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> Research > Doctorate, post-doctorate

LGP2 - Ph.D. thesis defended in 2014

Ahlem ROMDHANE

December 12, 2014 - Fluid Mechanics, Energy, Processes [Thesis online]
Ph.D. title
Membrane separation processes for continuous production of nanocrystals of polysaccharides: experimental approach and modeling.
Supervision
Marc AUROUSSEAU, Professor, Grenoble INP-Pagora / LGP2 ♦♦ Agnès GUILLET, Associate Professor, Grenoble INP-Pagora / LGP2
Abstract
The current work investigates the use of cross flow microfiltration using ceramic membrane to fractionate the heterogeneous suspension obtained after starch hydrolysis in order to isolate starch nanocrystals. The final aim is to evaluate the possibility of coupling the filtration step to the hydrolysis step in a single production loop in order to enhance the starch nanocrystal production yield. The characterizations of the suspension (particle size and charge) obtained with the classic production process indicates that it was a mixture of starch nanocrystal aggregates and starch residues, individualized starch nanocrystals represent only 5 % of the initial starch. The fractionation study was done using two pilot plans, in a dead end configuration at laboratory scale (plate membrane) and in a cross flow configuration at semi-industrial scale (tubular membrane). Design of experiments methodology was used to optimize the fractionation efficiency when filtering a neutral suspension considering the effect of filtration parameter on the transmission yield and membrane fouling. In the optimized condition, it was possible to recover 25 % of starch nanocrystals while keeping the permeate flux at its highest value. Mean diameter of the recovered particle was less than 300 nm. At this condition, it was also possible to recover the starch nanocrystals directly from the acidic mixture obtained at the end of the hydrolysis step. The analysis of fouling mechanism using dead end filtration experiments highlights that membrane fouling occurs because a cake bult up at the membrane surface. This study investigates also the use of ceramic ultrafiltration membrane in a diafiltration process in order to purify the acidic suspension from soluble molecules without modifying particle size distribution which is a promising technique for a large scale production.
Other members of the jury
Murielle RABILLER BAUDRY, Professeur, Université de Rennes 1 ♦♦ Marc HERAN, Maître de Conférences HDR, Polytech Montpellier ♦♦ Sami BOUFI, Professeur, Université de Sfax (Tunisie) ♦♦ Évelyne Mauret, Professeur, Grenoble INP-Pagora

Nicolas FULLERINGER

December 11, 2014 - Fluid Mechanics, Energy, Processes [Thesis online]
Ph.D. title
Contribution to the study of friction phenomena. Application to paper materials.
Supervision
Jean-Francis BLOCH, Associate Professor, Grenoble INP-Pagora / LGP2
Abstract
The optimization of numerous technological processes requires a deep understanding of the paper friction phenomena. This thesis aims to better understand these phenomena in order to improve the envelopes separation in franking machines.
First, standardized methods for measuring the paper-on-paper friction force having proved limited in terms of repeatability and experimental conditions, two measurement methods ̶ low and high speed ̶ were developed. Similarly, the friction measurement has been adapted to the different contacts encountered in franking machines.
Secondly, these methods have been used to study the mechanisms of friction with the paper material including the dependency of the paper-on-paper friction to length of the displacement, the influence of both temperature and humidity on the paper-on-paper friction, and the main frictional properties of the envelope-on-envelope, rollers-on-paper, and pads-on-paper contacts, respectively.
Thirdly, a comprehensive model of the envelopes separation in a franking machine was created. This process aims at displacing, with no damage, only the bottommost envelope of a stack of envelopes. This model allows to identify, characterize and propose an optimization of the main process parameters.
Other members of the jury
Marie-Ange BUENO, Professor, Université de Haute Alsace ♦♦ Maxence BIGERELLE, Professor, Université de Valenciennes et du Hainaut-Cambrésis ♦♦ Carlos CANUDAS DE WIT, Research Director, INRIA ♦♦ Thomas MATHIA, Research Director, École Centrale de Lyon ♦♦ Laurent FARLOTTI, Innovation & IP Director, Neopost

