. [10]. Sando F., Sanado H., Shibasaki Y., Endo, T. Star Polymer Synthesis from ε-Caprolactone Utilizing Polyol/Protonic Acid Initiator. Macromolecules 2002; 35 (3): 680-683. [11]. Lou X., Detrembleur C., Jérôme R. Living Cationic Polymerization of δ-Valerolactone and Synthesis of High Molecular Weight Homopolymer and Asymmetric Telechelic and Block Copolymer. Macromolecules 2002; 35 (4): 1190-1195. [12]. Persson P.V., Schroder J., Wickholm K., Hedenström E., Iversen T. Selective Organocatalytic Ring-Opening Polymerization: A Versatile Route to CarbohydrateFunctionalized Poly(ε-caprolactones). Macromolecules 2004; 37 (16): 5889-5893. [13]. Gazeau-Bureau S., Delcroix D., Martin-Vaca B., Bourissou D., Navarro C., Magnet S. Organo-Catalyzed ROP of ϵ-Caprolactone: Methanesulfonic Acid Competes with Trifluoromethanesulfonic Acid. Macromolecules 2008; 41 (11): 3782-2784. [14]. Kunioka M., Wang Y., Onozawa S-Y. Polymerization of Poly(ε-caprolactone) Using Yttrium Triflate. Polymer Journal 2003; 35 (5): 422-429. 45

9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France [15]. Uygun M., Kahveci M.U., Odaci D., Timur S., Yagci Y. Antibacterial Acrylamide Hydrogels Containing Silver Nanoparticles by Simultaneous Photoinduced Free Radical Polymerization and Electron Transfer Processes. Macromol. Chem. Phys., 2009; 210 (21): 1867-1875. [16]. Dawson-Andoh B., Matuana L. High density polyethylene-wood flour composite lumber: efficacy of two proprietary biocides in the control of fungal colonization and discoloration. European J. of Wood and Wood Products 2007; 65 (5): 331-334. [17]. Yagci Y., Sangermano M., Rizza G. A visible light photochemical route to silver–epoxy nanocomposites by simultaneous polymerization–reduction approach. Polymer 2008; 49 (24): 5195-5198. [18]. Sangermano M., Yagci Y., Rizza G. In Situ Synthesis of Silver−Epoxy Nanocomposites by Photoinduced Electron Transfer and Cationic Polymerization Processes. Macromolecules 2007; 40 (25): 8827-8829. [19]. Yagci Y., Sahin O., Ozturk T., Marchi S., Grassini S., Sangermano M. Synthesis of silver/epoxy nanocomposites by visible light sensitization using highly conjugated thiophene derivatives. Reactive and Functional Polymers 2011; 71 (8): 857-862. [20]. García NL, Ribba L., Dufresne A., Aranguren M., Goyanes S. Physico-Mechanical Properties of Biodegradable Starch Nanocomposites. Macromol Mater Eng. 2009; 294 (3): 169-177.

46


Three steps synthesis process to obtain core/shell nanoparticles serving as capsules for effective drug delivery Enaam Jamal Al Dine1, 3*, Joumana Toufaily3, Alexandra Schejn2, Thibault RoquesCarmes2, Mounir Kassir3, Houssam Obeid3, Tayssir Hamieh3, Eric Gaffet1, Sophie Marchal4, Raphaël Schneider2, Halima Alem1 1. Institut Jean Lamour (IJL), UMR CNRS 7198, Université de Lorraine, Département N2EV, Parc de Saurupt CS50840 54011 Nancy, France. 2. Laboratoire Réaction et Génie des Procédés (LRGP), UMR CNRS 7274, Université de Lorraine, 1 rue Grandville 54001 Nancy, France. 3. Laboratory of Materials, Catalysis, Environment and Analytical Methods, Faculty of Sciences I, Lebanese University, Campus Rafic Hariri, Beirut, Lebanon 4. Institut Cancérologie de Lorraine, 6 Avenue de Bourgogne CS 30519 54519 Vandœuvre-lès-Nancy, France Email : * [email protected] Abstract The effective drug delivery to specific areas of the body and the monitoring of their release induced many researches to develop smart nanomaterials which can be used to achieve both objectives at one time. In this context, we are developing new nanoparticles which may serve as capsules to selectively deliver drugs to cancer cells. The nanoparticles are composed of a fluorescent semiconductor quantum dot core, namely zinc oxide and a shell consisting of thermo-responsive co-polymer which is able to adapt its macromolecular properties with temperature. Hence, it displays a collapse temperature which can be adjusted to a certain value in physiological media by tuning the composition of the two polymers. Below this temperature the copolymer chains are swollen in the medium and above they collapse on the surface of the nanoparticles resulting in the release of the drug which is incorporated inside. The synthesis process of the nanoparticles involved three steps. The synthesis of the quantum dots using sol-gel method as a first step followed by grafting an initiator on the surface using an organosilane which is ((chloromethyl) phenylethyl) trimethoxysilane). The last step was the growing of the copolymer which is composed of two well known biocompatible polymers; 2-(2-methoxyethoxy) ethyl methacrylate (MEO2MA) and hydroxyl-terminated oligo (ethylene glycol)

methacrylate

(HOEGMA).

ARGET-ATRP

47

was

chosen

as

a

convenient


polymerization technique which reduces copper catalyst concentrations to values of the order of 10 ppm by the introduction of an excess amount of reducing agent in the reaction. The prepared samples were characterized by different techniques. High resolution transmission electron microscopy was used to characterize the structure of the nanoparticles. The results showed that the particles were well dispersed and had fairly homogeneous and spherical shape with an average diameter of about 6-7 nm. The thermo-sensitive behavior of the resulting nanoparticles was quantitatively studied with the aid of dynamic light scattering. The size of the particles was measured as a function of the temperature. For each sample, different temperatures were obtained in water and physiological media. For example, the sample with the 80 % composition of MEO2MA had a collapse temperature of 36 °C in water. All the samples exhibit similar photoluminescence emission spectra centered at about 540 nm. When the temperature is increased over the collapse temperature, the particles start to lose their luminescence properties due to the aggregation when the copolymer chains collapse on the surface of the nanoparticles. The loss of the luminescence properties due to the change of temperature reveals also the temperature dependence properties of the NPs. Cytotoxicity tests were made and results showed that these nanoparticles are not toxic at low concentrations. Preliminarily experiments were performed to study the release of the drug from the nanoparticles and it was almost clear that the concentration of the drug increases in the medium with increasing the temperature.

Keywords: effective drug delivery, organosilane, smart nanomaterials, ethylene glycol, cytotoxicity,

48


Effect of Sb in Se90X10 (X = In, Zn) thermal properties M. Belhadji and M. Heireche Physics Department, Ahmed Benbella University 1, Oran, Algeria

Abstract The effect of antimony (Sb) addition in SeIn and SeZn glassy system is studied by differential scanning calorimetry (DSC), important physical properties, such as variation of average coordination number, transition temperature, fragility parameter and thermal stability. The values of average coordination number were found to increase with increasing Sb content, while the others properties were in decrease. By adding more Sb atoms, the glassy system becomes less stable thermally. According to the GibbsDimarzio model, some parameters was determined.

Keywords: Chalcogenide glasses; DSC; SeInSb; SeZnSb, glass transition, crystallization process, coordination number.

49


Organized metallic nanostructures via polymer self-assembly Ali Issa1,3, Joumana Toufaily3, Maher Khanafer1,3, Suzanna Akil2, Tayssir Hamieh3, Pierre M. Adam1, Safi Jradi 1,* 1.

Laboratoire de Nanotechnologie et d’Instrumentation Optique, Institut Charles Delaunay, STMR-UMR 6281 CNRS, Université de Technologie de Troyes, 12 rue Marie Curie - CS 42060, 10004 Troyes Cedex - France. 2. Laboratoire de Chimie et Physique, Université de Lorraine, 1 Bd Arago, 57070 Metz, France 3. Laboratory of Materials, Catalysis, Environment and Analytical Methods, Faculty of Sciences I, Doctorate School of Science and Technology, Lebanese University, Beirut, Lebanon. * Email of corresponding author: [email protected]

Abstract The 'bottom-up' nanofabrication of hybrid materials via self-assembly appears as an interesting way to obtain organized metallic nanoparticles (MNPs). The wide usage of these MNPs as a plasmonic materials in many applications including electronics (1) photonics (2)(3) catalysis(4) biological imaging (5)(6) drug delivery, sensors and surface enhanced Raman scattering (SERS) (7)(8)(9) illustrate the light on the need to use a simple, easy and cheap method of fabrication taking into consideration the influence of physicochemical parameters on the dimensional characteristics of the hybrid nanostructures. A new approach for surface nanostructuring was innovated by means of metallic nanoparticles organized in a thin homopolymer film (PMMA) on a silicon substrate (cf. Figure 1).

Figure 1: (1) the mixture before adding acetone; (2) after adding acetone; (3) spin coating on a semi conductive substrate; (4) Initial evaporation of the acetone and the formation of vesicles; (5): "A" Schematic representation of the vesicle; SEM images showing vesicles "B" before and "C" after their explosion; AFM "D" and SEM "E" images of the film obtained from the solution containing the couple PMMA/ metallic salt.

50


The originality of this simple self-assembling is that structuring was obtained in one step, in addition that no reducing agent was used nor preliminary functionalization of the surface was done. The mixture containing PMMA, metallic salt and solvents was deposited on the semi conductive substrate by using spin coating. After the complete evaporation of solvents, a film of polymer drilled by metallic nanoparticle (MNP) rings was obtained. A wide range of Metallic salts “Mn+ (NO3-)n (M: Ag, Au, Mn, Mg, Cr, Cu, Ni, Eu, Pr, Nd, Pm, Sm, Tb, Dy, Tm, Ca, Zr, Fe, Co, Zn, Al,…) were introduced to the PMMA film using the same method. The key parameters of this new method were defined and the mechanism of this synthesis which takes place on the substrate surface was explained by studying the influence of various physicochemical parameters (solvents, speed of evaporation, and nature of surface) on the organization of the MNPs. Keywords: Auto assemblage de polymère, Résonance plasmonique de surface, Matériaux nanostructurés, Nanoparticules métalliques, nanoséparation de phase. Acknowledgments: Financial support of the "Conseil Régional Champagne-Ardenne", NanoMat (www.nanomat.eu) by the "Ministère de l’enseignement supérieur et de la recherche", the DRRT (Délégation Régionale à la Recherche et à la Technologie) of Champagne Ardenne, and the Labex ACTION Project (contract ANR-11-LABX- 01-01) is acknowledged.

References [1] J. H. Lee, D. O. Kim, G. S. Song, Y. Lee, S. B. Jung and J. D. Nam,Macromol. Rapid Commun., 2007, 28, 634. [2] M. J. Li, H. Zhang, J. H. Zhang, C. L. Wang, K. Han and B. J. Yang, J. Colloid Interface Sci., 2006, 300, 564. [3] S. Kubo, Z. Z. Gu, D. A. Tryk, Y. Ohko, O. Sato and A. Fujishima, Langmuir, 2002, 18, 5043. [4] T. Ishida, K. Kuroda, N. Kinoshita,W.Minagawa and M. J. Haruta,J. Colloid Interface Sci., 2008, 323, 105. [5] L. R. Hirsch, A. M. Gobin, A. R. Lowery, F. Tam, R. A. Drezek,N. J. Halas and J. L. West, Ann. Biomed. Eng., 2006, 34, 15. [6] T. M. Lee, A. L. Oldenburg, S. Sitafalwalla, D. L. Marks, W. Luo, F. J. J. Toublan, K. S. Suslick and S. A. Boppart, Opt. Lett., 2003, 28, 1546. [7] S. Akil-Jradi, S. Jradi, J. Plain, J.-L. Bijeon, C. Sanchez, R. Bachelot and P. Royer, Chem. Commun., 2011, 47, 2444. [8] A. Shamsaiea, J. Heima, A. A. Yanik and J. Irudayaraj, Chem. Phys. Lett., 2008, 461, 131. [9] Irene Izquierdo-Lorenzo, Safi Jradi and Pierre-Michel Adam, Direct laser writing of random Au nanoparticle three-dimensional structures for highly reproducible micro-SERS measurements, RSC Adv., 2014, 4, 4128

51


Fabrication of true 3D polymer nanostructures with sub-100 nm feature sizes via femtosecond direct laser writing based on two-photon polymerization

Ying Peng1, Safi Jradi1,*, Suzanna Akil2, Renaud Bachelot1 1.

2.

