The ferro-, pyro- and piezoelectric properties of poly(vinylidene fluoride-co-trifluoroethylene) P(VDF-TrFE) have created interest with regard to its application in aqueous and ambient surroundings for sensors, functional coatings, and in the field of life sciences. P(VDF-TrFE) thin films are usually applied via spin-coating, but dip-coating will be advantageous especially for irregularly shaped substrates. The morphology of dip- and spin-coated semi-crystalline thin films is studied as a function of both the film thickness and the annealing temperature. The characterization of the films is carried out by grazing incidence wide-angle X-ray scattering (GIWAXS), X-ray reflectometry (XRR), and infrared reflection absorption spectroscopy (IRRAS). Atomic force microscopy measurements (AFM) are used to examine the resulting topography. It is found that both spin- and dip-coated thin films crystallize in the desired edge-on orientation, but the overall crystallinity after dip-coating is decreased compared to the spin-coated films of comparable thickness and the resulting roughness is increased. The higher roughness is most probably caused by the slower evaporation of the solvents and a secondary crystallization process at the air-polymer interface.

Hypothesis: Interphase properties in composites, adhesives and protective coatings can be predicted on the basis of interfacial interactions between polymeric precursor molecules and the inorganic surface during network formation. The strength of molecular interactions is expected to determine local segmen-tal mobility (polymer glass transition temperature, Tg) and cure degree. Experiments: Conventional analysis techniques and atomic force microscopy coupled with infrared (AFM-IR) are applied to nanocomposite specimens to precisely characterise the epoxy-amine/iron oxide inter-phase, whilst molecular dynamics simulations are applied to identify the molecular interactions under-pinning its formation. Findings: Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and high-resolution AFM-IR mapping confirm the presence of nanoscale under-cured interphase regions. Interfacial segregation of the molecular triethylenetetraamine (TETA) cross-linker results in an excess of epoxy functionality near synthetic hematite, (Fe2O3) magnetite (Fe3O4) and goethite (Fe(O)OH) particle surfaces. This occurs independently of the variable surface binding energies, as a result of entropic seg-regation during the cure. Thermal analysis and molecular dynamics simulations demonstrate that restricted segmental motion is imparted by strong interfacial binding between surface Fe sites in goethite, where the position of surface hydroxyl protons enables synergistic hydrogen bonding and elec-trostatic binding to Fe atoms at specific sites. This provides a strong driving force for molecular orienta-tion resulting in significantly raised Tg values for the goethite composite samples. (C) 2022 Elsevier Inc. All rights reserved.

Structural templating with homogeneous template layers is one of the strategies for controlling the orientation of small molecular absorbers in the photoactive layer of an organic solar cell to increase its power conversion efficiency. A main challenge thereby is the energetic alignment of the template molecules to the photoactive and charge-transporting materials. In the present study, the effects of a cluster-like template layer of ellagic acid (EA) on the morphology and optical properties of side-chain-substituted dicyanovinyl quaterthiophene (DCV4T-Et-2) thin films are discussed. In the monolayer regime, J-aggregation of DCV4T-Et-2 is confirmed. Insertion of the EA template layer leads to an improved aggregation behavior and formation of J-aggregates in DCV4T-Et-2 films near the EA interface. The orientation of DCV4T-Et-2 molecules in 30 nm thick films changes from "edge-on" to "face-on" due to a pi-pi interaction between the flat-lying EA molecules and the DCV4T-Et-2 molecules. The face-on orientation by templating is preserved in blend layers with C-60, and a considerable increase in the crystallinity of the DCV4T-Et-2 phase in the blend is induced. Organic solar cells based on templated DCV4T-Et-2:C-60 active layers exhibit more than a 50% increase in the efficiency compared to nontemplated active layers. The short-circuit current density and the fill factor are significantly improved. Although the energetic alignment of EA is not ideal, no additional open-circuit voltage losses were observed with templating, due to the cluster-like morphology of the EA layer. Our results demonstrate a cluster-like templating approach with the novel template molecule EA to tailor the molecular orientation, crystallinity, and consequently optical properties of organic semiconducting molecules without significant energetic losses favorable for use in organic electronics.

