Elucidating the assembly of nanoparticle organic hybrid materials (NOHMs) near an electrode interface with varying potential using neutron reflectivity.

A critical concern regarding electrolyte formulation in an electrochemical environment is the impact of the interaction of the multiple components (i.e., supporting electrolyte or additive) with the electrode surface. Recently, liquid-like neat Nanoparticle Organic Hybrid Materials (NOHMs) have been considered as an electrolyte component to improve the transport of redox-active species to the electrode surface. However, the structure and assembly of the NOHMs near the electrode surface is unknown and could significantly impact the electrode-electrolyte interface. Hence, we have investigated the depth profile of polyetheramine (HPE) polymer and NOHM-I-HPE (nanoparticles with ionically bonded HPE polymer) in deuterated water (D2O) in the presence of two different salts (KHCO3 and ZnCl2) near two different electrode surfaces using neutron reflectometry. Moreover, the depth profile of the NOHM-I-HPE near the electrode surface in a potential has also been studied with in situ reflectivity experiments. Our results indicate that a change in the chemical structure/hydrophilicity of the electrode surface does not significantly impact the ordering of HPE polymer or NOHM-I-HPE near the surface. This study also indicates that the NOHM-I-HPE particles form a clear layer near the electrode surface immediately above an adsorbed layer of free polymer on the electrode surface. The addition of salt does not impact the layering of NOHM-I-HPE, though it does alter the conformation of the polymer grafted to the nanoparticle surface and free polymer sequestered near the surface. Finally, the application of negative potential results in an increased amount of free polymer near the electrode surface. Correlating the depth profile of free polymer and NOHM-I-HPE particles with the electrochemical performance indicates that this assembly of free polymer near the electrode surface in NOHM-I-HPE solutions contributes to the higher current density of the system. Therefore, this holistic study offers insight into the importance of the assembly of NOHM-I-HPE electrolyte and free polymer near the electrode surface in an electrochemical milieu on its performance.

Quantitative Evaluation of the Hierarchical Porosity in Polyimide Aerogels and Corresponding Solvated Gels.

Aerogels are promising materials for many aerospace applications, including high-performance antennae and flexible insulation, because of their inherent low density and high surface areas. Polymer aerogels, especially polyimide aerogels, provide excellent mechanical properties beyond traditional silica aerogels while maintaining the required thermal stability. Polyimide aerogel surface area, porosity, and pore volume are important properties; however, these measurements are traditionally conducted on the aerogel after removal of the solvent. Because of this, the impact of synthetic control and solvent presence on the nanoscale to mesoscale structure of polyimide aerogels in functional applications is unclear. In this report, we use small-angle neutron scattering to determine the dry and solvated skeletal strut size and composition of polyimide aerogels to deduce the impact of solvation on the structure of complex aerogel struts. Our results show that the aerogel contains a hierarchical assembly of pores, with pores present both within and between the supporting struts. This translates to a material with solvent in the larger pores, as well as absorbed in the supporting polyimide skeleton. The amount of solvent uptake in the struts varies with the solvent and polyimide properties. The insight from these results provides pathways to determine the correlations between aerogel nano- and mesoscale structural characteristics, fabrication processes, and their performance in functional applications such as polymeric battery separators. These results also broaden the characterization tools of polymeric aerogels that differentiate between dry and solvated nano- and mesoscale structures that exist in common operating conditions.

The interplay of thermodynamics and kinetics: imparting hierarchical control over film formation of self-stratified blends.

Spin casting has become an attractive method to fabricate polymer thin films found in organic electronic devices such as field-effect transistors, and light emitting diodes. Many studies have shown that altering spin casting parameters can improve device performance, which has been directly correlated to the degree of polymer alignment, crystallinity, and morphology of the thin film. To provide a thorough understanding of the balance of thermodynamic and kinetic factors that influence the stratification of polymer blend thin films, we monitor stratified polymer blend thin films developed from poly(3-hexylthiophene-2,5-diyl) and poly(methyl methacrylate) blends at controlled loading ratios, relative molecular weights, and casting speed. The structures of these thin films were characterized via neutron reflectivity, and the results show that at the fastest casting speed, polymer-polymer interactions and surface energy of the polymers in the blend dictate the final film structure, and at the slowest casting speed, there is less control over the film layering due to the polymer-polymer interactions, surface energy, and entropy simultaneously driving stratification. As well, the relative solubility limits of the polymers in the pre-deposition solution play a role in the stratification process at the slowest casting speed. These results broaden the current understanding of the relationship between spin casting conditions and vertical phase separation in polymer blend thin films and provide a foundation for improved rational design of polymer thin film fabrication processes to attain targeted stratification, and thus performance.