Laboratoire de Nanotechnologie et d’Instrumentation Optique, Institut Charles Delaunay, STMR-UMR 6281 CNRS, Université de Technologie de Troyes, 12 rue Marie Curie - CS 42060, 10004 Troyes Cedex – France Laboratoire de Chimie et Physique, Université de Lorraine, 1 Bd Arago, 57070 Metz, France

* E-mail: [email protected]

Abstract In this work, we demonstrate the capability to fabricate three-dimensional (3D) structures with 75 nm resolution using direct laser writing (DLW) based on two-photon polymerization. The composition of the photopolymerizable solution was tuned in order to show a strong chemical non-linearity effect by adding free radical inhibitors. The influence of the inhibitor concentration, laser power and scan speed on the resolution of as-prepared structures is also investigated. It is observed that, with the optimized inhibitor-containing formulation, the resolution is significantly improved as the scan speed increased (400 µm/s).

52


Specific Cationic Photoinitiators for Near UV and visible LEDs: Iodonium vs. Ferrocenium Structures Haifaa Mokbel1,2, Joumana Toufaily2, Frederic Dumur3 ,Damien Campolo3 ,Didier Gigmes3, Jean Pierre Fouassier4, *Joanna Ortyl5, Tayssir Hamieh2 ,*Jacques Lalevée1 1. Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15, rue Jean Starcky, 68057 Mulhouse Cedex, France; 2. Laboratory of Materials, Catalysis, Environment and Analytical Methods (MCEMACHAMSI), EDST and Faculty of Sciences I, Lebanese University, Campus Rafic Hariri, Beirut, Lebanon 3. Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, F-13397 Marseille, France; 4. ENSCMu-UHA, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France ; 5. Faculty of Chemical Engineering and Technology, Cracow University of Technology,Warszawska 24, Cracow 31-155, Poland. Email of corresponding author: [email protected] ; [email protected]

Abstract Over the last decades, there has been a growing interest for the industrial application of photoinitiated cationic polymerization (CP) reactions [1-3] which have several advantages over the free radical polymerization (FRP). Onium salts [1-6] have been extensively studied as photoinitiators (PI) for CP. Among them, diaryliodonium and triarylsulfonium are commercially important. They consist in a cationic moiety and a counter anion [6]. The nucleophilicity of the anion is an important parameter affecting the performance:of the polymerization reaction. Although onium salts exhibit a relatively low absorption above 320 nm, their spectral response can be extended, with more or less success, into the near-UV and visible spectral regions by photosensitization. The design and development of novel highperformance cationic photoinitiating systems (PIs) directly adapted to light-emitting diodes (LEDs) as irradiation devices (especially near UV and visible LEDs) are still a challenge and clearly attract a great attention in the photopolymerization field [2,7]. Two iodonium salts based on a coumarin chromophore (P3C-P and P3C-Sb, shown in Scheme 1) are investigated for polymerization upon light emitting diode irradiations (LEDs). They work as onecomponent photoinitiators. When one of the phenyl substituent of diaryliodonium is changed for a coumarin chromophore, the corresponding absorption spectra are shifted to longer wavelengths (350 nm vs 250 nm for iodonium based-coumarine and diaryliodonium, respectively).

53


Scheme 1. Investigated compounds.

Therefore, the newly proposed iodonium salts are efficient to initiate the cationic polymerization of an epoxide (under air), and an divinylether (in laminate) monomer under violet LEDs (centered at 385 and 405 nm). Interpenetrating polymer network (IPN) can also be obtained through a concomitant cationic/radical polmerization of an epoxy/acrylate blend. The achieved performance will be compared to that of a ferrocenium salt (DC 1200). We would like to explore the role of the anion and the dark reaction. The polymerization reaction are followed by the real time FTIR spectrscopy. The excited state processes are investigated by laser flash photolysis (LFP) and electron spin resonance spin trapping (ESR). We are also interest to understand the absorption properties and the bond cleavage (Scheme 2) by molecular orbital calculations, carry out steady state photolysis and, finally, elaborate a mechanism for the initiation step.

Cationic Polymerization: epoxy, vinylether BDE(C-I)A = 45.66 kcal mol-1 B

A

Ph●

Coum-I●+

BDE(C-I)B = 61.37 kcal mol-1 PhI●+

Coum●

Interpenetrated Polymer Network Synthesis (IPN)

Specific Cationic Photoinitiators for Near UV and visible LEDs: Iodonium vs. Ferrocenium Structures.

Scheme 2. Reaction mechanism.

Keywords: iodonium salt, ferrocenium salt, cationic polymerization, photoinitiators, light emitting diode (LED), interpenetrated polymer network (IPN).

References [1]. a) Crivello J.V., Photoinitiators for Free Radical, Cationic; Anionic Photopolymerization, 2nd ed.; John Wiley & Sons: Chichester,1998; b) Photoinitiated Polymerization, Belfied KD, Crivello JV, Eds., ACS Symp. Ser. 847, Washington DC, 2003; c) Fouassier JP, Photoinitiator, Photopolymerization and Photocuring: Fundamentals and Applications; Hanser Publishers, Munich Vienna: New York, 1995; d) Davidson S, Exploring the Science, Technology and Application of UV and EB Curing; Sita Technology Ltd: London, 1999; e) 54

9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France Photochemistry and Photophysics of Polymer Materials, Allen NS, Ed., Wiley: New York, 2010. [2]. Fouassier JP, Lalevée J, Photoinitiators for Polymer Synthesis-Scope, Reactivity, and Efficiency; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2012. [3]. a) Yagci Y, Macromol. Symp. 2006, 240, 93–101; b) Kahveci MU, Gilmaz AG, Yagci Y, in Photochemistry and Photophysics of Polymer Materials, Allen NS, Eds, Wiley, USA, 2010, 421-478,; c) Yagci Y, Jockusch S, Turro NJ, Macromolecules.2010, 43, 624–639. [4]. a) Crivello JV, in Dyes and Chromophores in Polymer Science, Lalevée J, Fouassier,JP, Eds., ISTE Wiley, London, 2015; b) Sangermano M, Razza N, Crivello JV, Macromolecular Materials and Engineering. 2014, 299, 775-793. [5]. a) Jandt KD and Mills RW, Dent. Mater. 2013, 29, 605-617; b) Robert F and Karlicek J, in UV-LED, eds. C. Cordon and C. Miller, RadTech International, Bethesda, MD, 2013; c) Rahiotis C, Patsouri K, Silikas N, Kakaboura A, J. Oral Sci. 2010, 52, 187-195; d) Leonard DL, Charlton DG, Roberts HW, Cohen ME, J. Esthet. Restor. Dent. 2002, 14, 286-295; e) Karsten R and Beck M, Radtech Report Winter. 2011, 26-31. [6]. a) Crivello JV, Lam JHW, Macromolecules. 1977, 10, 1307-1315; b) Crivello JV, Lam JHW, J. Polym. Sci., Part A: Polym. Chem, 1978, 16, 2441-2451; c) Crivello JV, Lam JHW, J. Polym. Sci., Part A: Polym. Chem, 1979, 17, 977-999; d) Hartwing A, Harder A, Luhring A, Schroder H, European Polymer Journal. 2001, 37, 1449-1455. [7]. Xiao P, Zhang J, Dumur F, Tehfe MA, Morlet-Savary F, Graff B, Gigmes D, Fouassier J.P. Lalevée J. Prog. Polym. Sci. 2015, 41, 32-66.

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Metallic nanoparticles: new strategies of nanofabrication and characterization of their near-field thermal properties Safi Jradi1, Lama Zaarour1, Suzanna Akil1,2, Irene Izquierdo-Lorenzo1, Pierre Michel Adam1, Jérôme Plain1, Renaud Bachelot1 1

Institut Charles Delaunay, STMR-UMR 6281 CNRS, Laboratoire de Nanotechnologie et d'Instrumentation Optique, Université de Technologie de Troyes, 12 Rue Marie Curie, 10000, Troyes, France. 2 Laboratoire de Chimie et Physique- - Approche Multi-échelle des Milieux Complexes (LCP-A2MC), Université de Lorraine, 1 Bd Arago, 57070 Metz Technopôle, France. Email of corresponding author: [email protected]

Abstract Nobel metal nanoparticles have attracted great interest thanks to their original optical, thermal and chemical properties which are related to the Localized Surface Plasmonic Resonance (LSPR) effect. Indeed, the excitation of the LSPR leads to an enhancement of the electromagnetic field at the particle surface [1]. Some of this concentrated energy could be efficiently converted into heat [2]. Thus, plasmonic nanoparticles can act as efficient nanosource of heat and light. This ability to locally heat at the nanoscale opens the path for promising achievements in nanotechnology and especially for nanoscale control of electromagnetic field and temperature distribution allowing local chemical reactions, phase transition, material growth to be produced upon excitation [3]. These original phenomena are investigated in a wide range of applications such as biological imaging, detection of chemicals, photocatalysis, photothermal cancer therapy, and drug release [2]. For their optimal use in the above mentioned applications, the fabrication, dispersion, assembling and organization issues of the plasmonic NPs should be addressed. Additionally, a deep understanding of the local optical and thermal properties of photoexcited plasmonic NPs as a function of various structural and photonic parameters is required. In particular, the possibility to control and manipulate the thermal energy at the nanoscale is a key element in numerous emerging applications of plasmonics [3]. Today, one of the challenges in thermoplasmonics is to measure and image the temperature generated around a single plasmonic nanostructure. a

h

e NP d’or

b

Excitation

d c

Polymère thermosensible

Nanoréaction

Référence

j Particule excitée

l excitation

Impression du profil de chaleur

i

f

k

g

Figure 1: (a,b,c,d): Examples of metallic nanostructures fabricated by (a,b) direct laser writing and (c,d) polymer self-assembly. (e) Illustration of the near-field nanopolymerization approach. (f,g) excitation of single gold nanoparticle at 780 nm using a tightly focused laser beam. (h) AFM image showing unexcited (reference) and excited GNPs: the polymer is obtained by nanopolymerization in the vicinity of GNP after excitation and 56

9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France heating showing the possibility of print the heat profile. (i) Profile of AFM image from both reference and excited particle. (j) Extinction spectra of GNPs of different diameters done by e-beam lithography. (k) : evolution of the polymer extent (primary axis) as a function of GNP’s diameter. The evolution shows a correlation between the polymer extent (in nm) and ∆l which is the difference between the resonance wavelength and the excitation one.

In this paper, new approaches of fabrication of metal NPs will be presented (figures 1-a, 1-b, 1-c, and 1-d). In particular, spatially controlled fabrication methods based on photodewetting or photochemical reduction processes and using a tightly-focused laser beam were developed [4,5,6]. Secondly, we investigated the thermal properties of photoexcited GNPs using a recently developed approach of nanoscale chemical imaging based on thermo-polymerizable formulations (figures 1-e, 1-f, and 1-g). In particular, we used molecular thermo-probes to characterize the local heat profile in the vicinity of an isolated GNP under optical excitation. For this, we developed a set of thermopolymerizable formulations. Each one is characterized by a different and controlled polymerization temperature threshold (Tth), which can be adjusted by the weight percent of the initiator system. As in the photomolecular imaging we developed in the past [1] the resulting fingerprint of the temperature distribution around a single metal nanoparticle is imaged by AFM (see figures 1-h and 1-i). In particular, we show the possibility of imaging the heat distribution with a spatial resolution better than 40 nm. By tuning the excitation wavelength, we show that the photo-induced heating of the temperature can be tuned according to the extinction spectrum (see figures 1-j and 1-k). Finally, by using a set of thermopolymerizable solution characterized by different threshold temperatures (Tth) to determine qualitatively the minimum of temperature reached around the nanoparticle. The results show that the temperature reached close to the photo-excited nanoparticle (femtosecond laser at 780 nm, 150 fs and 80MHz) exceeds 180 ° C. Studies are underway to obtain both the extinction and nearfield thermal signature of single and dimer gold nanoparticles at different wavelengths. Keywords: Gold Nanoparticles, Nanofabrication, Radical mediated photoreduction, Self-assembly, Thermoplasmonics, Nanoscale polymerization, Single particle detection, Molecular imaging. Acknowledgments: Financial support of the "Conseil régional Champagne-Ardenne", NanoMat (www.nanomat.eu) by the "Ministère de l’enseignement supérieur et de la recherche", the DRRT (Délégation Régionale à la Recherche et à la Technologie) of Champagne Ardenne, and the Labex ACTION Project (contract ANR-11-LABX- 01-01) is acknowledged. References [1] C. Deeb, R. Bachelot, J. Plain, A.-L. Baudrion, S. Jradi, et al., "Quantitative analysis of localized surface plasmons based on molecular probing", ACS Nano vol.4, n° 8 (2010), 4579-4586. [2] G. Baffou, R. Quidant, Thermo-plasmonics: using metallic nanostructures as nano-sources of heat, Laser & Photonics Reviews 7 (2013) 171–187 [3] G. Baffou, R. Quidant, and F. Javier Garcia de Abajo, Nanoscale Control of Optical Heating in complex plasmonic systems, American Chemical Society (4), 709-716. [4] X. Zeng, S. Jradi, J. Proust, R. Bachelot, X.-P. Zhang, P. Royer, J. Plain, "Direct functionalization of an optical fiber by a plasmonic nanosensor", Optics letters, 2011, vol.36, p. 2919-2921. [5] S. Jradi, et al., "Spatially controlled synthesis of silver nanoparticles and nanowires by photosensitized reduction", Nanotechnology, 2010, vol.21, p. 095605-1-7 [6] I. Izquierdo-Lerenzo, S. Jradi, P.M. Adam, "Direct laser writing of random Au nanoparticles threedimensional structures for highly reproducible micro-SERS measurements", RSC Adv., 4,4128-4133, 2014 57


New Approach for the Synthesis of Uniform Gold Nanoparticles

R. Omar 1,2*, J. Toufaily 1, T. Hamieh 1, S. Jradi 3, H. Mortada1, A. En-Naciri 2, S. Akil 2

1. Laboratory of Materials, Catalysis, Environmental and Analytical Methods, Faculty of Sciences I, Doctoral School for Sciences and Technology, Lebanese University, Lebanon. 2. Laboratoire de Chimie-Physique Approche Multiéchelle des Milieux Complexes (LCPA2MC), Université de Lorraine, 1 Boulevard Arago, 57070 Metz, France.