Ellagic acid (EA), an antioxidant from fruits or other plants, has recently evoked interest in the field of organic electronics because of its weak electron donor properties. In this work, the preparation of uniaxial pi-stacked EA films by thermal evaporation on different surfaces is reported for the first time. The (102) lattice plane of the pi-electron system was confirmed as the contact plane for one monolayer equivalent on Ag(111) by low-electron energy diffraction. X-ray and atomic force microscopy measurements revealed nanocrystalline grains with an average inplane size of 50 nm and considerably smaller average out-of-plane crystallite sizes (16-25 nm) in films of 16-75 nm thickness. The influence of different substrates was minor compared to the effect of the film thickness. An increase in the in-plane density of grains at larger film thicknesses was deduced from the trend in their uniaxial optical properties. Weak and strong intermolecular H-bonding interactions were identified in the EA crystal lattice, while a surplus of weak H-bonding was observed for the nanocrystallites in thin films, as compared to bulk EA. Finally, EA was coevaporated with the semiconducting thiophene molecule DCV4T-Et-2 to demonstrate principle interactions with a guest molecule by H-bonding analysis. Our results illustrate the feasibility of applying EA films as alignment layers for templating other semiconducting organic films used in organic electronic devices.

Polymer brushes not only represent emerging surface platforms for numerous bioanalytical and biological applications but also create advanced surface-tethered systems to mimic real-life biological processes. In particular, zwitterionic and nonionic polymer brushes have been intensively studied because of their extraordinary resistance to nonspecific adsorption of biomolecules (antifouling characteristics) as well as the ability to be functionalized with bioactive molecules. However, the relation between antifouling behavior in real-world biological media and structural changes of polymer brushes induced by surface preconditioning in different environments remains unexplored. In this work, we use multiple methods to study the structural properties of numerous brushes under variable ionic concentrations and determine the impact of these changes on resistance to fouling from undiluted blood plasma. We describe different mechanisms of swelling, depending on both the polymer brush coating properties and the environmental conditions that affect changes in both hydration levels and thickness. Using both fluorescent and surface plasmon resonance methods, we found that the antifouling behavior of these brushes is strongly dependent on the aforementioned structural changes. Moreover, preconditioning of the brush coatings (incubation at a variable salt concentration or drying) prior to biomolecule interaction may significantly improve the antifouling performance. These results suggest a new simple approach to improve the antifouling behavior of polymer brushes. In addition, the results herein enhance the understanding for improved design of antifouling and bioresponsive brushes employed in biosensor and biomimetic applications.

Epoxy-amine resins continue to find widespread use as the binders in protective and decorative organic coatings, as the matrix in composite materials, and as adhesives. In service, exposure to the environment ultimately results in oxidative deterioration of these materials, limiting the performance lifetime. Defining this auto-oxidation process is therefore a key challenge in developing more durable high-performance materials. In this study, we investigate oxidative degradation of a model resin based on diglycidyl ether of bisphenol-A (DGEBA) and an aliphatic amine hardener, triethylenetetraamine (TETA). Using infrared spectroscopy, we find that prior to the expected detection of formate groups (corresponding to the well-known radical oxidation mechanism of DGEBA), a band at 1658 cm(-1) forms, associated with amine cross-linker oxidation. Infrared microspectroscopy, in-situ heated ATR-infrared, Raman spectroscopy and AFM-IR techniques are thus employed to investigate the early stages of resin oxidation and demonstrate strong parallels between the initial stages of cured resin degradation and the auto-oxidation of TETA cross-linker molecules. (C) 2020 The Authors. Published by Elsevier Ltd.

Determining microplastics in environmental samples quickly and reliably is a challenging task. With a largely automated combination of optical particle analysis, Fourier transform infrared (FT-IR), and Raman microscopy along with spectral database search, particle sizes, particle size distributions, and the type of polymer including particle color can be determined. We present a self-developed, open-source software package for realizing a particle analysis approach with both Raman and FT-IR microspectroscopy. Our software GEPARD (Gepard Enabled PARticle Detection) allows for acquiring an optical image, then detects particles and uses this information to steer the spectroscopic measurement. This ultimately results in a multitude of possibilities for efficiently reviewing, correcting, and reporting all obtained results.

