P 20
Design, synthesis and characterization of non-fullerene molecular acceptors for
organic solar cells
Pierre JOSSE
[email protected]
MOLTECH-Anjou, Angers
Category :
฀ Matière
Molécules
฀ Matériaux
The synthesis of active materials for organic solar cells (OSCs) is a focus of considerable
attention. Multi-disciplinary research effort in device fabrication and design of donor materials has
led to rapid progress. On the other hand, fullerene derivatives have served as the standard electronacceptor materials for almost two decades. However, despite of large electron affinity, high electronmobility and isotropic charge-transport, fullerenes derivatives present several drawbacks such as low
absorption in the visible spectrum, limited structural tunability of energy levels and relatively high
cost and environmental impact. In this context, polymeric and molecular non-fullerene acceptors
have received increasing attention in recent years.
Figure 1. Structure of the DPP and TII based molecular
acceptors
Very recently, we have reported the synthesis and preliminary evaluation of two electronacceptors built, in few steps, by attaching electron-withdrawing phthalimide groups on two central
chromophore blocks namely the thienoisoindigo (TII) and diketopyrrolopyrrole (DPP) through the use
of acetylenic linkages (Figure 1).1 Once blended with the P3HT power conversion efficiencies (PCEs) of
ca 0.4% and 3.3% were achieved for TII and DPP based devices respectively. It is noteworthy that, to
the best of our knowledge, (i) these efficiencies rank among the highest reported so far for a
diketopyrrolopyrrole based molecular acceptor material in BHJ solar cells and (ii) it is the very first
example of thienoisoidingo based material used as a non-fullerene electron acceptor.
Consequently, these promising results will be discussed in this contribution. Moreover, in our
continuing commitment towards simplified chemical structures of active OPV materials, ongoing
approaches will be also introduced.
Funding and acknowledgement : Ministère de la recherche
(1)
Josse, P.; Dalinot, C.; Jiang, Y.; Dabos-Seignon, S.; Roncali, J.; Blanchard, P.; Cabanetos, C. Journal of
Materials Chemistry A 2016, 4, 250.
P 21
Forensic Research using Isotope Intra-Molecular Experiments (FRIIME):
Development and use of quantitative 13C and 15N NMR spectrometry
JOUBERT – Valentin
[email protected]
Chimie et Interdisciplinarité : Synthèse, Analyse et Modélisation (CEISAM), Nantes
Category:
฀ Matière
฀ Molécules
฀ Matériaux
This thesis finan ed y Agen e Nationale de la ‘e he he (ANR) add esses the uestion: Can the
intramolecular stable isotope composition be used to enhance the Forensic Intelligence capabilities
to track the origin of home-made explosives and psychoactive substances?
In the battle against the illicit drugs market, methodologies have been developed1 to address origin
determination and trafficking route dismantlement for various scheduled molecules: this is the
concept of drug profiling. In this research project, the same objective will be pursued but using the
powerful intrinsic marker of the isotopic content of the molecules in question.
By resorting to a cutting edge isotopic nuclear magnetic resonance (NMR) methodology, will
investigate the position-specific distribution of isotopes in two common explosives, two well-known
cutting agents used with illicit drugs and one new psychoactive substance. Isotopic 13C NMR will be
applied to target molecules in order to refine the data obtained by Isotope Ratio Measurement –
Mass Spectrometry (irm-MS)2, as has already been demonstrated for counterfeiting of medicines3.
Furthermore, isotopic 15N NMR will be developed as a very pertinent contribution to the analyses of
explosives. By collecting a larger number of parameters characteristic of the studied products than
are currently obtainable, a new strategic and tactical paradigm will be made available to Law
Enforcement Agencies enabling models of greater sophistication and predictive power to be
developed, including the origins of raw materials and chemical reaction pathways used to
manufacture targeted products.
Innovative spin-offs from this thesis can be expected in the following areas:
Qualification of 700 MHz NMR spectrometer, equipped with a cryo-probe is a good
opportunity to meet this challenge and to establish the isotopic 15N NMR methodology. That
is why, it will be primordial to determine the accuracy and the repeatability of these
measurement. For this, ethanol 13C and acetic acid 13C- bi labeled will use and the global
isotopic composition carried out by irm-MS will compare with NMR experiment.
Rationalization of the connection between forensic science and intelligence-led policing:
more data on position-specific isotope, 13C and 15N composition of home-made explosives
(ammonium nitrate and urea nitrate) from different manufacturing processes, on
psychoactive drugs (meta-chlorophenylpiperazine) , and on different cutting agents
(caffeine, phenacetin). These data will serve to build refined models with which to combat
crime.
An improved, more robust methodology through the high-precision isotopic
characterization of a drug or an explosive for determining the origin of the raw materials
and/or the manufacturing process will be established.
To fulfil its purposes, this thesis is built as a Collaborative Research Project associating two public
partners: 1) the academic research team of the Isotope Analysis Group (EBSI) of CEISAM (Nantes),
providing its innovative NMR platform, and 2) the French Police Forensic Institute: INPS (Lyon),
providing a long-term experience in illicit drug profiling, including the use of its own irm-MS.
Funding and acknowledgement to ANR for the funding of this project and thanks INPS Lyon to its
expertise and experience in the areas of illicit drugs and explosives.
