Mikhail Malanin

Spectroscopic Examinations of Hydrogen Bonding in Hydroxy‐Functionalized ADMET Chemistry

Wide-angle X-ray scattering (WAXS) and temperature-dependent Fourier transform infrared spectroscopy (FTIR) spectroscopy are used to study hydrogen bonding interactions of a hydroxyl-functionalized polyethylene (PE) prepared by acyclic diene metathesis (ADMET) chemistry. The hydroxyl polymer exhibits an orthorhombic unit cell structure with characteristic reflection planes at (110) and (200), comparable to pure crystalline PE. These data unequivocally demonstrate that the OH branch is excluded from the PE lamellae. Furthermore, the polymer melts 100 °C higher than all previous analogous polymers possessing precision placed long aliphatic branches that also are excluded from PE lamellae. Temperature-dependent FTIR spectroscopy from ambient to 150 °C, followed by cooling to 125 °C supports exclusion of the hydroxyl group from the crystalline lattice. It is concluded that these hydroxyl groups form stable physical networks in the amorphous region via hydrogen bonding and are important for the overall morphology of such polymers.

On-line preferential solvation studies of polymers by coupled chromatographic-Fourier transform infrared spectroscopic flow-cell technique.

Qualitative and quantitative comparison between liquid chromatography (LC) and LC coupled with Fourier transform infrared spectroscopy (LC-FTIR) to evaluate preferential solvation phenomenon of polymers in a mixed solvent has been performed. These studies show that LC-FTIR technique leads to detailed structural information without the requirement for determination of additional parameters for quantitative analysis except calibration. Appropriate experimental conditions for preferential solvation study have been established by variation of polymer concentration, molar mass and eluent content.

Plant pressure sensitive adhesives: similar chemical properties in distantly related plant lineages.

AbstractMain conclusionA mixture of resins based on aliphatic esters and carboxylic acids occurs in distantly related generaPeperomiaandRoridula, serving different functions as adhesion in seed dispersal and prey capture. According to mechanical characteristics, adhesive secretions on both leaves of the carnivorous flypaper Roridula gorgonias and epizoochorous fruits of Peperomia polystachya were expected to be similar. The chemical analysis of these adhesives turned out to be challenging because of the limited available mass for analysis. Size exclusion chromatography and Fourier transform infrared spectroscopy were suitable methods for the identification of a mixture of compounds, most appropriately containing natural resins based on aliphatic esters and carboxylic acids. The IR spectra of the Peperomia and Roridula adhesive resemble each other; they correspond to that of a synthetic ethylene–vinyl acetate copolymer, but slightly differ from that of natural tree resins. Thus, the pressure sensitive adhesive properties of the plant adhesives are chemically proved. Such adhesives seem to appear independently in distantly related plant lineages, habitats, life forms, as well as plant organs, and serve different functions such as prey capture in Roridula and fruit dispersal in Peperomia. However, more detailed chemical analyses still remain challenging because of the small available volume of plant adhesive.

Temperature-Dependent Reinforcement of Hydrophilic Rubber Using Ice Crystals

This is the first study on the impact of ice crystals on glass transition and mechanical behavior of soft cross-linked elastomers. A hydrophilic elastomer such as epichlorohydrin–ethylene oxide–allyl glycidyl ether can absorb about ∼40 wt % of water. The water-swollen cross-linked network exhibits elastic properties with more than 1500% stretchability at room temperature. Coincidently, the phase transition of water into solid ice crystals inside of the composites allows the reinforcement of the soft elastomer mechanically at lower temperatures. Young’s modulus of the composites measured at −20 °C remarkably increased from 1.45 to 3.14 MPa, whereas at +20 °C, the effect was opposite and the Young’s modulus decreased from 0.6 to 0.03 MPa after 20 days of water treatment. It was found that a part of the absorbed water, ∼74% of the total absorbed water, is freezable and occupies nearly 26 vol % of the composites. Simultaneously, these solid ice crystals are found to be acting as a reinforcing filler at lower temperatures. The size of these ice crystals is distributed in a relatively narrow range of 400–600 nm. The storage modulus (E′) of the ice crystal-filled composites increased from 3 to 13 MPa at −20 °C. The glass transition temperature (−37 °C) of the soft cross-linked elastomer was not altered by the absorption of water. However, a special transition (melting of ice) occurred at temperatures close to 0 °C as observed in the dynamic mechanical analysis of the water-swollen elastomers. The direct polymer/filler (ice crystals) interaction was demonstrated by strain sweep experiments and investigated using Fourier transform infrared spectroscopy. This type of cross-linked rubber could be integrated into a smart rubber application such as in adaptable mechanics, where the stiffness of the rubber can be altered as a function of temperature without affecting the mechanical stretchability either below or above 0 °C (above the glass temperature region) of the rubber.

