Multivariate process trajectories for molecular description of MF thermal curing and correlation with hydrolytic stability

During curing of thermosetting resins the technologically relevant properties of binders and coatings develop. However, curing is difficult to monitor due to the multitude of chemical and physical processes taking place. Precise prediction of specific technological properties based on molecular properties is very difficult. In this study, the potential of principal component analysis (PCA) and principal component regression (PCR) in the analysis of Fourier transform infrared (FTIR) spectra is demonstrated using the example of melamine-formaldehyde (MF) resin curing in solid state. FTIR/PCA-based reaction trajectories are used to visualize the influence of temperature on isothermal cure. An FTIR/PCR model for predicting the hydrolysis resistance of cured MF resin from their spectral fingerprints is presented which illustrates the advantages of FTIR/PCR compared to the combination differential scanning calorimetry/isoconversional kinetic analysis. The presented methodology is transferable to the curing reactions of any thermosetting resin and can be applied to model other technologically relevant final properties as well.     

Examining the Impact of Squaric Acid as a Crosslinking Agent on the Properties of Chitosan-Based Films

Hydrogels based on chitosan are very versatile materials which can be used for tissue engineering as well as in controlled drug delivery systems. One of the methods for obtaining a chitosan-based hydrogel is crosslinking by applying different components. The objective of the present study was to obtain a series of new crosslinked chitosan-based films by means of solvent casting method. Squaric acid—3,4-dihydroxy-3-cyclobutene-1,2-dione—was used as a safe crosslinking agent. The effect of the squaric acid on the structural, mechanical, thermal, and swelling properties of the formed films was determined. It was established that the addition of the squaric acid significantly improved Young’s modulus, tensile strength, and thermal stability of the obtained materials. Moreover, it should be stressed that the samples consisting of chitosan and squaric acid were characterized by a higher swelling than pure chitosan. The detailed characterization proved that squaric acid could be used as a new effective crosslinking agent.     

Crystallization,structure, and enhanced mechanical property of ethylene-octene elastomer crosslinked with dicumyl peroxide

Crosslinking of polyolefin elastomer (POE, ENGAGE™ 8480) with Dicumyl Peroxide (DCP) can have effects on its crystallization dynamics, crystal structure, and properties. The POE crosslinked uniformly has significantly lower crystalline ability than the one with only amorphous phase crosslinked, which, in turn, has weaker crystalline ability than neat POE. The crystallinity and melting point depend on how the POE is crosslinked. The neat POE and POE crosslinked in amorphous phase only, are investigated with DSC and in-situ tensile/synchrotron radiation (WAXD/SAXS). In situ tensile/synchrotron X-ray during a uniaxial stretching process indicates that severe crystal fragmentation is observed at a strain around 45%, and with further increase in strain. The stress in the crosslinked POE is significantly larger than neat POE. For both samples, crystal orientation increases sharply within the strain range up to 88% where orientation-induced new crystals aligned in stretching direction are observed. The long period increases more in stretching direction for the crosslinked POE, consistent with larger stress in this sample, and the stress difference is more pronounced at large strains (27.3 vs. 10.9 MPa at a strain 435%). Permanent set of the crosslinked POE is smaller, consistent with less oriented crystals observed after the test for permanent set.     

Design,preparation, and characterization of new high-refractive index hybrid organic–inorganic polysiloxanes: Innovative coatings for optoelectronic applications

The current demand for high-refractive index materials is very high due to their importance in optoelectronic applications. Such materials already exist in the market, but they present many disadvantages. They might contain toxic metals; their preparation can be challenging or produce high quantity of waste. Consequently, there is an urgent need to produce new friendly coatings with high-refractive index. Hybrid organic–inorganic polysiloxanes can offer a solution to this problem. They can be easily prepared from nontoxic alkoxy silanes using the sol–gel chemistry process. Herein, a series of new hybrid polysiloxanes are synthesized from the monomer 1–(2–(triethoxysilyl)ethyl)triphenylsilane and other silanes. The preparation of the macromolecules is optimized at both stages of the sol–gel process. The polymers are characterized by gel permeation chromatography and NMR spectroscopy. Spin coating of the materials on silicon wafers, followed by film thickness and refractive index measurements, indicates that the new polysiloxanes can have refractive indexes as high as 1.6 with thicknesses varying from 2200 to 3700 nm. Consequently, it is expected that the new materials described in this report are valuable for optoelectronic applications such as high-dielectric constant (high-k) gate oxides, interlayer high-k dielectrics, or high-refractive index abrasion resistant coatings.     

