Two Steady-State Adsorption Modes of Phosphonic Acids on Aluminum Surfaces.

The phosphonic acid (PA) surface treatment on various metal substrates is of high industrial relevance, and the PA molecular structure significantly affects its quality. In this work, systematic variation of the PA molecular steric and electron environment helps discern two steady-state adsorption modes on an aluminum surface. The PA molecular structure was varied systematically, which included inorganic phosphorus acid, alkyl phosphonic acids, and phenyl phosphonic acids. To explore their in situ dynamics of adsorption/desorption on the electrochemically unstable aluminum, techniques such as electrochemical impedance spectroscopy and inductively coupled plasma optical emission spectrometry were employed. A range of different types of interfacial layers are formed on the aluminum surface, namely, from the dissolution-limiting physisorbed layer to a quasi-inhibiting chemisorbed layer on the aluminum surface in acidic (pH ≈ 2.2) solution. Presented findings establish the dynamic steady-state nature of this type of interface. They reveal fundamental relationships among adsorbent steric or electronic effects, the steady-state interface morphology, and the steady-state aluminum dissolution rate. The study brings also a more differentiated molecular structure-related description of the aluminum dissolution inhibition of PAs and relates it to molecular density functional theory calculations.

Adjustable film properties of cellulose nanofiber and cellulose nanocrystal composites.

A novel nanocomposite comprised of cellulose nanocrystals (CNCs) and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) oxidized cellulose nanofibers (TOCNFs) was prepared through solution casting to evaluate potential improvements of the mechanical performance compared to individual reinforcements alone. Such materials can be implemented as mechanical reinforcements in polymer composites, especially when less weight is desired. Dissipative particle dynamics (DPD) simulations, in combination with polarized light microscopy and atomic force microscopy, were analyzed to evaluate the morphology of these combined cellulose nanomaterial (CNM) films. Our results indicate that TOCNFs provide enhanced translational mobility to CNCs which become incorporated near the crystalline domains of TOCNFs. This mobility enables CNCs to increase the rigidity of the network without sacrificing elongation and toughness. The combination of these materials provides improved ultimate tensile strength and elongation without sacrificing the Young's modulus. Therefore, a combination of these materials can be used to develop nanocomposites with enhanced mechanical properties.

Structure-Property Relationship in Melt-Spun Poly(hydroxybutyrate-co-3-hexanoate) Monofilaments.

Poly(hydroxybutyrate-co-3-hexanoate) (PHBH) is a biodegradable thermoplastic polyester with the potential to be used in textile and medical applications. We have aimed at developing an upscalable melt-spinning method to produce fine biodegradable PHBH filaments without the use of an ice water bath or offline drawing techniques. We have evaluated the effect of different polymer grades (mol% 3-hydroxy hexanoate, molecular weight etc.) and production parameters on the tensile properties of melt-spun filaments. PHBH monofilaments (diameter < 130 µm) have been successfully melt-spun and online drawn from three different polymer grades. We report thermal and rheological properties of the polymer grades as well as morphological, thermal, mechanical, and structural properties of the melt-spun filaments thereof. Tensile strengths up to 291 MPa have been achieved. Differences in tensile performance have been correlated to structural differences with wide-angle X-ray diffraction and small-angle X-ray scattering. The measurements obtained have revealed that a synergetic interaction of a highly oriented non-crystalline mesophase with highly oriented α-crystals leads to increased tensile strength. Additionally, the effect of aging on the structure and tensile performance has been investigated.

Local Structural Fingerprints of Nanoparticle-Bound Polymer Layers.

The molecular structure of bound layers at attractive polymer-nanoparticle interfaces strongly influences the properties of nanocomposites. Thus, a unifying theoretical framework that can provide insights into the correlations between the molecular structure of the bound layers, their thermodynamics, and macroscopic properties is highly desirable. In this work, molecular dynamics simulations were used in combination with local fingerprint analysis of configurational entropy and interaction energy at the segmental scale, with the goal to establish such physical grounds. The thickness of bound polymer layers is found to be independent of the polymer chain length, as deduced from density oscillations at the surface of a nanotube. The local configurational entropy of layers is estimated from pair correlations in equilibrium structures. By plotting mean layer entropy vs internal energy on a phase diagram, a one-to-one equivalence is established between the local structures of layers and their thermodynamic properties. Moreover, a gradient in local dynamics of segments in bound layers under equilibrium is observed normal to the nanoparticle surface. The relaxation times of individual layers show correspondence to their phase diagram fingerprints, thus suggesting that a unified perspective can be envisioned for such materials built on the grounds of locally heterogeneous interfaces.