Monitoring the Effects of Illumination on the Structure of Conjugated Polymer Gels Using Neutron Scattering.

We demonstrate a protocol to effectively monitor the gelation process of a high concentration solution of conjugated polymer both in the presence and absence of white light exposure. By instituting a controlled temperature ramp, the gelation of these materials can be precisely monitored as they proceed through this structural evolution, which effectively mirrors the conditions experienced during the solution deposition phase of organic electronic device fabrication. Using small angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) along with appropriate fitting protocols we quantify the evolution of select structural parameters throughout this process. Thorough analysis indicates that continued light exposure throughout the gelation process significantly alters the structure of the ultimately formed gel. Specifically, the aggregation process of poly(3-hexylthiophene-2,5-diyl) (P3HT) nano-scale aggregates is negatively affected by the presence of illumination, ultimately resulting in the retardation of growth in conjugated polymer microstructures and the formation of smaller scale macro-aggregate clusters.

Tunable synthetic control of soft polymeric nanoparticle morphology.

With a growing variety of nanoparticles available, research probing the influence of particle deformability, morphology, and topology on the behavior of all polymer nanocomposites is also increasing. In particular, the behavior of soft polymeric nanoparticles in polymer nanocomposites has displayed unique behavior, but their precise performance depends intimately on the internal structure and morphology of the nanoparticle. With the goal of providing guidelines to control the structure and morphology of soft polymeric nanoparticles, we have examined monomer starved semi-batch nano-emulsion polymerizations that form organic, soft nanoparticles, to correlate the precise structure of the nanoparticle to the rate of monomer addition and crosslinking density. The synthesis method produces 5-20 nm radii polystyrene nanoparticles with tunable morphologies. We report small angle neutron scattering (SANS) results that correlate synthetic conditions to the structural characteristics of soft polystyrene nanoparticles. These results show that the measured molecular weight of the nanoparticles is controlled by the monomer addition rate, the total nanoparticle radius is controlled by the excess surfactant concentration, and the crosslinking density has a direct effect on the topology of each nanoparticle. These studies thus provide pathways to control these 3 structural characteristics of the nanoparticle. This research, therefore provides a conduit to thoroughly investigate the effect of structural features of soft nanoparticles on their individual properties and those of their polymer nanocomposites.

The importance of solvent quality on the modification of conjugated polymer conformation and thermodynamics with illumination.

Device efficiency in key organic electronic devices such as organic photovoltaics, field transistors, and light emitting diodes has long been known to be closely tied to the conformation of the conjugated polymer chains which make up the active layers. Our previous results show that light exposure can have a profound effect on the structure and assembly of these optoelectronic materials in solution. In order to advance our understanding of the role which solvent quality plays in this phenomenon, we have further studied the modulation of these illumination dependent structural changes on the key benchmark conjugated polymers P3HT and MEH-PPV as a function of solvent quality over a wide range of polymer solubilities. Analysis of this data indicates that use of poorer conjugated polymer solvents ultimately results in larger absolute alterations to polymer conformation, denoting the crucial role which solution thermodynamics plays in this generic effect. This discovery opens the door to controlling final device morphology through careful manipulation of solvent composition during solution based device casting techniques, moving our efforts closer to the development of a powerful, non-destructive, and tunable method for light-driven control of polymer conformation in novel light-responsive organic materials.

Big Effect of Small Nanoparticles: A Shift in Paradigm for Polymer Nanocomposites.

Polymer nanocomposites (PNCs) are important materials that are widely used in many current technologies and potentially have broader applications in the future due to their excellent property tunability, light weight, and low cost. However, expanding the limits in property enhancement remains a fundamental scientific challenge. Here, we demonstrate that well-dispersed, small (diameter ∼1.8 nm) nanoparticles with attractive interactions lead to unexpectedly large and qualitatively different changes in PNC structural dynamics in comparison to conventional nanocomposites based on particles of diameters ∼10-50 nm. At the same time, the zero-shear viscosity at high temperatures remains comparable to that of the neat polymer, thereby retaining good processability and resolving a major challenge in PNC applications. Our results suggest that the nanoparticle mobility and relatively short lifetimes of nanoparticle-polymer associations open qualitatively different horizons in the tunability of macroscopic properties in nanocomposites with a high potential for the development of advanced functional materials.

Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites.