Molecularly imprinted macroporous polymer monolithic layers for L-phenylalanine recognition in complex biological fluids

In present work, the development of macroporous monolithic layers bearing the artificial recognition sites toward L-phenylalanine has been carried out. The set of macroporous poly(2-aminoethyl methacrylate-co-2-hydroxyethyl methacrylate-co-ethylene glycol dimethacrylate) materials with average pore size ranged in 340–1200 nm was synthesized. The applicability of Hildebrand's and Hansen's theories for the prediction of polymer compatibility with porogenic solvents was evaluated. The dependences of average pore size on theoretically calculated parameters were plotted. The linear trend detected for Hansen's theory has indicated the high suitability of this approach to select appropriate porogens. The synthesized monolithic MIP layers were tested toward the ability to rebind phenylalanine-derivative in microarray format. The influence of such factors as average pore size of the material, the concentration of template molecule in polymerization mixture, interaction time of analyte with its imprinted sites on binding efficiency were studied. The developed materials demonstrated good analyte rebinding from buffer solution with recognition factors 2.5–3.4 depending on the MIP sample. The comparable rebinding efficiency was also detected when the analysis was carried using complex biological media. The selectivity of phenylalanine binding from the equimolar mixture of structural analogues was 81.9% for free amino acid and 91.2% for labeled one.     

Structural insights into peptide self-assembly using photo-induced crosslinking experiments and discontinuous molecular dynamics

Determining the structure of the (oligomeric) intermediates that form during the self-assembly of amyloidogenic peptides is challenging because of their heterogeneous and dynamic nature. Thus, there is need for methodology to analyze the underlying molecular structure of these transient species. In this work, a combination of fluorescence quenching, photo-induced crosslinking (PIC) and molecular dynamics simulation was used to study the assembly of a synthetic amyloid-forming peptide, Aβ_16-22. A PIC amino acid containing a trifluormethyldiazirine (TFMD) group—Fmoc(TFMD)Phe—was incorporated into the sequence (Aβ*_16–22). Electrospray ionization ion-mobility spectrometry mass-spectrometry (ESI-IMS-MS) analysis of the PIC products confirmed that Aβ*_16–22 forms assemblies with the monomers arranged as anti-parallel, in-register β-strands at all time points during the aggregation assay. The assembly process was also monitored separately using fluorescence quenching to profile the fibril assembly reaction. The molecular picture resulting from discontinuous molecule dynamics simulations showed that Aβ_16-22 assembles through a single-step nucleation into a β-sheet fibril in agreement with these experimental observations. This study provides detailed structural insights into the Aβ_16-22 self-assembly processes, paving the way to explore the self-assembly mechanism of larger, more complex peptides, including those whose aggregation is responsible for human disease.     

Gelation via cationic chelation/crosslinking of acrylic‐acid‐based polymers

The gelation characteristics of acrylic‐acid‐based polymers in the presence of a range of cationic species, namely Ca²⁺, Mg²⁺ and Al³⁺, were investigated using in situ rheological measurements during photo‐polymerisation. Fourier transform mechanical spectroscopy was used to identify the gel point, using the Winter–Chambon criteria which allow the gel point to be pinpointed by establishing the sample spanning network and quantitatively determining stiffness, relaxation exponent, gel stiffness and fractal dimensions. The results showed that the gelation processes were greatly influenced by the type of cationic species that was used in the syntheses. At the gel point, more open network clusters were formed when Al³⁺ cations were used instead of Ca²⁺ cations or Mg²⁺ cations, all relating to chloride salts. Although the concentrations of the chelating/crosslinking aluminium species affected the kinetics of the gelation, the critical gel characteristics were hardly affected. Also the solubility of the chosen aluminium salt was shown to dictate the crosslinking rates and the properties of the critical gels. The extents of the reactions and the types of network formed at the gel point and beyond indicated that reactions between the Al³⁺ ions and COOH sites, from growing poly(acrylic acid) molecular chains, differ from those exhibited by Mg²⁺ and Ca²⁺ ions. All of the chelation/crosslinking reactions met the criteria of low mutation number (N_mu), such that in all cases N_mu ? 1. © 2019 Society of Chemical Industry     

