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ABSTRACT: This paper presents a study of the polymer-filler interfacial effects on
filler dispersion and mechanical reinforcement in Polystyrene (PS) / silica
nanocomposites by direct comparison of two model systems: un-grafted and
PS-grafted silica dispersed in PS matrix. The structure of nanoparticles has
been investigated by combining Small Angle Neutron Scattering (SANS)
measurements and Transmission Electronic Microscopic (TEM) images. The
mechanical properties were studied over a wide range of deformation by
plate/plate rheology and uni-axial stretching. At low silica volume fraction,
the particles arrange, for both systems, in small finite size non-connected
aggregates and the materials exhibit a solid-like behavior independent of the
local polymer/fillers interactions suggesting that reinforcement is dominated
by additional long range effects. At high silica volume fraction, a continuous
connected network is created leading to a fast increase of reinforcement whose
amplitude is then directly dependent on the strength of the local
particle/particle interactions and lower with grafting likely due to
deformation of grafted polymer.
07/2011;
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ABSTRACT: Complementary neutron and X-ray small angle scattering results give prominent information on the asphaltene nanostructure. Precise SANS and SAXS measurements on a large q-scale were performed on the same dilute asphaltene–toluene solution, and absolute intensity scaling was carried out. Direct comparison of neutron and X-ray spectra enables description of a fractal organization made from the aggregation of small entities of 16 kDa, exhibiting an internal fine structure. Neutron contrast variation experiments enhance the description of this nanoaggregate in terms of core–shell disk organization, giving insight into core and shell dimensions and chemical compositions. The nanoaggregates are best described by a disk of total radius 32 Å with 30% polydispersity and a height of 6.7 Å. Composition and density calculations show that the core is a dense and aromatic structure, contrary to the shell, which is highly aliphatic. These results show a good agreement with the general view of the Yen model (Yen, T. F.; et al. Anal. Chem.1961, 33, 1587–1594) and as for the modified Yen model (Mullins, O. C. Energy Fuels2010, 24, 2179–2207), provide characteristic dimensions of the asphaltene nanoaggregate in good solvent.
The Journal of Physical Chemistry B 05/2011; 15(21):6827–6837. · 3.70 Impact Factor
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ABSTRACT: A short introduction to soft condensed matter (polymers, colloids,
surfactants) is presented, with particular emphasis to recent progres and
applications of small angle scattering. The text is in French.
02/2011;
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ABSTRACT: We investigate the dispersion mechanisms of nanocomposites made of well-defined polymer (polystyrene, PS) grafted-nanoparticles (silica) mixed with free chains of the same polymer using a combination of scattering (SAXS/USAXS) and imaging (TEM) techniques. We show that the relevant parameter of the dispersion, the grafted/free chains mass ratio R tuned with specific synthesis process, enables to manage the arrangement of the grafted nanoparticles inside the matrix either as large and compact aggregates (R < 0.24) or as individual nanoparticles dispersion (R > 0.24). From the analysis of the interparticles structure factor, we can extract the thickness of the spherical corona of grafted brushes and correlate it with the dispersion: aggregation of the particles is associated with a significant collapse of the grafted chains, in agreement with the theoretical models describing the free energy as a combination of a mixing entropy term between the free and the grafted chains and an elastic term of deformation of the grafted brushes. At fixed grafting density, the individual dispersion of particles below the theoretical limit of R = 1 can be observed, due to interdiffusion between the grafted and the free chains but also to processing kinetics effects, surface curvature and chains poly dispersity. Mechanical analysis of nanocomposites show the appearance of a longer relaxation time at low frequencies, more pronounced in the aggregated case even without direct connectivity between the aggregates. Correlation between the local structure and the rheological behavior suggests that the macroscopic elastic modulus of the nanocomposite could be described mainly by a short-range contribution, at the scale of the interactions between grafted particles, without significant effect of larger scale organizations.
12/2010;
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ABSTRACT: The effect of silica nanoparticles on transient microemulsion networks made of microemulsion droplets and telechelic copolymer molecules in water is studied, as a function of droplet size and concentration, amount of copolymer, and nanoparticle volume fraction. The phase diagram is found to be affected, and in particular the percolation threshold characterized by rheology is shifted upon addition of nanoparticles, suggesting participation of the particles in the network. This leads to a peculiar reinforcement behaviour of such microemulsion nanocomposites, the silica influencing both the modulus and the relaxation time. The reinforcement is modelled based on nanoparticles connected to the network via droplet adsorption. Contrast-variation Small Angle Neutron Scattering coupled to a reverse Monte Carlo approach is used to analyse the microstructure. The rather surprising intensity curves are shown to be in good agreement with the adsorption of droplets on the nanoparticle surface.
