Amorphous Polymer Matrix Research Articles

Biofilm Formation by Chromoblastomycosis Fungi Fonsecaea pedrosoi and Phialophora verrucosa: Involvement with Antifungal Resistance.

Patients with chromoblastomycosis (CBM) suffer chronic tissue lesions that are hard to treat. Considering that biofilm is the main growth lifestyle of several pathogens and it is involved with both virulence and resistance to antimicrobial drugs, we have investigated the ability of CBM fungi to produce this complex, organized and multicellular structure. Fonsecaea pedrosoi and Phialophora verrucosa conidial cells were able to adhere on a polystyrene abiotic substrate, differentiate into hyphae and produce a robust viable biomass containing extracellular matrix. Confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM) showed the tridimensional architecture of the mature biofilms, revealing a dense network of interconnected hyphae, inner channels and amorphous extracellular polymeric material. Interestingly, the co-culture of each fungus with THP-1 macrophage cells, used as a biotic substrate, induced the formation of a mycelial trap covering and damaging the macrophages. In addition, the biofilm-forming cells of F. pedrosoi and P. verrucosa were more resistant to the conventional antifungal drugs than the planktonic-growing conidial cells. The efflux pump activities of P. verrucosa and F. pedrosoi biofilms were significantly higher than those measured in conidia. Taken together, the data pointed out the biofilm formation by CBM fungi and brought up a discussion of the relevance of studies about their antifungal resistance mechanisms.

Dielectric Properties and Energy Storage of Hybrid/Boron Nitride/Titanium Carbide/Epoxy Nanocomposites

In this study, hybrid boron nitride (BN)/titanium carbide (TiC)/epoxy resin composite nanodielectrics were manufactured and characterized. Their morphological and structural characterization was conducted via scanning electron microscopy (SEM) images and X-ray diffraction (XRD) patterns, whereas the dielectric behavior was studied by means of broadband dielectric spectroscopy (BDS). Dielectric measurements were carried out from 30 to 160 °C and from 10−1 to 106 Hz, respectively. The dielectric results revealed the existence of three relaxation mechanisms, which from high to low frequencies, at constant temperature, refer to re-arrangement of polar-side groups (β-relaxation) of the macromolecular chains, transition from glassy to rubbery state of the amorphous polymer matrix (α-relaxation) and interfacial polarization (IP) between the polymer matrix and the nanofillers. It was found that, in general, nanodielectrics exhibited enhanced dielectric properties mainly due to the high dielectric permittivity of TiC and the fine dispersion of the fillers, confirmed also by the SEM images. Dynamic analysis conducted for the α-relaxation showed a Vogel–Fulcher–Tammann dependence on temperature. The ability of energy storing of the nanocomposites was examined via their energy density. Optimum performance is exhibited by the 5 phr TiC/1 phr BN/epoxy nanocomposite, reaching an energy storing ability nine times greater than the unfilled matrix.

All-atomistic molecular dynamics study of the glass transition of amorphous polymers

Glass transition is an intensively studied topic but many questions in this regard remain unaddressed. This is an important phenomenon related to the physical and mechanical properties of amorphous polymer materials. In this study, existing and newly performed all-atomistic molecular dynamics (MD) simulations of polycarbonate (PC) and poly-(methyl methacrylate) (PMMA) cooling processes were analyzed to address their glass transitions from a molecular perspective. Additionally, potential energy, radius of gyration, dihedral transition, and end effects were characterized. Further analyses were performed to characterize the individual degrees of freedom (DoFs) by the variance, correlation between two DoFs by the correlation coefficient, and collective motions by instantaneous normal mode (INM) analysis. Various DoFs experienced glass transition at temperatures slightly different from the glass transition temperature T g , presumably owing to their different spatial scales and chemical environments. This suggests that the experimentally observed broad T g may be attributed to a similar hierarchy of motions. Collective motions characterized by INM revealed slightly different behaviors for PC and PMMA. • T g of million-atom atomistic models of PC and PMMA were investigated by MD. • Potential energy, Rg, dihedral transition, end effect across T g were characterized. • Abrupt variance uprises and peaks in correlation showed local DoFs' responses to T g . • Hierarchy of local DoFs' characteristic temperatures possibly widened T g range. • INM showed responses to T g at low mode and differences between PC and PMMA.

