The present work describes the synthesis of new versatile polyurea (PU) and polyurethane (PUR) matrices, including different chain extenders, which facilitate the design of distinct, tunable properties, and high-performance derivatives. These polymers can be used for various defense and security applications, such as coatings for ballistic protection, CBRN protection, binders for energetic formulations, etc. Combining aliphatic and aromatic molecules in PU or PUR structures enables the synthesis of polymers with improved and controllable thermo-mechanical properties. Thus, for polyurea synthesis, we utilized two types of polymeric aliphatic diamines and three types of aromatic chain extenders (1,1’-biphenyl-4,4’-diamine, benzene-1,2-diamine, and 1,2-diphenylhydrazine). An analogous method was used to synthesize polyurethane films by employing one polymeric aliphatic polyol and three types of aromatic chain extenders (benzene-1,3-diol, benzene-1,4-diol, and benzene-1,2,3-triol). Subsequently, various analytic techniques (Fourier transform infrared spectroscopy–attenuated total reflectance (FTIR-ATR), single cantilever dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), frequency-dependent shear modulus survey, tensile tests, water contact angle measurements, and scanning electron microscopy (SEM) with energy-dispersive X-ray analysis (EDX)) have been utilized to characterize the synthesized materials and to evaluate the influence of each chain extender on their final properties.

The increasingly harsher and more complex international and European environmental legislation drives the current development of “greener” energetics materials and munitions. The aerospace and defense industries rely on extensive research in the formulation and scale-up production of polymer-bonded explosives (PBX). In this context, this paper aims to present a versatile method for obtaining “green” PBX formulations based on two high explosives (hexogen (RDX) and octogen (HMX)) and acrylic acid—ethyl acrylate copolymeric binders. This study developed an innovative “eco-friendly” technology for coating the RDX and HMX crystals, allowing straightforward and safer manufacture of PBX, avoiding the use of traditional organic solvents. At the same time, these polymeric binders are soluble in water at a slightly alkaline pH and insoluble at acidic or neutral pH, thus ensuring a safer manipulation of the energetic materials during their entire life cycle and a facile recovery of the explosive in its original shape and morphology in demilitarization. The PBX formulations were characterized via specific analytical tools to evaluate the influence of their composition on the safety and performance characteristics: scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), alkaline pH solubility tests, differential thermal analysis (DTA), impact sensitivity test (BAM Fall Hammer Test), friction sensitivity test (BAM Friction Test), electrostatic sensitivity test (ESD), vacuum stability test, small scale shock reactivity test (SSRT), detonation velocity test. The “green” PBX formulations obtained through a simple and innovative coating method, based on the polymeric binders’ adjustable water solubility, demonstrated remarkable energetic performances and a facile recovery of the explosive crystals by the dissolution of the polymeric binder at pH 11 and 30 °C.

Developing a controlled method for obtaining hybrid enzymatic-based interfaces for sensing application require the use of a multiuse, reusable sensor. By controlling the interface characteristics in terms of the surface chemistry, thickness, and roughness, a tailored response toward various toxic compounds can be obtained, regarding both materials used as active surfaces and fabrication methods. Herein, we report a preliminary study on using a laser-based method (i.e., matrix-assisted pulsed laser evaporation, or MAPLE) for obtaining active polymeric–enzymatic interfaces as hybrid or layered coatings for detecting toxic vapors. The MAPLE fabrication consisted of the simultaneous alternating evaporation of layers of polyethylenimine (PEI) and acetylcholinesterase (AchE) in order to obtain active surfaces as both hybrid PEI-AchE and a PEI/AchE layered coating, respectively. The deposition processes of the polymer and enzyme were carried out using a double-target system and a Nd:YAG pulsed laser, operating at 0.45 J/cm² fluences with a wavelength of 266 nm and a repetition rate of 10 Hz. Fourier transform infrared spectroscopy revealed no significant changes in the functional groups of both hybrid and layered coatings compared with the initial material. The thickness and roughness, as well as the morphologies of the coatings revealed by atomic force microscopy and scanning electron microscopy showed coatings thicker than two μm that had smooth surfaces and average roughness values below six nm. The sensors were tested with simulants for nerve gases and pesticides containing phosphonate ester groups, namely dimethyl methylphosphonate (DMMP) and diisopropyl methylphosphonate (DIMP), and a different sensitivity was shown to the selected chemical agents for each of the sensors. The best sensitivities for DMMP and DIMP obtained by using a PEI-AchE coated sensor are 65 kHz and 200 kHz, respectively, whereas the best sensitivity when using multilayered interfaces is 30 kHz and 10 KHz for DIMP and DMMP, respectively.