Antistatic Fibers for High-Visibility Workwear: Challenges of Melt-Spinning Industrial Fibers.

Safety workwear often requires antistatic protection to prevent the build-up of static electricity and sparks, which can be extremely dangerous in a working environment. In order to make synthetic antistatic fibers, electrically conducting materials such as carbon black are added to the fiber-forming polymer. This leads to unwanted dark colors in the respective melt-spun fibers. To attenuate the undesired dark color, we looked into various possibilities including the embedding of the conductive element inside a dull side-by-side bicomponent fiber. The bicomponent approach, with an antistatic compound as a minor element, also helped in preventing the severe loss of tenacity often caused by a high additive loading. We could melt-spin a bicomponent fiber with a specific resistance as low as 0.1 Ωm and apply it in a fabric that fulfills the requirements regarding the antistatic properties, luminance and flame retardancy of safety workwear.

X-ray data about the structural response of melt-spun poly(3-hydroxybutyrate) fibers to stress and temperature.

Mechanical properties of as-spun, aged and stress-annealed melt-spun poly(3-hydroxybutyrate) (P3HB) fibers are presented in section 1.1. Section 1.2 presents tables with stress/temperature conditions and exposure times during in-situ laboratory WAXD and SAXS experiments, and section 1.3 presents azimuthal profiles of the corresponding WAXD patterns with extracted orientation factors of the α-crystals. Section 1.4 presents the extracted long-spacings, coherence lengths and crystal sizes from SAXS patterns. The corresponding fits of meridional and transversal SAXS profiles are shown in sections 1.5 and 1.6, respectively. In-situ synchrotron measurements during tensile drawing of differently pre-annealed P3HB fibers are presented in section 1.7. A detailed description of the tensile, SAXS/WAXD measurements and analysis is given in the experimental section 2. The laboratory SAXS/WAXD measurements during stress annealing were performed with a Bruker Nanostar U diffractometer (Bruker AXS, Karlsruhe, Germany) and a heating stage H+300 (Bruker AXS, Germany). Different weights were attached to the fibers during heating to apply stress. The synchrotron measurements during tensile drawing were performed at the cSAXS beamline at the Swiss Light Source of the Paul Scherrer Institute in Switzerland. The fibers were drawn with a TS 600 tensile stage (Anton Paar GmbH, Austria) using a 5 N load cell. For more information see 'Structural response of melt-spun poly(3-hydroxybutyrate) fibers to stress and temperature' [1].

Structurally Tunable pH-responsive Phosphine Oxide Based Gels by Facile Synthesis Strategy.

Design and synthesis of nanostructured responsive gels have attracted increasing attention, particularly in the biomedical domain. Polymer chain configurations and nanodomain sizes within the network can be used to steer their functions as drug carriers. Here, a catalyst-free facile one-step synthesis strategy is reported for the design of pH-responsive gels and controlled structures in nanoscale. Transparent and impurity free gels were directly synthesized from trivinylphosphine oxide (TVPO) and cyclic secondary diamine monomers via Michael addition polymerization under mild conditions. NMR analysis confirmed the consumption of all TVPO and the absence of side products, thereby eliminating post purification steps. The small-angle X-ray scattering (SAXS) elucidates the nanoscale structural features in gels, that is, it demonstrates the presence of collapsed nanodomains within gel networks and it was possible to tune the size of these domains by varying the amine monomers and the nature of the solvent. The fabricated gels demonstrate structure tunability via solvent-polymer interactions and pH specific drug release behavior. Three different anionic dyes (acid blue 80, acid blue 90, and fluorescein) of varying size and chemistry were incorporated into the hydrogel as model drugs and their release behavior was studied. Compared to acidic pH, a higher and faster release of acid blue 80 and fluorescein was observed at pH 10, possibly because of their increased solubility in alkaline pH. In addition, their release in phosphate buffered saline (PBS) and simulated body fluid (SBF) matrix was positively influenced by the ionic interaction with positively charged metal ions. In the case of hydrogel containing acid blue 90 a very low drug release (<1%) was observed, which is due to the reaction of its accessible free amino group with the vinyl groups of the TVPO. In vitro evaluation of the prepared hydrogel using human dermal fibroblasts indicates no cytotoxic effects, warranting further research for biomedical applications. Our strategy of such gel synthesis lays the basis for the design of other gel-based functional materials.

