We study the intrinsic Raman signatures of single layer graphene (SLG) dispersed in degassed water without additives, so called ‘‘eau de graphene” (EdG) and compare them to those of suspended SLG. The Raman signatures of SLG superimpose to those of water. The most characteristic signature of SLG in EdG is a narrow and symmetric 2D band with a width depending on processing conditions. The position of the G and 2D bands indicate moderate biaxial compressive strain and weak n doping. The intensity of the D band and the width of the G band are discussed in terms of point-defect density and flake size. We show that point defects can be easily cured by preparing thin films from EdG and annealing at 800°C.

Curing kinetics of an industrially important printedcircuitboard (PCB) base material (epoxy–phenol/glass fillers)were studied by isothermal differential scanning calorimetry(DSC) measurements between 150 and 190°C, as relevant curingtemperatures for the PCB industry. The extent of cure was calculatedby integration of the exothermic peak and normalizationby the total heat of reaction (obtained by nonisothermal DSC).Although the cross-linking was completed above 180°C, thekinetic profiles show two regimes: one fast and one slow. Thekinetic parameters have been elucidated using an isoconversionalmodel-free kinetic method, with the exact method of Friedman,to give to the PCB manufacturers a road map to predict curingbehavior of base material. The linearity of Arrhenius plots wassatisfactory. The apparent activation energy of curing reactionhas been found to increase with the degree of conversion. Theelucidation of the kinetic parameters allows us to propose anaccurate and predictive description of the curing kinetics withinthe fast regimen of reaction (i.e., without vitrification). Finally,we discuss how these kinetic measurements and models can becompleted and optimized.

Liquid crystal ordering is an opportunity to develop novel materials and applications with spontaneouslyaligned anisotropic particles [1,2]. In this way, the organization of graphene flakes in liquid crystals provides new methodologies for the still challenging structural characterization of such materials. In this work, we will present a review of our recent results in the preparation and characterization of lyotropic LC made from concentrated aqueous suspensions based graphene oxide (GO) and/or reduced graphene oxide (RGO), and we will show some of ours preliminary approaches to achieve large and well-ordered domains of lyotropic liquid crystals. According with literature, for graphene, it is known that GO flakes easily disperse in water and spontaneously form liquid crystals at high concentrations. However, most of their electronic functionalities are lost during the oxidation treatments. RGO is of greater interest since a large part of functionalities are recovered but chemical reduction of GO in water generally results in the aggregation of the flakes. We recently showed how to obtain water-based RGO liquid crystals stabilized by surfactant molecules [3]. Structural and thermodynamic characterizations provide statistical information on the dimensions of the graphene flakes, which are found to be comparable with those of neat graphene oxide flakes. We have started to combined these new liquid crystals with nanoparticles, these graphene-based LC/Nanoparticles composites being useful to design coatings and functional materials.
References
[1] Yuan J.; Luna A.; Neri W.; Zakri C.; Schilling T.; Colin A.; Poulin, P. Graphene liquid crystal retardedpercolation for new high-k materials. Nat. Commun. 6:8700 (2015) doi: 10.1038/ncomms9700
[2] Zakri, C.; Blanc, C.; Grelet, E.; Zamora-Ledezma, C.; Puech, N.; Anglaret, E.; and Poulin, P. Liquid crystals ofcarbon nanotubes and graphene. Phil. Trans. R. Soc. A., 371, 20120499, pp 1-15 (2013)
[3] Zamora-Ledezma, C.; Puech, N.; Zakri, C.; Grelet, E.; Moulton, S. E.; Wallace, G. G.; Gambhir, S.; Blanc, C.;Anglaret, E.; and Poulin, P. Liquid Crystallinity and Dimensions of Surfactant-Stabilized Sheets of ReducedGraphene Oxide. J. Phys. Chem. Lett., 3 (17), pp 2425–2430 (2012)

Processing routes and characterization methods commonly used in carbon nanotubes research require agood dispersion of nanotubes in liquid media. In particular, single walled carbon nanotubes (SWNT) mustbe dispersed, preferably as individuals in order to tap their full potential in optical applications [1]. Onesensitive probe of dispersion is photoluminescence (PL), since it is quenched as long as semiconductingSWNT are bundled with metallic ones. However, the detailed interpretation of the mechanismsresponsible for PL and the relation between PL intensity and dispersion state are still a matter ofcontroversy [2].
In this work, we present new insights on the near infrared photoluminescence of aqueous suspensions ofSWNT stabilized by bile salts surfactants. In one hand, the dispersion of the nanotubes is probed byabsorption spectroscopy, where the absorption coefficient shows high sensitivity to nanotube exfoliation.On the other hand, we revisit the interpretation of the NIR-PL spectra, and we discuss the differentphysical mechanisms responsible of the PL, i.e. Direct Excitonic Transitions (DET), Exciton-PhononCoupling (EPC), and Exciton Energy Transfer (EET) between nanotubes [3-7]. Finally, we discuss thekinetics of PL as a function of sonication time and debundling/exfoliation of SWNT (Figure 1).
References
[1] S. M. Bachilo, et al. Science, 298 (2002). pp 2361-2366.
[2] V.C Moore, et al. Nano letters, 3 (2003). pp 1379-1382.
[3] T. Ando, J. Phys. Soc. Jpn, 66(4) (1997). pp. 1066-1073.
[4] J. Maultzsch, et al. PRB, 72(24) (2005). pp. 241402.
[5] F. Wang, et al. Science, 308(5723) 2005. pp. 838-841.
[6] S. Chou, et al. PRL, 94(12) (2005), pp. 127402.
[7] P. Tan, et al. PRL, 99(13) (2007) pp. 137402.

Nous discutons les signatures Raman de nanotubes de carbone monofeuillets (single-wall carbon nanotubes,SWNT) et de feuillets de graphène monofeuillets (single layer graphene, SLG) dispersés dans l’eau (fig. 1) et leurorigine physique. Les encres de SWNT sont stabilisées avec des tensio-actifs. Les études optiques dans le procheinfrarouge permettent de mesurer simultanément le signal Raman et le signal de photoluminescence caractéristiquedes nanotubes dispersés à l’échelle individuelle (fig. 2, gauche). Le signal de PL est sensible à l’environnementdiélectrique des nanotubes et permet d’étudier les interactions avec le tensio-actif [1]. A fortes concentrations, lesSWNT forment des phases cristal liquide et l’étude de la polarisation des signaux Raman/PL conduit à la mesure du paramètre d’ordre orientationnel [2]. Les encres de SWNT peuvent être déposées par jet d’encre, les textures des dépôts et leur conductivité électrique dépendent de la concentration des encres [3].
Des encres de graphène SLG, baptisées ‘‘eau de graphène’’ peuvent être préparées sans tensioactif en dispersant despolyélectrolytes de SLG dans de l’eau dégazée [4]. Les signatures Raman des SLG dispersées dans l’eau sontvoisines de celles des SLG suspendues dans l’air (fig. 2), avec des décalages modérés des bandes principales quisont discutées en terme de dopage et de contraintes mécaniques [5]. Les défauts ponctuels observés sur les SLG dispersées dans l’eau peuvent être facilement éliminés par un recuit des dépôts à 800°C.
References
[1] F. Torres-Cañas et al, J. Phys. Chem. C 119 (2015), pp. 703-709
[2] C. Zamora-Ledezma et al, J. Phys. Chem. C 115 (2011), pp. 3272-3278
[3] F. Torres-Cañas et al, Mat. Res. Exp. 4 (2016)
[4] G. Bepete et al, Nature Chem. 9 (2016), pp. 347-352
[5] G. Bepete et al, J. Phys. Chem. C 120 (2016), pp. 28204-28214

Most of the potential applications in carbon nanotubes and graphene-based composites require suitable methods for making aligned assemblies on a large scale. Liquid crystal ordering is an opportunity to develop such materials and applications [1]. In this talk, we will present a review of our recent results in the preparation and characterization of lyotropic liquid crystals based on concentrated aqueous suspensions, stabilized by surfactants, of single-walled carbon nanotubes (SWNT) or reduced graphene oxide (RGO). In the first part we will focus on anisotropic conductive films, which are prepared by shearing and drying the LC. In particular, we will show how the electrical conductivity anisotropy increases with the orientational order parameter of the nematic liquid crystal. The order parameter can be tuned by controlling the length and entanglement of the nanotubes [1-2]. In the second part we present recent results on the morphology and anisotropy of thin conductive lines of SWCNT, inkjet-printed. Its Their morphology can be tuned from rail track to quasi-continuous lines by increasing nanotube concentration and drop density. The average order parameter is in the range 0.2–0.4 for all samples. The electrical resistivity is larger for rail tracks with respect to continuous layers, due to large amounts of electrical dead-ends in and between the inner edges of rail tracks [4]. Finally we will present how to prepare water-based Graphene Oxide (GO), and Reduced Graphene Oxide (RGO) liquid crystals stabilized by surfactant molecules. We will discuss their structural and thermodynamic characterizations, which provide indirect but statistical information on the organizations and dimensions of the graphene flakes [1-3].
1. C. Zakri et al, Phil. Trans. R. Soc. A. 371 (2013) 201204995(15)
2. Zamora-Ledezma, C. et al. J. Phys. Chem. Lett., 3 (17), pp 2425–2430 (2012)
3. Yuan J. et al. Nat. Commun. 6:8700 doi: 10.1038/ncomms9700 (2015).
4. F. Torres-Canas et al, Mater. Res. Express. DOI: 10.1088/2053-1591/aa5687 (2017)