12/2010;
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ABSTRACT: We studied by small-angle neutron scattering (SANS) the polymer chain conformation in model silica/polystyrene (PS) nanocomposites. Using the zero average contrast method, we can properly match silica signal to directly measure the form factor of a single PS chain. An important effort has been put to eliminate the silica scattering using two distinct approaches (called respectively “three” and “four” components methods) leading to analogue results. By combining SANS data with small-angle X-ray scattering (SAXS) measurements and transmission electronic microscopy (TEM) images on the same samples, we obtain a very clear result about the effect on polymer chain conformation of the filler dispersion, either at low filler volume fraction, where silica arrange in small aggregates or at higher concentration where it forms a connected network. From SANS the chain conformation in nanocomposites is identical to the one without silica in a large q range illustrating that the chain conformation remains independent of the filler dispersion whatever the silica connectivity or the polymer molecular weight. This result opens the way to a better overview of the polymer chain conformation contribution, especially adsorption or chain mobility modification effects, in the complex mechanical reinforcement mechanisms of nanocomposites. However, at low q, an unexpected shoulder appears in the SANS curves: this effect does not vary in a systematic way neither with chain molecular weight nor with silica concentration. The non reproducibility of these observations could be related to unusual phase separation between normal and deuterated chains.
11/2010;
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ABSTRACT: In this paper we present a direct measurement of stretched chain conformation in polymer nanocomposites in a large range of deformation using a specific contrast-matched small angle neutron scatttering (SANS) method. Whatever are the filler structure and the chain length the results show a clear identity of chain deformation in pure and reinforced polymer and offer more insight on the polymer chain contribution in the mechanical reinforcement. It suggests that glassy layer or glassy paths, recently proposed, should involve only a small fraction of chains. As a result, the remaining filler contribution appears strikingly constant with deformation as explained by continuous locking-unlocking rearrangement process of the particles.
Physical Review E 09/2010; 82(3 Pt 1):031801. · 2.26 Impact Factor
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ABSTRACT: We present a new convenient and efficient "grafting from" method to obtain well defined polystyrene (PS) silica nanoparticles. The method, based on Nitroxide-Mediated Polymerization (NMP), consists to bind covalently the alkoxyamine, which acts as initiator controller agent, at the silica nanoparticles surface in two steps. The first step is a reaction between the aminopropylsilane and the silica particles in order to functionalize the particles surface with amino group. In a second step, the initiating-controlling alkoxyamine moiety is introduced via an over grafting reaction between the amino group and the N-hydroxysuccinimide based MAMA-SG1 activated ester. To simplify both their chemical transformation and the polymerization step, the native silica particles, initially dispersed in water, have been transferred in an organic solvent, the dimethylacetamide, which is also a good solvent for the polystyrene. The synthesis parameters have been optimized for grafting density, conversion rates, and synthesis reproducibility while keeping the colloidal stability and to avoid any aggregation of silica particles induced by the inter-particles interaction evolution during the synthesis. After synthesis, the final grafted objects have been purified and the non-grafted polymer chains formed in the solvent have been washed out by ultra filtration. Then the particles have been studied using Small angle Neutron Scattering (SANS) coupled to neutron contrast variation method. To optimize the contrast conditions, both hydrogenated and deuterated monomers have been used for the synthesis. A refined fitting analysis based on the comparison on two models, a basic core-shell and the Gaussian Pedersen model, enables us to fit nicely the experimental data for both the hydrogenated and deuterated grafted case. Differences are seen between grafting of normal or deuterated chains which can be due to monomer reactivity or to neutron contrast effect variations. The synthesis and the characterization method established in this work constitute a robust and reproducible way to design well defined grafted polymer nanoparticles. These objects will be incorporated in polymer matrices in a further step to create Nanocomposites for polymer reinforcement.
05/2010;
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ABSTRACT: We present here a study of the adsorption of asphaltenes on hydrophilic and hydrophobic solid surfaces by coupling measurements of adsorption isotherms on the macroscopic scale on silica powder with measurements of the structure of the adsorbed asphaltene layer on the microscopic scale obtained by neutron reflectivity on flat silicon wafers. Under good-solvent conditions, if adsorption isotherms reveal that the interaction potential between asphaltenes and the surface is slightly higher for the hydrophilic surface than for the hydrophobic one, then the mechanism of adsorption is similar in both cases because all samples exhibit the same local structure of the adsorbed asphaltene layer: it is a solvated monolayer with thickness of the same order of magnitude as the size of the asphaltene aggregates in the bulk. The surface excess, gamma, is thus always of the same order (approximately 3 mg/m2). The adsorption process induces a densification of the aggregates at the interface because the adsorbed monolayer is much less solvated than aggregates in bulk solution. When a bad solvent is progressively added, the asphaltene adsorbed layer keeps its monolayer structure as long as the bulk flocculation threshold is not reached. Above the threshold, the size of the asphaltene adsorbed layer grows and forms a multilayer structure.