Silicon is one of the most promising anode materials for high energy density lithium ion batteries (LIBs) due to its high theoretical capacity and natural abundance. Unfortunately, significant challenges arise due to the large volume change of silicon upon lithiation/delithiation which inhibit its broad commercialization. An advanced binder can, in principle, reversibly buffer the volume change, and maintain strong adhesion toward various components as well as the current collector. In this work, we present the first report on the applicability of polyvinyl butyral (PVB) polymer as a binder component for silicon nanoparticles-based LIBs. Characteristic binder properties of commercial PVB and polyacrylic acid (PAA) polymers are compared. The work focuses on polymer mixtures of PVB polymers with PAA, for an improved binder composition which incorporates their individual advantages. Different ratios of polymers are systematically studied to understand the effect of particular polymer chains, functional groups and mass fractions, on the electrochemical performance. We demonstrate a high-performance polymer mixture which exhibits good binder-particle interaction and strong adhesion to Cu-foil. PAA/PVB-based electrode with a Si loading of similar to 1 mg/cm(2) tested between 0.01 and 1.2 V vs. Li/Li+ demonstrate specific capacities as high as 2170 mAh/g after the first hundred cycles. (C) The Author(s) 2019. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License.

Intrinsic conducting polymers are promising candidates for bioelectronic devices due to their structural kinship to biological matter combined with electronic functionality. For sophisticated nano‐scaled bioelectronic devices, P3RT‐type polythiophene derivatives bearing water‐soluble, biocompatible sidechains are particularly appealing due to their well‐defined molecular structure and controllable end‐group composition. However, their employment in bioelectronic devices is not as straightforward as expected. Challenging is their poor performance due to, e.g., the low charge carrier concentration in the native state. Partial oxidation of these polymers by strong electron acceptors, so‐called p‐type doping, can increase the charge carrier concentration, and thus, the conductivity. The solution‐based molecular p‐type doping of such a water‐soluble polythiophene derivative by the dopant tetrafluoro‐tetracyano‐quinodimethane is reported. The mechanism of the doping process is thoroughly investigated by a combination of spectroscopic techniques covering the UV‐VIS and IR regions. Furthermore, the morphological and electronic properties of polymer thin films are examined as a dependence on the dopant concentration.

Catalysis by enzymes on surfaces has many applications. However, strategies for efficient enzyme immobilization with preserved activity are still in need of further development. In this work, we investigate polyelectrolyte brushes prepared by both grafting-to and grafting-from with the aim to achieve high catalytic activity. For comparison, self-assembled monolayers that bind enzymes with the same chemical interactions are included. We use the model enzyme glucose oxidase and two kinds of polymers: anionic poly(acrylic acid) and cationic poly(diethylamino)methyl methacrylate. Surface plasmon resonance and spectroscopic ellipsometry are used for accurate quantification of surface coverage. Besides binding more enzymes, the "3D-like" brush environment enhances the specific activity compared to immobilization on self-assembled monolayers. For grafting-from brushes, multilayers of enzymes were spontaneously and irreversibly immobilized without conjugation chemistry. When the pH was between the pI of the enzyme and the p Ka of the polymer, binding was considerable (thousands of ng/cm2 or up to 50% of the polymer mass), even at physiological ionic strength. However, binding was observed also when the brushes were neutrally charged. For acidic brushes (both grafting-to and grafting-from), the activity was higher for covalent immobilization compared to noncovalent. For grafting-from brushes, a fully preserved specific activity compared to enzymes in the liquid bulk was achieved, both with covalent (acidic brush) and noncovalent (basic brush) immobilization. Catalytic activity of hundreds of pmol cm-2 s-1 was easily obtained for polybasic brushes only tens of nanometers in dry thickness. This study provides new insights for designing functional interfaces based on enzymatic catalysis.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Herein, we report on the use of a combined setup of quartz-crystal microbalance, with dissipation monitoring and spectroscopic ellipsometry, to comprehensively investigate the covalent immobilization of an enzyme to a polymer layer. All steps of the covalent reaction of the model enzyme glucose oxidase with the poly(acrylic acid) brush by carbodiimide chemistry, were monitored in-situ. Data were analyzed using optical and viscoelastic modeling. A nearly complete collapse of the polymer chains was found upon activation of the carboxylic acid groups with N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide and N-Hydroxysuccinimide. The reaction with the amine groups of the enzyme occurs simultaneously with re-hydration of the polymer layer. Significantly more enzyme was immobilized on the surface compared to physical adsorption at similar conditions, at the same pH. It was found that the pH responsive swelling behavior was almost not affected by the presence of the enzyme.