3. Institut Charles Delaunay, LNIO et STMR - UMR6281 CNRS, Université de Technologie de Troyes, 12 rue Marie Curie - CS 42060, 10004 Troyes, France. *Corresponding author: [email protected]

Abstract

Gold nanoparticles have attracted and raised interest due to their potential applications in chemical and biochemical sensing for low traces molecule detection [1,2], in tumor ablation [3,4], and Lab-On Chip technologies [5].

In this context, we actually develop new gold nanoparticles (GNPs) synthesis method which is based on the use of polymer nanoporous structures as reactors for GNPs elaboration. The process is gold precursor-loaded polymer self-assembly-induced the formation of GNPs. In the present project, we aim to understand the mechanism behind the formation of uniform NPs. Thus, a physico-chemical study based on the variation of the experimental parameters is required to tune the optical and physical properties of GNPs. Such structural properties are 58


generally difficult to obtain by chemical ways as compared to our process. Moreover, the control of NPs shape and size will allow us to determine the plasmon band of the NPS and to define their sensing features. Then, bio-sensing measurements based on SERS (Surface Enhanced Raman Spectroscopy) phenomenon and using bacteria as target molecules will be performed in order to evaluate the SERS enhancement factor of the synthesized systems.

Refernces

1. Akil S., Jradi S., Plain J., Adam P.-M., Bijeon, J.-L., Sanchez C., Bachelot R. and Royer P., Chemical communications 2011, 47, 2444. 2. Akil S., Jradi S., Plain J, Adam P.-M., Bijeon, J.-L., Bachelot R. and Royer P. 2012, RSC Advances, 2, 7837. 3. Hirsch L. R., Stafford R. J., Bankson J. A., Sershen S. R., Rivera B., Price R. E., Hazle J. D., Halas N. J. and J. West L., Proc. Natl. Acad. Sci. U. S. A. 2003, 100, 13549. 4. Dreaden E. C. and El-Sayed M. A., Acc. Chem. Res. 2012, 45, 1854. 5. Matsui, J., Akamatsu, K., Hara, N., Miyoshi, D., Nawafune, H., Tamaki, K. and Sugimoto N. 2005, Analytical Chemistry, 77, 4282.

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A simple method for synthesizing zinc oxide (ZnO) nanostructured thin films

N. Hamzaoui1,2, M. Ghamnia1

1. Laboratoire des Sciences de la Matière Condensée (LSMC), Département de Physique, Faculté des Sciences, Université d’Oran es-sénia, Oran, Algérie. 2. Centre Interdisciplinaire de Nanoscience de Marseille (CINAM-CNRS), Campus de Luminy, 13288, Marseille, France. Corresponding author: [email protected]

Abstract In this work, we use a low-cost, unreported and simple method for synthesizing zinc oxide (ZnO) micro/nanostructured thin films. This method labeled microdroplets technique was tested on the synthesis of various samples of zinc oxide and the results are interesting. Optical microscope, Auger electron spectroscopy (AES) and atomic force microscope (AFM) were performed to ascertain the formation and characterization of ZnO films. Through the optical images, the surface appears to be inhomogeneous, textured and formed by microstructures and fractals. Auger electron spectroscopy confirms the chemical composition of ZnO. The ratio of the auger signals (Izn-LMM/IO-KLL) is around 1 indicating the stoichiometry of ZnO surfaces. AFM showed the morphology of ZnO films and the morphology of the ZnO micro- and nanoparticles which have spherical and oval shapes of different size. The morphology of the films is affected by the effect of the concentration. Key words: Synthesis, Microdroplets, ZnO, nanoparticles, AES, AFM

60


Etude in-situ de la synthèse de matériaux composites base céramique

Hafida Boutefnouchet 1*, Caroline Curfs1 1. Laboratoire de Métallurgie et Génie des Matériaux (LMGM), Département de Métallurgie, Faculté de l’ingénieur, Université de Annaba, B.P. 12 (23000). 2. European Synchrotron Radiation Facility, Grenoble, France Email: *[email protected]

Résumé Le développement des matériaux composites nécessite une grande maitrise des procédés d’élaboration. Dans la synthèse par combustion auto-propagée (SHS), la réaction est fortement exothermique et l’énergie libérée au cours de la synthèse permet d’entretenir la réaction jusqu’à la conversion totale des réactifs et l’obtention du produit final (figure 1). Les avantages qu’offre cette technique en matière de processus, de l’économie et de simplicité, font de la SHS, un procédé compétitif avec les procédés conventionnels, dans la fabrication d’une large gamme de matériaux, notamment réfractaires [1].

Figure 3.Schéma du principe de la méthode SHS

L’une des applications de ce type de réaction est la synthèse du carbure de titane. En effet, La réaction Ti + C = TiC est très facile à mettre en œuvre par ce procédé, de plus la chaleur de 61


formation de TiC (~ 184 KJ/ mol) et le point de fusion très élevé du produit (> 3300 K), font que l’ignition de la réaction est facile et la formation du produit final est directe, en moins d’une seconde. Néanmoins, ce dernier est caractérisé par une grande porosité, due en partie à une porosité du compact en cru, Ti-C. L’introduction d’un diluant, à caractère inerte ou réactif, dans le mélange réactionnel de départ, va agir sur la cinétique de la réaction et la microstructure du produit de synthèse [2]. Par ailleurs, à cause des vitesses très élevées et du temps de synthèse extrêmement court, des techniques de caractérisation ultrarapides sont nécessaires. La diffraction des rayons X utilisant le rayonnement synchrotron s’avère une technique bien adaptée pour étudier en temps réel ces réactions [3].

Figure 4. Résultats de la DRX résolue en temps : cas du système Ti-C-Ni

L’objectif principal de ce travail consiste en une meilleure compréhension des mécanismes réactionnels intervenant lors de la formation de carbure de titane par combustion autopropagée en présence d’un diluant métallique le nickel et d’un mélange à caractère thermite le NiO-Al. Pour ce faire, des expériences de diffraction X résolue en temps ont été réalisées en transmission avec un temps d’acquisition de 0.03 s, assurant ainsi un suivi des changements cristallographique dans le cœur des matériaux et la détermination des étapes intermédiaires au cours de la synthèse. Cette étude a été complétée par une analyse par le raffinement Rietveld de l’ensemble des spectres obtenus, ce qui a permis d’exploiter à meilleur profit, les informations liées aux changements structuraux observés.

62


Le microscope électronique à balayage (MEB) a été utilisé pour la caractérisation des produits de synthèse.

Mots clés: carbure de titane ; cermets ; synthèse combustion ; diffraction X résolue en temps.

Références [1]. Badhuri SB, Badhuri S, Combustion Synthesis in Non-equilibrium Processing of Materials. (ed. C. Suryanarayama), Pergamon Materials Series. 1999, 289-309. [2]. D. Vrel, Synthèse de matériaux céramiques par combustion auto-entretenue de poudres, Thèse de doctorat, Paris XIII. 1995. [3]. J.C. Labiche, O. Mathon, S. Pascarelli, M.A. Newton, G.G. Ferre, C. Curfs, G. Vaughan, A. Homs, F. Carreiras, The fast readout low noise camera as a versatile X-ray detector for time resolved dispersive extended X-ray absorption fine structure and diffraction studies of dynamic problems in materials science, chemistry, and catalysis, The Review of Scientific Instruments. 2007, 091301.

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The Role of Inverse Gas Chromatography in the Characterization of Pharmaceutical Materials

Seell A. Ramanaiah CSIR-Research Associate, Department of Chemistry, Sri Venkateswara University, Tirupati-517502, Andhra Pradesh, INIDIA. Corresponding Author: [email protected] , Mobile: +91-8985026400

Abstract Inverse gas chromatography (IGC) is a sensitive, useful, popular and quite versatile technique for physico-chemical characterization of pharmaceutical materials. In addition, surface energy analyzer (SEA), a new-generation IGC, which uses fixed probe surface coverage method instead of the fixed probe concentration method traditionally utilized by standard IGC systems, can provide a more accurate and precise information. Surface energetics plays an important role in understanding materials. The surface free energy of solids provides crucial surface information, which is useful across the industries. In pharmaceutical industry, it is helpful in understanding the drug stability, milling, granulation, dispersibility, adhesion, wetting and dissolution, etc1–5. Knowledge of the detailed surface behavior of pharmaceutical solids is crucial for understanding their solubility and their use in pharmaceutical industry.

Instead of an

analytical technique, IGC is considered as a materials characterization technique. The thermodynamic data are useful in the pharmaceutical industry during processing and formulation. For example higher dispersive surface free energy is associated with increased propensity for dispersive interaction. The drugs with higher dispersive surface free energy will adhere strongly with the inert carrier or lubricant. Hence, the knowledge of dispersive surface free energy of drugs and excipients can be applied to understand and control the rate of drug release in the human body. Surface thermodynamics properties of pharmaceutical materials have been discussed in light of dispersive surface free energy and Lewis acid-base

64


properties. Further, how pharmaceutical materials can behave under different temperature as well as relative humidity conditions will also be discussed.

References [1]. S. Ramanaiah, Vikram Karde, P.Venkateswarlu, Chinmay Ghoroi, RSC Adv., 2015, 5, 4871248719 [2]. S. C. Das, Q. Zhou, D. a V Morton, I. Larson and P. J. Stewart, Eur. J. Pharm. Sci., 2011, 43, 325–333. [3]. X. Han, L. Jallo, D. To, C. Ghoroi and R. Davé, J. Pharm. Sci., 2013, 102, 2282–2296. [4]. V. Karde and C. Ghoroi, Int. J. Pharm., 2014, 475, 351–363. [5]. U. V Shah, D. Olusanmi, A. S. Narang, M. A. Hussain, J. F. Gamble, M. J. Tobyn and J. Y.Y. Heng, Int. J. Pharm., 2014, 472, 140–147.

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Allylic oxidation of cyclohexene over ruthenium-doped titanium-pillared clay

Ilhem Rekkab-Hammoumraoui*, Ahmed Dali, Abderrahim Choukchou-Braham and Redouane Bachir

Laboratoire de Catalyse et Synthèse en Chimie Organique, Faculté des Sciences, Université A. Belkaid – Tlemcen.

Email : [email protected]

Abstract Ruthenium-doped H-Montmorillonite (H-Mont) and Ti-pillared clay (Ti-PILC) were prepared then studied for oxidation of cyclohexene, with tert-butylhydroperoxide (TBHP) as the oxygen source. The Ti-PILC support was prepared by hydrolysis of Ti(OC3H7)4 with HCl. The synthesized Ru/Ti-PILC and Ru/H-Mont catalysts were characterized by chemical analysis, surface area/pore volume measurements, Fourier transform infrared (FTIR) spectroscopy, X ray powder diffraction (XRD), and UV–vis-diffuse reflectance spectroscopy (UV–vis-DRS). Both catalysts can selectively oxidize cyclohexene through allylic oxidation to give 2-cyclohexene-1-one as the major product, and 2-cyclohexene-1-ol as the minor product. The influence of reaction time, temperature, catalyst amount, and substrate/oxidant ratio was also investigated to find the optimal reaction for cyclohexene oxidation to get the highest conversion. The catalysts were reused in four consecutive runs.