1. Silvestre, V. et al. , J. Pharm. Biomed. Anal. 50, 336–341 (2009).
2. Julien, M. et al. , Talanta 147, 383–389 (2016).
3. Remaud, G. S. et al. , Eur. J. Pharm. Sci. 48, 464–473 (2013).
P 22
DevelopmentofNewOrganicElectrodeMaterialsforRechargeableLithiumBatteries
AliaJOUHARA
[email protected]
IMN-CNRSUMRC6502,UniversitédeNantes,2,RuedelaHoussinière,44322Nantes,France
Category:
Matière
!Molécules !Matériaux
Abstract
Today there is great interest in developing alternative low cost, high energy and environmentally
friendly solutions for rechargeable batteries. An interesting concept consists in switching from
inorganic to organic matter-based electrodes.1 First, organic compounds are composed of quite
naturally abundant chemical elements (C, H, N, O, S, in particular) and if properly designed, they
could be generated from renewable resources (biomass). Second, organics can operate from
dissolved to solid state (including polymers) in aqueous or nonaqueous electrolytes making them
versatile in terms of electrochemical storage devices. Third, the richness of organic chemistry
providesgreatopportunitiesforfindingnovelandinnovativeelectrodematerials.
Currently, many organic compounds are being considered as electrode materials and display good
electrochemicalbehaviorsuchasquinones,organosulfidescompounds,nitroxide-basedpolymersor
carboxylate-based molecules.2 They also offer different electrochemical activities as p- and n-type
systems in agreement with Hünig’s classification.3 This study is focused on the synthesis and
characterization of new organic material of the quinone family based on exotic aromatic core
structures such as triptycene and iptycène. There electrochemical performances will be presented
andcomparedtoothercommonquinonederivatives.
Fundingandacknowledgement:AllocationsduMinistèredelaRecherche
(1) Poizot,P.;Dolhem,F.EnergyEnviron.Sci.2011,4(6),2003.
(2) Liang,Y.;Tao,Z.;Chen,J.Adv.EnergyMater.2012,2(7),742.
(3) Deuchert,K.;Hünig,S.Angew.Chem.Int.Ed.Engl.1978,17(12),875.
P 23
Modelling the Ni – S system at the atomic scale
Anna KARPIŃSKA
[email protected]
Institut des Materiaux Jean Rouxel (IMN – UMR6502), CNRS – Universit de Nantes, 2 rue de la Houssini re, BP
32229, 44 322 Cedex 3 Nantes, FRANCE
Categor : Mat riau
_________________________________________________________________________________________
The segregation to grain boundaries (GBs) of non – metal impurities may drastically change
the mechanical properties of a pure metallic polycrystal. In the case of a Ni bulk, it is well-known - for
centuries! - that even few ppm of S induce Ni embrittlement, the mechanism of which being still
debated. Recent atomic-scale computations partly unveil it, by focusing either on the electronic
structure [1], or on the crystalline structure of the Ni - S system [2].
The keypoint is that these results can hardly be correlated, as each computation technique
employed (i) does handle for a specific and isolated mechanism so that any coupling between
chemistry and structure is neglected, (ii) deals with only one limit of the range of the S-content within
the GB, and (iii) cannot account for all possible structures of Gbs, that can be computationnaly
untractable. The ultimate aim of this work is to study the coupling between
S-enrichment and the atomic-scale description of a given GB structure, whatever the GB. Indeed
recent NanoSIMS measurements [3] revealed that S - segregation is strongly anisotropic within
a same polycrystal. Our approch is two-fold:
a) in one hand we plan to measure the GB segregation enthalpy of sulphur for different grain
boundary types (bicrystals), including the Sigma5(012). This will be achieved by measuring the sulphur
grain boundary concentration using WDS after equilibration at different temperatures and for different
sulphur bulk concentrations.
b) in a second hand, we plan to simulate the GB enrichment in the semi - grand - canonical
ensemble, at the atomic - scale. This requires to describe the Ni - Ni, Ni - S and S - S interatomic bonds
while remaining computationally tractable. We computed the cohesive energy, equilibrium lattice
parameter, elastic constants and surface energies for pure Ni by comparing the ReaxFF potential to
more classical approaches (EAM, ADP) that are suitable to describe the fcc metals as well as the alloy
combinations of these elements and show the limitations of the ReaxFF potential. Similarly, S
adsorption energies onto Ni surfaces and S insertion into the Sigma5(012) GB will be discussed.
[1] M. Yamaguchi, M. Shiga, H. Kaburaki, Grain Boundary Decohesion by Impurity Segragation in a Nickel –
Sulfur System (2005)
[2] H. P. Chen, R. K. Kalia, E. Kaxiras, G. Lu, A. Nakano, K. Nomura, A. C. T van Duin, P. Vashishta
and Z. Yuan, Embrittlement of Metal by Solute Segragation – Induced Amorphization (2010)
[3] F. Christien, C. Downing, K. L. Moore, C. R. M. Grovenor, Quantification of grain boundary equilibrium
segregation by NanoSIMS analysis of bulk samples (2012)
P 24
Preparation of selective radium resins for medical applications
Soumaya – KHALFALLAH
[email protected]
SUBATECH, Nantes
Category:
Matière
X Molécules
Matériaux
Abstract
Radium was first discovered in 1898 by Marie and Pierre Curie. It is the heaviest known alkaline earth
metal ion and the only radioactive one. Due to its chemical properties, radium has been a topic of
many scientific researches. AREVA Med has notably developed a new process for producing highpurity lead-212 (212Pb), a rare radioactive isotope. 212Pb is a radionuclide in the decay chains of 232Th
which is currently at the heart of a promising research project in nuclear medicine to develop new
treatments against cancer. An important target of this scientific research is the development of high
selective and stable resin for the extraction of 224Ra, a decay product of 232Th chain and a parent
nuclide of Pb-212. The resin prepared should contain a selective complexing agent for Ra
immobilized on a solid support. Several molecules were synthesized and tested for
retention/selectivity tests after impregnation or immobilization on an inert support.
Figure1: Examples of calixarenes and crown-ethers
Key words: Radium, resin, calixarene, crown-ether, selective, stable.
