Fluoropolymers have long served as potent oxidizers for metal-based pyrolant designs for the preparation of energetic materials. Commercial perfluoropolyethers (PFPEs), specifically known as Fomblins®, are well-known to undergo accelerated thermal degradation in the presence of native metals and Lewis acids producing energetically favorable metal fluoride species. This study employs the use of PFPEs to coat nano-aluminum (n-Al) and under optimized stoichiometric formulations, harness optimized energy output. The PFPEs serve as ideal oxidizers of n-Al because they are non-volatile, viscous liquids that coat the particles thereby maximizing surface interactions. The n-Al/PFPE blended combination is required to interface with an epoxy-based matrix in order to engineer a moldable/machinable, structurally viable epoxy composite without compromising bulk thermal/mechanical properties. Computational modeling/simulation supported by thermal experimental studies showed that the n-Al/PFPE blended epoxy composites produced an energetic material that undergoes latent thermal metal-mediated oxidation. Details of the work include the operationally simple, scalable synthetic preparation, thermal properties from DSC/TGA, and SEM/TEM of these energetic metallized nanocomposite systems. Post-burn analysis using powder XRD of this pyrolant system confirms the presence of the predominating exothermic metal-mediated oxidized AlF₃ species in addition to the production of Al₂O₃ and Al₄C₃ during the deflagration reaction. Details of this first epoxy-based energetic nanocomposite entrained with a thermally reactive formulation of PFPE coated n-Al particles are presented herein.

Poly(methyl methacrylate) (PMMA) was added to aluminum/poly(vinylidene fluoride) (Al/PVDF) energetic blends to enhance melt flow rate and adhesion in a fused deposition modeling (FDM) manufacturing scenario. Composites were successfully printed with up to 30 wt% nano-scale Al after PMMA addition. Melt flow rate increased with increasing PMMA content. This resulted in a partially fluorinated binder that can facilitate high solids loadings and can be easily printed with a standard FDM 3D printer. PMMA addition promoted nucleation of the electroactive β-phase PVDF, which suggests the potential to print piezoelectric, energetic composites. Thermal stability was assessed using differential scanning calorimetry and thermogravimetric analysis. Results verified that composite stability decreased with increasing PMMA and Al content, however, decomposition onset temperatures for all concentrations remained well above printing temperatures. Burn rates at higher Al loadings (e.g., fuel rich) showed a decreasing trend. Analysis of post burn soot revealed α-AlF₃ and amorphous carbon char as the primary reaction products. Combustion performance results indicate that although PMMA may serve as a heat sink, the reaction between Al and PVDF was not significantly affected by PMMA addition. These findings indicate that by changing PMMA concentrations, rheology, piezoelectric content, thermal properties and combustion performance can be altered to suit specific needs.

Nucleophilic addition–elimination of ortho- or para-substituted phenols to aryl trifluorovinyl ethers (TFVEs) in N,N-dimethylformamide was studied. Using sodium hydride as a base afforded vinyl substitution products R–Ar–O–CFCF–O–Ar–R′, where R or R′ = H, Br, OMe, tert-Bu, or Ph. The vinyl substitution products produced mixtures of (Z)/(E)-isomers and this isomer ratio was influenced by substitution with more sterically encumbered phenol nucleophiles. Reactions using caesium carbonate afforded addition products R–Ar–O–CHFCF₂–O–Ar–R′ whereas upon dehydrofluorination using sodium hydride produced vinyl substitution products. The preparation of vinyl substituted and addition products proceeded in overall good isolated yields and were elucidated using ¹H and ¹⁹F NMR, GC-MS, and X-ray analysis. Vinyl substituted products were inert to UV light and chemical reactivity using common polymerization promoters. Thermal activation of the (Z)/(E)-fluoroolefin (-CFCF-) was observed at an onset of 310 °C in nitrogen using differential scanning calorimetry (DSC) producing insoluble network material. The synthesis, characterization, and mechanism for stereoselectivity are discussed.

Since initially being reported, fluorinated silica nanometer-sized particles (F-SiNPs) have gained much interest in the scientific community, due to their unique properties. These properties, include, low surface energies, increased mechanical strength, thermal robustness, and chemical resistance, and are a direct result of the incorporation of fluorine with a nanometer-sized silica network. This review aims to summarize the synthetic methods that have, and are still, being utilized to prepare these specialized materials. Following this, applications for F-SiNPs, with an emphasis on recent examples, will be presented in further detail.

New thermally cross-linkable and/or post-functionalizable perfluorocyclobutyl (PFCB) polymers containing Meldrum's acid moieties have been successfully prepared via the thermal cyclopolymerization of a new Meldrum's acid functionalized aromatic trifluorovinyl ether (TFVE) monomer.

Fluorinated polyhedral oligomeric silsesquioxane (F-POSS) compounds were prepared by employing a facile, corner-capping methodology. Using this modular approach, fluorocarbons with varying degree of fluorine content and architecture were installed on the POSS cage of a partially condensed trisilanol. The melting properties of the F-POSS derivatives showed various influence by Si…F contacts via intermolecular packing assembly. All F-POSS compounds were characterized by ¹H, ¹³C, ¹⁹F, and ²⁹Si NMR spectrometry, X-ray crystallography, thermal and elemental combustion analysis.