66

9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France Table: Cyclohexene oxidation in presence of catalysts and supports Selectivity (%) Catalyst

Conv

TBHP

(%)

Consumption

OH

O

(%) OH

O

OH

Blank

0

0

0

0

0

0

H-Mont

0

3

0

0

0

0

Ti-PILC

26

42

89

11

0

0

5% Ru/H-Mont

22

31

33

67

0

0

5% Ru/Ti-PILC

59

73

13

87

0

0

Keywords: ruthenium, montmorillonite, Ti-PILC, cyclohexene, allylic oxidation.

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Plasmon induced oxidation of glycerol: Highly efficient and selective oxidation by supported gold nanoparticles using visible light at ambient temperature Zeinab Chehadi 1,3, Joumana Toufaily 3, Souraya Zaid 2, Jean-Sebastien Girardon 2, Mickaël Capron 2, Franck Dumeignil 2, Tayssir Hamieh 3, Renaud Bachelot 1, Safi Jradi 1,* 1. Laboratoire de Nanotechnologie et d’Instrumentation Optique, Institut Charles Delaunay, STMR-UMR 6281 CNRS, Université de Technologie de Troyes, 12 rue Marie Curie - CS 42060, 10004 Troyes Cedex - France. 2. Université Lille Nord de France, F-59000, Lille, France; CNRS UMR8181, Unité de Catalyse et Chimie du Solide, UCCS, F-59655 Villeneuve d’Ascq, France. 3. Laboratory of Materials, Catalysis, Environment and Analytical Methods, Faculty of Sciences I, Doctorate School of Science and Technology, Lebanese University, Beirut, Lebanon. Email of corresponding author: [email protected]

Abstract

Noble metal nanoparticles have attracted considerable attention since historical times due to their unique optical properties. The free electron gas of such NPs can undergo a resonant oscillation in the visible part of the spectrum. This resonant electronic oscillation is known by Localized Surface Plasmon Resonance (LSPR)

[1]

. The excitation of the LSPR leads to an

enhancement of the electromagnetic field at the particle surface [2]. Some of this concentrated energy is converted into heat [3]. Thus, plasmonic nanoparticles can act as efficient nanosource of heat, light or energetic electrons. The ability to locally heat at the nanoscale opens the path for promising achievements in nanotechnology and especially for nanoscale control of temperature distribution, chemical reactions, phase transition, material growth, photothermal cancer therapy, and drug release

[4]

. In particular, excited Gold NanoParticles (GNPs) can

serve as both local nanoscale-heat sinks and catalysts to drive heterogeneous catalytic reactions at room temperature in the absence of macroscoping heating

[5]

been applied for many reactions such as water and hydrogen splitting

. This approach has

[6, 7]

. Moreover, the

nanostructures of silver were used to drive oxidation reactions such as ethylene epoxidation, CO oxidation and NH3 oxidation [8, 9] under visible light.

68


Here we demonstrate the feasibility of this “nanoplasmonic” catalysis on an industrial application reaction. Indeed we report that oxidation of glycerol (co-product of biodiesel production) can be catalyzed at room temperature by green laser excitation of supported GNPs. Visible irradiation of the Plasmon band of GNPs in the presence of base under an oxygen atmosphere results in the formation of oxidation products such as glyceric acid and tartronic acid, while the reaction does not occur in the absence of laser irradiation. 93% of glycerol was converted after 2 h of reaction at ambient temperature (Figure 1-A). The influence of the support type and laser power on the oxidation rate and product selectivity was investigated. It seems like GNPs/TiO2 are significantly more efficient than GNPs/ZnO and GNPs/Al2O3. B

A

Figure 1: A: The conversion of glycerol under different conditions. B: The productivity at different times

Keywords: Laser assisted catalysis, Plasmonic heating, gold nanoparticles, oxidation of glycerol, LSPR.

Acknowledgments: Financial support of the "Conseil Régional Champagne-Ardenne", NanoMat (www.nanomat.eu) by the "Ministère de l’enseignement supérieur et de la recherche", the DRRT (Délégation Régionale à la Recherche et à la Technologie) of Champagne Ardenne, and the Labex ACTION Project (contract ANR-11-LABX- 01-01) is acknowledged.

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References [1]. Matthew E. Stewart, Christopher R. Anderton, Lucas B. Thompson, Joana Maria, Stephen K. Gray, John A. Rogers, and Ralph G. Nuzzo, Nanostructured plasmonic sensors, Chem. Rev 108 (2008) 494. [2]. Claire Deeb, Renaud Bachelot, Jérôme Plain, Anne-Laure Baudrion, Safi Jradi, et al., "Quantitative analysis of localized surface plasmons based on molecular probing", ACS Nano vol.4, n° 8 (2010), 4579-4586. [3]. Guillaume Baffou, Romain Quidant, Thermo-plasmonics: using metallic nanostructures as nano-sources of heat, Laser & Photonics Reviews 7 (2013) 171–187 [4]. Guillaume Baffou, Romain Quidant, and F. Javier Garcia de Abajo, Nanoscale Control of Optical Heating in complex plasmonic systems, American Chemical Society (4), 709-716. [5]. Guillaume Baffou and Herve Rigneault, Femtosecond-pulsed optical heating of gold nanoparticles, Physical Review B 84 (2011), 1098-10121. [6]. Shaunak Mukherjee, Florian Libisch, Nicolas Large, Oara Neumann, Lisa V. Brown, Jin Cheng, J. Britt Lassiter, Emily A. Carter, Peter Nordlander, and Naomi J. Halas, Hot Electrons Do the Impossible: Plasmon-Induced Dissociation of H2 on Au, Nano lett., 2013 (13), 240247. [7]. Z. Qu, M. Cheng, W. Huang, & X. Bao, Formation of subsurface oxygen species and its high activity toward CO oxidation over silver catalysts, J. Catal. 229 (2005), 446-458. [8]. L. Gang, B. G. Anderson, J. van Grondelle, & R. A. van Santen, Low temperature selective oxidation of ammonia to nitrogen on silver-based catalysts, Appl. Catal. B 40 (2003), 101– 110. [9]. Phillip Christopher, Hongliang Xin and Suljo Linic, Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures, Nature chemistry 3 (2011), 467-472.

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Modification of TiO2 nanoparticules «Study of the selectivity in photocatalysis» Hawraa Ayoub1, Joumana Toufaily1, Mounir Kassir1, Houssam Obeid1, Thibault Roques-Carmes2, Frédéric Villieras3, Tayssir Hamieh1 1. Laboratory of Materials, Catalysis, Environment and Analytical Methods, Faculty of Sciences I, PRASE-EDST, Lebanese University, Campus Rafic Hariri, Beirut, Lebanon 2. LRGP - ENSIC - Université de Lorraine, 1, rue Grandville, Nancy, France 3. Laboratoire Environnement et Minéralurgie, LEM, Nancy, France, UMR756

Abstract

In the wake of modern industry the concept of environmental problems soon followed as the negative side effects of the industrial expansion became more and more pronounced. Awareness of environmental issues has increased enormously from the first complaints about fish deaths and damaged water reservoirs in the beginning of the last century. Many industries use synthetic dyes and pigments that may find their way into natural waterways. The paper, printing, pharmaceutical, textile and food industries are among major users of dyes in their daily activities. Most of the dyes are synthetic in nature. They contain organic compounds with functional groups, such as carboxylic (–COOH), amine (–NH2), and azo (–N=N–) groups, and have complex aromatic structures which make them virtually nonbiodegradable and non-oxidizable. The characteristics of these dye compounds have generated some challenging environmental problems, such as reducing the percentage of light penetrating into the water which reduces photosynthetic activity in aquatic media. A low concentration of visible dye is intolerable and can cause a health hazard for humans. At present, there are more than 100,000 dyes available commercially (of which azo dyes, represent about 70% on weight basis), and over 1 million tons dyes are produced per year, of which 50% are textile dyes [1]. In India alone, dyestuff industry produces around 60,000 metric tons of dyes, which is approximately 6.6% of total colorants used worldwide [2]. The largest consumer of the dyes is the textile industry accounting for two third of the total production of dyes [3] 71


In this work, the adsorption and photocatalytic capacity of TiO2 P25 Degussa in removal of methyl orange and bromothymol blue were investigated. The titania material has been characterised by several analytical methods, as XRD, FT-IR, and ZP. The results showed that pH=3 is the optimal pH for the removal of MO; whereas pH=10 is the best for BTB removal. At pH=3, TiO2 showed a better degradation capacity for MO, while it is better for BTB at pH=10. The results obtained proved that the degradation of the pollutants is affected by factors other than the adsorption capacity mainly the structure of the pollutant, binding groups, interactions, solubility and pH.

References [1]. Boyter HA (2007) Environmental legislations USA. Environmental aspects of textile dyeing. Woodhead, Cambridge, England. [2]. Teli MD (2008) Textile coloration industry in India. Color Technol 124: 1-13. [3]. Anjaneyulu Y, Chary NS, Raj DSS (2005) Decolourization of industrial effluentsavailable methods and emerging technologies. Rev Environ Sci Biotechnol 4: 245–273.

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Dépollution des eaux avec des nanoparticules d’oxydes de fer et de ferrites Nabil Tabaja1,2,3, Joumana Toufaily3, Sandra Casale1, D. Brouri1,2, Anne Davidson1,2, Tayssir Hamieh3 1. Sorbonne Universités, UPMC Université Paris 06, LRS, 4 place Jussieu, 75005 Paris, France 2. Université Libanaise, Ecole doctorale des sciences et technologie, Hadath, Beyrouth, Liban 3. CNRS UMR 7197, UPMC, Laboratoire de Réactivité de Surface, 4 place Jussieu, 75005 Paris, France 4. Laboratoire de Matériaux, Catalyse, Environnement et Méthodes Analytiques (MCEMACHAMSI), EDST, Université Libanaise, Campus Hariri, Hadath, Beyrouth, Liban E-mail of corresponding author: [email protected]; [email protected] Résumé Parmi les polluants les plus toxiques, les pesticides qui sont utilisés dans l’agriculture sont particulièrement dérangeants, à cause de leur stabilité qui empêche leur décomposition naturelle par les micro-organismes. Des méthodes d’oxydation avancées telles que celles décrites à partir de nanoparticules d’oxyde de titane seraient applicables mais cet oxyde ne s’active que sous irradiation UV et n’est pas magnétique. Des solutions alternatives pourraient être proposées avec des nanoparticules d’autres oxydes semi-conducteurs qui absorbent dans le visible. C’est le cas des nanoparticules d’oxydes de fer mais avec ces oxydes des problèmes de photo-corrosion (et de lixiviation) ont été mis en évidence. Dans ce travail, des synthèses de catalyseurs à base de nanoparticules de ferrites (Co, Ni, Zn et Cd) dispersées sur des silices mésoporeuses de type SBA-15 sont décrites. Les sels métalliques qui servent de précurseurs ont été déposés par la méthode à deux solvants. Les propriétés structurales, texturales, morphologiques ainsi que les propriétés optiques des catalyseurs ont été étudiées par DRX à grands angles, spectroscopie UV-Visible-NIR, microscopie électronique à transmission comme à balayage, et fluorescence des rayons X. Les catalyseurs ont ensuite été testés pour la réaction d’oxydation photocatalytique à la lumière visible d’un polluant agricole commun (un fongicide, le carbendazime), figure (1). La plupart des échantillons obtenus contiennent soit des nanoparticules de ferrites, cubiques avec une maille de type spinelle proche de celle attendue pour de la magnétite Fe3O4 (ICDD 71-6336) et/ou de la maghémite -Fe2O3 (ICDD 83-0112), soit des nanoparticules de structure hématite. La non détection de la raie de diffraction indicée (111) pour les échantillons Fe/Ni 73


est un fort argument en faveur d’une maille dérivant de la maghèmite. Le paramètre de maille est soit plus grand, soit plus petit que celui attendu pour les deux oxydes de fer, en accord avec les différences de rayons ioniques attendues (article fondateur sur les rayons ioniques de Shannon et Prewitt, Acta. Crystallogr. B 25 (1969) 925) [1]. De rares échantillons (Co/Fe et Ni/Fe en particulier) contiennent également de la würtzite de structure FeO ainsi que des phases dérivées MxFe(1-x)O seules et/ou en mélange avec une phase spinelle. Les spectres UV-visible-NIR ont été analysés à partir de courbes représentant (E*F(R))2 en fonction de E (Tauc plot pour un transfert électronique direct) [2]. E est la photo-énergie exprimée en eV et F(R), la transformé de Kubelka-Munk [3] du signal tel que mesuré en réflexion, R% (figure (2)). Des absorptions sont observées dans le NIR et dans le visible et sont associées à des transferts de charge entre cations localisés en sites Oh. Des lacunes en oxygène ont également été mises en évidence grâce à un pic observé pour une

20

100

Ferrites Ni/SBA-15

Reflectance

Concentration carbendazime (mg.L-1)

énergie de l’ordre de 0,65 eV.