Rapid Scan In-Situ FT-IR Curing Studies of Low-Temperature Cure Thin Film Polymer Dielectrics in Solid State

Rapid scan in-situ Fourier Transform Infrared Spectroscopy (FT-IR) was used to characterize the cure process of two common low-temperature cure thin film polymer materials for wafer-level packaging applications. Beside a discussion of the spectral changes during the cure reaction, aspects of quantification the degree of cure will be shown. First, a photosensitive low-temperature cure ester-type polyimide precursor was investigated. As this material is a negative working photosensitive polyimide precursor, the impact of the photo-crosslinking on the imidization rate will be discussed in comparison to unexposed films. It will be shown, that at certain temperature / time conditions the exposure dose should be carefully adjusted to yield fully imidized films with minimized cure temperatures. Second, the thermosetting process of a low-k polymer dielectric based on divinyl siloxane bis-benzocyclobutene (DVS bis-BCB) was studied. Due to the chemical nature of the DVS bis-BCB resin a highly crosslinked network is formed during the cure process. Especially above 80% degree of cure at temperatures below 210°C a significant reduction of the reaction rate was measured. A two step cure process was developed, which can minimize the process time at elevated temperatures and yield a rather high degree of conversion in a reasonable process time. Both polymer cure reactions are characterized by a chemically-controlled and a diffusion controlled region with significant different reaction rates. Based on the aforementioned results a time, temperature and conversion dependent kinetic / diffusion model was used to describe the experimental data quantitatively. This model allows calculating very precisely the conversion in dependence on both, temperature and time, which will help to optimize the cure process for the two thin film polymers with respect to thermal budget and / or process time. Therefore this paper shows a method, which will help comparing different thin film polymer formulations regarding cure kinetics. Modeling of the data allows optimizing the process conditions to meet the temperature requirements in the area of wafer-level packaging and 3D integration.

Correlation of crystal alignment with interphase content in oriented high density polyethylene cast films

The microstructure and crystalline morphology of high density polyethylene (HDPE) cast films prepared in a wide range of draw ratios (1.6 to 148.8) were investigated. The flow-induced orientation of crystalline and amorphous phases was characterized using Fourier transform infrared spectroscopy (FTIR). The results showed that the draw ratio has a crucial role on the orientation state of the cast films. Scanning electron microscopy (SEM) images also confirmed this influence. The crystallinity of the films was examined using both differential scanning calorimetry (DSC) and Raman spectroscopy. Moreover, considering a three-phase structure (i.e. crystal, amorphous and interphase) for semi-crystalline polyethylene, Raman spectroscopy was also employed to estimate the amount of the so-called interphase in the HDPE cast films. As a result, the interphase content was found to decrease by increasing the applied draw ratio. The origin of this dependency was suggested to be due to a coil–stretch transition during elongation flow and the subsequent disentanglement. On the other hand, remarkable differences were observed in the CH2 bending vibration features of the Raman spectra of the cast films which were correlated with the applied draw ratios and with the calculated crystalline orientation functions.

Smart functional polymer coatings for paper with anti-fouling properties

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.