Effective thermo-viscoelastic behavior of short fiber reinforced thermo-rheologically simple polymers: An application to high temperature fiber reinforced additive manufacturing

This paper presents a procedure for the estimation of the effective thermo-viscoelastic behavior in fiber-reinforced polymer filaments used in high temperature fiber-reinforced additive manufacturing (HT-FRAM). The filament is an amorphous polymer matrix (PEI) reinforced with elastic short glass fibers treated as a single polymer composite (SPC) holding the assumption of thermo-rheologically simple matrix. Effective thermo-viscoelastic behavior is obtained by implementing mean-field homogenization schemes through the extension of the correspondence principle to continuous variations of temperature by using the time–temperature superposition principle and the internal time technique. The state of the fibers in the composite is described through the use of probability distribution functions. Explicit forms of the effective properties are obtained from an identification step, ensuring the same mathematical structure as the matrix behavior. The benchmark simulations are predictions of residual stress resulting from the cooling of the representative elementary volumes (REVs) characterizing the composite filament. The computation of the averaged stress in the benchmarking examples is achieved by solving numerically the stress–strain problem via the internal variables’ framework. Reference solutions are obtained from Fast Fourier Transform based full-field homogenization simulations. A comparative analysis is performed, showing the reliability of the proposed homogenization procedure to predict residual stress against extensive computations of the macroscopic behavior of a given microstructure.

Scratch and multi-pass scratch behavior of poly (methyl methacrylate) (PMMA)

Polymer materials with high specific strength properties are widely used in engineering applications. Poly (methyl methacrylate) (PMMA) is a rigid and brittle thermoplastic with a high glass transition temperature. It is used in many engineering applications due to its low density, lightweight, high transparency, chemical resistance, and high toughness properties. Intense research efforts have been carried out in recent years regarding the scratching behavior of polymers. The scratch test is performed by moving a hard abrasive indenter across the surface of relatively soft material and is used to determine the mechanical resistance of the surfaces of materials. Scratches on the surfaces of amorphous polymeric materials such as PMMA cause optical and mechanical performance loss. For this reason, it is important to determine the scratching behavior of materials under different operating conditions. Within the scope of the study, the scratching behavior and multi-pass scratch behavior of PMMA were investigated. Experimental studies were carried out with Rockwell and Vickers abrasive indenters at different scratch force and velocity values. Scratch and wear marks were examined by means of an optical microscope, optical profilometer and Scanning Electron Microscope (SEM), and scratch hardness, volumes removed, surface topographies and surface morphologies are presented. It has been observed that these results vary remarkably depending on the type of abrasive indenter, scratch force and velocity.

Modeling of the Electrotransport Process in PP-Based and PLA-Based Composite Fibers Filled with Carbon Nanofibers.

Polypropylene and polylactide-based composite fibers have been produced by a melt technology. Long vapor-grown carbon fibers (CNFs) have been used as electrical conductivity fillers. It is clearly shown by experimental methods that the CNFs are evenly distributed in the polymer matrix, orienting themselves along the direction of fiber extrusion and retaining their initial dimensions. It is shown that for composites fibers based on crystallizing (polypropylene) and amorphous (polylactide acid) polymer matrix, the dependence of electrical resistance on the filler concentration is percolation character and can be described as a double Boltzmann function. Four sections are identified on the dependences of the electrical resistance on the filler concentration for composite fibers, and the reasons for this character of this dependence on the formation of electrically conductive circuits are analyzed. Investigated in this work are the PP-based and PLA-based composites filled with carbon nanofibers that can be used as antistatic, shielding materials, or as sensors.