Funding : « CARAT » project - Progra
e D’i vestisse e t d’Ave ir PSPC
P 25
Modeling of deep etching of Silicon using Bosch Process
Le Dain - Guillaume
[email protected]
Institut des Matériaux Jean Rouxel, Nantes
Category :
฀ Matière
฀ Molécules
X Matériaux
Microelectronics nowadays needs to create high aspect ratio trenches in Silicon for the use of
Systems In Package (SIP) or the development of Through-Silicon Via (TSV). One technique for this
kind of deep etching of silicon is Bosch Process [1]. Bosch process uses alternance between an
etching pulse of SF6 plasma and a deposition pulse of C4F8 plasma for creation of highly anisotropic
trenches. Furthermore plasma etching techniques have great advantages, high reproducibility and
fastness of etching. Therefore understanding of Bosch Process mechanisms is of big interest for
industrials. To study the Bosch Process, we developed a model based on multiscale approach [2].
First, a global 0D model give information as fluxes of species and electronic temperature by simulate
kinetics of SF6 and C4F8 plasmas with reactor parameters as pressure and power. This data are used
as entries for both sheath model and surface model. Sheath model, based on Monte-Carlo algorithm,
simulate ion transport trough the sheath, sheath is the electronic depletion area between plasma
and substrate surface. The Ion Energy and Angular Distributions Functions (IEADF) obtain by this
simulation serve as data entries for surface model. Surface model uses both fluxes of species and
IEADF to simulate the plasma-surface interaction. This model uses a Monte-Carlo-like algorithm to
simulate phenomena as chemical etching by adsorption of fluorine, physical etching by sputtering of
ions or chemical deposition of fluorocarboned polymer on the substrate. At the end, we obtain
profiles which demonstrate high accuracy with deep trenches profiles visualized by SEM images and
we have only needed to send engine parameters of reactor to the model.
Funding and acknowledgement : STmicroelectronics Tours
References
1. F. Laermer, A. Schilp, K.Funk and M.Offenberg in IEEE Int. Conf. On MEMS (1999) pp. 211-216
2. A. Pateau Simulation Multi-échelle de la gravure profonde du Silicium par Procédé Bosch Ph. D Thesis,
Université de Nantes, 2014
P 26
D-hadron angular correlations in pp collisions at 7 TeV and in p-Pb collisions at 5.02
TeV with ALICE at the LHC
Faha – LEHAS
[email protected]
Subatech, Nantes / BBL, Utrecht
Category :
X Maère
Molécules
Matériaux
The azimuthal angular correlation between prompt D mesons (D*, D0 and D+) and charged
particles is sensitive to the fragmentation process of charm quarks. According to the
flavour conservation principle in QCD, heavy quarks are produced in pairs and they are
created back to back in their center of mass. This characteristic makes angular correlation
studies a useful tool to understand charm jet production and fragmentation in pp
collisions. It is also interesting to study the underlying charm production and fragmentation
mechanism in Pb-Pb collisions as well as the study of heavy-quark interaction with the
medium created in these heavy-ion collisions. D-meson angular correlations in pp collisions
are also considered as a reference for those in p-Pb and Pb-Pb collisions and those in p-Pb
collisions are used to study the effects due to the presence of cold nuclear matter. We
report on D-hadron correlation distributions measured in pp collisions at 7 TeV and in p-Pb
collisions at 5.02 TeV with ALICE at the CERN-Large Hadron Collider. D mesons are
measured in the transverse momentum interval of 3 < pT(D) < 16 GeV/c and associated
tracks for pT(assoc) > 0.3 GeV/c. Comparisons with dedicated Monte Carlo simulations
using the PYTHIA and POWHEG event generators are also discussed. They show good
agreement within uncertainties.
Funding and acknowledgement : CNRS, Région Pays de la Loire
P 27
Grid%sampling-optimization-of-electron-emission-study:-interpolation-of-density-and-of-external-potential-!!!!
LEMA!–!Charline!!
[email protected]!
IMMM,!Le!mans!
Category!:!!
!Matière!!!!!!
♦!Molécules!!!!! ! !Matériaux!!!!!!!
!
The! motivation! of! this! work! is! to! describe! the! irradiation! of! systems! going! from! nanometer! to!
macroscopic!scale,!by!a!variety!of!electromagnetic!perturbations.!Indeed,!there!are!specific!methods!
available!on!each!scale.!And!the!difficulty!is!to!take!into!account!the!coupling!of!these!different!scales.!
In!this!respect,!specific!developments!on!multiFscale!and!multiFgrid!approaches!are!important!to!be!
developed,!given!the!timescales,!the!complexity!and!the!size!of!systems.!We!start!by!optimizing!the!
gridFsampling!method!in!existing!quantum!codes*,!based!on!the!TimeFDependent!DensityFFunctional!
Theory!(TDDFT).!First!results!show!that!the!computational!size!can!be!reduced,!maintaining!a!negligible!
variation! of! observables! such! as! energy! and! ionization,! through! a! space! interpolation! of! the! total!
density!⍴ !and!of!the!external!potential-pot.!
t’=t+dt
⍴N(x,t)
potN (x,t)
Interpolation
f(x0 +ph) =
(" #$%)"('$()
f(x0 ) -
f(x ) –
-2
()
'+% "(" #$))
*
('$%)"(" #$))
f(x1 ) +
f(x ) +
-1
*
(" #$ %)"('+()
()
(" #$%)(" #$))
)
f(x2 )
⍴2N+1(x’,t)
pot2N+1 (x’,t)
Smoothing
⍴’N(x,t)
pot’N (x,t)
Time
Propagation
⍴N(x,t’)
potN (x,t’)
t=t’
!