15

Ferrites Co/SBA-15 10

Ferrites Zn/SBA-15 5

TiO2 P25 Degussa

Fe(6)_Ni(6)_CYC_Cl Fe(6)_Zn(6)_CYC_NO3 Fe(6)_Co(6)_CYC_Cl

Fe(6)_Cd(6)_CYC_NO3 Fe(6)_Zn(6)_CYC_Cl

80 60 40

Ferrites Cd/SBA-15

20

0

Fig.0 1.50 Réactions photocatalytiques 100 150 200 250 300 350 Temps (min) d’oxydation du carbendazime sur différents catalyseurs de ferrites

Fig. 400 2. Spectres en Diffuse 1400Réflexion 2400 (nm) (gammes UV Wavelenght visible NIR). Des bandes caractéristiques dues à des transferts de charges entre cations sont bien visibles dans le NIR.

Mots-clés: SBA-15, Spinelle, Hématite, Réplication, POA, Ferrites

Références [1]. R.D. Shannon, Acta Crystallographica Section A, vol. 32, no. 5, pp. 751-767, 1976. [2]. J. Tauc, R. Grigorovici, Vancu A. Phys. Stat. Solid., vol. 15, pp. 627-636, 1996 [3]. Q. Li, R.C. Xie, Y.W. Li, E.A. Mintz, J.K. Shang, Envir. Sci. Technol., vol. 41, pp. 50505056, 2007. 74


Oxidative Desulfurization Catalysts, an Alternative to Hydro Desulfurization; Study of the Support Structure

Zahraa Youssef1,2, Roukaya Hamiye1,2, Christine Lancelot1, Joumana Toufaily2, Tayssir Hamieh2 1. UCCS Laboratory (Unité de Catalyse et Chimie du Solide) in Lille 1 University 2. MCEMA Laboratory (Laboratory of Materials, Catalysis, Environment and Analytical Methods) EDST, Faculty of Sciences, Lebanese University

Abstract The deep desulfurization of diesel oil and transportation fuels to reduce the sulfur level has become an important research subject as more stringent fuel specifications have emerged, restricting the sulfur limit to 10 ppm for gasoline and diesel fuel according to Euro-IV standards [1, 2]. Conventional Hydrodesulfurization (HDS) is the most important and common industrial process. It is based on the removal of sulfur (aliphatic and acyclic) in

S

form. However, HDS is less efficient in removing refractory sulfur compounds especially DBT. And to achieve low sulfur goals with current HDS technology, higher temperature, higher pressure, larger reactor volume, and more active catalysts are essential. On this basis, in the past four decades, alternative desulfurization techniques have been investigated extensively; among which oxidative desulfurization (ODS) has drawn wide attention [1, 3-7]. In ODS the refractory sulfur compounds are easily oxidized to their corresponding sulfones, which are subsequently removed by extraction, adsorption, distillation, or decomposition. ODS is conducted at milder P & T conditions, has high efficiency and selectivity and requires no Hydrogen consumption [8-10]. Heteropolyacids (HPA) are inorganic, nanosized metal-oxide cluster anions [1, 11-13]. HPA’s are employed in homogeneous systems as acid and oxidation catalysts in many reactions including ODS [14, 15]. But their utility for industrial application has been limited notably due to their low surface area (1-10

/g), low thermal stability and difficulties of separation

and recovery. These limitations can be overcomed by their heterogenization onto large surface area supports. Therefore, due to the unique properties of periodic mesoporous silica based materials; such as SBA-15 and COK-12, these can constitute an efficient support [2, 14]. 75


SBA-15 and COK-12; silica based materials of highly 2D ordered mesoporous hexagonal structure, are successfully prepared according to literature [16, 17]. Pluronic P123 triblock copolymer (

) is used as the surfactant and tetraethyl orthosilicate (TEOS) and

sodium silicates as silica sources for the preparation of SBA-15 and COK-12 respectively. These two supports are gently dry impregnated with varying loadings of W 30% wt.). The HPA used is phosphotungstic acid (

(5, 10, 20 and

). Raman analysis indicates

that the HPA is preserved on these supports. Small and wide Powder X-ray diffraction (XRD) patterns and nitrogen sorption analysis indicate the formation of well-defined highly ordered mesoporous materials of high specific surface area. It also shows that the pore volume and the BET specific surface area are very high even after the introduction of the phosphotungstic acid but they decrease with increasing tungsten loadings. The two series of catalysts (5, 10, 20 and 30%

/SBA-15) and (5, 10, 20 and 30%

/COK-12) are tested for their oxidative

desulfurization performance with model fuel (50 ppm of DBT in Dodecane). Methanol is the solvent used to wash the adsorbed sulfur compounds off the catalyst after ODS test is performed. Methanol proved to be an efficient washing solvent for catalysts’ recovery after ODS through methanol-mediated reformation of the keggin structure with no leaching observed. In our study of the species formed during different reactions and to investigate what happens when different molybdenum and tungsten precursors supported on different supports (Alumina and SBA-15) are in contact with different oxidizing agents, several conclusions are attained. The Raman analysis of different supports (alumina and SBA-15) and catalysts (20 Mo/Al

, 30 Mo/SBA-15 and 30 W

/SBA-15) under different conditions with various W

and Mo precursors and oxidizing agents (

and t-BHP) is performed. It reveals the

formation of various species due to some interactions taking place. Keywords: Mesoporous materials; Heteropolyacids; SBA-15; COK-12; Phosphotungstic acid; ODS

References [1]. R. Wang, G. Zhang, H. Zhao, "Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil," Catalysis Today, vol. 149, p. 117–121, 2010. [2]. B. Li, W. Ma, J. Liu, C. Han, S. Zuo, X. Li, "Synthesis of the well-ordered hexagonal mesoporous silicate incorporated with phosphotungstic acid through a novel method and its catalytic performance on the oxidative desulfurization reaction," Catalysis Communications, vol. 13, p. 101–105, 2011.

76

9th International Conference on Material Sciences (CSM9), August 26-28, 2015, ENSIC, Nancy, France [3]. D. Liu, "Doctoral Thesis, CATALYTIC OXIDATIVE DESULFURIZATION OF A MODEL DIESEL," B.S., Tianjin Univeristy, China, 2010. [4]. L. Cedeno-Caero, H. Gomez-Bernal, A. Fraustro-Cuevas, H. D. Guerra-Gomez, R. CuevasGarcia, "Oxidative desulfurization of synthetic diesel using supported catalysts Part III. Support effect on vanadium-based catalysts," Catalysis Today, vol. 133–135, p. 244–254, 2008. [5]. [5] Mei, Hai; Mei, B.W; Yen, Teh Fu, "A new method for obtaining ultra-low sulfur diesel fuel via ultrasound assisted oxidative desulfurization," Fuel, vol. 82, no. 4, pp. 405-414, 2003. [6]. [6] F. Al-Shahrani, T. Xiao, S. A. Llewellyn, S. Barri, Z. Jiang, H. Shi, G. Martinie, M. L.H. Green, "Desulfurization of diesel via the H2O2 oxidation of aromatic sulfides to sulfones using a tungstate catalyst," Applied Catalysis B: Environmental, vol. 73, p. 311–316, 2007. [7]. [7] Yan, Xue‐Min, et al. "Oxidative desulfurization of diesel oil using mesoporous phosphotungstic Acid/SiO2 as catalyst." Journal of the Chinese Chemical Society 54.4 (2007): 911-916. [8]. [8] J.M. Campos-Martin, M.C. Capel-Sanchez, P. Perez-Presas, J.L.G. Fierro, "review on Oxidative Processes of Desulfurization of Liquid Fuels," Instituto de Catálisis y Petroleoquímica, CSIC, Marie Curie 2, Cantoblanco, E-28049 Madrid, Spain. [9]. [9] D. Liu, "Doctoral Thesis, CATALYTIC OXIDATIVE DESULFURIZATION OF A MODEL DIESEL," B.S., Tianjin Univeristy, China, 2010. [10]. [10] L. Cedeno-Caero, H. Gomez-Bernal, A. Fraustro-Cuevas, H. D. Guerra-Gomez, R. Cuevas-Garcia, "Oxidative desulfurization of synthetic diesel using supported catalysts Part III. Support effect on vanadium-based catalysts," Catalysis Today, vol. 1033–135, p. 244–254, 2008. [11]. [11] P. Gouzerh, M. Che, "Polyoxometalates (POMs) revisited and the “missing link” between the bottom up and top down approaches," l’actualité chimique, p. 298, 2006. [12]. [12] N. JOO, "Doctoral thesis: NEW FUNCTIONALIZED POLYOXOMETALATES (POMs) FOR MOLECULAR MEMORY DEVICES COMPATIBLE WITH A CMOS PROCESSING," GRENOBLE UNIVERSITY, 2010. [13]. [13] V. Dufaud, F. Lefebvre, "Review on Inorganic Hybrid Materials with Encapsulated Polyoxometalates," Materials, vol. 3, pp. 682-703, 2010. [14]. [14] V. Dufaud, F. Lefebvre, G. P. Niccolai, M. Aouine, "New insights into the encapsulation and stabilization of heteropolyacids inside the pore walls of mesostructured silica materials," Journal of Materials Chemistry, vol. 19, p. 1142–1150, 2009. [15]. [15] Y. Ren, B. Yue , M. Gu, H. He, "Progress of the Application of Mesoporous SilicaSupported Heteropolyacids in Heterogeneous Catalysis and Preparation of Nanostructured Metal Oxides," Materials, vol. 3, pp. 764-785, 2010. [16]. [16] J. Jammaer, A. Aerts, J. D’Haen, J. Won Seo, J. A. Martens, "Synthesis and characterization of cok-12 ordered mesoporous silica at room temperature under buffered quasi neutral pH," Scientific Bases for the Preparation of Heterogeneous Catalysts, pp. 681684, 2010. [17]. [17] M. VIALPANDO, A. AERTS, J. PERSOONS, J. MARTENS, G. VAN DEN MOOTER, "Evaluation of Ordered Mesoporous Silica as a Carrier for Poorly Soluble Drugs: Influence of Pressure on the Structure and Drug Release," JOURNAL OF PHARMACEUTICAL SCIENCES, vol. 100, no. 8, p. 3411–3420, 2011.

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Electrodeposition of Sb2Se3thin films via the route of Electro-Chemical Atomic Layer Epitaxy (EC-ALE) Fatima HAIDAR1 3, Joumana TOUFAILY3, Yuan CHEN1, Annie PRADEL1, Michel RIBES1, Marie-Christine RECORD2, Ahmad ELMOLL1 3, Tayssir HAMIEH3 1. 1, Institut Charles Gerhardt Montpellier, Équipe Chalcogénures et Verres, CC1503, Université Montpellier II, F-34095 Montpellier Cedex 5, France. 2. IM2NP, UMR CNRS 7334, Aix-Marseille Université, FST St Jérôme, Av. Escadrille Normandie-Niemen, F-13397 Marseille Cedex 20, France. 3. Laboratory of Materials, Catalysis, Environment and Analytical Methods (MCEMACHAMSI), EDST and Faculty of Sciences I, Lebanese University, Campus Rafic Hariri, Beirut, Lebanon

Abstract Electrochemical Atomic Layer Epitaxy, abbreviated as EC-ALE, was put forward by Gregory and Stickney in 1991 in America[1]. EC-ALE is a method for preparing thin-film compounds at room temperature, which is based on the alternate underpotential deposition (UPD) of atomic layers of the elements to make up a compound. UPD is a surface-limited electrochemical phenomenon that makes the deposition generally limited to an atomic layer. In every cycle one monolayer of the compound is obtained, and the thickness of the deposit will only depend on the number of cycles. Each cycle consists in a series of individual steps, and each step can be optimized independently, resulting in well-controlled deposits. In this work, the EC-ALE technique was used to prepare Sb2Se3 thin films on the platinum substrates. The electrochemical behavior and the way to obtain UPD atomic layers of selenium and antimony on platinum substrate have been investigated by means of cyclic voltammetry, anodic potentiodynamic scanning and coulometry. After the electrochemical parameter optimization, three atomic layers of Sb2Se3 compound is obtained via the route of EC-ALE, and the deposit is characterized by atomic force microscopy (AFM),Scanning Electron Microscopy (SEM), and RAMAN spectral analysis. Keywords: Sb2Se3, ECALE, thermoelectric materials, nanomaterials. Reference [1] B. W. Gregory, J. L. Stickney, J. Electroanal. Chem. 300 (1991) 543.