Daniele SETTE

December 11, 2014 - Materials, Mechanical, Civil Engineering, Electrochemistry [Thesis online]
Ph.D. title
Functional printing: from the study of printed layers to the prototyping of flexible devices
Supervision
Anne BLAYO, Lecturer-Researcher, Grenoble INP-Pagora / LGP2 ♦♦ Christophe POULAIN, CEA Grenoble
Abstract
In the last decade, functional printing has gained a large interest for the manufacturing of electronic components. It stands aside to silicon technologies and specifically targets markets of large area devices (screens, photovoltaics) and flexible electronics (RFID antennas, sensors, smart textiles).
In this work, inkjet printed silver layers are characterized depending on the printing conditions and the required post-printing annealing. The evolution of their microstructure, electrical and mechanical properties is investigated as a function of the annealing temperature. The correlation of the measurements with theoretical models supports the experimental methods that were developed. The knowledge of the printed silver layers assets and the optimization of the printing process lead to the design, fabrication and characterization of flexible electronics devices: a 17 GHz band-pass filter printed on plastic, a flexible vacuum micro-sensor working on the Pirani principle, and a 250 µm thick membrane switch for keyboards. Finally, all printed RF capacitors were realized by stacking Barium Strontium Titanate dielectric and silver printed layers.
These prototypes exhibit performances near the state-of-the-art and suggest new opportunities for printing technologies. This thesis offers a thorough study of inkjet printed silver layers and assess their potential for the manufacturing of flexible devices.
Other members of the jury
Panagiota MORFOULI, Professor, Grenoble INP-Phelma ♦♦ Reinhard BAUMANN, Professor, Chemnitz University of Technology (Allemagne) ♦♦ Yvan BONNASSIEUX, Professor, École Polytechnique, Palaiseau ♦♦ Mohamed SAADAOUI, Doctor, École des Mines de Saint-Etienne

Etzael ESPINO PEREZ

December 11, 2014 - Environmental Science
Ph.D. title
Development of renewable nanocomposites for packaging by the functionalization of polysaccharide nanocrystals
Supervision
Sandra DOMENEK, Associate Professor, AgroParisTech ♦♦ Julien BRAS, Associate Professor, Grenoble INP-Pagora / LGP2
Abstract
The creation of nanocomposites is one of the promising technologies for adapting the mechanical and barrier properties of biobased and biodegradable polymers to the requirements of commodity products such as food packaging.
The Panagro project aimed at the creation of fully organic nanocomposites by the distribution of cellulose nanocrystals (CNC) inside polylactide (PLA). Compatibility between nanocharges and polymer is one of the challenges in the development of nanocomposites. The Panagro project proposed rise to this challenge in designing the cellulose nanocrystals surface with a double functionality, insuring compatibility and modifying barrier properties of the nanocomposites towards organic vapours.
Two versatile surface grafting methods respecting the principles of green chemistry were developed and aromatic molecules were grafted using ozone activation, radical initiation and grafting of the surface in aqueous solvents, or using the reactants as solvents be in situ solvent exchange. The increase of compatibility of PLA and CNC was evidenced by the increase in rubbery storage modulus of nanocomposites and constant gas barrier properties. The permeability of the aromatic probe anisole was decreased due to the distribution of CNC inside PLA and was in addition decreased by the interaction with the aromatic surface grafts.
Other members of the jury
Éliane ESPUCHE, Professor, Université Claude Bernard Lyon 1 ♦♦ Stéphane  MARAIS, Professor, Université de Rouen ♦♦ Youssef HABIBI, Associate Professor, CRP Henri Tudor ♦♦ Philippe ROGER, Professor, Université Paris-Sud 11 ♦♦ Naceur BELGACEM, Professor, Grenoble INP-Pagora ♦♦ Alma  ROMAN, Associate Professor, Universidad Autónoma del Estado de Hidalgo, Mexique ♦♦ Alain GUINAULT, Research Engineer, Arts et Métiers ParisTech

