Informations Générales

Sujet proposé: Engineering approaches to achieve sustainability: modification of biopolymers and use
of less-refined resources to obtain bio-based plastics to substitute single-using plastics.
[Approches techniques en réponse au développement durable : modification des biopolymères et
utilisation de ressources moins raffinées pour obtenir des plastiques biosourcés destinés à remplacer
les plastiques à usage unique.]

Spécialité du doctorat envisagé (discipline) : Génie des procédés, Sciences des matériaux
Université d’inscription : Université Paris-Saclay, CentraleSupélec
École Doctorale : Sciences mécaniques et énergétiques, matériaux et géosciences – SMEMaG (ED
579)

Directeur de thèse et co-encadrant :

Directeur de thèse :
Prof. Pedro AUGUSTO, Directeur adjoint de la Chaire de Biotechnologie, CentraleSupélec,
pedro.augusto@centralesupelec.fr
Co-encadrement :
Dr. Brahim MAZIAN,
Dr. Sylvain FORET

Laboratoire d’accueil : Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec,

Université Paris-Saclay, CEBB - campus recherche de Pomacle (près de Reims).

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 Proposed topic

Engineering approaches to achieve sustainability: modification of biopolymers and use of less-

refined resources to obtain bio-based plastics to substitute single-using plastics.

Abstract
There is an urgent need to reduce the impact of single-use plastics worldwide. Conventional
plastics are associated with environmental and social-economical constraints: they are produced from
non-renewable resources, whose reserves are concentrated in some specific countries, and although
potentially recyclable, their micro-plastic residues cross-contaminate the environment. As alternatives,
literature brings different examples of natural biopolymers as renewable resources to produce bio-
plastics. However, two concerns can be associated with this approach. Firstly, the use of refined/purified
molecules, although technologically adequate, generates residues, whose impact must be considered.
Secondly, by producing bio-based plastics from the noblest part of the agro-resources, it competes with
food production, with potential ethical and social-economical concerns. This project will study and
develop new biobased materials to substitute single-use plastics using local less refined resources of
starch and applying processes to enhance their performance. Physical and green chemical treatments
will be evaluated to enhance the material properties. The materials will be produced by extrusion and/or
compression-moulding techniques, to overcome the main limitation of current research, which is focused
on the casting technique (which is interesting on a laboratory scale, but limited to scale up). Considering
different applications, the materials will be evaluated considering a broad screening of properties
(mechanic, thermic, acoustic, electromagnetic, and interaction with different fluids and products,
including the simulation of the human body). By balancing a rigorous scientific approach with an
innovative potential to solve major societal issues – namely using Biomaterial Science to enhance the
sustainability of human production, it is expected to obtain results with both academic and industrial
importance.

Keywords: biomaterials, biodegradable plastics, valorisation of by-products, material sciences,

biomaterials science, process engineering, polymers, sustainability, sustainable development.

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 Sujet proposé

Approches techniques en réponse au développement durable : modification des biopolymères

et utilisation de ressources moins raffinées pour obtenir des plastiques biosourcés destinés à
remplacer les plastiques à usage unique

Résumé
Réduire l’impact des plastiques à usage unique sur la planète devient de plus en plus
indispensable. Les plastiques conventionnels sont associés à des contraintes environnementales et
socio-économiques : ils sont produits à partir de ressources non renouvelables, dont les réserves sont
concentrées dans certains pays spécifiques, et bien que potentiellement recyclables, leurs résidus
micro-plastiques contaminent l'environnement. Comme alternatives, la littérature apporte différents
exemples de biopolymères naturels issus de ressources renouvelables pour produire les bioplastiques.
Cependant, deux problèmes peuvent être associés à cette approche. Premièrement, l'utilisation de
molécules raffinées/purifiées, bien que technologiquement adéquate, génère des résidus dont l'impact
doit être considéré. Deuxièmement, en produisant les plastiques biosourcés à partir de la partie la plus
noble des agro-ressources, elle entre en concurrence avec la production alimentaire, avec des
préoccupations éthiques et socio-économiques potentielles. Ce projet étudiera et développera de
nouveaux matériaux biosourcés pour remplacer les plastiques à usage unique en utilisant des
ressources locales moins raffinées d'amidon et en appliquant des processus pour améliorer leurs
performances. Des traitements physiques et chimiques verts seront évalués pour améliorer les
propriétés des matériaux. Les matériaux seront produits par la voie fondue en utilisant des techniques
d'extrusion et/ou de moulage par compression, afin de surmonter la principale limite de la recherche
actuelle, qui se concentre sur la voie liquide ’casting’ (qui est intéressante à l'échelle du laboratoire,
mais limitée à l'échelle supérieure). Compte tenu des différentes applications, les matériaux seront
évalués sur la base d'un large éventail de propriétés (mécaniques, thermiques, acoustiques,
électromagnétiques, interaction avec différents fluides et produits, y compris la simulation du corps
humain). En équilibrant une approche scientifique rigoureuse avec un potentiel innovant pour résoudre
des problèmes sociétaux majeurs - à savoir l'utilisation de la science des biomatériaux pour améliorer
la durabilité de la production humaine, il est prévu d'obtenir des résultats ayant une importance à la fois
académique et industrielle.

Mots clés : biomatériaux, plastiques biodégradables, valorisation des sous-produits, sciences des
matériaux, science des biomatériaux, génie des procédés, polymères, durabilité, développement
durable.