78


Design of new tubular ceramic membranes using a double layered MFI thin film Ali Said1,2, Joumana Toufaily2, Lionel Limousy1, Jalal Halawani2, Tayssir Hamieh2, Jean Daou1*. 1. Université de Haute-Alsace (UHA), CNRS, Equipe Matériaux à Porosité Contrôlée (MPC), Institut de Science des Matériaux de Mulhouse (IS2M) UMR 7361, ENSCMu, F-68093 Mulhouse 2. Laboratory of Materials, Catalysis, Environment and Analytical Methods Faculty of Sciences, Section I, Lebanese University Campus Rafic Hariri, Hadath, Lebanon. * Corresponding author: [email protected]

Zeolites are very well-known materials especially for their controlled porosity, their crystalline structures, but also for the different applications where they can be used (catalysis, air treatment,...) [1]. During the past ten years, a lot of developments have been done on the preparation of zeolite membranes for pervaporation applications [2]. The present work explores new developments in the preparation zeolite membranes dedicated to the filtration of salty water. More particularly, we prepared MFI films on specific macroporous alumina tubular supports used for nanofiltration applications. There are different key steps which influence the formation of the MFI films: the cleaning procedure of the substrate, the hydrothermal synthesis conditions, the use of a secondary growth method for when preparing a bi-layered membrane [3-6]. A complete characterization of the mono and the bi-layered membranes was carried out using various techniques, such as X-ray diffraction, scanning electron microscopy, X-ray fluorescence, energy dispersive X-ray spectroscopy, mercury porosimetry and nitrogen sorption measurements. Results show that a dense, continuous and highly crystallized thin film of MFI has been obtained on the α-alumina support after the secondary growth experiment (see Figure 1). The weight of zeolite deposited on the support was also estimated by nitrogen sorption measurement using the method of mass assessment. The MFI membrane was stabilized by pure water filtration tests until the hydraulic permeability reached a plateau. This conditioning step was necessary to reach an equilibrium state of the hydraulic membrane performances. Particularly, hydration of the MFI layer was a crucial step of the conditioning process, which leads to the modification of the MFI surface properties. The hydraulic permeability of the mono and bi-layer MFI membrane decreased rapidly at the beginning of the conditioning process, and stabilized after 15 hours to reach 1.08 × 10-14 m3.m-2 and 1.02 × 10-15 m3.m-2 respectively. Filtration tests were then carried out with a neutral molecule (VB 12) in order to evaluate the mean pore radius of the mono and the bi-layered membranes. A rejection rate of 5% was obtained with the monolayer MFI 79


membrane, while it reaches a value of 50% with the bi-layered one. These results lead to mean pore radii corresponding to 6.4 and 1.7 nm respectively. It means that even after the synthesis of the second MFI layer, the membrane porosity remains higher than the porous diameter of the zeolite. Filtration may occur at the interface of the MFI crystals.

Figure 1: SEM images of the unseeded (a) and seeded (b) MFI monolayer membrane (bottom layer). SEM images of the surface of MFI bilayer membrane (c) obtained after hydrothermal treatment on seeded MFI monolayer membrane and the thickness (d) of the MFI mono and bilayer membranes.

Keywords: Coating, Filtration, Membrane, Water treatment References [1]. Martinez C, Corma A, zeolites, reference module in chemistry, molecular sciences and chemical engineering, from comprehensive inorganic chemistry ii (second edition), 2013, 5, 103-131. [2]. Van der Bruggen B, Comprehensive Membrane Science and Engineering, 2010, 3, 135-163. [3]. Lauridant N, Daou T.J, Arnold G, Soulard M, Nouali H, Patarin J, Faye D, Microporous and Mesoporous Materials, 2012, 152, 1-8. [4]. Lauridant N, Daou T.J, Arnold G, Patarin J, Faye D, Microporous and Mesoporous Materials, 2013, 166, 79-85. [5]. Lauridant N, Daou T.J, Arnold G, Nouali H, Patarin J, Faye D, Microporous Mesoporous Materials, 2013, 172, 36-43. [6]. Daou T.J, Lauridant N, Arnold G, Nouali H, Patarin J, Faye D, Chemical Engineering Journal, 2014, 234, 66-73.

80


Polystyrene-b-Poly(4-vinylpyridine): Synthesis by ATRP and Characterization by Inverse GC Mohammad Rajab*1,2, Joumana Toufaily1, Karine Mougin2, Aissam Airoudj2, Kamal Hariri1, Tayssir Hamieh1 1. Laboratory of Materials, Catalysis, Environment and Analytical Methods, EDST and Faculty of Sciences, Section I, Lebanese University Campus Rafic Hariri, Hadath, Lebanon 2. Institut de Science des Matériaux de Mulhouse (IS2M), CNRS, UPR 9096, 15 Rue Jean Starcky, B.P. 2488 - 68057, Mulhouse Cedex, France *Email address: [email protected]

Abstract Block copolymers are a special class of polymers in the large family of soft matter. These latter can simply be considered as consisting of at least two fragment of different chemical nature of the polymer, joined together by a junction – type of covalent bond. The copolymer, polystyrene-poly(4-vinyl pyridine) is revealed to be a very interesting copolymer used for technological applications may for

example, to compete with

conventional copolymers such as polystyrene- polymethylmethacrylate (PS-PMMA). The atom transfer radical polymerization ATRP is a type of controlled radical polymerization which appeared in 1994. It is necessary to know the superficial characteristics of polymers. Inverse gas chromatography (IGC) is capable to characterize the area properties (area, energy, heat of adsorption, and specific interaction of the surface area) of polymeric materials and recently pharmaceuticals. IGC is a real source of physiochemical data. It can be applied to observe the interaction between polymers and organic solvent systems under the conditions approaching infinite dilution of the volatile component. The target of this work is, the synthesis of diblock copolymers of the type PS-P4VP by two successive ATRP using (1-bromoethyl)benzene as an initiator, as well as the characterization of the polymer, and to its physic- chemical properties by IGC. In this work, we are interested in the synthesis of linear diblock copolymer Polystyrene-bPoly(4-vinylpyridine) or simply PS-P4PVP by controlled radical polymerization, ATRP, kind. 81


This synthesis is performed in two successive steps with the (1- bromoethyl)benzene as initiator. The first part of the synthesis, allows the realization of block polystyrene having a terminal function, Bromine (Br) permits the grafting of the second successive block P4VP. Chemical analysis of this copolymer is carried out by RMN -1H, the molecular weight is determined by size exclusion chromatography and its thermal stability is examined by TGA. The ICGI was used to study the superficial properties and the thermodynamic properties of PS-P4VP. The different values of Vn obtained after adsorption of several probe molecules on the solid copolymer, have allowed to calculate the thermodynamic values of:

,

et

, that are used to calculate the values of KD and KA by using Hamieh's model: the obtained results have clearly demonstrated that the synthesized diblock copolymer is of basic character.

Figure 1. Schematic representation of the used synthesis strategy for PS-P4VP

Keywords: polystyrene-poly(4-vinyl pyridine), IGC, ATRP, superficial properties of copolymers.

82


Synthesis of nanoporous materials for molecular decontamination I. Kabalan1,2, B. Lebeau1, M.-B. Fadlallah2, J. Toufaily2, T. Hamieh2, J.P. Bellat3, J. Daou1,* 3. Université de Haute-Alsace (UHA), CNRS, Equipe Matériaux à Porosité Contrôlée (MPC), Institut de Science des Matériaux de Mulhouse (IS2M) UMR 7361, ENSCMu, F-68093 Mulhouse 4. Laboratory of Materials, Catalysis, Environment and Analytical Methods Faculty of Sciences, Section I, Lebanese University Campus Rafic Hariri, Hadath, Lebanon. 5. Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université de Bourgogne, 9 Av. A. Savary, BP 47870, F-21078 Dijon Cedex, France * Corresponding author: [email protected]

Abstract Volatile organic compounds (VOCs) are the most common organic pollutants. Among the various solutions to this pollution, the use of molecular adsorbents appears as a potential alternative for the control of contamination. The porous materials have many advantages due to their low cost, their physical characteristics and their useful properties related to their structure and their large surface area. However, conventional synthesis of zeolites generally lead to micrometer size crystals. The capacity and the kinetics of adsorption that are sensitive to the diffusion and the surface phenomenons could be potentially improved by the use of zeolite nanocrystals or hierarchical products (micro / mesoporous). These nanomaterials have high potential due to their small size and their exalted outer surface that promotes access of pollutants and improving the adsorption capacity.1,2 Here, *BEA structure-type zeolites have been synthesized with different morphologies : microcrystals, nanocrystals and nanosponges. The purity and the porous texture have been characterized by using XRD, SEM and nitrogen adsorption techniques. Their adsorption properties were examined by thermogravimetry using n-hexane as model molecule of VOC. The n-hexane adsorption capacity of the zeolites was multiplied by 7 in the case of nanosponges and by 6 in the case of the nanocrystals compared to microcrystals (693 mg / g vs 103 mg / g and 591 mg / g vs 103 mg / g, respectively).

83


Figure 1: SEM images of *BEA-type zeolite with different morphologies. Keywords : *BEA type zeolites, nanocrystals, nanosponges, adsorption of n-hexane. References 1. I. Kabalan, G. Rioland, H. Nouali, B. Lebeau, S. Rigolet, M.B. Fadlallah, J. Toufaily, T. Hamieh, T.J. Daou, RSC Adv., 2014, 4, 37353-37358. 2. J. Schick, T.J. Daou, P. Caullet, J-L. Paillaud, J. Patarin and C. Mangold-Callarec, Chem. Commun., 2011, 47, 902-904.

84


Synthesis of Nanostructure Carbon Thin Films by Microwave Plasma-Enhanced Chemical Vapor Deposition Ahmed Wasfi, Hammad Humud, Mohammed Ismael Physics department, College of Science, University of Baghdad

Abstract: In this work, hydrogenated amorphous carbon (a-C: H) thin films have been prepared from methane gas using microwave plasma enhanced chemical vapor deposition (MPECVD). The microwave plasma system was designed and built in our laboratory. The maximum attained plasma electron temperature and density were (0.65 eV) and (1.448x1018 cm-3), respectively. The effect of argon/methane mixing ratio on the optical and chemical bonding properties of the films, which deposited on glass substrate, were investigated. FTIR spectroscopy was used to study the chemical bonding of the deposited films. While, X-ray diffraction results indicated a broad peak ranging from 15 to 35 in 2θ angle confirms the amorphous nature of the carbon films. In addition, AFM was used to study the morphological characteristics and to monitor the nanostructure under the influence of different mixing ratios of argon with methane. The distribution of granularity ranged from 30 to 140 nm, and the average diameters were 94.39-81.92 nm, also the root mean square roughness was increased with the increasing of the argon/methane mixing ratio. The optical energy gap (E g) decreased from 2.76 to 2.40 eV with increasing deposition pressure from 0.5 to 1.5 mbar, moreover Eg decreased when argon to methane ratio was increased. The reported experimental results of the optical and structural properties of the films proposed that it is possible to control the film growth rate and optical energy gap and accordingly improve photoconductivity by proper selection of deposition parameters.