Fmoc-protected amino acids as luminescent and circularly polarized luminescence materials based on charge transfer interaction

Fluorenylmethyloxycarbonyl (Fmoc)-protected amino acids are effective building blocks in self-assembled architectures at hierarchical levels, which however show limited luminescent properties and chiroptical activities. Here we introduce a charge-transfer strategy to build two-component luminescent materials with emerged circularly polarized luminescence properties. A library of Fmoc-amino acids was built, which selectively form charge-transfer complexes with the electron-deficient acceptor. Embedding in amorphous polymer matrix or physical grinding could trigger the charge-transfer luminescence with adjusted wavelengths in a general manner. X-ray diffraction results suggest the multiple binding modes between donor and acceptor. And, the solution-processed coassembly could selectively exhibit circularly polarized luminescence with high dissymmetry g-factors. This work illustrates a noncovalent charge-transfer strategy to construct luminescent and chiroptical organic composites based on the easy-accessible and economic chiral N-terminal aromatic amino acids.

Drug-Biopolymer Dispersions: Morphology- and Temperature- Dependent (Anti)Plasticizer Effect of the Drug and Component-Specific Johari-Goldstein Relaxations.

Amorphous molecule-macromolecule mixtures are ubiquitous in polymer technology and are one of the most studied routes for the development of amorphous drug formulations. For these applications it is crucial to understand how the preparation method affects the properties of the mixtures. Here, we employ differential scanning calorimetry and broadband dielectric spectroscopy to investigate dispersions of a small-molecule drug (the Nordazepam anxiolytic) in biodegradable polylactide, both in the form of solvent-cast films and electrospun microfibres. We show that the dispersion of the same small-molecule compound can have opposite (plasticizing or antiplasticizing) effects on the segmental mobility of a biopolymer depending on preparation method, temperature, and polymer enantiomerism. We compare two different chiral forms of the polymer, namely, the enantiomeric pure, semicrystalline L-polymer (PLLA), and a random, fully amorphous copolymer containing both L and D monomers (PDLLA), both of which have lower glass transition temperature (Tg) than the drug. While the drug has a weak antiplasticizing effect on the films, consistent with its higher Tg, we find that it actually acts as a plasticizer for the PLLA microfibres, reducing their Tg by as much as 14 K at 30%-weight drug loading, namely, to a value that is lower than the Tg of fully amorphous films. The structural relaxation time of the samples similarly depends on chemical composition and morphology. Most mixtures displayed a single structural relaxation, as expected for homogeneous samples. In the PLLA microfibres, the presence of crystalline domains increases the structural relaxation time of the amorphous fraction, while the presence of the drug lowers the structural relaxation time of the (partially stretched) chains in the microfibres, increasing chain mobility well above that of the fully amorphous polymer matrix. Even fully amorphous homogeneous mixtures exhibit two distinct Johari–Goldstein relaxation processes, one for each chemical component. Our findings have important implications for the interpretation of the Johari–Goldstein process as well as for the physical stability and mechanical properties of microfibres with small-molecule additives.

Efficient Room-Temperature Phosphorescence from Discrete Molecules Based on Thianthrene Derivatives for Oxygen Sensing and Detection

In this work, two thianthrene (TA) derivatives, 1-phenylthianthrene (TA1P) and 2-phenylthianthrene (TA2P), were synthesized with single-phenyl modification for pure organic discrete-molecule room-temperature phosphorescence (RTP). They both show the dual emission of fluorescence and RTP in amorphous polymer matrix after deoxygenation, as a result of a new mechanism of folding-induced spin-orbit coupling (SOC) enhancement. Compared with TA1P, TA2P exhibits a higher RTP efficiency and a larger spectral separation between fluorescence and RTP, which is ascribed to the substituent effect of TA at the 2-position. With decreasing oxygen concentration from 1.61% to 0%, the discrete-molecule TA2P shows an about 18-fold increase in RTP intensity and an almost constant fluorescence intensity, which can make TA2P as a self-reference ratiometric optical oxygen sensing probe at low oxygen concentrations. The oxygen quenching constant (K SV) of TA2P is estimated as high as 10.22 KPa−1 for polymethyl methacrylate (PMMA)-doped film, and even reach up to 111.86 KPa−1 for Zeonex®-doped film, which demonstrates a very high sensitivity in oxygen sensing and detection. This work provides a new idea to design pure organic discrete-molecule RTP materials with high efficiency, and TA derivatives show a potential to be applied in quantitative detection of oxygen as a new-generation optical oxygen-sensing material.

