The performance of organic photovoltaic (OPV) material systems are hypothesized to depend strongly on the intermolecular arrangements at the donor:fullerene interfaces. A review of some of the most efficient polymers utilized in polymer:fullerene PV devices, combined with an analysis of reported polymer donor materials wherein the same conjugated backbone was used with varying alkyl substituents, supports this hypothesis. Specifically, the literature shows that higher-performing donor-acceptor type polymers generally have acceptor moieties that are sterically accessible for interactions with the fullerene derivative, whereas the corresponding donor moieties tend to have branched alkyl substituents that sterically hinder interactions with the fullerene. To further explore the idea that the most beneficial polymer:fullerene arrangement involves the fullerene docking with the acceptor moiety, a family of benzo[1,2-b:4,5-b']dithiophene-thieno[3,4-c]pyrrole-4,6-dione polymers (PBDTTPD derivatives) was synthesized and tested in a variety of PV device types with vastly different aggregation states of the polymer. In agreement with our hypothesis, the PBDTTPD derivative with a more sterically accessible acceptor moiety and a more sterically hindered donor moiety shows the highest performance in bulk-heterojunction, bilayer, and low-polymer concentration PV devices where fullerene derivatives serve as the electron-accepting materials. Furthermore, external quantum efficiency measurements of the charge-transfer state and solid-state two-dimensional (2D) (13)C{(1)H} heteronuclear correlation (HETCOR) NMR analyses support that a specific polymer:fullerene arrangement is present for the highest performing PBDTTPD derivative, in which the fullerene is in closer proximity to the acceptor moiety of the polymer. This work demonstrates that the polymer:fullerene arrangement and resulting intermolecular interactions may be key factors in determining the performance of OPV material systems.

We examine the effects of asphaltenes upon the crystallization behavior of a model waxy oil. Yield stress measurements on the model waxy oils with asphaltenes isolated from Shengli crude oil showed that both the relative amount of wax to asphaltenes and the aggregation state of the asphaltenes affected the crystallization properties of the wax. At very low asphaltene concentrations and high wax concentrations, the yield stress of the waxy gel is not significantly affected. At higher asphaltene concentrations, the asphaltenes significantly degraded the microscopic structure of the wax network and drastically reduced the yield stress. There is a threshold ratio of ∼100 paraffin/asphaltene molecules for such behavior. Asphaltenes produced large decreases in yield stress when they were highly aggregated. Oscillatory testing showed that in such cases asphaltene−asphaltene interactions contributed to the gel strength, in addition to the wax platelet interactions. Asphaltenes increased the wax precipitation temperature at high concentrations when large aggregates were present. However, at lower concentrations where the asphaltenes were less aggregated they suppressed precipitation. The aliphatic nature of the Shengli asphaltenes is an important determinant of the observed decrease in precipitation temperature and yield stress.

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The effect of asphaltenes on the effectiveness of wax control polymers was studied using a model waxy oil and a set of polymers with controlled crystalline and polar/aromatic content. The effect of crystalline content was examined with a set of maleic anhydride copolymers with alkyl appendages of different lengths. Different polar and/or aromatic functionalities were incorporated into the maleic anhydride copolymers (MAC) and poly(ethylene butene) polymers to probe potential interactions with the asphaltenes. The performance of the polymers was measured by testing their effect upon precipitation temperature, gelation temperature, and yield stress. Some polymers provided little or no benefit. Others had significant effects, reducing precipitation temperatures up to 1.9 °C, gelation temperatures up to 37 °C, and yield stresses up to 2200-fold for solutions of 8 wt % wax. Polymer efficacy was almost entirely determined by the crystalline functionality incorporated into the polymer rather than the presence of polar functionality designed to target interactions with the asphaltenes. The performance of the polymers is attributed to the ability of the polymers to coprecipitate with the wax. Comparison with previously published results using the same wax showed that the selectivity of the MACs was strongly affected by wax concentration, not because the quantity of wax overwhelmed the polymer, but because the range of wax precipitation temperatures increased above that of the polymer. Comparison of the effect of polymers in solutions with and without asphaltenes showed that asphaltenes had different effects on polymer performance, depending on the property being measured (precipitation temperature, gelation temperature, or yield stress).