Epoxy resins remain some of the most widely used industrial materials, comprising the matrix component of many paints, adhesives, and structural composites. Extensive interphase structures within epoxies have often been proposed on the basis of thin film studies, where thickness-dependent thermal and chemical properties are commonly observed. The nature of these regions, thought to extend up to hundreds of micrometers into resins, is therefore widely considered to control properties such as the fracture toughness of composites and the adhesion and corrosion resistance of epoxy coatings formed on metal oxides. Nonetheless, little is understood about the formation mechanism and extent of interphase regions. Here, we first confirm the thickness-dependent curing properties of diglycidyl ether of bisphenol A (DGEBA) cross-linked with triethylenetetramine (TETA). Increased levels of residual epoxy are consistently measured for thinner films, but this is found to be substrate-independent (on gold or carbon steel). Furthermore, transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses rule out organometallic formation by amine complexation by the absence of iron in nanoscale regions around the interface. Instead, it is shown that the excess epoxy in thin films develops as a result of amine consumption at the air-polymer interface. Finally, nanoscale functional group mapping of cross sections is achieved using atomic force microscopy-infrared (AFM-IR) analysis, and this demonstrates that no chemical gradient exists within films. We therefore conclude that no buried nanoscale chemical interphase is formed within the epoxy-amine coatings.

The development of bioengineered surface coatings with stimuli-responsive properties is beneficial for a number of biomedical applications. Environmentally responsive and switchable polymer brush systems have a great potential to create such smart biointerfaces. This study focuses on the bioconjugation of cell-instructive peptides, containing the arginine-glycine-aspartic acid tripeptide sequence (RGD motif), onto well-defined polymer brush films. Herein, the highly tailored end-grafted homo polymer brushes are either composed of the polyelectrolyte poly(acrylic) acid (PAA), providing the reactive carboxyl functionalities, or of the temperature-responsive poly(N-isopropylacrylamide) (PNIPAAm). Of particular interest is the preparation of grafted-to binary brushes using both polymers and their subsequent conversion to RGD-biofunctionalized PNIPAAm-PAA binary brushes by a carbodiimide conjugation method. The bioconjugation process of two linear RGD-peptides Gly-Arg-Gly-Asp-Ser and Gly-Arg-Gly-Asp-Ser-Pro-Lys and one cyclic RGD-peptide cyclo(Arg-Gly-Asp-D-Tyr-Lys) is comparatively investigated by complementary analysis methods. Both techniques, in situ attenuated total reflectance Fourier transform infrared spectroscopy measurements and the in situ spectroscopic ellipsometric analysis, describe changes of the brush surface properties due to biofunctionalization. Besides, the bound RGD-peptide amount is quantitatively evaluated by ellipsometry in comparison to high performance liquid chromatography analysis data. Additionally, molecular dynamic simulations of the RGD-peptides themselves allow a better understanding of the bioconjugation process depending on the peptide properties. The significant influence on the bioconjugation result can be derived, on the one hand, of the polymer brush composition, especially from the PNIPAAm content, and, on the other hand, of the peptide dimension and its reactivity.