Langmuir 05/2009; 25(7):3991-8. · 4.19 Impact Factor
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ABSTRACT: We are presenting a new method of processing polystyrene-silica nanocomposites, which results in a very well-defined dispersion of small primary aggregates (assembly of 15 nanoparticles of 10 nm diameter) in the matrix. The process is based on a high boiling point solvent, in which the nanoparticles are well dispersed, and controlled evaporation. The filler's fine network structure is determined over a wide range of sizes, using a combination of Small Angle Neutron Scattering (SANS) and Transmission Electronic Microscopy (TEM). The mechanical response of the nanocomposite material is investigated both for small (ARES oscillatory shear and Dynamical Mechanical Analysis) and large deformations (uniaxial traction), as a function of the concentration of the particles. We can investigate the structure-property correlations for the two main reinforcement effects: the filler network contribution, and a filler-polymer matrix effect. Above a silica volume fraction threshold, we see a divergence of the modulus correlated to the build up of a connected network. Below the threshold, we obtain a new additional elastic contribution of much longer terminal time than the matrix. Since aggregates are separated by at least 60 nm, this new filler-matrix contribution cannot be described solely with the concept of glassy layer (2nm).
05/2009;
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ABSTRACT: We present here a study of the adsorption of asphaltenes on hydrophilic and hydrophobic solid surfaces by coupling measurements of adsorption isotherms on the macroscopic scale on silica powder with measurements of the structure of the adsorbed asphaltene layer on the microscopic scale obtained by neutron reflectivity on flat silicon wafers. Under good-solvent conditions, if adsorption isotherms reveal that the interaction potential between asphaltenes and the surface is slightly higher for the hydrophilic surface than for the hydrophobic one, then the mechanism of adsorption is similar in both cases because all samples exhibit the same local structure of the adsorbed asphaltene layer: it is a solvated monolayer with thickness of the same order of magnitude as the size of the asphaltene aggregates in the bulk. The surface excess, Gamma, is thus always of the same order ( approximately 3 mg/m(2)). The adsorption process induces a densification of the aggregates at the interface because the adsorbed monolayer is much less solvated than aggregates in bulk solution. When a bad solvent is progressively added, the asphaltene adsorbed layer keeps its monolayer structure as long as the bulk flocculation threshold is not reached. Above the threshold, the size of the asphaltene adsorbed layer grows and forms a multilayer structure.
Langmuir 02/2009; · 4.19 Impact Factor
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ABSTRACT: We present a new material which displays anisotropic and mechanical properties tuneable during synthesis under magnetic field. It is formulated by mixing aqueous suspensions of polymer nanolatex and magnetic nanoparticles, coated by a thin silica layer to improve their compatibility with the polymeric matrix, followed by casting. The magnetic properties of these nanoparticles enable their pre-orientation in the resulting nanocomposite when cast under magnetic field. Detailed insight on dispersion by Small Angle Neutron Scattering (SANS) shows chainlike nanoparticle aggregates aligned by the field on the nanometer scale. Applying strain to the nanocomposite parallel to the particle chains shows higher mechanical reinforcement, than when strain is transverse to field. . SANS from strained samples shows that strain parallel to the field induce an organization of the chains while strain perpendicular to the field destroys the chain field-induced ordering. Thus improved mechanical reinforcement is obtained from anisotropic interconnection of nanoparticle aggregates.
Advanced Materials 06/2008; 20(13):2533 - 2540. · 13.88 Impact Factor
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ABSTRACT: We have developed a specific protocol to study with SANS measurements, the structure of the interfacial film layer in water-in-oil emulsions stabilized by asphaltene. Using the contrast matching technique available for neutron scattering, we have access to both the composition and the quantity of interface. The results obtained give us a view of the asphaltene aggregates in the interfacial film, which are structured as a monolayer and show a direct correlation between the size of asphaltene aggregates in solution and the thickness of the film layer. The organization of the interface has been studied as a function of several parameters such as the quantity of resins, i.e., the size of aggregates, the pH of the aqueous phase, and the aging time of the emulsions and the consequences of these variations on the macroscopic stability of these emulsions. We show that the key parameter for the stability is the inter-asphaltene aggregate interaction inside the film layer. Changing the attractive/repulsive balance between the aggregates in the film at the microscopic scale, by changing the aggregate's size or the aggregate's ionization, has a direct incidence on the quantity of water recovered after centrifugation: the stronger the attraction between aggregates in the film, the more stable the emulsion is.
