In this study we investigate the formation of non-covalent electron donor-acceptor (EDA) interactions between polymers and single-walled carbon nanotubes (SWNTs) with the goal of optimizing interfacial adhesion and homogeneity of nanocomposites without modifying the SWNT native surface. Nanocomposites of SWNTs and three sets of polymer matrices with varying composition of electron donating 2-(dimethylamino)ethyl methacrylate (DMAEMA) or electron accepting acrylonitrile (AN) and cyanostyrene (CNSt) were prepared, quantitatively characterized by optical microscopy and Raman spectroscopy (Raman mapping, Raman D* peak shifts) and qualitatively compared through thick film composite visualization. The experimental data show that copolymers with 30 mol% DMAEMA, 45 mol% AN, 23 mol% CNSt and polyacrylonitrile homopolymer have the highest extent of intermolecular interaction, which translates to an optimum SWNT spatial dispersion among the series. These results are found to correlate very well with the intermolecular interaction energies obtained from quantum density functional theory calculations. Both experimental and computational results also illustrate that chain connectivity is critical in controlling the accessibility of the functional groups to form intermolecular interactions. This means that an adequate distance between interacting functional groups on a polymer chain is needed in order to allow efficient intermolecular contact. Thus, controlling the amount of electron donating or withdrawing moieties throughout the polymer chain will direct the extent of EDA interaction, which enables tuning the SWNT dispersion.
Polymer nanocomposites (PNCs) are materials based on a class of filled plastics that contain relatively small amounts of nanoparticles, which can impart improved structural, mechanical, and thermal properties relative to the neat polymer. However, the homogeneous dispersion of the nanoparticles into a polymer matrix is critical and an impeding factor for the controlled enhancement of PNC properties. In this work, we provide new insight into the importance of polymer chain connectivity and nanoparticle shape and curvature on the formation of noncovalent electron donor–acceptor (EDA) interactions between polymers and nanoparticles. This is accomplished by experimentally monitoring the dispersion of nanoparticles in copolymers containing varying amounts of functional moieties that can form noncovalent interactions with carbon nanoparticles with corroboration through density functional calculations. The results show that the presence of a minority of interacting functional groups within a polymer chain leads to an optimum interaction between the polymer and fullerene. Density functional theory calculations that identify the binding energy and geometry of the interaction between the functional monomers and fullerenes correspond very well with the experimental results. Moreover, comparison of these results to similar studies with single-walled carbon nanotubes (SWNT) indicate a distinct difference in the ability of EDA interactions to improve the dispersion of fullerenes relative to their impact on SWNT. Thus, the polymer chain connectivity, the polymer chain conformation, and size and shape of the nanoparticle modulate the formation of intermolecular interactions and directly impact the dispersion of the resultant nanocomposite.
Emulsified acids were traditionally used in acid fracturing, and more recently on matrix treatments of carbonate formations. The delayed nature of emulsified acids is useful in generating longer etched fractures or deeper wormholes. Emulsified acids also have higher viscosities than straight acid, which reduces fluid loss in acid fracturing applications and helps distribute acid more uniformly in formations with high-permeability contrast during matrix treatments. A new emulsified acid system is presented in this paper that is stable up to 350 F, highly retarded, and significantly more viscous than straight acid. Laboratory data comparing emulsified acid with straight acid are presented at temperatures ranging up to 350 F, including rheology and acid conductivity. Field case histories in the Smackover formation in Alabama over two years are presented. The field case histories show the improvements in production of oil and gas resulting from emulsified acid fracturing treatments in comparison with prior similar treatments done with straight acid. P. 391
Emulsified acids were traditionally used in acid fracturing, and more recently on matrix treatments of carbonate formations. The delayed nature of emulsified acids is useful in generating longer etched fractures or deeper wormholes. Emulsified acids also have higher viscosities than straight acid, which reduces fluid loss in acid fracturing applications and helps distribute acid more uniformly in formations with high-permeability contrast during matrix treatments. A new emulsified acid system is presented in this paper that is stable up to 350°F, highly retarded, and significantly more viscous than straight acid. Laboratory data comparing emulsified acid with straight acid are presented at temperatures ranging up to 350°F, including rheology and acid conductivity. Field case histories in the Smackover formation in Alabama over two years are presented. The field case histories show the improvements in production of oil and gas resulting from emulsified acid fracturing treatments in comparison with prior similar treatments done with straight acid.
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