It is generally believed that the strength of the polymer-nanoparticle interaction controls the modification of near-interface segmental mobility in polymer nanocomposites (PNCs). However, little is known about the effect of covalent bonding on the segmental dynamics and glass transition of matrix-free polymer-grafted nanoparticles (PGNs), especially when compared to PNCs. In this article, we directly compare the static and dynamic properties of poly(2-vinylpyridine)/silica-based nanocomposites with polymer chains either physically adsorbed (PNCs) or covalently bonded (PGNs) to identical silica nanoparticles (RNP = 12.5 nm) for three different molecular weight (MW) systems. Interestingly, when the MW of the matrix is as low as 6 kg/mol (RNP/Rg = 5.4) or as high as 140 kg/mol (RNP/Rg= 1.13), both small-angle X-ray scattering and broadband dielectric spectroscopy show similar static and dynamic properties for PNCs and PGNs. However, for the intermediate MW of 18 kg/mol (RNP/Rg = 3.16), the difference between physical adsorption and covalent bonding can be clearly identified in the static and dynamic properties of the interfacial layer. We ascribe the differences in the interfacial properties of PNCs and PGNs to changes in chain stretching, as quantified by self-consistent field theory calculations. These results demonstrate that the dynamic suppression at the interface is affected by the chain stretching; that is, it depends on the anisotropy of the segmental conformations, more so than the strength of the interaction, which suggests that the interfacial dynamics can be effectively tuned by the degree of stretching-a parameter accessible from the MW or grafting density.

Unexpected Molecular Weight Effect in Polymer Nanocomposites.

The properties of the interfacial layer between the polymer matrix and nanoparticles largely determine the macroscopic properties of polymer nanocomposites (PNCs). Although the static thickness of the interfacial layer was found to increase with the molecular weight (MW), the influence of MW on segmental relaxation and the glass transition in this layer remains to be explored. In this Letter, we show an unexpected MW dependence of the interfacial properties in PNC with attractive polymer-nanoparticle interactions: the thickness of the interfacial layer with hindered segmental relaxation decreases as MW increases, in sharp contrast to theoretical predictions. Further analyses reveal a reduction in mass density of the interfacial layer with increasing MW, which can elucidate these unexpected dynamic effects. Our observations call for a significant revision of the current understandings of PNCs and suggest interesting ways to tailor their properties.

Understanding the Impact of Poly(ethylene oxide) on the Assembly of Lignin in Solution toward Improved Carbon Fiber Production.

Carbon fiber produced from lignin has recently become an industrial scalable product with applications ranging from thermal insulation to reinforcing automobile bodies. Previous research has shown that mixing 1-2 wt %, of poly(ethylene oxide) (PEO) with the lignin before fiber formation can enhance the properties of the final carbon fibers. The research reported here determines the impact of adding PEO to a lignin solution on its assembly, focusing on the role of the lignin structure on this assembly process. Results indicate the addition of PEO anisotropically directs the self-assembly of the hardwood and softwood lignin by lengthening the cylindrical building blocks that make up the larger global aggregates. On the other hand, results from an annual lignin exhibit a shapeless, more complex structure with a unique dependence on the PEO loading. These results are consistent with improved carbon fibers from solutions of lignin that include PEO, as the local ordering and directed assembly will inhibit the formation of defects during the carbon fiber fabrication process.

Tuning of thermally induced sol-to-gel transitions of moderately concentrated aqueous solutions of doubly thermosensitive hydrophilic diblock copolymers poly(methoxytri(ethylene glycol) acrylate)-b-poly(ethoxydi(ethylene glycol) acrylate-co-acrylic acid).

We report in this article a method to tune the sol-to-gel transitions of moderately concentrated aqueous solutions of doubly thermosensitive hydrophilic diblock copolymers that consist of two blocks exhibiting distinct lower critical solution temperatures (LCSTs) in water. A small amount of weak acid groups is statistically incorporated into the lower LCST block so that its LCST can be tuned by varying solution pH. Well-defined diblock copolymers, poly(methoxytri(ethylene glycol) acrylate)-b-poly(ethoxydi(ethylene glycol) acrylate-co-acrylic acid) (PTEGMA-b-P(DEGEA-co-AA)), were prepared by reversible addition-fragmentation chain transfer polymerization and postpolymerization modification. PTEGMA and PDEGEA are thermosensitive water-soluble polymers with LCSTs of 58 and 9 °C, respectively, in water. A 25 wt % aqueous solution of PTEGMA-b-P(DEGEA-co-AA) with a molar ratio of DEGEA to AA units of 100:5.2 at pH = 3.24 underwent multiple phase transitions upon heating, from a clear, free-flowing liquid (<15 °C) to a clear, free-standing gel (15-46 °C) to a clear, free-flowing hot liquid (47-56 °C), and a cloudy mixture (≥57 °C). With the increase of pH, the sol-to-gel transition temperature (T(sol-gel)) shifted to higher values, while the gel-to-sol transition (T(gel-sol)) and the clouding temperature (T(clouding)) of the sample remained essentially the same. These transitions and the tunability of T(sol-gel) originated from the thermosensitive properties of two blocks of the diblock copolymer and the pH dependence of the LCST of P(DEGEA-co-AA), which were confirmed by dynamic light scattering and differential scanning calorimetry studies. Using the vial inversion test method, we mapped out the C-shaped sol-gel phase diagrams of the diblock copolymer in aqueous buffers in the moderate concentration range at three different pH values (3.24, 5.58, and 5.82, all measured at ~0 °C). While the upper temperature boundaries overlapped, the lower temperature boundary shifted upward and the critical gelation concentration increased with the increase of pH. The AA content in PTEGMA-b-P(DEGEA-co-AA) was found to have a significant effect on the pH dependence of T(sol-gel). For PTEGMA-b-P(DEGEA-co-AA) with a molar ratio of DEGEA to AA units of 100:10, the T(sol-gel) of its 25 wt % aqueous solution increased faster with the increase of pH than that of PTEGMA-b-P(DEGEA-co-AA) with a DEGEA-to-AA molar ratio of 100:5.2.