Schematic-representation-of-the-method-in-dynamic.-
!
-
Funding!and!acknowledgement!:!CNRS!F!Haute!Garonne!;!LPTFIRSAMC,!team!AGREGAT!;!IMMM,!Le!
Mans!
*http://www.pw:teleman.org/-
P 28
Study of the beta decay properties of exotic nuclei of interest for
reactor physics, nuclear structure and nuclear astrophysics, with
the Total Absorption Spectroscopy method (TAS)
Loïc – LE MEUR
[email protected]
Subatech, Nantes
Category :
Matière
The beta decay is the manifestation of the weak interaction in the nucleus, which
is able to turn a neutron into a proton (β - decay) or a proton into a neutron (β+
decay), with the emission of an electron and a antineutrino or a positron and a
neutrino, respectively. Because this is now a very well-known phenomenon, the β
decay is a good and an often used probe of interest for the nuclear structure. But
it also plays a crucial part in the nuclear reactors (reaction products, decay
heat...) and in the explosive nucleosynthesis (r-process). Nuclear databases
contain beta decay properties of nuclei of interest for these various 0elds of
research. In these databases, a non-negligible part of the data arises from
experiments having an excellent energy resolution, like Germanium detector for
instance (the aim being to detect each individual de-exciting gamma-ray).
However, these detectors su4er from the well-known Pandemonium e4ect [1]
(see Fig. 1), which is due to the very low geometrical and intrinsic e:ciency of
the detector beyond 1-2 MeV. To overcome this e4ect, new detectors have been
developed since the 90's based on the TAS (Total Absorption Spectroscopy)
method. These are 4π detectors with a high efficiency, but with a poorer energy
resolution than the germanium detectors, and aim to detect the de-exciting
gamma-ray cascade. At the cost of a complex but well under-controlled analysis
method [2], the Pandemonium e4ect is circumvented and the data are more
sensitive to the real beta feeding. I will present the TAS concept, as well as a brief
overview of the data analysis method and 0nally new data taken in 2014 at the
Jyvälkylä cyclotron facility, combining a new TAS detector, the DTAS, with the new
IGISOL4 facility and its double Penning trap.
Parent nucleus
Parent nucleus
Level 3
Level 2
Iβ
Level 3
Level 2
Iβ
Level 1
Level 1
Ground state
Ground state
Daughter nucleus
Real Feeding
Daughter nucleus
Apparent feeding
Fig 1. Pandemonium Eect – Compare to the real feeding, the detector doesn't see the de-exciting
gamma-ray from level 3 to 1 and from level 2 to 1. In this way, the decuded β-branching (Iβ) for
level 1 and the ground state are overestimated.
Funding : Université de Nantes
[1] J.C. Hardy, L.C. Carraz, B. Jonson, P.G. Hansen, Phys. Lett. B 71 (1977) 307.
[2] J.L. Tain, D. Cano-Ott, Nucl. Inst. and Methods in Physics Research A 571 (2007) 728
P 29
RF Magnetron Sputtering Deposition of Cubic Boron Nitride Film by Bi-step Process
Name – Haisheng LIN
email: [email protected]
Laboratory, City: Institut des Matériaux Jean Rouxel, Nantes
Category:
฀ Matière
฀ Molécules
Matériaux
Abstract:
Boron nitride, especially in its cubic phase (c-BN), is a significantly interesting material for various
technological applications thanks to its thermal, electrical, mechanical and optical properties.
Reports on the formation of c-BN by means of PVD, PACVD or even CVD methods indicate ion
bombardment of growing film as an essential condition [1]. Nevertheless, this high level of ion
bombardment has some drawbacks, namely high level of stress, which inhibits the deposition of thick
films.
This study deals with attempts to overcome these drawbacks by the use of bi-step process for c-BN
films deposition:
It is well know that the nucleation conditions [2, 3] need more ion bombardment and energy than
growth one. So our goal will be to optimise the nucleation conditions in order to synthesis c-BN films
by RF magnetron sputtering technique. After, as a second step, one has to change such conditions
during growth process in order to reduce the ion bombardment but with maintaining the c-BN
content as high as possible (Fig.1).
The structural properties and mainly c-BN content will then be correlated to the film compressive
stress thanks to a large set of techniques as SEM, AFM, XPS, FTIR, HRTEM and stress measurements.
Fig. 1 c-BN content and stress of (a) one step process and (b) bi-step process
Funding and acknowledgement : This research is partially supported by China Scholarship Council
References
[1] I. Bello et al, Diamond & Related Materials. 14, 1154 (2005).
[2] M.A. Djouadi et al, Diamond & Related Materials. 10, 1357-1362 (2001).
[3] Kulisch W, Freudenstein R, Thin Solid Films. 516(2), 216-222 (2007).
P 30
Toward the first total synthesis of Kidamycin
Thibaud MABIT
[email protected]
IMMM UMR CNRS 6283, Le Mans
Category :
฀ Matière
฀ Molécules
฀ Matériaux
The pluramycin family(a) represents a group of natural compounds first isolated from Streptomyces
pluricolorescens a d e hi iti g a ti i ro ial a d a titu oral a tivit . Plura
i s’ skeleto is a 4Hanthra[1,2-b]pyran-4,7,12-trione, also called ABCD tetracycle, functionalized by two desoxyaminosugars (referenced as rings E and F) by C-glycosidic linkages respectively in C8 and C10, and a side
chain in C1. Kidamycin 1, one of the earliest known members of this family, bears D-angolosamine and
N,N-dimethyl-L-vancosamine branched at C8 and C10, respectively, a 2-butenyl residue attached at C1
and two additional substituents, a methyl at C5 and a hydroxyl at C11.
