Innovative Measurement Techniques in Surface Science

We describe four new experimental techniques advanced during the last decade in the authors’ laboratory. The techniques include photon scanning tunneling microscopy; aberration‐corrected low‐energy electron microscopy in combination with photoelectron emission microscopy, microcalorimetry, and electron‐spin resonance spectroscopy. It is demonstrated how those techniques may be applied to solve fundamental problems in surface science with growing demands to tackle complex nanoscopic systems, and, in particular in catalysis science, which, without the availability of those techniques, would be difficult if not impossible to address.     

Miscibility diagrams of random copolymer blend systems

The miscibility of copolymers A_xB_1?x and A_yB_1?y, derived from the same monomer pair (A, B) but differing in composition, was studied. The systems (A, B) were (S, MMA), (BMA, MMA), (S, BMA), and (CIS, BMA) (S: styrene, CIS: p-chlorostyrene, MMA: methylmethacrylate, BMA: n-butylmethacrylate). Miscibility diagrams were recorded, at low and high temperatures, using cast films and dry films. All blend systems feature hightemperature miscibility gaps. Unusual effects of the compositions x and y on miscibility in blends A_xB_1?x/A_yB_1?y were observed. The classical prediction that miscibility should depend only on the composition difference |x – y| usually is too simple. It appears necessary to consider dyad interactions.     

Beam-helicity asymmetry in photon and pion electroproduction in the Δ(1232)-resonance region at Q2 = 0.35(GeV/c)2

The beam-helicity asymmetry has been measured simultaneously for the reactions p→epγ and p→epπ ⁰ in the Δ(1232)-resonance region at Q ² = 0.35(GeV/c)². The experiment was performed at MAMI with a longitudinally polarized beam and an out-of-plane detection of the proton. The results are compared with calculations based on dispersion relations for virtual Compton scattering and with the MAID model for pion electroproduction. There is an overall good agreement between experiment and theoretical calculations. The remaining discrepancies may be ascribed to an imperfect parametrization of some γ ^(*) N→πN multipoles, mainly contributing to the non-resonant background. The beam-helicity asymmetry in both channels (γ and π ⁰) shows a good sensitivity to these multipoles and should allow future improvement in their parametrization.     

Estimation of Lattice Enthalpies of Ionic Liquids Supported by Hirshfeld Analysis

New measurements of vaporization enthalpies for 15 1:1 ionic liquids are performed by using a quartz‐crystal microbalance. Collection and analysis of 33 available crystal structures of organic salts, which comprise 13 different cations and 12 anions, is performed. Their dissociation lattice enthalpies are calculated by a combination of experimental and quantum chemical quantities and are divided into the relaxation and Coulomb components to give an insight into elusive short‐range interaction enthalpies. An empirical equation is developed, based on interaction‐specific Hirshfeld surfaces and solvation enthalpies, which enables the estimation of the lattice enthalpy by using only the crystal‐structure data.     

Poly(paraphenylene sulfide) and Poly(metaphenylene sulfide) via Light‐Initiated SRN1‐Type Polymerization of Halogenated Thiophenols

In this work, the synthesis of various halogenated thiophenol derivatives is presented. These thiophenols are used as monomers in light‐initiated S_RN1‐type radical polymerization reactions. The method provides easy access to industrially relevant poly(paraphenylene sulfide) and poly(metaphenylene sulfide). The influence of the halide leaving group and of other substituents in the thiophenol monomer on the polymerization process is investigated.

     

Enhancing corrosion resistance of zinc-filled protective coatings using conductive polymers

Organic coatings containing zinc are amply used for the protection of metals, particularly steel structures. Ways to reduce the zinc content in the coating materials are sought for environmental and financial reasons. Our previous work (Kohl, Prog Org Coat 77:512–517, 2014; Kohl and Kalendová, Mater Sci Forum 818: 171–174, 2015a) suggested that one of the options consists in the use of conductive polymers in the formulation of the zinc coatings. The benefits of conductive polymers include nontoxicity, high stability, electric conductivity and redox potential. Previously we focussed on the effect of conductive polymers added to the organic coatings so as to complete the zinc volume concentration to 67%. The anticorrosion efficiency of the organic coatings was found to improve with increasing polyaniline phosphate or polypyrrole concentrations. Zinc content reduction in the system, however, did not attain more than 5%. The present work focusses on systems where the organic coatings are prepared with zinc having a pigment volume concentration PVC = 50%. Zinc content reduction in the system attains up to 20%. This work examines the mechanical and anticorrosion properties of the organic coatings with reduced zinc contents. The present work was devoted to the feasibility of using of conductive polymers in the formulation of coatings with reduced zinc contents. The conductive polymers included polyaniline, polypyrrole and poly(phenylenediamine); these were synthesised and characterised using physico-chemical methods. Polyphenylenediamine as a potential corrosion inhibitor has not been paid adequate attention so far. Subsequently, organic coatings with reduced zinc contents and containing the pigments at 0.5, 1 and 3% volume concentrations were formulated. The coatings were subjected to mechanical tests and accelerated corrosion tests to assess their mechanical and corrosion resistance. The corrosion resistance of the organic coatings was also studied by linear polarisation. The results of the mechanical tests, accelerated corrosion tests and linear polarisation measurements indicate that the organic coating properties get affected by the conductive polymer type as well as by the pigment volume concentration. The important finding is that the use of conductive polymers in coatings with reduced zinc contents was beneficial in all cases.     

Sustainability of microporous polymers and their applications

Microporous polymers (MPs) are studied for their intriguing chemistry and physics as well as their potential application in catalytic transformations, gas-separation processes, water purification and so on. Here, we critically review MPs with respect to the sustainability aspects of their synthesis as well as their applications that have sustainable character. Some MPs have been synthesized from monomers derived from biomass resources, but there is certainly a large potential for further developments. There are also opportunities to improve the sustainability of MP synthesis in terms of the use of solvents, catalysts, and related aspects. The applications of MPs in processes related to sustainability depend upon multiple properties. A rich and flexible chemistry is important to applications as catalysts for, among other useful reactions, the photoreduction of CO₂ and selective oxidation. The (ultra)micropore volume of MPs are crucial in gas-separation applications such as CO₂ capture, and the chemisorption of CO₂ on MP-tethered alkylamines could offer a means to remove that gas from dilute mixtures. When it comes to the storage of H₂ and CH₄ in MPs for onboard use in fuel cell or biogas cars, volumetric capacity is paramount, meaning that the density of the MPs must be considered. Finally, for use in separation and purifications from liquid mixtures (aqueous or hydrocarbon-based), crosslinked MPs are more limited than the solution-processable MPs that can be more easily processed into films and membranes.