Enhancing the quality of aged latent fingerprints developed by superglue fuming: loss and replenishment of initiator.

The recovery and identification of latent fingerprints from a crime scene are crucial to many investigations. The cyanoacrylate (superglue) fuming method (CFM), which develops fingerprints by growing a polymer coating over the print residue, is a powerful method but encounters severe limitations when prints are aged or exposed to harsh environmental conditions. We examine the aging process and how the changes that occur to a fingerprint residue over time influence the growth of polymer during development. We identify loss of initiator by erosion and degradation that, when coupled with a loss of water from the print residue, result in a decreased ability to polymerize ethylcyanoacrylate. Then, we present a methodology by which the ability of aged latent fingerprints to polymerize ethylcyanoacrylate is recovered. Two print enhancement agents, acetic acid and ammonia, are demonstrated to improve the growth of polymer from the print ridges by over an order of magnitude, while retaining the integrity of the print structure. Comparison between the two enhancement agents indicate that the enhancement occurs due to ridge coating by the ammonia or acetic acid and pH control of the latent print.

Understanding the chemistry of the development of latent fingerprints by superglue fuming.

Cyanoacrylate fuming is a widely used forensic tool for the development of latent fingerprints, however the mechanistic details of the reaction between the fingerprint residue and the cyanoacrylate vapor are not well understood. Here the polymerization of ethyl-cyanoacrylate vapor by sodium lactate or alanine solutions, two of the major components in fingerprint residue, has been examined by monitoring the time dependence of the mass uptake and resultant polymer molecular weight characteristics. This data provides insight into the molecular level actions in the efficient development of latent fingerprints by superglue fuming. The results show that the carboxylate moiety is the primary initiator of the polymerization process and that a basic environment inhibits chain termination while an acidic environment promotes it. The results also indicate that water cannot be the primary initiator in this forensic technique.

The effect of copolymer composition on the dynamics of random copolymers in a homopolymer matrix.

The effect of copolymer composition on the dynamics of random copolymers in a homopolymer matrix is studied using computer simulations within the framework of the bond-fluctuation model on blends containing low concentrations (10%) of A-B copolymers, where A and B are two different types of monomers, dispersed in a homopolymer matrix of chains with only A-type monomers. Four copolymer compositions were studied, phi(A)=0.33, phi(A)=0.5, phi(A)=0.66, and phi(A)=0.82, while maintaining a statistically random sequence distribution. For this study, we have only included intermolecular interactions between A and B monomers. Our results indicate, in agreement with experimental data, that copolymer composition has an impact on system dynamics. Analysis of the structure reveals that copolymers with majority A content are expanded in the homopolymer matrix, have fewer interchain copolymer-copolymer contacts, and are well dispersed in the homopolymer matrix. On the other hand, copolymers with lower A content form a more compact structure, have more interchain contacts, and form aggregates that are short lived. This in turn leads to slower system dynamics. Both the radius of gyration (Rg) and copolymer end-to-end vectors (Re) increase with increasing A content until phi(A)=0.66 and then decrease. Copolymers with lower A content form more compact structures as the repulsive interactions between unlike species are minimized by the copolymers folding back on themselves and forming aggregates of copolymer chains. Thus, these results provide insight into the variation of copolymer dynamics with composition in the system by documenting the correlation between the thermodynamics of this mixture, the conformation of a copolymer chain in a homopolymer matrix, and the dynamics of both components in this blend.