Oseltamivir phosphate loaded pegylated-Eudragit nanoparticles for lung cancer therapy: Characterization, prolonged release, cytotoxicity profile, apoptosis pathways and in vivo anti-angiogenic effect by using CAM assay.

The target of the current investigation was the delivery of oseltamivir phosphate (OSE) into the lung adenocarcinoma tissues by means of designing nanosized, non-toxic and biocompatible pegylated Eudragit based NPs and investigating their anticancer and antiangiogenic activity. The rationale for this strategy is to provide a novel perspective to cancer treatment with OSE loaded pegylated ERS NPs under favor of smaller particle size, biocompatible feature, cationic characteristic, examining their selective effectiveness on lung cell lines (A549 lung cancer cell line and CCD-19Lu normal cell line) and examining antiangiogenic activity by in vivo CAM analysis. For this purpose, OSE encapsulated pegylated ERS based NPs were developed and investigated for zeta potential, particle size, encapsulation efficiency, morphology, DSC, FT-IR, 1H NMR analyses. In vitro release, cytotoxicity, determination apoptotic pathways and in vivo CAM assay were carried out. Considering characterizations, NPs showed smaller particle size, cationic zeta potential, relatively higher EE%, nearly spherical shape, amorphous matrix formation and prolonged release pattern (Peppas-Sahlin and Weibull model with Fickian and non-Fickian release mechanisms). Flow cytometry was used to assess the apoptotic pathways using the Annexin V-FITC/PI staining assay, FITC Active Caspase-3 staining assay, and mitochondrial membrane potential detection tests. Activations on caspase-3 pathways made us think that OSE loaded pegylated ERS NPs triggered to apoptosis using intrinsic pathway. As regards to the in vivo studies, OSE loaded pegylated ERS based NPs demonstrated strong and moderate antiangiogenic activity for ERS-OSE 2 and ERS-OSE 3, respectively. With its cationic character, smaller particle size, relative superior EE%, homogenous amorphous polymeric matrix constitution indicated using solid state tests, prolonged release manner, highly selective to the human lung adenocarcinoma cell lines, could trigger apoptosis intrinsically and effectively, possess good in vivo antiangiogenic activity, ERS-OSE 2 formulation is chosen as a promising candidate and a potent drug delivery system to treat lung cancer.

Molecular Dynamics Modeling of Epoxy Resins Using the Reactive Interface Force Field

Predictive computational modeling of polymer materials is necessary for the efficient design of composite materials and the corresponding processing methods. Molecular dynamics (MD) modeling is especially important for establishing accurate processing-structure-property relationships for neat resins. For MD modeling of amorphous polymer materials, an accurate force field is fundamental to reliable prediction of properties. Reactive force fields, in which chemical bonds can be formed or broken, offer further capability in predicting the mechanical behavior of amorphous polymers subjected to relatively large deformations. To this end, the Reactive Interface Force Field (IFF-R) has been recently developed to provide an efficient means to predict the behavior of materials under these conditions. Although IFF-R has been proven to be accurate for some crystalline organic and inorganic systems, it has not yet been proven to be accurate for amorphous polymer systems. The objective of this study is to use IFF-R to predict the thermo-mechanical properties of three different epoxy systems and validate with experimental measurements. The results indicate that IFF-R predicts thermo-mechanical properties that agree closely with experiment. Therefore, IFF-R can be used to reliably establish mechanical properties of polymers on the molecular level for future design of new composite materials and processing methods.

Conformal three-dimensional interphase of Li metal anode revealed by low-dose cryoelectron microscopy

<h2>Summary</h2> Using cryogenic transmission electron microscopy, we revealed three-dimensional (3D) structural details of the electrochemically plated lithium (Li) flakes and their solid electrolyte interphase (SEI). As the SEI skin layer is largely composed of nanocrystalline LiF and Li₂O in amorphous polymeric matrix, when complete Li stripping occurs, the compromised SEI 3D framework buckles and wrinkles. The flexibility and resilience of the SEI skin layer plays a vital role in preserving an intact SEI 3D framework after Li stripping. The intact SEI network enables the nucleation and growth of newly plated Li inside the previously formed SEI network in subsequent cycles, preventing additional large amounts of SEI formation. In addition, cells cycled under the accurately controlled uniaxial pressure can further enhance the repeated utilization of the SEI and improve the Coulombic efficiency (CE) by up to 97%, demonstrating an effective strategy for reducing the formation of additional SEI and inactive "dead" Li.

