Macromolecular Structure and Vibrational Dynamics of Confined Poly(ethylene oxide): From Subnanometer 2D-Intercalation into Graphite Oxide to Surface Adsorption onto Graphene Sheets

Barroso‐Bujans, Fabienne; Fernandez-Alonso, Félix; Pomposo, José A.; Cerveny, Silvina; Alegría, Ángel; Colmenero, Juan

doi:10.1021/mz3001012

Cited by 41 publications

(58 citation statements)

References 23 publications

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“…Additionally, dielectric spectroscopy measurements show that the segmental motions become very fast and display an Arrhenius temperature dependence going through the bulk polymer T g . Similar results have recently been reported 130,131 for PEO intercalated into subnanometer graphite oxide (GO) layers. The segmental dynamics of poly(hexa(ethylene glycol) methacrylate) intercalated in a layered silicate (hydrophilic sodium montmorillonite)(Na + -MMT) has also been investigated by BS by Fotiadou et al 51 Figure 7 taken from the original publication 51 shows as an example the incoherent structure factor measured in the bulk polymer and in the intercalated polymer at a Q-value of 1.3 Å −1 and at different temperatures.…”

Section: Confinement In Polymer Systemssupporting

confidence: 86%

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Recent progress on polymer dynamics by neutron scattering: From simple polymers to complex materials

Colmenero

Arbe

2012

J Polym Sci B Polym Phys

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ABSTRACT:The recent (from 2010 onward) contributions of quasielastic neutron scattering techniques (time of flight, backscattering, and neutron spin echo) to the characterization and understanding of dynamical processes in soft materials based on polymers are analyzed. The selectivity provided by the combination of neutron scattering and isotopic-in particular, proton/deuterium-labeling allows the isolated study of chosen molecular groups and/or components in a system. This opportunity, together with the capability of neutrons to provide space/time resolution at the relevant length scales in soft matter, allows unraveling the nature of the large variety of molecular motions taking place in materials of increasing complexity. As a result, recent relevant works can be found dealing with dynamical process which associated characteristic lengths and nature are as diverse as, for example, phenyl motions in a glassy linear homopolymer like polystyrene and the chain dynamics of a polymer adsorbed on dispersed clay platelets. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 51: 2013 KEYWORDS: molecular dynamics; neutron scattering; relaxation POLYMER DYNAMICS AT DIFFERENT LENGTH AND TIME SCALES: FROM SIMPLE POLYMERS TO COMPLEX MATERIALSPolymers are composed of macromolecules which are built up by a large number N of monomer units linked together by covalent bonds. Because of this macromolecular nature, the structural and dynamic properties of polymeric systems strongly depend on a hierarchy of length and time scales. From a structural point of view, the random coil shape of linear polymer chains in the melt and glassy state-proposed by Flory in the 50s 1 -is nowadays well established by small angle neutron diffraction (SANS). At smaller length scales than those characteristic for the chain dimensions, the local arrangements of the atoms give rise to broad maxima in the static structure factor S(Q) also accessible by neutron diffraction. Usually, a first main peak centered at Q-values ≈ 1 . . . 1.5 Å −1 is present. The T-dependence of this maximum, following the expansion coefficient, indicates an interchain origin, that is, it mainly relates to correlations between atoms belonging to different chains (or to the same chain but well separated segments).2 A second peak located at ∼3 Å −1can also be usually found in S(Q). The small value of the associated characteristic length and its weak T-dependence indicate the intrachain nature of the correlations giving rise to this maximum. We also note that the broadening of the Bragg peaks found in polymers reveals a clear amorphous character. In fact, the features shown in S(Q) in polymeric systems are universal for amorphous materials, not only for polymers, and in particular for glass forming systems. Thus, a universal behavior common for all glass forming materials can also be expected in the dynamics, including the observation of the glass transition phenomenon. 3As anticipated, the complexity of amorphous polymers shows up not only in the structural propertie...

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Section: Confinement In Polymer Systemssupporting

confidence: 86%

“…130,131 By means of this technique, the vibrational density of states of intercalated PEO was determined, which strongly differs from that corresponding to bulk PEO (see Fig. 8).…”

Section: Confinement In Polymer Systemsmentioning

confidence: 99%

Recent progress on polymer dynamics by neutron scattering: From simple polymers to complex materials

Colmenero

Arbe

2012

J Polym Sci B Polym Phys

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“…11 Isothermal TGA data for PEO/G and neat PEO were fitted to a first-order reaction function, f(α)=(1-α) n , n = 1. The temperature dependence of the rate constants obtained from the fitting follows the Arrhenius equation (Figure 8b), in which it is apparent that the Ea for the thermal degradation of PEO adsorbed on G (28 kcal/mol) is considerably lower than that for neat PEO (48 kcal/mol).…”