Langmuir 11/2007; 23(21):10471-8. · 4.19 Impact Factor
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ABSTRACT: Polymer chains are grafted from silica nanobeads. The method consists in grafting first the initiator molecules on the silica surface. Then, the polymerization of styrene or n-butyl methacrylate using Atom Transfer Radical Polymerization, is conducted. The nanoparticles are kept in solution during the whole process to avoid irreversible aggregation. The state of dispersion of the grafted silica nanoparticles is followed by Small Angle Neutron Scattering, as well as the quantity and the spatial organisation of the polymer. This is done during the functionalisation and the polymerization, but also after purification where free polymer chains are eliminated. This permits to reach a quantitative level of SANS analysis from these purified particles, which is compared to chemical data given by Size Exclusion Chromatography and Thermogravimetric analysis.
Macromolecular Symposia 06/2005; 226(1):263 - 278.
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ABSTRACT: A study of the reinforcement effect of a soft polymer matrix by hard nanometric filler particles is presented. In the main part of this article, the structure of the silica filler in the matrix is studied by small angle neutron scattering (SANS), and stress–strain isotherms are measured to characterize the rheological properties of the composites. Our analysis allows us to quantify the degree of aggregation of the silica in the matrix, which is studied as a function of pH (4–10), silica volume fraction (3–15%) and silica bead size (average radius 78 and 96 Å). Rheological properties of the samples are represented in terms of the strain-dependent reinforcement factor, which highlights the contribution of the filler. Combining the structural information with a quantitative analysis of the reinforcement factor, the aggregate size and compacity (10–40%) as a function of volume fraction and pH can be deduced.In a second, more explorative study, the grafting of polymer chains on nanosilica beads for future reinforcement applications is followed by SANS. The structure of the silica and the polymer are measured separately by contrast variation, using deuterated material. The aggregation of the silica beads in solution is found to decrease during polymerization, reaching a rather low final aggregation number (less than ten).
Polymer. 01/2005;
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ABSTRACT: A short introduction to soft condensed matter (polymers, colloids, surfactants) is presented, with particular emphasis to recent progres and applications of small angle scattering. The text is in French.
Neutrons et matière molle.
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ABSTRACT: The present communication reports the first direct measurement of the conformation of a polymer corona grafted around silica nano-particles dispersed inside a nanocomposite, a matrix of the same polymer. This measurement constitutes an experimental breakthrough based on a refined combination of chemical synthesis, which permits to match the contribution of the neutron silica signal inside the composite, and the use of complementary scattering methods SANS and SAXS to extract the grafted polymer layer form factor from the inter-particles silica structure factor. The modelization of the signal of the grafted polymer on nanoparticles inside the matrix and the direct comparison with the form factor of the same particles in solution show a clear-cut change of the polymer conformation from bulk to the nanocomposite: a transition from a stretched and swollen form in solution to a Gaussian conformation in the matrix followed with a compression of a factor two of the grafted corona. In the probed range, increasing the interactions between the grafted particles (by increasing the particle volume fraction) or between the grafted and the free matrix chains (decreasing the grafted-free chain length ratio) does not influence the amplitude of the grafted brush compression. This is the first direct observation of the wet-to-dry conformational transition theoretically expected to minimize the free energy of swelling of grafted chains in interaction with free matrix chains, illustrating the competition between the mixing entropy of grafted and free chains, and the elastic deformation of the grafted chains. In addition to the experimental validation of the theoretical prediction, this result constitutes a new insight for the nderstanding of the general problem of dispersion of nanoparticles inside a polymer matrix for the design of new nanocomposites materials.
Macromolecules.
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ABSTRACT: Wepresent here the synthesis and structural characterization of new nanocomposites made of spherical magnetic nanoparticles of maghemite (γ-Fe2O3) dispersed in a polystyrene (PS) matrix. The γ-Fe2O3 nanoparticles, synthesized in aqueous media, were first gently transferred by dialysis in dimethylacetamide (DMAc), a polar solvent which is a good solvent for PS. Electrostatic repulsions enable to keep colloidal stability in DMAc. The nanocomposites were then processed by a controlled evaporation of DMAc of binary mixtures of γ-Fe2O3 nanoparticles and PS chains. The size of the nanoparticles ranges from 3.5 to 6.5 nm and can be changed without any modification of the nanoparticles' surface. The structural organization of the nanoparticles inside the polymer was determined as a function of the nanoparticles' size. It was performed by combining very high resolution SAXS measurements which permit to decrease the nanoparticles content down to very low values (Φmag ∼ 10-5) and TEM microscopy. Whatever the size, the nanoparticles are organized with a hierarchical structure that shows that their aggregation has been driven by a two-step process. At low spatial scale, dense primary aggregates composed of some tens of nanoparticles are formed whatever Φmag, resulting from the first aggregation step. For Φmag>10-4, these primary aggregates underwent a second aggregation step and are organized at larger scale in fractal aggregates of finite size of ∼200 nm of radius, with a dimension of 1.7. The size of the dense primary aggregates is almost constant when changing the nanoparticles radius; i.e., the mean aggregation number of primary aggregates decreases with an increase of the radius.
Macromolecules / J Macromolecules.