DYNAMIC THREE-POINTS-BENDING TEST MODE OF TWO AMORPHOUS POLYMER MATERIALS (PMMA, PC) FOR THEIR VISCOELASTIC AND MECHANICAL CHARACTERIZATION

This paper presents an approach to classifying amorphous polymer materials. Temperature is This classification involves the determination of mechanical and viscoelastic characteristics considered a descriptive variable to clarify the specific field of practical applications of amorphous polymers. according to the reference temperature characterizing the behaviour of polymer materials. The mechanical and viscoelastic characteristics of amorphous polymers such as methyl poly-methacrylate (PMMA), polycarbonate (PC) and imide poly ether (PEI) are determined through the three-point dynamically embedded test carried out in an adiabatic close enclosure. The complex dissipative or conservative modules according to the temperature are represented. The results obtained show that the fluidity index of these materials is linked to their viscosity, which is a determining property which is decisive for the choice of the technique of the application of the material. Our method of measuring properties is therefore, in principle, comparable to the techniques used in industrial development.

Photo-triggered surface relief formation of polystyrene films based on the Marangoni flow driven by a surface photoresponsive skin layer

Surface relief gratings (SRGs) are widely investigated in azobenzene-containing polymer films. We have recently demonstrated that a photoresponsive azobenzene layer existing only at the surface of a non-photoresponsive liquid crystalline polymer film can induce mass migration by patterned UV light irradiation, resulting in the SRG structure. This process is explained by the Marangoni flow triggered by the photoinduced surface tension change of the surface layer. In this work, we newly propose that the same strategy is applicable to an amorphous polymer material of polystyrene. The results obtained here indicate that photoinduced SRG formation is expanded for general amorphous polymers.

Nanostructured micronized solid dispersion of crystalline-amorphous metronidazole embedded in amorphous polymer matrix prepared by nano spray drying

In this study metronidazole drug was encapsulated by hydroxypropyl methylcellulose and polyvinylpyrrolidone polymers from solutions using nano spray drying technology. The influence of the process parameters and formulation variables were investigated on product morhology and structure, production yield and entrapment efficiency. The use of surface active admixtures (polyvinyl alcohol, Tween-80 and Pluronic F68) increased the product yield substantially. The entrapped metronidazole was partially in crystalline and amorphous state in both amorphous polymers as confirmed by DSC and powder X-ray diffraction measurements. In the composites with hydroxypropyl methylcellulose the degree of crystallinity was between 50.2 and 81.0%, and with polyvinylpyrrolidone between 35.0 and 50.0% (with respect to the drug content). Melting point decrease phenomena was observed by differential scanning calorimetry between bulk metronidazole and spray dried products. Peak broadening was indicated by powder X-ray diffraction measurements, which could be the result of formation of small drug crystallites. The TEM images showed beside the larger crystals (200–400 nm) a fraction of smaller crystals (20–50 nm in diameter), which are in good correlation with the calculated coherent scattering domain sizes of 19–87 nm based on X-ray data. The drug-polymer composites produced by nano spray drying process were identified as crystalline-amorphous nanostructured micronized solid dispersions.

Ambient, tunable room temperature phosphorescence from a simple phthalimide phosphor in amorphous polymeric matrix and in crystalline state

Harvesting triplet excitons via room temperature phosphorescence (RTP) from purely organic chromophores has been a formidable challenge, which has a potential applications in displays, lighting, and bio-imaging. Herein, a simple phthalimide phosphor derivative is reported, which exhibits visible cyan emissive phosphorescence in solution-processable thin films and orange-red emitting phosphorescence in the crystalline state. Presence of carbonyl group and the bromine atom in the molecular design effectively increases the inter-system crossing (ISC) and spin-orbit coupling efficiency (SOC) between singlet and triplet states, which play a crucial role in achieving efficient phosphorescence under ambient conditions.