Taking advantage of our experience in the total synthesis of natural compounds and in the
development of new methodologies in organic synthesis,(b) we project a novel total synthesis of
kidamycin 1. The challenge was here to propose a convergent fragment-assembly strategy with
modulable building blocks in order to open the route to the preparation of a range of pluramycins or
simplified analogues to be tested as potential therapeutic agents.
In this communication we will discuss the first results toward the first total synthesis of Kidamycin. Our
strategy is based on a key Diels-Alder reaction between diene 2 and a correctly glycosylated dienophile
3. (Figure 1) The effectiveness of our strategy has been demonstrated recently through the synthesis
of the kidamycine aglycone and our work is currently focused on the regio and stereoselective bisglycosylation of bicycle 4.
Figure 1 - Retrosynthetic analysis to Kidamycin 1
Funding and acknowledgement : ANR
(a) For a general review, see: Hansen, M. R.; Hurley, L. H. Acc. Chem. Res. 1996, 29, 249-258.
(b). 1) Maingot, L. ; Vu, N-Q. ; Collet, S. ; Guingant, A. ; Martel, A. ; Dujardin, G. Eur. J. Org. Chem. 2009, 3, 412422 ; 2) L. Foulgoc, D. Sissouma, M. Evain, S. Collet, A. Guingant; Synlett 2012, 768. 3) M. Pantin ; D. Zon ; R.
Vomiandry; L. Foulgoc; D; Sissouma; A. Guingant; S. Collet , Tetrahedron Lett. 2015, 56, 16, 2110
P 31
DevelopmentofatypeBcontainerformedicalisotopestransportation
MaddalenaMAIETTA
[email protected]
Arronax,SaintHerblain
Category:
Matière
Molécules ☒ Matériaux
TheCERN-MEDICISfacilityisanISOLDE(IsotopeSeparatorOnLineDEvice)spin-offdedicatedtoR&D
in life sciences and medical applications. Here batches of hundreds of megabecquerel of isotope
purifiedbyelectromagneticmassseparationandcombinedwithchemicalmethodswillbecollected
onaweeklybasis[1].
Figure1:CADreproductionoftheMedicisLaboratories[2]
Theactivitythresholdsforthenon-conventionalisotopesgivenbythecurrentEuropeanregulation
(A1 and A2 limit) are lower than the classical activity needed for human injection. Hence, the
transportationhastobemadethankstoaspecialtypeofcontainer(TypeB).
ThemainaimofthisPhDprojectistodevelopanewshippingcontainertotransportisotopesfrom
theproductionsitetothehospital’sradio-pharmacy.Todoso,thetypicalisotopesandtherelative
activities values for the shipment must be defined. The European and especially the French
regulationsforthetransportationmustbestudiedindetailstocharacterizethedifferentcategories
of containers. First dimensioning of the required shielding is done with Monte Carlo simulations
(Mcnpxcode).Thisisusedtoinsureacontactdoseratelimitsinaccordancetotheregulation.Once
the mechanical and radioprotection constraints defined and assessed, the homologation will begin
andaprototypewillbemanufacturedtoundergotheregulatorytests.Specificinnovations,suchas
directtransferofthecollectedisotopesfromtheMEDICISseparatorintothepackagingareforeseen
andunderstudy.
"MEDICIS-produced radioisotope beams for medicine" is a Marie Sklodowska-CurieInnovative
TrainingNetworkoftheHorizon2020EUprogram.
Fundingandacknowledgement:
ThisresearchprojecthasbeensupportedbyaMarieSkłodowska-CurieInnovativeTrainingNetworkFellowship
oftheEuropeanCommission'sHorizon2020Programmeundercontractnumber642889MEDICIS-PROMED.
1. R.M.dosSantosAugustoetal,CERN-MEDICIS(MedicalIsotopesCollectedfromISOLDE):ANew
Facility,Appl.Sci.2014,4,265-281;doi:10.3390/app4020265.
2. R.Augustosetal,PublicpresentationtotheMedicisDay15/10/2014,IntegratingSafetyintoMEDICIS
3.
project.
IAEASafetyStandards-RegulationsfortheSafeTransportofRadioactiveMaterial.2012Edition.
P 32
Synthesis,structuralandmorphologicalcharacterizationsofplasmapolymers/metal
hybridnanocomposites
Agapy–MANSOUR
[email protected]
IMMM,UniversitéduMaine,CNRSUMR-6283,F-72085LeMans
Category:
Matière
Molécules ⌧Matériaux
Recently,thereismuchinterestinnanocompositescomposedofmetalnanoparticlesdispersedina
dielectricmatrixduetotheirnovelfunctionalpropertiesofferinghostsofnewapplications[1,2].The
use of these nanocomposites has been suggested for various chemical, optical, magnetic and gas
sensors applications [3-5]. Polymers are particularly attractive as matrix. Consequently, various
approacheshavebeenreportedtoincorporatemetalnanoparticlesintosuchmaterials.
Ourpreviousstudieshaveallowedustogaincontrolofthesynthesisofpolymersorcopolymersby
plasmachemistryfromakinetic,structural,andmorphologicalpointofview[6,7].Forthispurpose,
theprocessoriginalityreliesonadualstrategy,associatingplasmadepositionundermildconditions,
andsimultaneouswet-chemicalimpregnationinvariousmetallicsolutionscontainingiron,copper,or
nickelions.
In order to understand the properties of materials, we must have a deep knowledge about their
structure and composition. The chemical structure and the microstructure of the metal / plasma
polymer nanocomposite films were characterized by means of X-ray photoelectron spectroscopy
(XPS). The surface morphology of the films was studied using scanning electron microscopy (SEM).