Raphaël BARDET

November 14, 2014 - Materials, Mechanical, Civil Engineering, Electrochemistry [Thesis online]
Ph.D. title
Nanocelluloses as potential materials for specialty papers
Supervision
Julien BRAS, Associate Professor, Grenoble INP-Pagora / LGP2 ♦♦ Naceur BELGACEM, Professor, Grenoble INP-Pagora / LGP2
Abstract
The original feature of this work is to investigate the contribution of two families of nanocellulose for their application within specialty papers. It exists two families of nanocellulose, i.e. Cellulose Nanocrystals (CNC) and Cellulose Nanofibers (CNF). It results in different properties in suspension and solid states. CNF with their ability to form entangled network are used as dispersive network for particles. In contrast, the self-assembly properties of CNC are used to obtain iridescent films. First, the films based on nanocellulose were considered as model layers. Then, results were implemented at the industrial scale within the papermaking process. It is proposed to use CNF based coating for saving opacifying pigments in lightweight paper, and manufacturing iridescent pigment to impart anti-counterfeiting properties. These sustainable and cost-effective approaches were then validated at pilot scale and by two patent applications.
Other members of the jury
Bernard CATHALA, Research Director, INRA Angers-Nantes Pays de la Loire ♦♦ Patrice MANGIN, Professor, Université du Québec à Trois-Rivières (Canada) ♦♦ Étienne FLEURY, Professor, INSA de Lyon ♦♦ Laurent HEUX, Research Director, Cermav

Maïté HURON

October 22, 2014 - Fluid Mechanics, Energy, Processes
Ph.D. title
Kinetic modeling of cellulose enzymatic hydrolysis: influence of substrate type and study of deactivation phenomena
Supervision
Dominique LACHENAL, Professor, Grenoble INP-Pagora / LGP2 ♦♦

Ning LIN

June 24, 2014 - Materials, Mechanical, Civil Engineering, Electrochemistry [Thesis online]
Ph.D. title
Cellulose nanocrystals: surface modification and advanced materials.
Supervision
Alain DUFRESNE, Professor, Grenoble INP-Pagora / LGP2
Abstract
The present work focuses on the properties of cellulose nanocrystals, their surface modification and development of advanced materials. Diverse approaches are employed on these nanoscaled substrates aiming to modify their surface properties and extend their use in highly sophisticated applications, such as postsulfation and desulfation, polymer grafting and adsorption, selective oxidation, molecular grafting, and ‘host-guest’ inclusion.
On the basis of surface modifications, properties analysis (for different sulfate group contents) and various nanomaterials derived from cellulose nanocrystals are investigated and prepared, including gradient sulfated nanocrystals, extruded nanocomposites, biocomposite sponges, and supramolecular hydrogels. The effect of gradient degrees of sulfate groups on cellulose nanocrystals to surface chemistry, morphology and physical properties are discussed, particularly four cross-section models are compared for the determination of the surface degree of substitution on cellulose nanocrystals.
A novel strategy involving a double-polymer-layer shield and physical and/or chemical compatibilization of cellulose nanocrystals is proposed, in order to realize both improvement of thermal stability and promotion of compatibility for nanocrystals with non-polar polymeric matrices during processing by melt-extrusion. With the idea of participating as crosslinking aid for the construction of advanced materials, selectively oxidized cellulose nanocrystals (with oxidized microfibrillated cellulose as comparison) are introduced in alginate for the development of biocomposite sponges with improved mechanical stability or structural stability. Through the smart design of in situ ‘host−guest’ inclusion between chemically modified cellulose nanocrystals and cyclodextrin, two hydrophilic polysaccharides are combined in supramolecular hydrogels for use as drug delivery.
In a word, this dissertation contributes to the advances of cellulose nanocrystals in the topics of property analysis and application development.
Other members of the jury
Étienne FLEURY, Professor, INSA de Lyon ♦♦ Christoph WEDER, Professor, Université de Fribourg (Switzerland) ♦♦ Jean-Marie RAQUEZ, Researcher, Université de Mons (Belgium) ♦♦ Alessandra DE ALMEIDA LUCAS, Researcher, Universidade Federal de São Carlos (Brazil) ♦♦ Jin HUANG, Professor, Wuhan University of Technology (China)

