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Hierarchical assembly of hard/soft nanoparticles holds great potential as reinforcements for polymer nanocomposites with tailored properties. Here, we present a facile strategy to integrate polystyrene-grafted carbon nanotubes (PSgCNT) (0.05-0.3 wt %) and poly(styrene-b- [isoprene-ran-epoxyisoprene]-b-styrene) block copolymer (10 wt %) into epoxy coatings using an ultrasound-assisted noncovalent functionalization process. The method leads to cured nanocomposites with core-shell block copolymer (BCP) nanodomains which are associated with carbon nanotubes (CNT) giving rise to CNT-BCP hybrid structures. Nanocomposite energy dissipation and reduced Young's Modulus (E∗) is determined from force-distance curves by atomic force microscopy operating in the PeakForce QNM imaging mode and compared to thermosets modified with BCP and purified carbon nanotubes (pCNT). Remarkably, nanocomposites bearing PSgCNT-BCP conjugates display an increase in energy dissipation of up to 7.1-fold with respect to neat epoxy and 53% more than materials prepared with pCNT and BCP at the same CNT load (0.3 wt %), while reduced Young's Modulus shows no significant change with CNT type and increases up to 25% compared to neat epoxy E∗ at a CNT load of 0.3 wt %. The energy dissipation performance of nanocomposites is also reflected by the lower wear coefficients of materials with PSgCNT and BCP compared to those with pCNT and BCP, as determined by abrasion tests. Furthermore, scanning electron microscopy (SEM) images taken on wear surfaces show that materials incorporating PSgCNT and BCP exhibit much more surface deformation under shear forces in agreement with their higher ability to dissipate more energy before particle release. We propose that the synergistic effect observed in energy dissipation arises from hierarchical assembly of PSgCNT and BCP within the epoxy matrix and provides clues that the CNT-BCP interface has a significant role in the mechanisms of energy dissipation of epoxy coating modified by CNT-BCP conjugates. These findings provide a means to design epoxy-based coatings with high-energy dissipation performance. Fil: Garate, Hernán. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina Fil: Bianchi, Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina Fil: Pietrasanta, Lia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina Fil: Goyanes, Silvia Nair. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina Fil: D`accorso, Norma Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina

Fil: Cambiasso, Javier. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Fisica; Argentina

International audience; Phase separation of thermo-responsive polymers in solution is a complex process, whose understanding is essential to screen and design materials with diverse technological applications. Here we report on a method based on dynamic light scattering (DLS) experiments to investigate the phase separation of thermo-responsive polymer solutions and precisely define the transition temperature (T$_{PS}$). Our results are applied on hydroxypropylcellulose (HPC) solutions as an important biosourced green water-soluble polymer. As determined by DLS, the amplitudes of the fast and slow modes of relaxation dynamics evolve as temperature gets closer to the phase transition point eventually leading to phase separation. The evolution of relaxation modes with temperature is markedly different for concentrations below the overlap concentration (c*) (dilute regime), above c* (semi-dilute regime) and above the entanglement concentration (c$_e$). In the three cases though, the fast and slow mode amplitudes undergo a sharp transition in a narrow temperature range, defining accurately the phase separation locus. The results agree with turbidimetric analysis for the phase transition determination but with a better precision. Our results also show that the one-phase dynamics and phase separation dynamics in the two-phase region are only in continuity for c 4 c e , revealing mechanistic details about the HPC phase separation process. Above T PS we identify a temperature range where the intensity autocorrelation function has a single-exponential shape. In the latter regime, we monitor the growth kinetics of polymer domains and provide clues to rationalize the stabilizing effects of the interfaces leading to the arrested-like phase separation behavior observed for HPC.

We report an investigation of the mechanisms involved in the formation of nanostructured epoxy thermosetting systems using highly epoxidized poly(styrene-b-isoprene-b-styrene) (eSIS) block copolymer at three different stages of the curing process. In the uncured state, polystyrene (PS) blocks self-assembled in sphere-like nanodomains with a short-range order, while epoxidized polyisoprene (ePI) subchains were initially miscible with the epoxy precursors. As the curing reaction proceeded, the PS nanodomains became gradually distorted switching to bigger and less organized structures. This effect is due to reaction-induced microphase separation of ePI subchains which became immiscible with the epoxy system as the curing process occurs. However, this demixing process was partial because of the reaction between ePI subchains and the epoxy matrix, which reduced ePI subchains mobility. Non expulsed ePI fraction increased the epoxy matrix mean glass transition temperature (Tg) in (20−25) °C. Moreover, it was demonstrated that the epoxidation degree of ePI subchains affected the final obtained nanostructured pattern of the thermosetting materials, switching from distorted and interconnected sphere-like nanodomains when the epoxidation degree is 65% to sphere-like nanostructures for 100% of epoxidation. Fil: Garate, Hernán. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; Argentina; Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires; Argentina; Fil: Mondragón, Iñaki. Universidad del País Vasco. Escuela Politecnica. Departamento de Ingeniería Química y Medio Ambiente; España; Fil: D'accorso, Norma Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; Argentina; Fil: Goyanes, Silvia Nair. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires; Argentina

International audience; Herein, a novel polymeric porous membrane was developed, without the use of any organic solvent in the initial dope solution and using a biobased polymer derived from cellulose: Hydroxypropylcellulose (HPC). HPC was dissolved in water (20 wt%) and the phase separation was induced by increasing the temperature above the Lower Critical Solution Temperature (LCST) of the polymer solution, around 40 °C in the concentration range concerned in this study. To fix the membrane morphology and to prevent any resolubilization in water during filtration tests, a chemical crosslinking was performed using Glutaraldehyde. The phase diagram of HPC/water system was first studied and not only the cloud point but also the spinodal curves were determined using optical transmission techniques. It was exhibited that HPC phase diagram is very weakly dependent on concentration up to large concentrations and that the metastable region is very small, i.e. the cloud point and the spinodal curves are very close in a large range of concentration. The membrane stability was tested in water and some organic solvents, thus demonstrating the efficiency of the chemical crosslinking during membrane formation. The swelling and mechanical properties of HPC membranes were also investigated depending on the operating condition during membrane formation, showing that the temperature ramp during the membrane formation, from initial to final temperature, have a significant effect on the crosslinking efficiency and hence on the swelling properties. Finally, adding a porogen (PEG200) into the collodion, filtration tests were performed and exhibited that the membrane filtration properties depend on the temperature ramp as well, showing higher water flux for the highest temperature ramp tested.