The percentage of Fe, Cu and Ni were performed using an energy dispersive X-ray analysis unit
coupledtoSEM.TheAFMimageswereobtainedusingascanningprobemicroscopeinnoncontact
mode.Allthesetechniquesshowthepresenceofmetalnanoparticlesembeddedindifferentmatrix
polymers constituting of either fluorinated monomer or an amino one. It should be noted that
literaturereportsnostudyontriphasiccompositesofcopolymers/metalwhichwillbethetopicof
ourcomingstudy.
Fundingandacknowledgement:(Bourseministériel,RégionPaysdelaLoire)
1.
Faupel,F.etal.Depositionofnanocompositesbyplasmas.Contrib.toPlasmaPhys.47,537–544(2007).
2.
Peter, T. et al. Metal/polymer nanocomposite thin films prepared by plasma polymerization and high
pressuremagnetronsputtering.Surf.CoatingsTechnol.205,S38–S41(2011).
3.
Bandgar,D.K.etal.Ammoniasensingpropertiesofpolyaniline/α-Fe2O3hybridnanocomposites.Synth.
Met.204,1–9(2015).
4.
Patil, U. V. et al. Room temperature ammonia sensor based on copper nanoparticle intercalated
polyanilinenanocompositethinfilms.Appl.Surf.Sci.339,69–74(2015).
5.
Dalavi, D. S. et al. Nanoporous network of nickel oxide for ammonia gas detection. Mater. Lett. 146,
103–107(2015).
6.
Debarnot, D., Mérian, T. & Poncin-Epaillard, F. Film Chemistry Control and Growth Kinetics of Pulsed
Plasma-PolymerizedAniline.PlasmaChem.PlasmaProcess.31,217–231(2011).
7.
Chahine, C., Poncin-Epaillard, F. & Debarnot, D. Plasma Copolymerization of Fluorinated and Acrylate
Monomers:KineticsandChemicalStructureStudy.PlasmaProcess.Polym.12,493–501(2015).
P 33
Plastic waste valorization by mechanical recycling
Joachim – MARIS
[email protected]
Institut des Molécules et Matériaux du Mans (IMMM), UMR CNRS 6283, Université du Maine, Avenue Olivier
Messiaen, 72085 Le Mans Cedex 9
Category :
฀ Matière
฀ Molécules
x Matériaux
With continuous growth for more than 50 years, global production in 2014 rose to 311
million tonnes, meaning a 3.9% increase compared to 2013.(1) This plastic consumption is an
important source of waste. In 2012, in France, the plastic waste collected was estimated at 3.5
millions tons.(2) Only 17% has been recycled when 44% has been recycled for glasses and 60% for
cardboard-paper. This quite low rate can be explained:
a)
by a low uptake rates of sources of plastic waste,
b)
by complexity and financial cost of plastic’s sorting,
c)
by the mixture of the different waste sources,
d)
by the low cost of the virgin raw material,
e)
by a loss of properties because of aging and impurities and
f)
by the incompatibility of polymers.
This poster presents the different processes of recycling and recovery routes and a focus on
mechanical recycling. Mechanical recycling of mixed plastic waste is a technological challenge, due to
the presence of a wide variety of commodity polymers in waste streams. Recycled mixed polymeric
blends usually have low compatibility between the different polymeric components which leads to
significantly downgraded properties and consequently, less-valuable end-products. Mechanical
recycling can be improved by compatibilization of the blends. The four most promising strategies for
the compatibilization of complex blends of usual plastic waste will be described and illustrated:
compatibilization by copolymers, compatibilization by nanoparticles, compatibilization by reactive
polymers and compatibilization by coupling reactions.
Funding : ANRT and Veolia
This work was made in collaboration with Institut Supérieur de Plasturgie d'Alençon (ISPA), Institut
des Molécules et Matériaux du Mans (IMMM) and Veolia Recherche et Innovation (VERI).
References:
1. PlasticsEurope. Plastics - the Facts 2015: an Analysis of European Plastics Production, Demand and Waste
Data 2015.
2. Cabinet Deloitte. Analyse de la chaîne de valeur du recyclage des plastiques en France; 2015.
(Calibri, italics, 10, left aligned)
P 34
Helicenesderivativesforchiralmaterials
Kévin-MARTIN
[email protected]
LaboratoireMOLTECH-Anjou,Angers,France.
Catégory: Matière
Molécules
☒Matériaux
Introductionofchiralityintetrathiafulvalene(TTF)hasbeeninvestigatedbyourgroupsinceseveral
years and has recently provided the first experimental observation of the electrical magneto-chiral
effectinabulkmolecularconductor.1
Helicenes2areoriginalhelicalπ-conjugatedmoleculeswithremarkablechiropticalproperties.3Their
associationwiththeTTFunitprovidesnewhelicalprecursorswithinterestingchiropticalproperties
whichcanbemodulatedaccordingtotheTTFredoxstate.Also,wecanexpectoriginalarchitectures
in the solid state, with the presence of π-π stacking between helicene units and S…S interaction
betweenTTFs.4
Figure1EDT-TTF-[n]helicene(n=4,6)
Such chiral electroactive precursors are of great interest since they might allow the preparation of
chiralconductingmaterials.
Fundingandacknowledgement:RégionPaysdelaLoire.
1
F.Pop,P.Auban-Senzier,E.Canadell,G.L.J.A.Rikken,N.Avarvari,Nat.Commun.2014,5:3757,
DOI:10.1038/ncomms4757.
2
Y.Shen,C.-F.Chen,Chem.Rev.2012,112,1463.
3
F.Furche,R.Ahlrichs,C.Wachsmann,E.Weber,A.Sobanski,F.Vögtle,S.Grimme,J.Am.Chem.Soc.2000,
122,1717.