X-ray data from a cyclic tensile study of melt-spun poly(3-hydroxybutyrate) P3HB fibers: A reversible mesophase.

Wide-angle x-ray diffraction (WAXD) patterns that show mesophases in core-sheath bicomponent fibers and amorphous fibers are presented in section 1.1 of the article. Section 1.2 presents molecular dynamics simulations and scattered intensity calculations of stretched P3HB chains. Sections 1.3-1.6 summarize WAXD and small-angle x-ray scattering (SAXS) data analysis from a tensile study of melt-spun P3HB fibers. Azimuthal profiles are extracted from 2D WAXD patterns at various angular regions and the positions of equatorial reflections and corresponding d-spacings are summarized. Additionally, the extracted structural parameters from SAXS images are summarized. The tensile stress calculations, crystal orientation calculations, applied intensity corrections, calculations of long spacings, coherence lengths and lamellar diameters are explained in the methods subsections 2.3.1-2.3.7. WAXD and SAXS measurements of P3HB fibers were recorded on a Bruker Nanostar U diffractometer (Bruker AXS, Karlsruhe, Germany). The recorded WAXD/SAXS patterns were analyzed with the evaluation software DIFFRAC.EVA (version 4.2., Bruker AXS, Karlsruhe, Germany) and python codes. For more information see 'Tensile study of melt-spun poly(3-hydroxybutyrate) P3HB fibers: Reversible transformation of a highly oriented phase' (Perret et al., 2019).

A Review of Multiscale Computational Methods in Polymeric Materials.

Polymeric materials display distinguished characteristics which stem from the interplay of phenomena at various length and time scales. Further development of polymer systems critically relies on a comprehensive understanding of the fundamentals of their hierarchical structure and behaviors. As such, the inherent multiscale nature of polymer systems is only reflected by a multiscale analysis which accounts for all important mechanisms. Since multiscale modelling is a rapidly growing multidisciplinary field, the emerging possibilities and challenges can be of a truly diverse nature. The present review attempts to provide a rather comprehensive overview of the recent developments in the field of multiscale modelling and simulation of polymeric materials. In order to understand the characteristics of the building blocks of multiscale methods, first a brief review of some significant computational methods at individual length and time scales is provided. These methods cover quantum mechanical scale, atomistic domain (Monte Carlo and molecular dynamics), mesoscopic scale (Brownian dynamics, dissipative particle dynamics, and lattice Boltzmann method), and finally macroscopic realm (finite element and volume methods). Afterwards, different prescriptions to envelope these methods in a multiscale strategy are discussed in details. Sequential, concurrent, and adaptive resolution schemes are presented along with the latest updates and ongoing challenges in research. In sequential methods, various systematic coarse-graining and backmapping approaches are addressed. For the concurrent strategy, we aimed to introduce the fundamentals and significant methods including the handshaking concept, energy-based, and force-based coupling approaches. Although such methods are very popular in metals and carbon nanomaterials, their use in polymeric materials is still limited. We have illustrated their applications in polymer science by several examples hoping for raising attention towards the existing possibilities. The relatively new adaptive resolution schemes are then covered including their advantages and shortcomings. Finally, some novel ideas in order to extend the reaches of atomistic techniques are reviewed. We conclude the review by outlining the existing challenges and possibilities for future research.

Atomistic Modelling of Confined Polypropylene Chains between Ferric Oxide Substrates at Melt Temperature.

The interactions and conformational characteristics of confined molten polypropylene (PP) chains between ferric oxide (Fe2O3) substrates were investigated by molecular dynamics (MD) simulations. A comparative analysis of the adsorbed amount shows strong adsorption of the chains on the high-energy surface of Fe2O3. Local structures formed in the polymer film were studied utilizing density profiles, orientation of bonds, and end-to-end distance of chains. At interfacial regions, the backbone carbon-carbon bonds of the chains preferably orient in the direction parallel to the surface while the carbon-carbon bonds with the side groups show a slight tendency to orient normal to the surface. Based on the conformation tensor data, the chains are compressed in the normal direction to the substrates in the interfacial regions while they tend to flatten in parallel planes with respect to the surfaces. The orientation of the bonds as well as the overall flattening of the chains in planes parallel to the solid surfaces are almost identical to that of the unconfined PP chains. Also, the local pressure tensor is anisotropic closer to the solid surfaces of Fe2O3 indicating the influence of the confinement on the buildup imbalance of normal and tangential pressures.