This study describes a simple, practical, inexpensive, improved, and efficient novel method for obtaining polyurea-polyurethane-multiwall carbon nanotubes (MWCNTs) nanocomposites with enhanced mechanical properties, and their experimental testing in a dynamic regime. SEM and micro-CT investigations validated the homogeneity of the nanocomposite films and uniform dispersion of the nanofiller inside the polymeric matrix. The experimental measurements (TGA, DSC, DMA, and tensile tests) revealed improved thermal and mechanical properties of these new materials. To demonstrate that these nanocomposites are suitable for ballistic protection, impact tests were performed on aluminum plates coated with the polyurea-polyurethane MWCNTs nanocomposites, using a Hopkinson bar set-up. The experimental testing in the dynamic regime of the polyurea- polyurethane-coated aluminum plates confirmed that the nanocomposite layers allow the metal plate to maintain its integrity at a maximum force value that is almost 200% higher than for the uncoated metallic specimens.

The present work investigates, for the first time, the synthesis and properties of some nanocomposite (NC) hydrogels obtained by the aqueous solution free radical polymerization of N-vinylpyrrolidone (NVP) in the presence of Laponite XLG (XLG) as a crosslinker, in comparison with the corresponding hydrogels prepared by using two conventional crosslinking divinyl monomers: N,N′-methylenebisacrylamide (MBA) and tri(ethylene glycol) divinyl ether (DVE). The structure and properties of the hydrogels were studied by FTIR, TEM, XRD, SEM, swelling and rheological and compressive mechanical measurements. The results showed that DVE and XLG are much better crosslinking agents for the synthesis of PNVP hydrogels than MBA, leading to larger gel fractions and more homogeneous network hydrogels. The hydrogels crosslinked by either DVE or XLG displayed comparable viscoelastic and compressive mechanical properties under the experimental conditions employed. The properties of the XLG-crosslinked hydrogels steadily improved as the clay content increased. The addition of XLG as a second crosslinker together with a divinyl monomer strongly enhanced the material properties in comparison with the hydrogels crosslinked by only one of the crosslinkers involved. The FTIR analyses suggested that the crosslinking of the NC hydrogels was the result of two different interactions occurring between the clay platelets and the PNVP chains. Laponite XLG displayed a uniform distribution within the NC hydrogels, the clay being mostly exfoliated. However, a small number of platelet agglomerations were still present. The PNVP hydrogels described here may find applications for water purification and in the biomedical field as drug delivery systems or wound dressings.

The issue of heavy metal and radionuclide contamination is still causing a great deal of concern worldwide for environmental protection and industrial sites remediation. Various techniques have been developed for surface decontamination aiming for high decontamination factors (DF) and minimal environmental impact, but strippable polymeric nanocomposite coatings are some of the best candidates in this area. In this study, novel strippable coatings for heavy metal and radionuclides decontamination were developed based on the film-forming ability of polyvinyl alcohol, with the remarkable metal retention capacity of bentonite nanoclay, together with the chelating ability of sodium alginate and with “new-generation” “green” complexing agents: iminodisuccinic acid (IDS) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC). These environmentally friendly water-based decontamination solutions are capable of generating strippable polymeric films with optimized mechanical and thermal properties while exhibiting high decontamination efficiency (DF ≈ 95–98% for heavy metals tested on glass surface and DF ≈ 91–97% for radionuclides ²⁴¹Am, ⁹⁰Sr-Y and ¹³⁷Cs on metal, painted metal, plastic, and glass surfaces).