Polymers, Volume 8, Issue 1 (January 2016) – 23 articles

In fibrous composites, tensile strength of reinforcements exhibits a stochastic nature, and the mechanical properties of the composites are significantly influenced by such strength variability. The present study aims at providing a comparative investigation of the influence of the statistical variation in fiber strength on the tensile properties of unidirectional composites reinforced by bamboo fibers. Monte-Carlo simulations coupled with the linear- and power-law Weibull distributions are performed to conduct numerical predictions for damage evolution and strength variability of the composites, and the predicted mean strength and failure strain are compared with the experimental results. The Weibull parameters used are achieved through the Maximum Likelihood Estimation with multiple data sets of fiber lengths. Fiber strength statistics is found to have an effect on composite mechanical properties. The results further indicate that the use of the power-law model is relatively efficient for modeling purposes in comparison to the linear-law model, which could be attributed to fiber diameter variation. Full article

Polymeric biomaterials are widely used in a wide range of biomedical applications due to their unique properties, such as biocompatibility, multi-tunability and easy fabrication. Specifically, polymeric hydrogel materials are extensively utilized as therapeutic implants and therapeutic vehicles for tissue regeneration and drug delivery systems. Recently, hydrogels have been developed as artificial cellular microenvironments because of the structural and physiological similarity to native extracellular matrices. With recent advances in hydrogel materials, many researchers are creating three-dimensional tissue models using engineered hydrogels and various cell sources, which is a promising platform for tissue regeneration, drug discovery, alternatives to animal models and the study of basic cell biology. In this review, we discuss how polymeric hydrogels are used to create engineered tissue constructs. Specifically, we focus on emerging technologies to generate advanced tissue models that precisely recapitulate complex native tissues in vivo. Full article

Phase behavior and its effects on crystallization in an extruded poly(trimethylene terephthalate) (PTT)/phenoxy resin blend were studied with time-resolved light scattering (TRLS), optical microscopy (OM), differential scanning calorimetry (DSC), and small-angle X-ray scattering (SAXS). During annealing in the molten state, a two-phase structure with unique periodicity and phase connectivity was developed by liquid–liquid phase separation. After the formation of the phase-separated structure, the blend was homogenized by the interchange reactions between the two polymers. The crystallization behavior of PTT predominantly depended on the phase morphology developed during annealing. The pre-existing phase structures disturbed the lamellar orientation, resulting in a poorly ordered spherulitic superstructure. Full article

The focus in the field of biomedical engineering has shifted in recent years to biodegradable polymers and, in particular, polyesters. Dozens of polyester-based medical devices are commercially available, and every year more are introduced to the market. The mechanical performance and wide range of biodegradation properties of this class of polymers allow for high degrees of selectivity for targeted clinical applications. Recent research endeavors to expand the application of polymers have been driven by a need to target the general hydrophobic nature of polyesters and their limited cell motif sites. This review provides a comprehensive investigation into advanced strategies to modify polyesters and their clinical potential for future biomedical applications. Full article

Injury or damage to tissue and organs is a major health problem, resulting in about half of the world’s annual healthcare expenditure every year. Advances in the fields of stem cells (SCs) and biomaterials processing have provided a tremendous leap for researchers to manipulate the dynamics between these two, and obtain a skin substitute that can completely heal the wounded areas. Although wound healing needs a coordinated interplay between cells, extracellular proteins and growth factors, the most important players in this process are the endogenous SCs, which activate the repair cascade by recruiting cells from different sites. Extra cellular matrix (ECM) proteins are activated by these SCs, which in turn aid in cellular migrations and finally secretion of growth factors that can seal and heal the wounds. The interaction between ECM proteins and SCs helps the skin to sustain the rigors of everyday activity, and in an attempt to attain this level of functionality in artificial three-dimensional (3D) constructs, tissue engineered biomaterials are fabricated using more advanced techniques such as bioprinting and laser assisted printing of the organs. This review provides a concise summary of the most recent advances that have been made in the area of polymer bio-fabrication using 3D bio printing used for encapsulating stem cells for skin regeneration. The focus of this review is to describe, in detail, the role of 3D architecture and arrangement of cells within this system that can heal wounds and aid in skin regeneration. Full article

The research presented in this paper is an experimental study and numerical analysis on mechanical behavior of the adhesively-bonded joint between FRP sandwich bridge deck and steel girder. Generally, there are three typical stress states in the adhesively-bonded joint: shear stress, tensile stress, and combination of both. To realize these stress states in the adhesively-bonded joint during tests, a specific loading device is developed with the capacity of providing six different loading angles, which are 0°(pure tension), 18°, 36°, 54°, 72° and 90°(pure shear). Failure modes of adhesively-bonded joints are investigated. It indicates that, for the pure shear loading, the failure mode is the cohesive failure (near the interface between the adhesive layer and the steel support) in the adhesive layer. For the pure tensile and combined loading conditions, the failure mode is the combination of fiber breaking, FRP delamination and interfacial adhesion failure between the FRP sandwich deck and the adhesive layer. The load-bearing capacities of adhesive joints under combined loading are much lower than those of the pure tensile and pure shear loading conditions. According to the test results of six angle loading conditions, a tensile/shear failure criterion of the adhesively-bonded joint is obtained. By using Finite Element (FE) modeling method, linear elastic simulations are performed to characterize the stress distribution throughout the adhesively-bonded joint. Full article