Enhanced impact strength of compatibilized poly(lactic acid)/polyamide 11 blends by a crosslinking agent

Maleated poly(lactic acid) (PLA-g-MA) was prepared through melt grafting of maleic anhydride onto a PLA backbone with the aid of a radical initiator. PLA-g-MA thus formed was incorporated into PLA/polyamide 11 (PA11) blends as a reactive compatibilizer. By morphological observation, it was assessed that PLA-g-MA lowered the interfacial energy and strengthened the interface between PLA and PA11. However, the compatibilized PLA/PA11 blends did not show significant improvement of impact strength compared with noncompatibilized PLA/PA11 blends. Measurements of the molecular weight and impact strength of PLAs compounded with various amounts of radical initiators revealed that decreased molecular weight of PLA by the radical initiator used for the preparation of PLA-g-MA is responsible for this unexpected result. To compensate the decrease of the molecular weight, a crosslinking agent was incorporated in the preparation step of PLA-g-MA. It was found that the crosslinking agent is effective in preventing the molecular weight reduction. As a result, the impact strength of the PLA/PA11 blend was enhanced to a great extent by the PLA-g-MA prepared with the crosslinking agent.     

One‐shot radical polymerization of vinyl monomers with different reactivity accompanying spontaneous delay of polymerization for the synthesis of double‐network hydrogels

Double‐network hydrogels were conveniently synthesized by the one‐shot radical polymerization of an ionic monomer for the first network and a non‐ionic monomer for the second network in the presence of crosslinkers by simultaneous addition of the monomers, that is, one‐shot and spontaneous two‐step polymerization accompanying the delay of polymerization of a second network monomer. We analyzed the polymerization process based on the conversion of each monomer during the reaction in the absence of crosslinkers. Then we fabricated the double‐network hydrogels using several polymerization systems consisting of a conjugated monomer and a non‐conjugated monomer in the presence of the dual crosslinkers. We analyzed the swelling, mechanical and viscoelastic properties of hydrogels synthesized by one‐shot radical polymerization to confirm the production mechanism and the network structure of the hydrogels. © 2020 Society of Chemical Industry     

Enhanced mechanical toughness of carbon nanofibrous-coated surface modified Kevlar reinforced polyurethane/epoxy matrix hybrid composites

High-performance Kevlar fiber had extensively been explored to upgraded mechanical properties of the advanced composites. Therefore, this study aimed a challenging work to grow carbon nanofibers onto the Kevlar fiber to improve its fiber-matrix interaction properties. It was successfully done through inexpensive flame deposition as well as modification of matrix with hybrid resin using polyurethane-epoxy mixture. A hand-layup method had been adopted to manufacture the composite laminates. The chemical and surface structures of the prepared laminae were examined by scanning electron microscopy, Raman spectroscopy, X-ray diffraction, and the composite's properties were evaluated tensile test, compact tension (CT) fracture test, fractography, and differential scanning calorimetry. The surface modified Kevlar laminae with CNF were used as reinforcing layer in the epoxy and PU/epoxy hybrid resin matrices. CNF-coated heated Kevlar reinforced laminated PU/epoxy hybrid composites (CNF-Kev/PU-Epoxy) showed highest elongation 47% and fracture toughness (11.7 MPa√m) along with good UTS 139 MPa. Therefore, these hybrid nanocomposites developed by simple inexpensive method would be the potential candidates for several advanced applications particularly in defense, automobile, aerospace, and spacecraft applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48802.