In this work we report the covalent functionalization of multiwalled carbon nanotubes (MWCNTs) with polyacrylonitrile (PAN) and polyvinylpyridine (PVP) by the graft from method. Differences in the electronic distribution of both polymers resulted in different interaction between polymers and the nanotubes. It was found that PVP chains wrapped the nanotubes while nanotubes functionalized with PAN presented PAN chains forming amorphous entanglements on the nanoscale linked to the MWCNTs. Differences in the conformation between both polymers and the MWCNTs can be attributed to interactions between the aromatic groups in PVP and the MWCNTs through π–π stacking. The absence of aromatic groups in the case of the PAN chains favours the interaction between them. The functionalization efficiency was characterized using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and UV–vis spectroscopy, while morphological changes were characterized by high resolution transmission electron microscopy.

To be used as templates for nanostructured thermosets, a commercial poly(styrene-b-isoprene-b-styrene) (SIS) block copolymer (BCP) was epoxidized by three different epoxidation procedures. An exhaustive analysis of methodologies using metal catalyzed/hydrogen peroxide, dimethyldioxirane (DMDO), and meta-chloroperbenzoic acid (m-CPBA) was performed to obtain reactive BCPs. The DMDO approach was the best strategy to obtain highly epoxidized SIS BCP (85 mol %) without formation of side products. Careful control in BCP epoxidation by metal catalyzed/hydrogen peroxide and m-CPBA approaches led to a maximum epoxidation degree (ED) of approximately 60 mol % without the formation of side products. The ED by metal catalyzed/hydrogen peroxide strategy could be further increased to 69 mol %, but a significant amount of crosslinking, ring opening, and polymer chain scission reactions were detected by spectroscopic and chromatographic techniques. The miscibility of epoxidized BCPs with diglycidyl ether of bisphenol-A epoxy system before and after curing was analyzed to develop nanostructured epoxy thermosets. For ED higher than 69 mol %, BCPs were miscible, while those with lower ED presented macrophase separation. Highly epoxidized BCPs obtained by the DMDO methodology were successfully used to obtain ordered nanodomains inside the epoxy matrix, as determined by atomic force microscopy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

The synergistic effect of using polystyrene-grafted multi-walled carbon nanotubes (PSgMWCNT) and a surfactant in the dispersion of MWCNT in a self-assembled poly(styrene-b-isoprene-b-styrene) (SIS) block copolymer is reported. The functionalization of MWCNT with polystyrene achieved by the grafting-from approach is not enough to disperse them in the SIS block copolymer. However, a high dispersion of PSgMWCNT in SIS is achieved when dodecanethiol (DT) was added through composite preparation, without affecting the SIS capacity to self-assemble in ordered cylinders. Suspensions of PSgMWCNT without DT and not functionalized MWCNT with DT presented low stability forming aggregates in less than 10 min. On the contrary, the stability of PSgMWCNT suspension in the presence of DT was dramatically enhanced to more than two weeks. This synergistic effect is due to interactions between PSgMWCNT and DT molecules, as proved by UV–Vis spectroscopy.

Controlling nanodomain morphology of nanostructured epoxy thermosets is critical to modulate the mechanical properties of the cross-linked matrix. In this contribution, we demonstrate that this can be achieved by using a suitable block copolymer containing an epoxy soluble block with the ability to react toward the epoxy system during curing. For this purpose we designed an epoxidized poly(styrene-b-isoprene-b-styrene) block copolymer incorporating amine-reactive functionalities (eSIS-AEP) in the epoxidized block as modifier for an epoxy system, which allowed the formation of nanostructured thermosets with controlled spherelike nanodomain morphology. The eSIS-AEP was obtained in two steps from poly(styrene-b-isoprene-b-styrene) (SIS) block copolymer by controlled epoxidation of the olefinic block followed by partial oxirane ring-opening reaction using 1-(2-aminoethyl)piperazine as nucleophile. Before the curing reaction it was observed that poly(styrene) blocks self-assembled to form ordered spherelike nanostructures in blends of eSIS-AEP with epoxy precursors. Since the amine-reactive moiety was incorporated to the block copolymer so that it could react toward diglicidyl ether of bisphenol A (DGEBA) at a similar temperature than the DGEBA/hardener reaction, the epoxy miscible block of eSIS-AEP (ePI-AEP) was able to react with DGEBA during curing. Once the cross-linked network was formed, the initially obtained spherelike nanodomains were preserved, indicating that no reaction-induced microphase separation of ePI-AEP subchains occurred. A completely different scenario was ascertained for epoxidized SIS block copolymer, which conducted to nonspherical nanodomains due to the uncontrolled epoxidized poly(isoprene) demixing process during the curing reaction. These results demonstrate the importance of the epoxy soluble block being reactive toward the epoxy precursors to control the morphology of the obtained nanostructure. Fil: Garate, Hernán. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina Fil: Goyanes, Silvia Nair. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina Fil: D'accorso, Norma Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina