Nanocomposites graphène/polymères : rôle de la viscoélasticité, mise en oeuvre par assemblage forcé, et étude de l’interface

Graphene is an atomically thick, two-dimensional nano-sheet with advanced mechanical, electrical, and thermal properties. As a result, the addition of graphene and graphene derivative nanoparticles to polymer matrices has been a major strategy towards development of new materials in the field of composites. However, from a fundamental point of view, the origins of the advanced properties of graphene-based nanocomposites have been little investigated. In particular, changes in the viscoelastic properties of the polymer matrix due to specific interactions between the polymer and the graphene reinforcing elements can cause higher than expected apparent reinforcement. In addition, there is little work on characterizing the strength of the interface between the graphene used for reinforcement and the polymer matrixes. From a more engineering point of view, the design of polymer nanocomposites made of in-plane oriented graphene to create a two-dimensionally reinforced structure has also not been previously undertaken. The present dissertation is composed of three major works focusing on these problems.The first part focuses on how to use a viscoelastic micromechanics approach to account for the effects of glass transition temperature Tg changes to correct the apparent stiffening of graphene oxide nanocomposites. It is found that graphene oxide stiffens the polymer matrices by increasing the Tg, which significantly modifies their thermo-viscoelasticity. This leads to apparent reinforcements that are not due to the stiffness of the graphene oxide itself, and largely explains anomalously high moduli reported in the literature for such graphene oxide/polymer matrix nanocomposites.The second part focuses on a forced assembly multi-layer co-extrusion method to create films made of alternating layers of neat polymer / oriented graphene nanoplatelet filled polymer. The morphology of the layers (35 ~ 40 nm thick) containing oriented graphene was established by electron microscopy. Mechanical properties of the materials were determined and the two-dimensional stiffening could be related to the oriented graphene nanoplatelets in the layered films. Taking into account the change of Tg, more than 100% intrinsic reinforcement was estimated for 2 wt % of graphene in the nanolayers. The results were analyzed and interpreted via an analytical model based on Mori-Tanaka analysis.The third part focuses on extending a nano-bubble inflation method to the investigation of a novel graphene nano-sandwich with the purpose of investigation of the graphene / polymer interface. At small strains, significant mechanical reinforcement was observed for both graphene-reinforced rubbery and glassy PEMA layers. The interfacial mechanics between graphene and polymer layers was investigated and a “yield-like” interfacial slip was observed in the mechanical response of the nano-sandwich structures.Le graphène est une nanoparticule bidimensionnelle d'épaisseur atomique présentant des propriétés uniques, qu'elles soient mécaniques, électriques ou thermiques. Ceci ajouté à une faible densité et une très grande surface spécifique, fait que l'ajout de graphène et de nanoparticules dérivées (oxyde de graphène, graphite exofilé) pour renforcer des matrices polymères est devenu un sujet d'études d'intérêt majeur dans le domaine des nanocomposites. Cependant, l'influence de la variation de la viscoélasticité de la matrice due à l'ajout de graphène ainsi que la mécanique interfaciale reste aujourd'hui peu étudiée. De plus, il n'existe aujourd'hui pas de procédé permettant d'obtenir des nanocomposites présentant du graphène dans le plan orienté dans une matrice polymère afin de réaliser un renforcement à deux dimensions. Ce travail de thèse est composé principalement de trois projets portant sur ces problèmes.La première partie de ce travail se concentre sur la façon d'utiliser l'approche micromécanique viscoélastiques pour soustraire l'effet de changement de Tg pour corriger la rigidité apparente de nanocomposites d'oxyde de graphène. On a ainsi trouvé que l'oxyde de graphène rigidifie « indirectement » les matrices polymères en augmentant de manière significative la Tg de la matrice, ce qui modifie largement la viscoélasticité du matériau. Le mécanisme de renforcement est ainsi largement causé par cet effet plutôt que du fait de la rigidité de l'oxyde de graphène lui-même.La deuxième partie se concentre sur l'utilisation d'un procédé de mise en œuvre innovant, la coextrusion multinanocouches, ou assemblage forcé, pour créer des films nanocomposites constitués de couches alternées de polymères et de polymères chargés de nanoplaquettes de graphène orientées. Cette orientation est induite par le nanoconfinement imposé par le procédé. La morphologie des couches (35 ~ 40 nm d'épaisseur) contenant du graphène orienté a été étudiée par microscopie électronique. Les propriétés mécaniques des matériaux ont été déterminées et le renforcement bidimensionnel a pu être corrélé à une orientation (imparfaite) des nanoplaquettes de graphène dans les films stratifiés.La troisième partie se concentre sur l'utilisation de la méthode de l'inflation de nano-bulle pour obtenir les réponses mécaniques d'un « nano-sandwich » (nanofilm de polymère / feuille de graphène / nanofilm de polymère). Aux petites déformations, des renforts mécaniques significatifs ont été observées pour le système PEMA / graphène, tant à l'état caoutchouteux qu'à l'état vitreux. Les mécanismes d'interface entre le graphène et les polymères ont été étudiés et un glissement interfacial a été observé