4
T.Biet,A.Fihey,T.Cauchy,N.Vanthuyne,C.Roussel,J.Crassous,N.Avarvari,Chem.Eur.J.2013,19,13160.
P 35
Fabrication of a passive saturable absorber based on the deposition of graphene on a
tapered fiber
Paul – MOUCHEL
[email protected]
Laboratoire de Photonique d’Angers (LPhiA), Angers
Category :
X Matière
Molécules
Matériaux
Abstract :
The reduction of the diameter of a single mode fiber allows the propagation of clad modes. This
phenomenon lets the evanescent field interact with the medium in contact with the tapered fiber. By
depositing graphene in solution on the waist of the taper, it is possible to create a passive saturable
absorber.
The fabrication of tapers with a waist diameter from 8 µm to 23 µm based on a standard single mode
fiber at 1550 nm is mastered. As the modes HE11 and HE12 interfere in the taper [1], the transmission
is periodic with the elongation of the waist; thus the tapers are packaged prior to the deposition of
graphene in order maximize the transmission. Once packaged, the loss of the component is less than
0.5 dB.
Such a passive saturable absorber can be easily integrated in the cavity of a fiber laser so as to trigger
it in the mode-lock regime and obtain an ultrafast laser.
Graphene is well deposited along the waist of the tapered fiber.
Funding and acknowledgement : ANRT
[1] Investigation of power oscillations along tapered monomode fibers, F. Gonthier, Applied Optics, 26(3), pp
444-449, 1987.
P 36
Chiral Molecular Conductors
Nabil MROWEH
[email protected]
Moltech Anjou, Angers
Category:
฀ Matière
x Molécules
x Matériaux
Chirality is a fundamental property of the matter which influenced a lot of advances in physics,
chemistry and life sciences [1].
Tetrathiafulvalene (TTF) and its derivatives represent the most important family of electroactive
precursors [2] extensively used for the preparation of crystalline molecular conductors and
superconductors. Chirality was first introduced in TTFs in the middle of 1980s by Dunitz and Wallis [3]
thus opening opportunities in the development of chiral molecular conductors.
Introduction of chiral information in tetrathiafulvalene precursors represents a powerful strategy
towards the preparation of crystalline materials in which the combination of chirality and conducting
properties might allow the observation of the electrical magnetochiral anisotropy effect [4].
Scheme.1 Chiral TTF precursors
In the present work of this project (Molecular chiral conductors) the objective is to synthesize and
characterize new families of TTF precursors, then to investigate their electro-magnetochiral
anisotropy and try to discover new magneto-chiral effects.
Funding: ANR
[1] Wagnière,G. H. On Chirality and the Universal Asymmetry,Wiley-VCH, Weinheim(2007).
[2] Yamada, J.-L. TTF Chemistry: Fundamentals and Applications of Tetrathiafulvalene Springer-Verlag (2004).
[3] Dunitz, J. D., Karrer, A. & Wallis, J. D. Chiral metals? A chiral substrate for organic conductors and
superconductors. Helv. Chim. Acta 69, 69–70 (1986).
[4] Pop, F., Auban-Senzier, P., Canadell, E., Rikken, G. L. J. A. & Avarvari, N. Electrical magnetochiral anisotropy
in a bulk chiral molecular conductor. Nature Commun. 5, 3757 (2014).
P 37
Nanostructured soft-hard magnetic materials with controlled architecture
Name – SURNAME: Van Tang NGUYEN
email: [email protected]
Laboratory, City : Institute of Molecule and Materials, Le Mans
Category :
฀ Matière
฀ Molécules
x Matériaux
Abstract
Recent development in advanced technology requires a growing need of permanent magnet
with high energy product being able to work at high temperature (
and with competitive
prices, which can not be met by three traditional families of permanent magnets. This can be solved
by using an innovative concept to produce a new family of high performance magnet called spring –
magnet principle de eloped i 9 ’ [ ] that bases on the exchange coupling between hard and soft
magnetic phases.
MnAl magnet has been considered as one of some rare-earth-free materials that exhibit
appreciable intrinsic properties, such as Ms = 0.6 M A m-1, K1 = 1.7 M J m-3, TC = 650 K [2]. The
ferromagnetic properties of MnAl magnet comes from the metastable tetragonal (L10 ordered) phase
(τ phase) in the composition range 50-60 at% Mn.
In our work, MnAl magnet is chosen to play as the hard phase in the spring exchange magnet,
and is prepared by both two techniques of arc melting and ball milling.
b)
a)
Fig.1 Xray-Diffraction spectra of Mn50Al50 alloy (a) and Mn56Al44 alloy (b) synthesized by ball milling and arc melting
techniques, respectively
As depicted in Fig.1 (a), aluminum is well dissolved after 10h of milling. Annealing at 1050 oC
i
hou afte that leads to the t a sfo atio of β phase i to high te pe atu e ε phase. Follo i g
heat t eat e t auses the t a sfo atio f o ε to the τ phase. Si ila phe o e o is also
observed in case of Mn56Al46 alloy (b) that is synthesized by arc- elti g te h i ue, e ept the τ phase
is also obtai ed di e tl afte elti g. Although e ei i g ε ith high pu it , β phase o γ 2 phase can
e fou d i
oth sa ples. This o fi s that τ phase is e se siti e to the o positio a d
etasta le; that is, it a de o pose i to sta le β a d γ 2 phases. Adding C has been proved to
prevent this decomposing.
Funding and acknowledgement: We would like to acknowledge Vietnamese government scholarship
and CNRS for their financial support.
References
[1]. Kneller, E. F.; Hawig, R. (July 1991). "The exchange-spring magnet: a new material principle for permanent
magnets". IEEE Transactions on Magnetics 27 (4): 3588–3560.
