Kevin M. Miller

Macropore‐infused nanocomposite emulsion thermosets (MINETs) offer a novel approach for multifunctional monoliths and carbon fiber composites (CFCs), leveraging tunable porosity and material compatibility to meet the demands of aerospace and energy applications. Using 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF ₄ ) and a propylene glycol‐ionic liquid (IL) triblock copolymer surfactant, we successfully stabilized an epoxy‐IL emulsion with compatibility with particles such as silica, super‐activated carbon (SAC), and graphene. Optimal surfactant levels (5.11% for SAC and graphene and 3.46% for silica) facilitated continuous IL phases, enhancing porosity and ionic conductivity, as confirmed by mass loss, mercury porosimetry, and ionic conductivity analyses. SEM revealed well‐defined nanostructures, while resin content adjustments highlighted a balance between mechanical integrity and conductivity. These advancements provide a strong foundation for integrating IL‐MINETs into multifunctional composites for structural power storage and flame‐resistant materials, with significant potential in aerospace and renewable energy systems. Ongoing work focuses on fluorinated IL surfactants to enhance conductivity and stability, as well as designing layered MINET composites for multifunctional applications.

The versatility of 1,1′-carbonyldiimidazole (CDI) as a reagent in a non-isocyanate synthesis of carbamate- and thiocarbamate-containing ionic liquids (ILs) is described herein. Through the initial reaction with various linear alcohols or thiols, followed by addition of 3-aminopropylimidazole, CDI was sequentially transformed into a series of imidazoles bearing a carbamate or thiocarbamate functional group. The imidazoles were further quaternized with various lengths of alkyl groups (C2–C12) and anion exchanges were performed, producing a small library of 20 room-temperature ILs. Fundamental temperature-dependent properties such as density, viscosity, and conductivity were determined for each material. All of the ILs were found to exhibit glass transition temperatures (T_g) below room temperature and conductivities of up to 10⁻³ S cm⁻¹ at 30 °C. Changes in the counteranion ([Br], [OMs], [OTf], [NTf₂], [NFBSI]) produced the greatest breadth of physicochemical properties.

Polymeric donors of gasotransmitters, gaseous signaling molecules such as hydrogen sulfide, nitric oxide, and carbon monoxide, hold potential for localized and extended delivery of these reactive gases. Examples of gasotransmitter donors based on polysaccharides are limited despite the availability and generally low toxicity of this broad class of polymers. In this work, we sought to create a polysaccharide H₂S donor by covalently attaching N‐thiocarboxyanhydrides (NTAs) to amylopectin, the major component of starch. To accomplish this, we added an allyl group to an NTA, which can spontaneously hydrolyze to release carbonyl sulfide and ultimately H₂S via the ubiquitous enzyme carbonic anhydrase, and then coupled it to thiol‐functionalized amylopectin of three different molecular weights (MWs) through thiol‐ene “click” photochemistry. We also varied the degree of substitution (DS) of the NTA along the amylopectin backbone. H₂S release studies on the six samples, termed amyl‐NTAs, with variable MWs (three) and DS values (two), revealed that lower MW and higher DS led to faster release. Finally, dynamic light scattering experiments suggested that aggregation increased with MW, which may also have affected H₂S release rates. Collectively, these studies present a new synthetic method to produce polysaccharide H₂S donors for applications in the biomedical field.

Dispersity (Ð or M_w/M_n) is an important parameter in material design and as such can significantly impact the properties of polymers. Here, polymer networks with independent control over the molecular weight and dispersity of the linear chains that form the material are developed. Using a RAFT polymerization approach, a library of polymers with dispersity ranging from 1.2—1.9 for backbone chain‐length (DP) 100, and 1.4—3.1 for backbone chain‐length 200 were developed and transformed to networks through post‐polymerization crosslinking to form disulfide linkers. The tensile, swelling, and adhesive properties were explored, finding that both at DP 100 and DP 200 the swelling ratio, tensile strength, and extensibility were superior at intermediate dispersity (1.3—1.5 for DP 100 and 1.6—2.1 for DP 200) compared to materials with either substantially higher or lower dispersity. Furthermore, adhesive properties for materials with chains of intermediate dispersity at DP 200 revealed enhanced performance compared to the very low or high dispersity chains.

