Dylan J. Boday

Recyclable, strong thermosets and organogels via paraformaldehyde condensation with diamines

Recyclable Thermoset Polymers The high mechanical strength and durability of thermoset polymers are exploited in applications such as composite materials, where they form the matrix surrounding carbon fibers. The thermally driven polymerization reaction is usually irreversible, so it is difficult to recycle the constituent monomers and to remove and repair portions of a composite part. García et al. (p. 732; see the Perspective by Long) now describe a family of polymers formed by condensation of paraformaldehyde with bisanilines that could form hard thermoset polymers or, when more oxygenated, produce self-healing gels. Strong acid digestion allowed recovery of the bisaniline monomers. A strong polymer formed by heating can be digested with strong acid to recover and recycle its bisaniline monomers. [Also see Perspective by Long] Nitrogen-based thermoset polymers have many industrial applications (for example, in composites), but are difficult to recycle or rework. We report a simple one-pot, low-temperature polycondensation between paraformaldehyde and 4,4ʹ-oxydianiline (ODA) that forms hemiaminal dynamic covalent networks (HDCNs), which can further cyclize at high temperatures, producing poly(hexahydrotriazine)s (PHTs). Both materials are strong thermosetting polymers, and the PHTs exhibited very high Young’s moduli (up to ~14.0 gigapascals and up to 20 gigapascals when reinforced with surface-treated carbon nanotubes), excellent solvent resistance, and resistance to environmental stress cracking. However, both HDCNs and PHTs could be digested at low pH (<2) to recover the bisaniline monomers. By simply using different diamine monomers, the HDCN- and PHT-forming reactions afford extremely versatile materials platforms. For example, when poly(ethylene glycol) (PEG) diamine monomers were used to form HDCNs, elastic organogels formed that exhibited self-healing properties.

Strong, Low-Density Nanocomposites by Chemical Vapor Deposition and Polymerization of Cyanoacrylates on Aminated Silica Aerogels

Strong polymer-silica aerogel composites were prepared by chemical vapor deposition of cyanoacrylate monomers onto amine-modified aerogels. Amine-modified silica aerogels were prepared by copolymerizing small amounts of (aminopropyl)triethoxysilane with tetraethoxysilane. After silation of the aminated gels with hexamethyldisilazane, they were dried as aerogels using supercritical carbon dioxide processing. The resulting aerogels had only the amine groups as initiators for the cyanoacrylate polymerizations, resulting in cyanoacrylate macromolecules that were higher in molecular weight than those observed with unmodified silica and that were covalently attached to the silica surface. Starting with aminated silica aerogels that were 0.075 g/cm(3) density, composite aerogels were made with densities up to 0.220 g/cm(3) and up to 31 times stronger (flexural strength) than the precursor aerogel and about 2.3 times stronger than an unmodified silica aerogel of the same density.

Mechanically reinforced silica aerogel nanocomposites via surface initiated atom transfer radical polymerizations

Here we report the preparation of mechanically robust silica aerogel polymer nanocomposites using surface-initiated atom transfer radical polymerization. This approach was used to grow poly(methyl methacrylate) (PMMA) with low polydispersities and establish the first structure–property relationship between the grafted PMMA molecular weight and bulk physical properties of the hybrid aerogel.

Synthesis and characterization of isosorbide-based polyphosphonates as biobased flame-retardants

A new isosorbide-based polyphosphate was synthesized and applied as a flame-retardant for polylactic acid (PLA). The storage modulus and glass transition temperature of PLA/polyphosphonate blends was unaffected by the inclusion of polyphosphonate, but moderate depressions of PLAs tensile strength (16%, 28%, and 45% reduction from PLA at a polyphosphonate mass percentage of 5%, 10%, and 15%, respectively) and strain-at-break (0%, 17%, and 30% reduction from PLA at a polyphosphonate mass percentage of 5%, 10%, and 15%, respectively) were observed. Modified UL-94 flammability testing indicated that isosorbide-based polyphosphonates are effective flame retardants for PLA and are able to self-extinguish flames in less than 2 s to achieve V2 and V0 ratings at polyphosphonate mass percentage of 5% and 15%, respectively. Fire test data indicates a gas phase mechanism that can quench the flame when no external radiant heat flux is present (e.g., in modified UL-94 testing) but does not affect the materials heat release rate in forced combustion (e.g., in cone calorimetry). Use of the biobased flame retardants described herein yields flame retardant PLA containing up to 97% by mass of bio-derived content.

Analysis of deprotonated acids with silicon nanoparticle-assisted laser desorption/ ionization mass spectrometry.