Jérémy BOUCHER

June 16, 2014 - Fluid Mechanics, Energy, Processes [Thesis online]
Ph.D. title
Study of the possibilities to produce hemicellulosic ethanol in a biorefinery.
Supervision
Christine CHIRAT, Associate Professor, Grenoble INP-Pagora / LGP2 ♦♦ Dominique LACHENAL, Professor, Grenoble INP-Pagora / LGP2
Abstract
This thesis deals with the production of bioethanol of second generation. Bioethanol is a sustainable fuel which can substitute gasoline. Nowadays, it is exclusively produced from food resources, which can have harmful fallout on food prices. That is why the development of a second generation ethanol, from lignocellulosic material, is mandatory. Among all the possible ways to produce such ethanol, this study is focused on the production of ethanol from hemicelluloses in a kraft pulp mill using softwood as raw material.
Softwood hemicelluloses are mainly constituted of galactoglucomannanes (GGM). These polymers are made of sugars which can be fermented into ethanol when they are into their monomer form. During the kraft process, cellulose is produced by removing the lignin from wood. The lignin is then burnt to produce energy. The GGM are also degraded and solubilised during the kraft process but their combustion is not very profitable. The aim of this study is to extract these hemicelluloses prior to the kraft process, hydrolyze them into monomers and then ferment them into ethanol.
The efficiency of different extraction treatments was evaluated. The two processes performed in acidic medium, autohydrolysis (hot water extraction) and acid hydrolysis (in the presence of sulfuric acid) are the most interesting. The acid hydrolysis enables the extraction and the hydrolysis into monomers of most of the GGM. The sugars can therefore be fermented directly. The autohydrolysis requires a secondary hydrolysis to achieve the depolymerization of the extracted GGM. This secondary hydrolysis is performed with an acid as catalyst. This two-step treatment shows two advantages: the cellulose is less damaged and the degradation of sugars extracted is reduced. This degradation has to be avoided because the degradation products cannot be fermented and they are known to inhibit the microorganisms used for the fermentation, which is one of the main issues for the production of second generation ethanol.
The direct fermentations of the hydrolysates, performed with a wild strain of Saccharomyces cerevisiae, allow to reach good yields after 24 hours. However, it might be necessary to increase the concentrations in sugars in the hydrolysates prior to the fermentation in order to raise the profitability of the process. Three processes were compared: evaporation, decrease of the L/W ratio and recycling of the hydrolysate. The evaporation is very efficient and enables to remove acetic acid and furfural, which are inhibitors of the fermentation. Recycling the hydrolysate increases the concentrations in sugars, but also their degradation. Reducing the L/W ratio is also efficient to increase the concentration.
The fermentation of a hydrolysate produced after an autohydrolysis and a secondary hydrolysis and concentrated to reach 100 g/L of hexoses was not successful because of the high concentration in inhibitors. Several strains of S. cerevisiae were acclimatized to this kind of hydrolysate in order to achieve the fermentation.
A complete process to produce ethanol and cellulose from wood chips was developed by taking into consideration industrial constraints. This study is a first step before its implementation in a kraft pulp mill.
Other members of the jury
Ana Paula DUARTE, Professor, University of Beira Interior (Portugal) ♦♦ Carole MOLINA JOUVE, Professor, INSA Toulouse ♦♦ Antoine MARGEOT, Research Engineer, IFP Énergies nouvelles

Oussama EL BARADAI

April 24, 2014 - Fluid Mechanics, Energy, Processes [Thesis online]
Ph.D. title
Elaboration of flexible lithium–ion electrodes by printing process.
Supervision
Didier CHAUSSY, Professor, Grenoble INP-Pagora / LGP2 ♦♦ Davide BENEVENTI, CNRS Researcher / LGP2 - Yann BULTEL, Professor, Grenoble INP / LEPMI
Abstract
The work describes the manufacturing of eco-sustainable lithium-ion electrodes without fluoro-based bindings and organic solvent, thanks to the utilization of celluloses derivatives and a conventional printing process.
The main breakthrough in this work is the formulation of water based inks containing either active particles of the anode (graphite) or cathode (LFP and carbon black) and a cellulosic based binding. Thus cellulose derivatives have a binding role of active materials by replacing fluoro-based binding commonly used and insure the cohesion of electrodes printed onto paper separator without affecting electronic conductivity. In this work a new assembling strategy was proposed.
In order to validate this new technique, a lithium-ion battery was manufactured by using a front/back printing strategy of separator with the integration of current collectors during printing stage.
Other members of the jury
Christine VAUTRIN, Professeur, Centre de Recherche sur la Matière Divisée (CRMD) ♦♦ Dominique GUYOMARD, Professeur, Institut des Matériaux Jean Rouxel (IMN) ♦♦ Christophe PIJOLAT, Professeur, Centre Sciences des Processus Industriels et Naturels

