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Jones, Brad Howard

Publications and source records attributed to Jones, Brad Howard.

At least 19 records

Static and Dynamic Thermomechanical Properties of Phase-Separated Epoxy Networks with Tuned Microstructures

Here, polymerization-induced phase separation is a useful method for the construction of heterogeneous epoxy networks with properties exceeding their homogeneous counterparts. In this work, we examine the static and dynamic thermomechanical properties of phase-separated epoxy networks salient to their application as encapsulants. Three heterogeneous epoxy-amine networks with nano-, meso-, and macro-phase-separated morphologies comprised of hard and soft domains are compared to a rigid, unstructured network. The glass transition profiles of the heterogeneous networks are complex, spanning many decades in the frequency domain. The nanophase-separated morphology leads to higher coefficient of thermal expansion, yet surprisingly is characterized by reduced residual stress. Under both quasi-static and dynamic compression (strain rates of order 10 –3 and 10 3 s –1 , respectively), the nanophase-separated network also exhibits higher modulus and strength. In split-Hopkinson bar experiments, the energy dissipation characteristics of the epoxy networks were nearly identical. Curiously, however, the Hugoniot response of the macro-phase-separated network determined by ballistic shockwave analysis indicates a remarkable ability of this material to mitigate shockwave propagation in comparison to many homogeneous and heterogeneous polymer materials. Collectively, this work reveals several previously unreported phenomena with respect to structure–property relationships in phase-separated epoxy networks, illustrating the potential value of systematically tuned microstructures for optimization of application-specific physical properties.

36 MATERIALS SCIENCE↗

Method of tuning physical properties of thermosets

Polymerization-induced phase separation enables fine control over thermoset network morphologies, yielding heterogeneous structures with domain sizes tunable over 1-100 nm. However, the controlled chain-growth polymerization techniques exclusively employed to regulate morphology at these length scales are unsuitable for most thermoset materials typically formed through step-growth mechanisms. By employing binary mixtures in place of the classic constituents of phase-separating thermosets—resin, curing agent, and secondary polymer—facile tunability over morphology can be achieved through a single compositional parameter. Indeed, this method yields morphologies spanning nano-scale to macro-scale, controlled by the relative reactivities and thermodynamic compatibility of the network components. Due to the connection between chain dynamics and microstructure in these materials, the tunable morphology enables exquisite control over glass transition and other physical and mechanical properties.

Jones, Brad Howard↗

Polymers depolymerizable by metathesis of a cleavable unit

Novel polymers are depolymerizable by metathesis of a cleavable unit. As an example, a series of linear and crosslinked polyurethanes were prepared that can be selectively depolymerized under mild conditions. Two unique polyols were synthesized bearing unsaturated units in a configuration designed to favor ring-closing metathesis to five- and six-membered cycloalkenes. These polyols were co-polymerized with toluene diisocyanate to generate linear polyurethanes and trifunctional hexamethylene- and diphenylmethane-based isocyanates to generate crosslinked polyurethanes. The polyol design is such that the ring-closing metathesis reaction cleaves the backbone of the polymer chain. Upon exposure to dilute solutions of Grubbs' catalyst under ambient conditions, the polyurethanes were rapidly depolymerized to low molecular weight, soluble products bearing vinyl and cycloalkene functionalities. These functionalities enabled further re-polymerization by traditional strategies for polymerization of double bonds. This general approach can be expanded to develop a range of chemically recyclable condensation polymers that are readily depolymerized by orthogonal metathesis chemistry.

Jones, Brad Howard↗

Use of latent metathesis polymerization systems for additive manufacturing

The invention is directed to latent metathesis-active resin compositions and additive manufacturing approaches. The latent metathesis-active compositions comprise at least one latent metathesis catalyst, at least one curable metathesis-active monomer, and optional fillers, photosensitizers, and/or a secondary monomer resin system for dual-cure. A method comprises extruding a latent metathesis-active resin from a dispensing apparatus and spatially triggering a ring-opening metathesis polymerization by directed irradiation with light or directed application of a thermal stimuli for direct-ink write printing of objects. Another method uses a latent metathesis-active resin for vat photopolymerization and stereolithographic printing of objects.

Appelhans, Leah↗