Keywords: nanostructure carbon thin films, microwave plasma, chemical vapor deposition

85


Oral Communications Symposium II: Materials and Bio-Engineering, Chemical, and petrochemical engineering, Photocatalysis and Photodynamic Therapy, Colloids, Environment, Food technology

12. Biomedical Engineering, Bio-Materials, 13. Materials, Membranes and chemical and petrochemical engineering 14. Photocatalysis and Photodynamic Therapy 15. Colloidal dispersions and industrial applications 16. Materials and Environmental Chemistry and Pollution of Earth 17. Treatment of Waters and Solid Wastes and Recycling Materials 18. Geology and Material Sciences 19. Valorization of Industrial and Agricultural Wastes 20. Materials and Food Technology 21. Quality Controls of Materials 22. Smart Materials

86


Liquefaction of cellulose into bioproducts in the presence of zirconia doped with W, Mo, Ta and Nb Amar Dandach1,2, Joumana Toufaily1, Tayssir Hamieh1, Mariam Karaki1, Ali Karout1, Nadine Essayem2

1. Laboratory of Materials, Catalysis, Environment and Analytical Methods. Lebanese University, Lebanon. 2. Institut de Recherches sur la Catalyse et l’Environnement de Lyon. Université Claude Bernard Lyon 1, France Email : [email protected]

Abstract The lignocellulosic biomass is abundant and generally considered as a sustainable resource to synthesize biofuels and valuable bioproducts. This biomass consists mainly of cellulose, the most important bio homo-polymer on the earth. Recent progresses on catalytic conversion of cellulose allowed the production of a wide rangeof chemicals products via heterogeneous catalysis. Especially, solid Lewis acid can be used to produce platform molecules suchas Lactic Acid LA. Globally the LA market was estimated to be about 700 kilo tons in 2013, but it is expected to reach about 2 thousands kilo tons by 2020, due to the wide range application of this molecule. For that, we have selected a list of catalysts based on zirconia doped with transition metals, Mo, Ta, Nb in order to compare their catalytic activities to W based zirconia which was previously shown to convert selectively microcrystalline cellulose into LA. Thus, this work aims to assay the influence of transition elements on cellulose conversion in aqueous phase under relatively mild conditions (under 190ᵒC and autogenic pressure) and to deeply evaluate the influence of these catalysts on LA selectivity. A native cellulose (MN100) was tested with different solid Lewis acid catalysts based on zirconia, modified with oxides of tungsten (WO3 / ZrO2), molybdenum (MoO3 / ZrO2), tantalum (Ta2O5 / ZrO2) and niobium (Nb2O5 / ZrO2). The reaction carried out in an aqueous phase at 190°C, conditions which were previously shown to be compatible with the stability of WO3/ZrO2. Celluloses conversions at 190ᵒC without catalyst were first investigated; we have tested two different types of cellulose (a native cellulose MN 100 and the

87


microcrystalline cellulose from SIGMA ALDRICH) to estimate their liquefaction and the products distribution in such hydrothermal conditions without catalyst.

Products yield ( %)

40 30 20 10 0

Microcristalline Cellulose liquefaction

Figure 1: Non catalytic reaction of two types of cellulose, microcrystalline cellulose and MN100. Reaction conditions: 1.6 g cellulose, 65 ml H2O, 190ᵒC, 1.2 MPa Ar autogenic pressure, 24 hrs.

According to the obtained results, we found that the addition of doped zirconia influences the cellulose liquefaction rate as well as the products selectivity. Comparing our tested catalysts, we observed that all zirconia samples converted efficiently the biomass (~48% conversion) and produce selectively LA. The observed ranking as regards to the cellulose liquefaction and lactic acid yield is as follows: WO3/ZrO2>MoO3/ZrO2>Ta2O5/ZrO2>Nb2O5/ZrO2. The best performances were observed for WO3/ZrO2leading to the higher yields of LA (~15% LA yield) ascribed to the Lewis-acidity of W species. This hypothesis was experimentally confirmed by testing ZrW with two different tungsten content (15.84% and 8.6% WO3), both the conversion of cellulose and LA selectivity increase with the augmentation of tungsten content. Another commercial tungsten zirconia catalyst has been tested; a remarkable promoting effect on the cellulose conversion (~54%) and on the LA selectivity (~20% LA) with reproducibility test of 4.68% was obtained.

88

Products yield ( %)


50 45 40 35 30 25 20 15 10 5 0

WO3/ZrO2 15.84%WO3 calcined at 600°C/3h MoO3/ZrO2 10.46%MoO3 calcined at 600h/3h Ta2O5/ZrO2 15%Ta2O5 calcined at 600°C/3h

Products yield ( %)

Figure 2: Bioproductsyields of cellulose conversion by different catalysts doped zirconia. Reaction conditions: 1.6 g cellulose, 0.68 g catalyst, 65 ml H2O, 190ᵒC, 1.2 MPa Ar autogenic pressure, 24 hrs.

50 45 40 35 30 25 20 15 10 5 0

WO3/ZrO2 15.84% WO3

WO3/ZrO2 8.6% WO3

Figure 3: Variation of bioproducts yields in function of W content doped in zirconia. Reaction conditions: 1.6 g cellulose, 0.68 g catalyst, 65 ml H2O, 190ᵒC, 1.2 MPaAr autogenic pressure, 24 hrs.

Characterization of the Lewis acidity of the different doped zirconia is still in progress in order to correlate with the activity ranking. Keywords: Liquefaction, cellulose hydrolysis, heterogeneous catalysts, Solid Lewis acid catalysts, Tungstated zirconia, Lactic acid.

89


Influence de la modification des catalyseurs sur leurs performances en HDS des gazoles Roukaya Hamiye1,2*, Joumana Toufaily2*, Carole Lamonier1, Christine Lancelot1, Pascal Blanchard1, Tayssir Hamieh2 1. Unité de Catalyse et de Chimie du Solide - UMR CNRS 8181, Université des Sciences et Technologies de Lille, 59655 Villeneuve d’Ascq Cedex, France 2. Laboratoire des Matériaux, Catalyse, Environnement et Méthodes Analytiques (MCEMA), Université Libanaise, Campus Rafic Hariri, Beyrouth, Liban [email protected]; [email protected]

Résumé Les émissions d’oxydes de soufre (SOx) lors de la combustion du pétrole et de ses distillats sont dues à la présence de soufre en leur sein. Outre les émissions nocives qu’il génère, le soufre est un poison de certains catalyseurs utilisés dans les procédés de raffinage ou dans les pots d’échappement. Toutes ces raisons ont incité les législateurs à fixer des spécifications de plus en plus draconiennes sur la teneur en soufre des carburants pétroliers. De telles spécifications imposent de réaliser une désulfuration plus poussée des produits pétroliers. Les catalyseurs conventionnels d’HDS n’ont pas une activité suffisante pour répondre aux spécifications requises. Pour cela, le développement de catalyseurs plus actifs par modification par des molécules organiques est parmi les options envisagées pour atteindre une désulfuration profonde. Dans cette étude, des catalyseurs conventionnels CoMo(P)/Al2O3 ont été préparés puis modifiés par la molécule du dibenzothiophène sulfone. Afin de comprendre l'effet de cette molécule modifiante, les performances catalytiques ont été évaluées en hydrodésulfuration d’une molécule modèle (thiophène) et d’une charge réelle dans les conditions opératoires d’un réacteur industriel. Mots clés: CoMo(P)/Al2O3, dibenzothiophène sulfone, hydrodésulfuration, thiophène, charge réelle.

Introduction Étant donné la raréfaction prévisible des pétroles légers, des pétroles de plus en plus lourds ainsi que des coupes provenant du charbon ou de la biomasse devront être utilisés. Ces coupes contiennent des quantités plus élevées d’azote, d’oxygène, de soufre et de métaux, ce qui nécessite une adaptation des catalyseurs et des procédés de désulfuration. Un catalyseur d'hydrodésulfuration (HDS) est généralement constitué d'un sulfure de molybdène (MoS 2) promus par du Co ou du Ni et dispersé sur une alumine de grande aire spécifique (200 m 2/g). Une nouvelle approche permettant d’améliorer les performances de ces catalyseurs a été récemment développée [1-5]. 90


Cette méthode consiste à modifier le précurseur oxyde conventionnel par des molécules organiques. Dans ce travail, deux catalyseurs ont été préparés, un CoMo/Al2O3 dopé par du phosphore

et

un

CoMo/Al2O3

formé

à

partir

d'hétéropolyanions

d'Anderson

Co2Mo10O38H4(Co). Ces précurseurs oxydes sont modifiés par des quantités variables de sulfone (0.1 à 1% en poids) en les imprégnant par une solution du DBTO2 (dibenzothiophène sulfone) dans l’acétonitrile. Les catalyseurs sont caractérisés par spectroscopie Raman et par diffraction des rayons X et leurs performances catalytiques

sont évaluées en

hydrodésulfuration du thiophène puis d’une charge réelle en micro-pilote dans des conditions proches des conditions industrielles.

Préparation des catalyseurs Les catalyseurs CoMo(P)/Al2O3 et CoMo/Al2O3 sont préparés par imprégnation à sec de l'alumine calcinée avec une solution aqueuse contenant respectivement : 1) L'heptamolybdate d’ammonium (HMA) Mo7O24(NH4)6,4H2O, le nitrate de cobalt Co(NO3)26H2O et l'acide phosphorique H3PO4 2) L’hétéropolyanion Co2Mo10 : L’imprégnation est suivie d’une maturation, d’un séchage puis d’une calcination pour obtenir les précurseurs oxydes. Ces précurseurs sont ensuite modifiés en les imprégnant par une solution du dibenzothiophène sulfone dans l’acétonitrile.

Test catalytique d’HDS du thiophène La sulfuration des catalyseurs s'effectue in situ par un mélange H2/H2S à 350 °C. Après un palier de 3 h le four est refroidi à 275 °C, température à laquelle le solide est mis en contact avec le flux d'H2 contenant le thiophène. Au cours de la réaction le mélange gazeux en sortie de réacteur est prélevé et injecté dans un chromatographe en phase gazeuse.

Test d'HDS de charge réelle en micro-pilote Les catalyseurs sont sulfurés in-situ par un mélange gazole/DMDS/H2 et les tests s'effectuent à trois températures 350, 360 et 370 °C, sous 35 bar d’H2.

Résultats et discussion Les catalyseurs ont été évalués et modifiés en HDS du thiophène. Les chromatogrammes obtenus après test montrent 5 pics de sortie : butane, butène 2 cis et trans, butène-1 et thiophène non converti ce qui permet de calculer le taux de conversion des catalyseurs. Les taux de conversion sont illustrés dans la figure 1. 91


Figure 1 : Taux de conversion des catalyseurs Les valeurs de conversion montrent une augmentation de l’activité catalytique de tous les catalyseurs modifiés. Ceci peut être dû à une sulfuration simultanée des métaux impliquant la formation de feuillets plus petits et augmentant ainsi le nombre de sites actifs ou à une diminution des interactions entre les métaux et le support favorisant la formation de feuillets plus empilés. L’activité catalytique est également étudiée en HDS du gazole à 11912 ppm soufre. Après test, le gazole initial ainsi que les effluents liquides sont analysés par fluorescence UV afin de déterminer la teneur en soufre résiduel, puis par chromatographe en phase gaz avec détecteur de soufre, permettant une analyse chromatographique des espèces soufrées. Les chromatogrammes obtenus pour le gazole initial et le gazole désulfuré sont représentés dans les figures 2 et 3.

Figure 3 : Gazole hydrodésulfuré à 100 ppm avec le catalyseur CoMo(P)/Al2O3

Figure 2 : Chromatogramme du gazole à 11912 ppm soufre

Le premier test d’HDS du gazole en micro pilote avec le catalyseur CoMoP non modifié montre une conversion totale de la plupart des composés soufrés avec persistance de quelques composés réfractaires à l’HDS.

92


Conclusions Ce travail présente l’influence de la modification des catalyseurs CoMo(P)/Al2O3 par des sulfones sur leurs performances en HDS du thiophène ainsi qu’en HDS de charge réelle. Les catalyseurs préparés restent bien dispersés après modification et les tests d’HDS du thiophène montrent une amélioration du taux de conversion des catalyseurs modifiés. Dans la suite du travail, les performances des catalyseurs modifiés seront évaluées en test d’HDS du gazole et l’effet de l’ajout des sulfones sur la formation de la phase active sera étudié en analysant ces catalyseurs par XPS et MET.