Forced assembly by multilayer coextrusion to create oriented graphene reinforced polymer nanocomposites

A potential advantage of platelet-like nanofillers as nanocomposite reinforcements is the possibility of achieving two-dimensional stiffening through planar orientation of the platelets. The ability to achieve improved properties through in-plane orientation of the platelets is a challenge and, here, we present the first results of using forced assembly to orient graphene nanoplatelets in poly(methyl methacrylate)/ polystyrene (PMMA/PS) and PMMA/PMMA multilayer films produced through multilayer coextrusion. The films exhibited a multilayer structure made of alternating layers of polymer and polymer containing graphene as evidenced by electron microscopy. Significant single layer reinforcement of 118% at a concentration of 2 wt % graphene was achieveddhigher than previously reported reinforcement for randomly dispersed graphene. The large reinforcement is attributed to the planar orientation of the graphene in the individual polymer layers. Anisotropy of the stiffening was also observed and attributed to imperfect planar orientation of the graphene lateral to the extrusion flow

The Study of a Journalism Which Is almost 99% Fake

With the rapid development of the media industry in China, fake news has become a severe problem. This paper identifies four types of fake news, with examples which include totally fake news, distorted fake news, fast news, and sensational journalism. The second part of the paper attempts to analyse the causes of fake news. The acceleration of the trend of media marketization, the loss of professional ethics by media practitioners, the influence of stakeholders, and the marketization of news value in university education, have all given rise to the emergence of fake news. The third part investigates the influence of fake news on society. Fake news can result in inappropriate policy making by the government. With the prevalence of fake news, public media literacy declines and social ethos becomes fickle. Finally, the paper attempts to explore possibly effective countermeasures, which involve establishing a fact-checking mechanism, calling for slow news instead of fast news, improving the public’s media literacy, and reforming the news paradigm, in order to resist fake news in future

Synthesis and Antioxidant Activity of Cationic 1,2,3-Triazole Functionalized Starch Derivatives

In this study, starch was chemically modified to improve its antioxidant activity. Five novel cationic 1,2,3-triazole functionalized starch derivatives were synthesized by using "click" reaction and N-alkylation. A convenient method for pre-azidation of starch was developed. The structures of the derivatives were analyzed using FTIR and H-1 NMR. The radicals scavenging abilities of the derivatives against hydroxyl radicals, DPPH radicals, and superoxide radicals were tested in vitro in order to evaluate their antioxidant activity. Results revealed that all the cationic starch derivatives (2a-2e), as well as the precursor starch derivatives (1a-1e), had significantly improved antioxidant activity compared to native starch. In particular, the scavenging ability of the derivatives against superoxide radicals was extremely strong. The improved antioxidant activity benefited from the enhanced solubility and the added positive charges. The biocompatibility of the cationic derivatives was confirmed by the low hemolytic rate (<2%). The obtained derivatives in this study have great potential as antioxidant materials that can be applied in the fields of food and biomedicine

A low phase noise high power Er-fiber frequency comb synchronized to the hydrogen maser clock by harmonic phase locking

We demonstrate a low phase noise all polarization-maintaining (PM) Er-fiber optical frequency comb (OFC) with low phase noise, which is synchronized to the hydrogen maser clock (HMC) using the 18th harmonic of the repetition rate for tight phase locking. The instability of the locked carrier envelope offset frequency is 1.24 × 10−18@1 s, the phase noise of the OFC is −96 dBc/Hz at 1 Hz offset, and the corresponding RMS timing jitter of the repetition rate is 62 fs (1 Hz–1 MHz). The residual frequency instability of the repetition rate (200 MHz) is 1.46 × 10−14@1 s, and the residual phase noise of the OFC normalized to 10 MHz is −138 dBc/Hz at 1 Hz offset and declines to about −160 dBc/Hz at the far-end, much lower than that of the HMC (−122 dBc/Hz at 1 Hz and −156 dBc/Hz at the far-end)

Polarization-multiplexed dual-comb fiber laser based on an all-polarization-maintaining cavity configuration

In this study, we present a polarization-multiplexed, erbium-doped dual-comb fiber laser based on an all-polarization-maintaining cavity configuration. We observed that the dual-comb fiber laser easily realized the self-starting mode-locking operation due to the non-linear amplifying loop mirror (NALM) with a non-reciprocal phase shifter. Furthermore, owing to the sharing of the NALM part, the two outputs from this laser configuration had similar center wavelengths, with small different repetition rates (∆frep). In the free-running operation, the standard deviation of relative stability for Δfrep of 2.09 kHz was measured to be 1.59 Hz, and the full width at half-maximum of the relative beat note between the two frequency combs in the optical frequency domain was approximately 1 kHz. These results show that the two frequency combs from this laser configuration have high relative stability and mutual coherence