Chemically modified silicon nanoparticles were applied for the laser desorption/negative ionization of small acids. A series of substituted sulfonic acids and fatty acids was studied. Compared to desorption ionization on porous silicon (DIOS) and other matrix-less laser desorption/ionization techniques, silicon nanoparticle-assisted laser desorption/ionization (SPALDI) mass spectrometry allows for the analysis of acids in the negative ion mode without the observation of multimers or cation adducts. Using SPALDI, detection limits of many acids reached levels down to 50 pmol/µl. SPALDI of fatty acids with unmodified silicon nanoparticles was compared to SPALDI using the fluoroalkyl silylated silicon powder, with the unmodified particles showing better sensitivity for fatty acids, but with more low-mass background due to impurities and surfactants in the untreated silicon powder. The fatty acids exhibited a size-dependent response in both SPALDI and unmodified SPALDI, showing a signal intensity increase with the chain length of the fatty acids (C12-C18), leveling off at chain lengths of C18-C22. The size effect may be due to the crystallization of long chain fatty acids on the silicon. This hypothesis was further explored and supported by SPALDI of several, similar sized, unsaturated fatty acids with various crystallinities. Fatty acids in milk lipids and tick nymph samples were directly detected and their concentration ratios were determined by SPALDI mass spectrometry without complicated and time-consuming purification and esterification required in the traditional analysis of fatty acids by gas chromatography (GC). These results suggest that SPALDI mass spectrometry has the potential application in fast screening for small acids in crude samples with minimal sample preparation.

Mechanical properties of hexylene- and phenylene-bridged polysilsesquioxane aerogels and xerogels

Bridged polysilsesquioxanes are increasingly used to prepare protective coatings, particulate chromatographic materials, and adsorbents. However, little is known about the mechanical properties of the materials and how they are influenced by the nature of the bridging group. In this paper, we have prepared monolithic xerogels and aerogels of hexylene- and phenylene-bridged polysilsesquioxanes and have measured their flexural strength and modulus. Consistent with their compact structure, the porous, glassy phenylene- and hexylene-bridged xerogels were hundreds of stronger than the analogous aerogels. The nature of the bridging group did not appear to affect the mechanical properties of the xerogels, in contrast, it presented a profound effect on the mechanical properties of the aerogels. Phenylene-bridged aerogels were brittle and 30% stronger than silica aerogels of the same density. However, the opaque hexylene-bridged aerogels were found to be elastic and appreciably weaker than the phenylene-bridged or silica aerogels.

Developments in Dynamic Covalent Chemistries from the Reaction of Thiols with Hexahydrotriazines

Dynamic covalent chemistries have garnered significant attention for their potential to revolutionize technologies in the material fields (engineering, biomedical, and sensors) and synthetic design strategies as they provide access to stimuli responsiveness and adaptive behaviors. However, only a limited number of molecular motifs have been known to display this dynamic behavior under mild conditions. Here, we identified a dynamic covalent motif-thioaminals-that is produced from the reaction of hexahydrotriazines (HTs) with thiols. Furthermore, we report on the synthesis of a new family of step-growth polymers based on this motif. The condensation efficiently proceeds to quantitative yields within a short time frame and offers versatility in functional group tolerance; thus, it can be exploited to synthesize both small molecule thioaminals as well as high molecular weight polymers from the step-growth polymerization of HTs with dithiols. Careful evaluation of substituted HTs and organic thiols supported by DFT calculations led to a chemically diverse library of polymers based on this motif. Finally, dynamic substitution reactions were employed toward the facile preparation of functional oligomers and macromolecules. This dynamic covalent motif is particularly attractive for a range of applications that include material design and drug delivery due to the economic feasibility of synthesis.

Bio-based materials for high-end electronics applications

During the past decade, a shift of focus onto greener alternatives to petroleum-based plastics has spurred the development of bio-based resins for plastic development. This has led to a positive marketing image for companies making the switch to resins from renewable resources. This shift of focus is further reinforced by corporations, which are committed to a reduction in their greenhouse gas emissions and product environmental footprints. Here, we present a perspective on the use of renewable materials in durable goods applications and the challenges and advantages associated with the use of renewable materials. Replacement of petroleum-based acoustic foam with that derived from sustainable resources and qualification of thermoplastic polylactic acid blends for enclosure covers has been demonstrated. The technical details of the materials development required for use in durable goods, and their characterization is also discussed.

Thermally Conductive-Silicone Composites with Thermally Reversible Cross-links

Thermally conductive-silicone composites that contain thermally reversible cross-links were prepared by blending diene- and dienophile-functionalized polydimethylsiloxane (PDMS) with an aluminum oxide conductive filler. This class of thermally conductive-silicones are useful as thermal interface materials (TIMs) within Information Technology (IT) hardware applications to allow rework of valuable components. The composites were rendered reworkable via retro Diels-Alder cross-links when temperatures were elevated above 130 °C and required little mechanical force to remove, making them advantageous over other TIM materials. Results show high thermal conductivity (0.4 W/m·K) at low filler loadings (45 wt %) compared to other TIM solutions (>45 wt %). Additionally, the adhesion of the material was found to be ∼7 times greater at lower temperatures (25 °C) and ∼2 times greater at higher temperatures (120 °C) than commercially available TIMs.

A neural network based method for predicting PCB glass weave induced skew

This paper proposes the use of a neural network based tool to predict the skew factor of PCB laminate differential channel designs. A multitude of differential stripline design scenarios are 3D modelled, each with a different expected within differential pair skew factor. The modelled data is used to train a neural network. The neural network is tested using an unseen set of design data in order to evaluate the goodness of its predictions. Preliminary results show this machine learned technique to be a viable way to predict PCB glass weave skew without the need to resort to intensive 3D modelling. This method has potential to shorten design cycles and simplify analysis while still achieving good simulation accuracy.