Références [1]. P. Mazoyer, C. Geantet, F. Diehl, C. Pichon, T.S. Nguyen, M. Lacroix, Oil & Gaz Science and Technology -Rev.IFP, 60 (5) (2005) 791-799 [2]. N. Frizi, Thèse, Université Lille1, 2004. [3]. S. Herry, Thèse, Université Lille1, 2006. [4]. N. Frizi, P. Blanchard, E. Payen, P. Baranek, C.Lancelot, M. Rebeilleau, C. Dupuy, J.P. Dath, Catalysis Today, 130 (2008) 32-40 [5]. N. Frizi, P. Blanchard, E. Payen, P. Baranek, C.Lancelot, M. Rebeilleau, C. Dupuy, Catalysis Today, 130 (2008) 272-282

93


Weight of Evidence method for landslide susceptibility assessment

Romina Secci1, Maria Laura Foddis1, Gabriele Uras1 1. University of Cagliari, Department of Civil and Environmental Engineering and Architecture, via Marengo 2, 09123, Cagliari, Italy Email of corresponding author: [email protected]; [email protected]

Abstract The problem of identifying areas having a higher propensity for the triggering of shallow landslides during extreme weather events is crucial in land use planning. In the last decade, the continuous growth of the available calculation power allowed to apply methods for evaluating

hazards

for

increasingly

complex

landslides.

Nevertheless,

a

correct

implementation depends on the deep knowledge of their limits of validity as well as on the appropriate choice of the factors which are presumed to affect the slope instability. In landslide processes the thickness of the debris layer plays a fundamental role. Knowing said thickness allows to identify the potentially mobilized volumes and to foreseen the size of potential damage. In various part of the World, the plans for the prevention of natural disasters arranged by the Civil Protection are based on the extrapolation of said data. To implement a realistic and accurate representation of the depth and geomechanical properties of incoherent deposits would greatly improve the calibration of models for landslide hazard assessment. In this work, Weight Of Evidence (WOE) method have been used for landslide susceptibility analysis in order to particular define the characteristics and the spatial distribution of the sloping deposits on a large area. The method has been applied to a study area, of above 140 km2, located in Capoterra’s countryside (South Sardinia, Italy). This area is characterized by granite outcrops affected by significant flooding and debris flow phenomena. The characteristics of stability and strength of the identified areas have been analyzed by building a geo database full of over 500 sample points. Using the location of the landslides, GIS data and topographic factors, such as soil and land use, the WOE method [1] allow to calculate each factor’s rating and to evaluate landslide susceptibility. The study area has been subdivided in two subareas the Training Area and Test Area (see Scheme 1).

94


Scheme 5. Training area and test area

The Training area has been used for the method assessment and the Test Area has been used for evaluate the performance of the WOE method in establishing the landslides release areas. The statistical analysis results for the prediction of the bimodal variable value, such as the presence/absence of detritus deposits, are represented by a map that associates each point to a color indicating the higher a posteriori probability of three classes: absence, possible presence, probable presence of detritus. A threshold of probability to evaluate the reliability of the prediction is fixed and the map is consequently reclassified. Comparing the map of the detritus with the map of debris obtained by aerial photographs and the detection campaign have been highlight that the method allow to predict correctly debris flow. Results have been subdivided in 4 classes: True Positive Fraction (TPF): percentage of the areas covered by debris and correctly estimated; False Positive Fraction (FPF): percentage of the areas predicted as covered by debris but in the reality not covered by debris False Positive Fraction (PSF); True Negative Fraction (TNF): percentage of the areas not covered by detrital layers and correctly estimated; False Negative Fraction (FNF): percentage of the areas predicted as not covered by debris but actually covered by debris. The TPF is commonly defined as the sensitivity of the method in determining the true positives, the specificity is defined as 1- FPF, and it is complementary to the ability of the method to minimize the stable areas erroneously identified as landslide. Recalculating the sensitivity and specificity for increasing levels of the threshold, different pairs of values have been obtained and plotted in ROC curves (Receiver Operating Characteristic) that has been used to assess the reliability of obtained results for both the Trainig Area and the Test Area (see Scheme 2).

95


Scheme 6. Results of the WEO method for the test area (left) and for the train area (right).

The possibility to implement an accurate and realistic representation of incoherent deposits in terms of their thickness and geomechanical properties of could greatly enhance the calibration of deterministic models for landslide hazard assessment. The WOE coupled with a stratigraphic, pedological, hydraulic and mechanical characterization of the studied area can be an useful tool to locate the sliding surface phenomena of the detrital layers. An advanced landslide susceptibility assessment allows to prefigure scenarios and simulate events that help to make decisions, to monitor the area, to develop risk prevention plans.

Keywords: Weight Of Evidence method, depth of the soil, slope stability, landslide risk.

Acknowledgements : This study has been funded by R.A.S. (Regione Autonoma della

Sardegna), Regional Law n° 7/2007 “Young researchers”. References [1]. AGTERBERG, F. P. AND CHENG, Q. (2002), Conditional Independence Test for Weightsof-Evidence Modeling, Natural Resources Research, 11(4), 249 – 255. [2]. FRATTINI P, CROSTA G, CARRARA A. (2010), Techniques for evaluating the performance of landslide susceptibility models. Engineering Geology 111 (2010) 62–72.

96


Total and Extractable Trace Elements in Upper Litani River Sediments, Lebanon

Walaa Diab 1,2, Joumana Toufaily1, Frédéric Villieras2, Hassan Lakiss3, Thibault Roques-Carmes4, Tayssir Hamieh1

1. Laboratory of Materials, Catalysis, Environment and Analytical Methods, Faculty of Sciences I, PRASE-EDST, Lebanese University, Campus Rafic Hariri, Beirut, Lebanon 2. Laboratoires Environment et Minéralurgie, LEM, Nancy, France, UMR756 3. Faculty of Engineering, Section III, Lebanese University, Campus Rafic Hariri, Beirut, Lebanon 4. LRGP - ENSIC - Université de Lorraine, 1, rue Grandville, Nancy, France Abstract

Sediments are important components of ecosystems in which toxic compounds accumulate through complex physical and chemical adsorption mechanisms which depend on the nature of the sediment matrix and the properties of adsorbed compounds. They are the principle sinks for heavy metals in aquatic environments. Determination of total element contents in sediments does not give an accurate estimate of their environmental impacts. Their speciation study provides important information on the potential availability of metals to biota under various environmental conditions. The toxicity of metals depends especially on their chemical forms rather than their total metal content. The present study focuses on the Upper Litani River basin in Lebanon. Earlier studies have focused on water quality and on total metal concentrations of the river sediments. The objectives of this work were first to identify possible sources of metals (geological and/or anthropogenic) and then to determine metal speciation (Fe, Cr, Cd, Zn, Pb, Cu and Mn) in the in the operationally defined sediment chemical fractions and metal speciation in river water. This would reflect on metal bioavailability and toxicity. Bed load sediments were collected from five sites representatives of the Upper Litani River basin during the dry season and the sediments were subjected to a total and a sequential chemical fractionation scheme on the 0). In the following study, the surface segregation in Ni(Ag) is characterized by an energy of segregation when a silver bulk atom is exchanged with a nickel atom of the alloy surface. The segregation energy is the balance between the energy of the half nickel crystal with a silver atom at a bulk site and the energy of the same half crystal a silver atom at a surface site (exchange between the bulk and the surface of a Ni atom and an Ag atom). Energies of segregation are calculated using a robust N-body interaction potential of the FinnisSinclair (EAM) type (RGL3/4) in an annealed Molecular Dynamics. 1 – The size effect related to the difference of atomic radii of solute and solvent atoms, 2 – The excess cohesion effect related to the difference of cohesive energies of metals, pure solvent and pure solute 3 – The alloy effect derived from heat of solution of the solute in the solvent. The energies corresponding to the three effects are calculated as was described in a previous study. In this study, we examine the effects of segregation of many atoms on the surface in order to compare the multi atomic energies of segregation to those for the monoatomic ones.

Surface (110) 10 28 14

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6

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Figure 11. Surface (110). the open circles correspond to the p1 planes and the filled circles the p0 plane.

DHNIAGm 2500 2000

DeltaH (meV)

1500 1000 500 0 -500 -1000 -1500 -1,5

-1

-0,5

0

0,5

1

1,5

m

Figure 12 Hexp[Ni(Ag)] vs m:Hexp[Ni(Ag)] is not known but must be positive, thus m ~ 0 is a good choice for Ni(Ag).

Keywords: Polyatomic Segregation, Surfaces, Atomistic Simulation, Nickel, Silver . References [1]. Lezzar B, Khalfallah O, Larere A, Paidar V, and Hardouin Duparc O, Acta Materialia, 2004 ; 52 2809. [2]. Hardouin Duparc O, Larere A, Lezzar B, Khalfallah O, and Paidar V, Journal of Materials Science, 2007 ; 40 1791. [3]. Lezzar B, Hardouin Duparc O, Khalfallah O, Larere A, and Paidar V, Physical and Chemical News, 2008 ; 41 46. [4]. Djerouni N.E.H, Hardouin Duparc O, and Khalfallah O, Physics Procedia, 2009 ; 2 1359. [5]. Paidar V, and Hardouin Duparc O, International Journal of Materials Research, 2009 ; 100 308.

236


Ab-initio and DFT study of the isomerisation kinetics of substituted decapentaene

D. TAHARCHAOUCHE1; A. LAKHZOUM1; Z. SKANDERI1; A. DJEBAILI1; 1. Laboratory of chemistry and environmental chemistry L.C.C.E - University of BatnaAlgeria Abstract

With the aim of finding an interpretation for the isomerization reaction of decapentaene by quantum methods, we have studied a series of three molecules giving the following results:  The studied segments (C10H12, C10H6Br6, C10H6I6) are very stable. This stability is justified by the HOMO-LUMO found energy gap. However, examination of the stability of several conformations shows that the trans conformer is more stable than the cis conformer in the general assembly.  According to the study of different reaction profiles, we noticed that the size and nature of the dopant plays a very important role on the evolution of the activation energy.  From the obtained values of the activation energy, we find that the speed constants of the isomerization reaction are in the order: k C10H12 >>k C10H6Br6>> k C10H6I6  The search for intermediate products during the transition Cis-Trans shows that the geometric parameters (angles and dihedral angles) are the most varied settings, this remark has been observed in the case of substituted and non-substituted PA.  The methods of calculations performed in this work are the Ab-initio and DFT methods, with the bases (6-31G, 3-21G **). All these calculations are performed with the Hyperchem software, where parameters obtained are in a closer order to those obtained with the Gaussian 03W software.

Examination of different molecules obtained during the Cis-Trans isomerization reaction shows that the total energy of the resulting intermediate product is of the order of -10487.05 eV, corresponding to 0.87 eV activation energy (23.67 kcal / mol).  With the same HF method (6237


31G and 3-21 G**), a close geometry was obtained for the intermediate product in the isomerization reaction with a total energy of 0.93 eV (25.30 kcal/mole), which shows that the different values of the activation energy obtained by the HF and DFT methods at the 6-31G level can be compared to those obtained by Ito, Montaner and Bernier.

Keywords: Ab-initio; DFT; kinetics; isomerisation; substituted decapentaene

238


Quantum study of different structures of the cis-trans transition of substituted polyacetylene by different methods: semi empirical AM1+PM6, HF (Ab-initio) and DFT (B3LYP)

Z. SKANDERI1; I. R. KRIBA1; A. DJEBAILI1*; J.P. CHOPART2 1. Laboratory of chemistry and environmental chemistry L.C.C.E - University of Batna Algeria 2. Laboratory of Dynamics & Interfaces – LACMDTI- University of Reims, France

Abstract

Our study aims to gather the maximum amount of information on the changes produced at the structural level (rotation, torsion, conversion) during the Cis-Trans transition (isomerization reaction) on one hand, and to examine the influence of different dopants or substituents on these kinetic parameters on the other hand. The results obtained through the optimization of molecules gave us the different distances and angles

according

to

the

methods

and

bases

applied

with

a

C2v

symmetry.

We were able to determine the total energies, the energy gap ΔE (HOMO-LUMO) of the two conformers Cis and Trans (the HF and DFT at 6-31G and 3-21G** levels) and finally a comprehensive analysis on the topological charges. The analysis of the results show that for the six molecules, the Trans conformer is energetically very stable compared to the Cis one, this stability is confirmed by the obtained values for the total energy. The increase in the stability energy leads to a less important HOMO-LUMO energy gap.

The analysis of the optimized geometrical parameters of the six molecules using the AM1 and PM6 methods, are in agreement with the experimental structures characterized by X-ray

239


diffraction. Finally, we were able to determine the reaction profiles of the Cis-Trans isomerization reactions of the polyacetylene in the gas phase, and to calculate the activation energy (Ea), as well as the diagrams of energies E (eV) based on the coordinates of the isomerization reaction of its molecules. All calculations performed in this study are carried out using the Hyperchem software.

Keywords:

substituted polyacetylene , semi empirical, HF (Ab-initio), DFT (B3LYP)

240