Section: Kinetics Of the Thermal Decomposition Of Peo Adsorbed On Gramentioning

confidence: 99%

“…27 In our case, XRD results suggest that the arrangement of polymers containing side groups in the GO interlayer is completely different from that of PEO, which is known to adopt a planar zig-zag conformation. [9][10][11] Figure 9: XRD of compounds of GO and PVME, PVA, PAA and PVP. XRD data of the PEO/GO intercalation compound and pristine GO are also shown.…”

Section: Hydrophilic Polymers With Side Groupsmentioning

confidence: 99%

“…PEO intercalates into the GO interlayer space, giving rise to a single molecular layer of thickness 3.0-3.4 Å. [9][10][11] Its concentration in the intercalate phase amounts to 22 ±2 wt% of the total PEO/GO mass. Neither the interlayer spacing nor the amount of PEO depends strongly on polymer chain length, a strong indication that the oligomer and polymer chains are forced to adopt a planar conformation in a monolayer arrangement, i.e., well-defined and extreme 2D confinement.…”

Section: Introductionmentioning

confidence: 99%

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Thermal Stability of Polymers Confined in Graphite Oxide

et al. 2013

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In this study, polymer-graphite oxide (GO) interactions are demonstrated to induce thermal instability in both the polymer and GO phase in conditions of maximum polymer uptake, in which the polymer chains are either intercalated into the GO interlayer or adsorbed on the GO sheets. We investigate the thermal stability of poly(ethylene oxide) (PEO) intercalated in GO (PEO/GO) in detail, using a combination of techniques including X-ray diffraction (XRD), thermogravimetry (TGA) and TGA-Mass Spectroscopy (TGA-MS) in dynamic (nonisothermal) and static (isothermal) modes. Our results show that intercalated PEO decomposes at 160 • C lower than neat PEO, and that GO decomposes at 50 • C lower than pristine GO, due to a synergistic instability between GO and intercalated PEO upon heating. Other hydrophilic polymers-such as poly(vinyl methyl ether) (PVME), poly(vinyl alcohol) (PAA), poly(vinyl pyrrolidone) (PVP) and poly(acrylic acid) (PAA)-forming polymer-adsorbed GO structures are also observed to decompose at noticeably lower temperatures than either pristine GO or their own corresponding neat polymers. Unlike PEO/GO intercalation compounds, the excess of PEO phase in PEO-GO composites decomposes at temperatures close to that of neat PEO, which demonstrates that those polymer chains far from the adsorbing GO surface are not significantly affected by the presence of GO sheets. Furthermore, isothermal TGA data for PEO/GO intercalation compounds with PEO chains from 5 to 2135 monomeric units are well described by an autocatalytic model similar to that we found for pristine GO in a previous study, which suggests that the overall decomposition of PEO/GO is dominated by the reduction and exfoliation of GO. However, when PEO is adsorbed on graphene substrate, which is thermally stable at the studied temperatures, the kinetic mechanisms follow a first-order reaction similar to neat PEO, but the decomposition occurs with a considerably lower activation energy.

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Significantly enhanced the properties of PE/GO composites with segregated structures via two‐step compound

Cao

Ren

Xin

et al. 2021

J of Applied Polymer Sci

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Conductive polymer composites (CPCs) have generated significant academic and industrial interest due to the wide applications in anti‐static materials, electromagnetic interface, sensor, and conductors. Nonetheless, the CPCs fabricated by conventional melt‐mixing applied to the scalable production generally have a very high percolation threshold, which always suffer from the various draw backs such as, high melt viscosities, low economic affordability, inferior mechanical properties, and solution compounding by reducing the viscosity improves the uniformity of nano‐particles. This work aims at building a segregated structure in polyethylene to enhance mechanical properties and electrical conductivity, by taking advantage of the solution compounding and melt‐blending methods. Based on the segregated structure, the composites showed the enhanced mechanical properties, thermal stabilities and antistatic properties with a low percolation threshold. In addition, the composite mechanism between graphene oxide and polyethylene and the structure‐performance relationship of the CPCs were elucidated and explored by SEM, TEM, and FTIR.

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Macromolecular Structure and Vibrational Dynamics of Confined Poly(ethylene oxide): From Subnanometer 2D-Intercalation into Graphite Oxide to Surface Adsorption onto Graphene Sheets

Cited by 41 publications

References 23 publications

Recent progress on polymer dynamics by neutron scattering: From simple polymers to complex materials

Recent progress on polymer dynamics by neutron scattering: From simple polymers to complex materials

Thermal Stability of Polymers Confined in Graphite Oxide

Significantly enhanced the properties of PE/GO composites with segregated structures via two‐step compound

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