The industrial production of prototypes made of polyurethane via silicone molds in the vacuum casting process is one of the most widespread applications of rapid tooling. The silicone molds show progressive deterioration, as the isocyanate component of the polyurethane resin diffuses into the mold cavity surface during the casting process, thus limiting their durability. Here, we present the first comprehensive description of the underlying chemical and physical mechanisms on a molecular level. It is shown that the isocyanate polymerizes inside the polydimethylsiloxane matrix with moisture to polyurea. Polyurea clusters, which emerge from the resulting interpenetrating polymer network with continuing isocyanate exposure, promote fissure formation under mechanical demolding stresses. The mechanism was investigated with a wide variety of characterization methods, and qualitative variations were demonstrated using different commercial materials. Influencing factors such as mold geometry, process flow, and different aspects of the material composition were examined experimentally. A thorough understanding of the deterioration mechanism paves the way for the development of durable molds and an economical midseries technology in plastics processing.

Thermally stabilized and subsequently carbonized nanofibers are a promising material for many technical applications in fields such as tissue engineering or energy storage. They can be obtained from a variety of different polymer precursors via electrospinning. While some methods have been tested for post-carbonization doping of nanofibers with the desired ingredients, very little is known about carbonization of blend nanofibers from two or more polymeric precursors. In this paper, we report on the preparation, thermal treatment and resulting properties of poly(acrylonitrile) (PAN)/poly(vinylidene fluoride) (PVDF) blend nanofibers produced by wire-based electrospinning of binary polymer solutions. Using a wide variety of spectroscopic, microscopic and thermal characterization methods, the chemical and morphological transition during oxidative stabilization (280 °C) and incipient carbonization (500 °C) was thoroughly investigated. Both PAN and PVDF precursor polymers were detected and analyzed qualitatively and quantitatively during all stages of thermal treatment. Compared to pure PAN nanofibers, the blend nanofibers showed increased fiber diameters, strong reduction of undesired morphological changes during oxidative stabilization and increased conductivity after carbonization.

The combined benefits of moisture-stable phosphonic acids and mesoporous silica materials (SBA-15 and MCM-41) as large-surface-area solid supports offer new opportunities for several applications, such as catalysis or drug delivery. We present a comprehensive study of a straightforward synthesis method via direct immobilization of several phosphonic acids and phosphoric acid esters on various mesoporous silicas in a Dean–Stark apparatus with toluene as the solvent. Due to the utilization of azeotropic distillation, there was no need to dry phosphonic acids, phosphoric acid esters, solvents, or silicas prior to synthesis. In addition to modeling phosphonic acids, immobilization of the important biomolecule adenosine monophosphate (AMP) on the porous supports was also investigated. Due to the high surface area of the mesoporous silicas, a possible catalytic application based on immobilization of an organocatalyst for an asymmetric aldol reaction is discussed.

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/admi.202200245.