[2]. J. M. D. Coey/Scripta Materialia 67 (2012) 524–529.
P 38
Design of photoactive species/graphene/metal nanowires for exploring new
optoelectronic behaviours
Daniel – FUNES
[email protected]
PMN Group, Institut des Matériaux Jean Rouxel, Nantes City
Category : Matériaux
Nano-optoelectronics is the answer to the technology of the future. Moore’s Law has been followed
since it was enunciated in the 70s until the date. According to this law the overall processing power
for computers would double every two years. But the nowadays Si-based microelectronics are
reaching a scale limit. The pass to nano-optoelectronics is a matter of time.
Nano-optoelectronics englobe the interaction light-matter and the information processing at the
nanometric scale. Different effects as nano-waveguiding, nano-sensing or nano-sourcing are
expected from this new technology area.
The aim of my PhD project is to discover new nano-optoelectronics effects by the combination of
plasmonics nanoparticles (NPs) and photoactive species in one dimension (1D) hybrid nanostructures
altogether with graphene. These kind of nanostructures and their light-matter interactions and
coupling have not been widely studied yet. The use of bottom-up approaches is also an advantage
with respect to previous studies because of their easier, faster and more versatile manipulation.
The nano-structures of these nanowires (NWs) are based on coaxial core-shell and segmented
geometries. The introduction of an insulating spacer will be necessary to avoid the quenching that Au
and graphene have over Photoluminescent species. The Fig 1 shows schematically the different
materials that my novel 1D nanostructures will include.
The preparation and characterization of 1D Au nanostructures and the first Au-photoactive speciesand graphene-[Au 1D nanostructures] have been a success. In Fig 2, a transmission electron
microscope (TEM) image of an Au NW surrounded by poly-3-octyl-thiophene (P3OT) is shown.
Further studies will be performed during the incoming year.
Fig 1. Diagram of the hybrid nanostructures to obtain in my project
Fig 2. TEM image of Au NWs + P3OT NTs Ø55nm
Funding and acknowledgement:
Enabling Excellence project has received funding from the European Union’s Horizon 2020 research
and innovation programme under the Marie Skłodowska-Curie grant agreement No 642742
CNRS-IMN
[1] http://www.mooreslaw.org/
[2] Jones, M. R., Osberg, K. D., Macfarlane, R. J., Langille, M. R. & Mirkin, C. A. Templated Techniques for the
Synthesis and Assembly of Plasmonic Nanostructures. Chemical Reviews 111, 3736–3827 (2011).
[3] Kang, K. A., Wang, J., Jasinski, J. B. & Achilefu, S. Fluorescence manipulation by gold nanoparticles: from
complete quenching to extensive enhancement. J. Nanobiotechnol 9, 10–1186 (2011).
[4] Zhao, Y. & Zhu, Y. Graphene-based hybrid films for plasmonic sensing. Nanoscale 7, 14561–14576 (2015).
[5] Xie, L., Ling, X., Fang, Y., Zhang, J. & Liu, Z. Graphene as a Substrate To Suppress Fluorescence in Resonance
Raman Spectroscopy. Journal of the American Chemical Society 131, 9890–9891 (2009).
[6] Reynes, O. & Demoustier-Champagne, S. Template Electrochemical Growth of Polypyrrole and GoldPolypyrrole-Gold Nanowire Arrays. J. Electrochem. Soc. 152, D130–D135 (2005).
[7] Garreau, A. & Duvail, J.-L. Recent Advances in Optically Active Polymer-Based Nanowires and Nanotubes.
Advanced Optical Materials 2, 1122–1140 (2014).
101
P 39
REDOX BEHAVIORS OF P AND N TYPE COMPOUNDS AS
NEGATIVE ELECTRODE MATERIALS FOR SODIUM AQUEOUS
BATTERIES
Sofia Perticararia, Pablo Jimenez Maneroa, Antonia Kotroniaa, Fabrice Odobelb, Yann Pellegrinb, Errol
Blartb, Dominique Guyomarda, Philippe Poizota and Joel Gaubichera
[email protected]
a
Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssiniere, BP32229,
44322 Nantes Cedex 3, France.
b
CEISAM, Chimie et Interdisciplinarité, Synthèse, Analyse, Modélisation, Faculté des Sciences et des
Techniques, Université de Nantes, 2, rue de la Houssinière, BP 92208, 44322 NANTES Cedex 3 (France)
Category : Matériaux
The increasing importance of renewable energy sources like sunlight and wind power connected to
the electrical grid has trigged the necessity of low cost energy storage systems. In this context,
sodium aqueous electrolyte ion-batteries constitute a new promising technology, which reduces the
cost, risk and environmental impact compared to other battery technologies. Today, the
performances of these batteries are limited however, by low capacity negative electrodes. To
address this issue, the electrochemical and physical behavior of several n and p type derivatives have
been investigated in neutral Li, Na, K and Mg aqueous supporting electrolytes. The long term
cyclability of diimide compounds involves close to one electron leading to high capacity values
(approx. 90-100 mAh/g) at low voltage. Very interestingly, electrochemical activity shows singular
features that unraveled a solid state disproportional mechanism favors by the instability of the
radical anion. Conversely, the extent of this reaction can be modulated according to the polarizability
of the counter cation or the extent of the conjugated backbone. Results also enable to rationalize the
capacity retention and the self-discharge mechanisms of these materials based on both
morphological and side reaction considerations. Our work also relates to soluble n type derivatives.
Thanks to pi-staking interactions on a carbon based electrode such materials can be reversibly cycled
in the adsorbed state at low potential. The electrochemical behavior as well as the long term stability
on cycling will be presented.
Funding and acknowledgement : CNRS, Région Pays de la Loire (Greenhope project).