We report investigations on the salt sensitivity of the thermoresponsive behavior of PNIPAAm brushes applying the quartz crystal microbalance coupled with spectroscopic ellipsometry technique. This approach enables a detailed study of the optical and mechanical behavior of the polymer coatings. Additional conclusions can be drawn from the difference between both techniques due to a difference in the contrast mechanism of both methods. A linear shift of the phase-transition temperature to lower temperatures with the addition of sodium chloride was found, similar to the behavior of free polymer chains in solution. The thermal hysteresis was found to be decreased by the addition of sodium chloride to the solution, hinting to the interaction of the ions with the amide groups of the polymer, whereby the formation of hydrogen bonds is hindered. The results of this study are of relevance to the application of PNIPAAm brushes in biological fluids and demonstrate the additional potential of the ion sensitivity besides the better known thermosensitivity.

Cellulose, as the main component of paper, is becoming more and more important for several high tech applications because of its beneficial properties, such as abundance, low cost, renewability, mechanical robustness and biocompatibility. To make cellulose accessable for new applications it is necessary to introduce new properties, which can be done by surface modification e.g. grafting of polymers onto surfaces. In this work, two comb copolymers, poly[(2-methyl-2-oxazoline methacrylate)-co-glycidyl methacrylate] and poly[(2-methacryloyloxyethyl phosphorylcholine)-co-glycidyl methacrylate], were synthesized by free radical polymerization of glycidyl methacrylate and oligo(2-methyl-2-oxazoline) as well as 2-methacryloyloxyethyl phosphorylcholine. After extensive characterization the polymers were covalently attached to thin cellulose model layers and filter paper using a one-step grafting-to approach. For the comprehensive analysis of these layers, thin cellulose films were fabricated on silicon wafers by spin coating of trimethylsilyl cellulose followed by acid hydrolysis which resulted in homogeneous layers as substrates for the grafting process of the functional polymers. The layers were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), atomic force microscopy (AFM) and energy-dispersive X-ray spectroscopy (EDX). To demonstrate the high potential of such polymer-modified cellulose materials, protein repellance of the cellulose films, containing peptidomimetic 2-methyl-2-oxazoline and zwitterionic phosphorylcholine groups after successful functionalization, is shown. Cell adhesion experiments using Bacillus subtilis, Escherichia coli and Saccharomyces cerevisiae indicate the considerable anti-fouling capacity against both Gram-positive and Gram-negatve bacteria as well as the yeast fungus.

Different in-situ methods were utilized to study thin film polyimide layers in the context of low-temperature cure processes <;230°. In-situ Fourier Transform Infrared Spectroscopy, temperature dependent Spectroscopic Ellipsometry and Thermal Analytical Methods were used to characterize the degree of imidization, glass transition temperature and thermal stability respectively. The final degree of imidization in the low-temperature cure region depends strongly on the UV induced network formation during the upstream Iithographic process. A higher crosslinking density reduces the degree of imidization from 97.5% for an unexposed layer to 73.2% for higher crosslinked film. Glass transition temperature and thermal stability are significantly reduced in the case of curing temperatures below 230°C. The glass transition temperature is decreased from 240°C to 218°C for cure temperatures of 350°C and 230°C respectively. The yielded film stress is reduced in parallel, which was proved by determination of wafer warpage and bow.

In recent years, many studies on the analysis of microplastics (MP) in environmental samples have been published. These studies are hardly comparable due to different sampling, sample preparation, as well as identification and quantification techniques. Here, MP identification is one of the crucial pitfalls. Visual identification approaches using morphological criteria alone often lead to significant errors, being especially true for MP fibers. Reliable, chemical structure-based identification methods are indispensable. In this context, the frequently used vibrational spectroscopic techniques but also thermoanalytical methods are established. However, no critical comparison of these fundamentally different approaches has ever been carried out with regard to analyzing MP in environmental samples. In this blind study, we investigated 27 single MP particles and fibers of unknown material isolated from river sediments. Successively micro-attenuated total reflection Fourier transform infrared spectroscopy (μ-ATR-FTIR) and pyrolysis gas chromatography-mass spectrometry (py-GCMS) in combination with thermochemolysis were applied. Both methods differentiated between plastic vs. non-plastic in the same way in 26 cases, with 19 particles and fibers (22 after re-evaluation) identified as the same polymer type. To illustrate the different approaches and emphasize the complementarity of their information content, we exemplarily provide a detailed comparison of four particles and three fibers and a critical discussion of advantages and disadvantages of both methods.