Dispersity (Ð or M_w/M_n) is an important parameter in material design and as such can significantly impact the properties of polymers. Here, polymer networks with independent control over the molecular weight and dispersity of the linear chains that form the material are developed. Using a RAFT polymerization approach, a library of polymers with dispersity ranging from 1.2—1.9 for backbone chain‐length (DP) 100, and 1.4—3.1 for backbone chain‐length 200 were developed and transformed to networks through post‐polymerization crosslinking to form disulfide linkers. The tensile, swelling, and adhesive properties were explored, finding that both at DP 100 and DP 200 the swelling ratio, tensile strength, and extensibility were superior at intermediate dispersity (1.3—1.5 for DP 100 and 1.6—2.1 for DP 200) compared to materials with either substantially higher or lower dispersity. Furthermore, adhesive properties for materials with chains of intermediate dispersity at DP 200 revealed enhanced performance compared to the very low or high dispersity chains.

Dispersity (Ɖ or Mw/Mn) is an important parameter in material design and as such can significantly impact the properties of polymers. Here polymer networks with independent control over the molecular weight and dispersity of the linear chains that form the material are developed. Using a RAFT polymerization approach a library of polymers with dispersity ranging from 1.2-1.9 for backbone chain-length (DP) 100, and 1.4-3.1 for backbone chain-length 200 were developed and transformed to networks through post-polymerization crosslinking to form disulfide linkers. The tensile, swelling, and adhesive properties were explored, finding that both at DP 100 and DP 200 the swelling ratio, tensile strength, and extensibility were superior at intermediate dispersity (1.3-1.5 for DP 100 and 1.6-2.1 for DP 200) compared to materials with either substantially higher or lower dispersity. Furthermore, adhesive properties for materials with chains of intermediate dispersity at DP 200 revealed enhanced performance compared to the very low or high dispersity chains.

The synthesis and characterization of a series of polyurethane ionenes using a non‐isocyanate approach is disclosed. Imidazole‐capped, urethane‐containing prepolymers are prepared by first reacting carbonyl diimidazole (CDI) with several poly(propylene glycol) (PPG) diols with variable molecular weight, followed by subsequent reaction with 3‐aminopropylimidazole (API). Polymerization with 1,4‐dibromomethylbenzene followed by anion exchange resulted in the desired polyurethane ionenes bearing the [NTf₂] counteranion as a series of viscous liquids. NMR and FTIR spectroscopy are used to characterize the intermediates and final ionenes, including molecular weight determination by end‐group analysis. A single glass transition temperature (T_g), as determined by differential scanning calorimetry (DSC), is observed for each ionene (−38 to −64 °C) with the T_g decreasing with increasing PPG molecular weight. Thermogravimetric analysis (TGA) indicated a two‐step decomposition for each ionene, with the first being degradation of the PPG segment, followed by the urethane/ionic segment. Microphase separation is observed from x‐ray scattering profiles with Bragg distances that increased with increasing PPG molecular weight. Ionic conductivity is found to be inversely dependent upon DSC T_g at lower temperatures (RT and below); however, at higher temperatures, conductivity appears to be more dependent upon the ability of ionic aggregates caused by phase separation to interact.

In this study, poly(ethylene terephthalate)‐block‐polyethylene (PET‐PE) multiblock copolymers (MBCPs) with block molar masses of ~4 or 7 kg mol⁻¹ and either alternating or random block sequencing, and a PE‐PET‐PE triblock copolymer (TBCP) of comparable total molar mass, were synthesized. To explore the effect of molecular architecture on compatibilization, both MBCPs and TBCPs were blended into 80/20 wt/wt mixtures of PET/linear low‐density PE (LLDPE). Compatibilization was remarkably efficient for all MBCP types, with the addition of 0.2 wt% yielding blends nearly as tough as PET homopolymer. Addition of MBCP also significantly decreases LLDPE dispersed phase sizes compared to PET/LLDPE neat blends, as much as 80% in as‐mixed blends and by a factor of 10 in post‐mixing thermally annealed samples. Conversely, the TBCP was less efficient at decreasing domain sizes of the blends and improving the mechanical properties, requiring loadings of 1 wt% to produce comparably tough blends. Peel tests of PET/BCP/LLDPE trilayer films showed that both MBCPs and TBCP all improve interfacial strength over a PET‐PE bilayer film by two orders of magnitude; however, when the BCPs were preloaded into LLDPE, only the MBCP containing films showed strong adhesion highlighting their potential utility as adhesive agents in multilayer films.