Abstract:Surface science, which includes the preparation, development and analysis of surfaces and coatings, is essential in both fundamental and applied as well as in engineering and industrial research. Contact angle measurements using sessile drop techniques are commonly used to characterize coated surfaces or surface modifications. Well-defined surfaces structures at both nanoscopic and microscopic level can be achieved but the reliable characterization by means of contact angle measurements and their interpretation often remains an open question. Thus, we focused our research effort on one main problem of surface science community, which is the determination of correct and valid definitions and measurements of contact angles. In this regard, we developed the high-precision drop shape analysis (HPDSA), which involves a complex transformation of images from sessile drop experiments to Cartesian coordinates and opens up the possibility of a physically meaningful contact angle calculation. To fulfill the dire need for a reproducible contact angle determination/definition, we developed three easily adaptable statistical analyses procedures. In the following, the basic principles of HPDSA will be explained and applications of HPDSA will be illustrated. Thereby, the unique potential of this analysis approach will be illustrated by means of selected examples.

No abstract

The migration and transport of polymerization initiators are problematic for commercially used polymerization procedures. For example, UV printing of packaging generates products with potentially harmful components that come in contact with food. Enlarging the size of the initiator is the only way to prevent contamination, e.g., by gas phase transport. In this manuscript, the synthesis and advanced and full analyses of novel nanoparticle-based types of non-migration, fragmenting and non-fragmenting photo-initiators will be presented in detail. This study introduces non-fragmenting/"Norrish type II" and fragmenting/"Norrish type I" ZnO nanoparticle-based initiators and compares them with two commercial products, a "Norrish type I" initiator and a "Norrish type II" initiator. Therefore, inter alia, the recently developed analysis involves examining the solidification by UV-vis and the double bond content by Raman. Irradiation is performed using absolute and spectrally calibrated xenon flash lights. A novel procedure for absolute and spectral calibration of such light sources is also presented. The non-optimized "Norrish type II" particle-based initiator is already many times faster than benzophenone, which is a molecular initiator of the same non-fragmenting type. This experimentally observed difference in reactive particle-based systems without co-initiators is unexpected. Co-initiators are normally an additional molecular species, which leads to migration problems. The discovery of significant initiation potential resulting in a very well-dispersed organic-inorganic hybrid material suggests a new field of research opportunities at the interface of physical chemistry, polymer chemistry and engineering science, with enormous value for human health.

We propose to use 3-hydroxyflavone as a versatile high performance visible light photoinitiator (PI) in combination with an amino acid (N-phenylglycine) for the free radical polymerization (FRP) of methacrylates in thick samples (e.g., 3D printing) or composites upon visible light exposure (light-emitting diode LED@405 nm or LED@477 nm). The high originality of this approach is the use of safer compounds in photoinitiating systems (combination flavone derivative/amino acid). 3-Hydroxyflavone can also be used in three-component systems with an iodonium salt and an amine for the cationic polymerization of epoxides upon exposure to near-UV light LED@385 nm. Also interestingly, a charge transfer complex (CTC) between N-phenylglycine NPG and iodonium salt gives also remarkable initiating performance for free radical polymerization of methacrylates upon mild light irradiation conditions (LED@405 nm). High polymerization initiating abilities are found, and high final reactive function conversions are obtained. The use of the new proposed initiating systems as materials for laser write or 3D printing experiments was also especially carried out with the formation of printed green fluorescent photopolymers. This green fluorescence obtained with naturally occurring 3-hydroxyflavone compound can be ascribed to the excited state intramolecular proton transfer ESIPT character. A full picture of the included photochemical mechanisms is given. Remarkably, the 3-hydroxyflavone/amino acid system is also very efficient for photocomposites synthesis with glass fibers (thick samples with good depth of cure) using UV or LED@395 nm conveyor.

Nano ZnO is able to photo‐initiate free‐radical polymerization of bulk acrylic esters. This kind of reaction is used in science and in industrial photocuring processes. Particle based initiators have the potential to solve the problem of migration. At the moment performance is not sufficient to utilize nanoparticle initiators for industrial applications. One way to improve the efficiency of the nanoparticles is to attach a modifier and to investigate the reactivity of the fragmentation products. Synthesis and reactivity improvement will be demonstrated using both computations and curing measurements made with a novel Raman–UV‐vis system. The combined system allows for real‐time in situ detection of the photopolymerization both in the transversal (deep‐) and in the lateral direction (area‐curing).