A multiscale simulation of amorphous polystyrene

A multiscale simulation method to investigate amorphous polymeric materials for vinyl polymer was applied for glassy polystyrene (PS) with different tacticity. PS chains were coarse-grained and then mapped onto the second nearest neighbor diamond (2nnd) lattice incorporating short- and long-range interactions from the modified rotational isomeric state (RIS) model and the discretized Lennard-Jones (LJ) potential function, respectively. Bulk PS structures composed of 14 chains with 42 monomer units was generated and equilibrated on lattice Monte Carlo (MC) simulation. The on-lattice properties including molecular size, conformational statistics and chain dynamics were compared. The chain mobility of neat PS melts with different stereochemistry are qualitatively ordered as: iPS < aPS << sPS. There is no clear correlation for these relative diffusions with molecular size and chain stiffness but can possibly be related to the intermolecular contribution i.e. chain packing among neighboring chains. Next, fully atomistic amorphous PS models at the bulk density were obtained by the reverse-mapping procedure to convert the coarse-grained chains to recover the missing atoms. After energy minimization, molecular and material properties including torsional angle distribution, solubility parameter, radial distribution function and neutron scattering intensity are determined and compared for amorphous PS structures.

Microwave-assisted establishment of efficient amorphous polymeric phosphorescent materials with ultralong blue afterglow

Through the assistance of microwave radiation, amorphous polymers based on polyacrylamide with color-tunable phosphorescence properties, ultralong afterglow and triplet lifetimes are realized.

Synthesis and characterization of montmorillonite/polyaniline composites and its usage to modify a commercial separator

Composites of montmorillonite (MMT) and polyaniline (PANI) were synthetized through a facile and inexpensive method. Two samples with different MMT:PANI ratios were studied and deeply characterized by XRD, TG, zeta potential, FTIR and XPS measurements. On one hand, the sample with ratio MMT:PANI = 87:13 was an intercalated composite, were polyaniline resides between the inorganic layers of the clay at a regular distance. On the other hand, the sample with ratio MMT:PANI = 12:88 was an exfoliated composite, where the inorganic sheets are immersed in an amorphous polymeric matrix. FTIR and XRD results indicated that in both samples, the emeraldine form of polyaniline was obtained. The composites were used to modify -by dr. blade technique- a commercial separator for lithium-ion batteries (LIBs) with the aim of increasing its wettability, ionic conductivity and electrochemical performance. The three-dimensional and multilayered network structure of the MMT/PANI composites led to an enhancement of the electrolyte uptake capacity (from 32% in bare separator to 137% and 168% for MMT/PANI_87/13 and MMT/PANI_12/88 modified separators, respectively, after 3 h). The presence of the coating membrane also led to an increase of the ionic conductivity by one order of magnitude in the modified separators respect to the unmodified one. These coated and non-coated separators were used to assemble full cells with LiNi1.5Mn0.5O4 as cathode active material. The capacity fade after 200 cycles was 20% lower in the cell with MMT/PANI_12/88 membrane in comparison with the bare separator. The enhancement of the electrochemical performance of the cells with the coated separator suggests that is a promising strategy to be used in LIBs.

Dielectric studies and alternating current conductivity studies of polymethylmethacrylate (PMMA) doped with ferric chloride (FeCl3) in varying concentration

To understand the variations that a filler bring on its insertion in a polymeric material, the authors developed composite films of thickness 100 μm by dispersing FeCl3 in different concentration (1%, 2%, 4%, 8%) in PMMA and characterized it for their electrical properties using WAYNE KERR 6500B Impedance analyzer. The variation of electrical parameters like dielectric constant (ε′), dielectric loss (ε″), loss tangent (tanδ) and a.c. conductivity (σ) with frequency in the range (100 Hz – 100 KHz) at ambient temperature were evaluated and analyzed. The study shows that PMMA which is a non-conducting amorphous polymeric material having moderate dielectric strength, on insertion of filler show improved values of dielectric constant and a.c. conductivity so as to be used for energy storage device.