Sébastien THIBERT

April 23, 2014 - Fluid Mechanics, Energy, Processes [Thesis online]
Ph.D. title
Study of the front side metallization of silicon solar cells.
Supervision
Didier CHAUSSY, Professor, Grenoble INP-Pagora / LGP2 ♦♦ Davide BENEVENTI, CNRS Researcher, LGP2 ♦♦ Nadège REVERDY-BRUAS, Associate Professor, Grenoble INP-Pagora / LGP2
Abstract
Energy is one of the main problems of this new millennium. The photovoltaic electricity should have a significant role in the future energy mix.
At an industrial scale, the front side metallization of silicon solar cells is performed by screen printing of a silver paste. This step is critical in production lines because it determines both their cost and their final performance. Consequently, it is necessary to limit the amount of printed silver paste while maximizing the cell efficiency.
The first part of this work is focused on the effects of the printing parameters on these two crucial aspects. To ensure the photovoltaic industry growth, the screen printing process should be replaced in coming years. The seed and plate concept is an innovative solution during which a first layer is printed and thickened by plating. Thanks to its flexibility and low pressure during printing, the flexographic printing process seems particularly well suited to meet the seed layer requirements at an industrial level. The second part of this work focuses on the development of this printing technique.
Other members of the jury
Mustapha LEMITI, Professor, Institut des Nanotechnologies de Lyon ♦♦ Didier GRAEBLING, Professor, Institut des Sciences Analytiques et de Physico-chimie pour l'Environnement et les Matériaux (IPREM) ♦♦ Jean-Jacques SIMON, Associate Professor, Institut Matériaux Microélectronique Nanosciences de Provence (IM2NP) ♦♦ Bernard BECHEVET, Scientific and technical advisor, MPO Energy

Carolina MORELLI-LIPARRELI

April 4, 2014 - Materials, Mechanical, Civil Engineering, Electrochemistry [Thesis online]
Ph.D. title
Development and study of the properties of films and molded parts of nano-bio-cellulose nanowhiskers and biodegradable polymers.
Supervision
Naceur BELGACEM, Professor, Grenoble INP-Pagora / LGP2

Frédéric POUYET

March 21, 2014 - Fluid Mechanics, Energy, Processes
Ph.D. title
New conditions of use of ozone for cellulosic pulp bleaching - Development of a green bleaching sequence.
Supervision
Dominique LACHENAL, Professor, Grenoble INP-Pagora / LGP2 ♦♦ Christine CHIRAT, Associate Professor, Grenoble INP-Pagora / LGP2
Abstract
In order to obtain white paper, the brown kraft pulp obtained from wood after a chemical treatment has to be bleached. Several chemical reagents can be used, including the efficient chlorinated agents. However, the use of those chlorinated agents leads to the generation of toxic compounds, among other issues. Other reagents such as ozone and peroxide can be used to partially or fully replace them, but the way they react with pulp components was not fully understood and they seemed to inevitably lead to a degradation of the end product.
The aim of this thesis was to design a greener bleaching sequence, giving high quality pulps without the use of chlorinated reagents. This was achieved thanks to a better understanding of the chemical reactions involved in the bleaching of pulp, and more specifically through a better apprehension of the possible reactions of ozone.
Other members of the jury
Stéphane GRELIER, Professor, Université Bordeaux 1 ♦♦ Dmitry EVTUGUIN, Associate Professor, University of Aveiro (Portugal) ♦♦ Göran GELLERSTEDT, Professor, KTH, Stockholm (Sweden)

Date of update May 18, 2018

Grenoble INP Institut d'ingénierie Univ. Grenoble Alpes