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Background and Context
There is a rising trend in developing alternatives with lower environmental impact for traditional
materials based on petroleum. This is the case of different plastics, which can be used as films, sheets,
foams or blocks for packaging, thermal isolation, mechanical protection, building blocks, and biomedical
applications, among many other uses. In fact, there is an urgent need to reduce the impact of single-
use plastics worldwide.
Although bio-based plastics can be obtained from refined biomolecules, such as isolated starch
and proteins, a more interesting, but challenging approach, is to produce the bioplastics from less refined
sources [1].
This Ph.D. project will study and develop new biobased materials to substitute single-use plastics
using less refined sources of starch and applying modification processes to enhance their performance.
Following the concept of circular economy and integral use of resources, the project will develop
strategies for using biomass of local importance to obtain bio-based plastics, and prospecting industrial
applications. Reactive extrusion, physical and green chemical treatments will be used as a strategy to
modify the structure of starchy sources and improve the material properties, with a reduced
environmental impact.
The right combination of experience and resources is available to aid enthusiastic candidates to
be successful in developing scientific research with innovative potential.

Research subject and work plan

Firstly, a prospection of starchy cultures produced in the “Grand Est” region of France [2] will be
conducted in relation to their potential to produce bioplastics. For instance, due to their composition and
production in the region, wheat and barley will certainly be evaluated. The project will work within the

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range of two extremes: the high refined biopolymer (pure starch) towards the non-refined material
(triturated grain).
Native starch and starchy mixture will be modified considering environmentally friendly
alternatives (green technologies), such as DHT, HMT, annealing and/or ozone [3]. This strategy will
result in new molecular interactions, potentially improving the material properties [4–8].
When using the less refined fractions, a challenge on applying lignocellulosic biomass can be
the difficult in solubilizing them adequately. If it is the case, the biomass will be modified by acid
hydrothermal treatment [9–11], using trifluoroacetic [12] or hydrochloric [13] acids. This work will use
the reactive extrusion as an innovative strategy to reduce the acid concentration and/or treatment time
and/or increase efficiency, limiting the environmental impact.
The plastics will be produced by extrusion technique [7,8]. It will be conducted in our new twin-
screw extruder, which contains 10 zones of independent temperature control, 2 zones of liquid injection,
a zone to recover possibly liquid phase by filtration, as well as the control of pressure and product
temperature, powder and product mass flow.
The plastics will be produced using starch and non-refined grain flours, isolated or in
combination, water or acid solutions as a solvent and other compounds to improve the plastic structure
and properties. Glycerol and/or monosaccharides [14] can be used as plasticisers - these can be
obtained directly from the by-product processed by the acid cooking. Different combinations of raw
materials, modification treatments and process conditions will be studied, focusing on obtaining bio-
based plastics with different structures and properties, thus targeting possible applications.
The general morphology of obtained plastics will be evaluated by optical and SEM microscopies,
while their internal porosity will be evaluated by x-ray nano-computed tomography (nanoCT). This
technique allows evaluating the size, distribution, geometry, tortuosity and connectivity of the pores
inside the plastic, as well as constructing a 3D model for numerical simulations [15].
Mechanical properties will be evaluated not only in relation to tensile assays, but also the material
behaviour under flexion and impact, thus covering different applications. Thermal properties will be
evaluated through DSC and TGA, as well as developing a specific system to measure thermal
conductivity (k). Dielectric properties (ε’, ε’’) and electric conductivity will be evaluated to understand the
response of the material to electromagnetic radiation. Light transmittance will be evaluated from UV to
visible light [7], once the agro-industrial by-products contain functional compounds with different
absorbances.
The interaction of the materials with the human body, including their biodegradation will be
evaluated [16], prospecting biomedical applications.
Moreover, the interaction of each material with water and oils will be evaluated by water vapor
diffusivity, using a method able to quantify molecular relaxation [17], contact angle (kinetics), solubility

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and absorption. Correlations between the material structure (in special porosity) and those properties
will enable find processing conditions to reach the desired performance. In special, the matrix relaxation
with water absorption, and the consequent sub-diffusive behaviour for water vapour transfer will be
evaluated by modelling[18], using a combination of the structural information and the macromolecular
conformation, as input parameters.
Finally, the evaluation of the results will enable propose possible applications, which will be
simulated in comparison with traditional plastics.
This project will balance a rigorous scientific approach with an innovative potential to solve major
societal issues – namely using Biomaterial Science to enhance the sustainability of human production.
Consequently, we expect enthusiastic candidates to help us to develop new bio-based materials for
industrial application.

Resources
The Chair of Biotechnology [19] of CentraleSupélec, backed by the Process Engineering and
Materials Laboratory (LGPM), is a leading group in France with vast experience in characterizing,
processing and valorising biomaterials. Our excellent analytical, imagery, instrumentation & design, pilot
plant and modelling platforms allow us to conduct cutting-edge research and development. For instance,
we recently installed a last generation extruder, rheometer and mechanical test machine in our
laboratory, which expanded the possibilities of research to produce bio-based materials. Some
examples of technologies available in our laboratory are confocal laser microscopy, Raman micro-
spectroscopy, structured light optical microscopy, environmental scanning electron microscopy, nano-
tomography, X-ray imaging, rheometer, mechanical testing machine, DSC, DVS, different
chromatographic techniques (HPLC-RI, HPLC-FLD, UHPLC-UV-MS, TIMS-TOF, IC, GC-MS/MS, µ-
GC) and a complete Instrumentation & Design platform. Moreover, our group has experience in
producing bio-based materials from biopolymers [4–8], as well as using different technologies to
enhance the performance of biopolymers [20–22].
In the host laboratory, the student will have a favourable and international environment and will
have access to the experimental devices specific to the thesis work and to the analytical tools necessary
for the characterization. The student will benefit from the support of technical staff trained in these tools
and will be able to rely on the laboratory's design, fabrication and instrumentation platform to develop
the original experimental approaches described in the work plan of this PhD. The simulation tools exist
in the form of codes developed in-house. The student's work will be mainly devoted to the use of these
tools.

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