In the presence of a small molecular protic initiator, immortal ring-opening polymerization (ROP) of lactide (LA) is a highly efficient strategy to synthesize polylactide in a controllable manner, while using polymeric alcohol as an initiator has been less investigated. A series of polymeric alcohols (PS–OH) composed of styrene and 4.3%–18% hydroxyl functional styrene (diethyl(hydroxy(4-vinylphenyl)methyl)phosphonate, St–OH) were synthesized through reversible addition-fragmentation transfer (RAFT) polymerization. Using PS–OH as an initiator, the immortal ROP of rac-LA was catalyzed by dibutylmagnesium (MgⁿBu₂) under various ratios of monomer to hydroxyl group within PS–OH to generate polystyrene-g-polylactide (PS–g–PLA) copolymers with different graft lengths. After thermal annealing at 115 °C, the PLA domain aggregated to nanospheres among the PS continuum. The size of the nanospheres, varying from 130.1 to 224.2 nm, was related to the graft density and length of PS–g–PLA. Nanoporous films were afforded through chemical etching of the PLA component. Full article

The processing of an originally non-porous 1D coordination polymer as monolithic gel, xerogel and aerogel is reported as an alternative method to obtain novel metal-organic porous materials, conceptually different to conventional crystalline porous coordination polymer (PCPs) or metal-organic frameworks (MOFs). Although the work herein reported is focused upon a particular kind of coordination polymer ([M(μ-ox)(4-apy)₂]_n, M: Co(II), Ni(II)), the results are of interest in the field of porous materials and of MOFs, as the employed synthetic approach implies that any coordination polymer could be processable as a mesoporous material. The polymerization conditions were fixed to obtain stiff gels at the synthesis stage. Gels were dried at ambient pressure and at supercritical conditions to render well shaped monolithic xerogels and aerogels, respectively. The monolithic shape of the synthesis product is another remarkable result, as it does not require a post-processing or the use of additives or binders. The aerogels of the 1D coordination polymers are featured by exhibiting high pore volumes and diameters ranging in the mesoporous/macroporous regions which endow to these materials the ability to deal with large-sized molecules. The aerogel monoliths present markedly low densities (0.082–0.311 g·cm⁻³), an aspect of interest for applications that persecute light materials. Full article

A series of energetic polymers, poly(vinyl 2,4,6-trinitrophenylacetal)-g-polyglycidylazides (PVTNP-g-GAPs), were synthesized via cross-linking reactions of PVTNP with three different molecular weight GAPs using toluene diisocyanate as the cross-linking agent. The structures of these energetic polymers were characterized by ultraviolet visible spectra (UV–Vis), attenuated total reflectance-Fourier transform-infrared spectroscopy (ATR-FTIR), and nuclear magnetic resonance spectrometry (NMR). The glass-transition temperatures of these energetic polymers were measured with differential scanning calorimetry (DSC) method, and the results showed that all the measured energetic polymers have two distinct glass-transition temperatures. The thermal decomposition behaviors of these energetic polymers were evaluated by differential thermal analysis (DTA), thermogravimetric analysis (TGA) and thermogravimetric analysis tandem infrared spectrum (TGA-IR). The results indicated that all the measured energetic polymers have excellent resistance to thermal decomposition up to 200 °C, and the initial thermal decomposition was attributed to the breakdown of azide group. Moreover, the sensitivity properties of these energetic polymers were measured with the national military standard methods and their compatibilities with the main energetic components of 2,4,6-trinitrotoluene (TNT)-based melt-cast explosive were evaluated by using the DTA method. The results indicate that these energetic polymers have feasible mechanical sensitivities and can be safely used with TNT, cyclotetramethylene tetranitramine (HMX), 1,1-diamino-2,2-dinitroethene (FOX-7), 3-nitro-1,2,4-triazol-5-one (NTO) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Full article

Polymers have been used extensively taking forms as scaffolds, patterned surface and nanoparticle for regenerative medicine applications. Angiogenesis is an essential process for successful tissue regeneration, and endothelial cell–cell interaction plays a pivotal role in regulating their tight junction formation, a hallmark of angiogenesis. Though continuous progress has been made, strategies to promote angiogenesis still rely on small molecule delivery or nuanced scaffold fabrication. As such, the recent paradigm shift from top-down to bottom-up approaches in tissue engineering necessitates development of polymer-based modular engineering tools to control angiogenesis. Here, we developed cationic nanocylinders (NCs) as inducers of cell–cell interaction and investigated their effect on angiogenic activities of human umbilical vein endothelial cells (HUVECs) in vitro. Electrospun poly (l-lactic acid) (PLLA) fibers were aminolyzed to generate positively charged NCs. The aninolyzation time was changed to produce two different aspect ratios of NCs. When HUVECs were treated with NCs, the electrostatic interaction of cationic NCs with negatively charged plasma membranes promoted migration, permeability and tubulogenesis of HUVECs compared to no treatment. This effect was more profound when the higher aspect ratio NC was used. The results indicate these NCs can be used as a new tool for the bottom-up approach to promote angiogenesis. Full article

The lifetime of singlet excitons in conjugated polymer films is a key factor taken into account during organic solar cell device optimization. It determines the singlet exciton diffusion lengths in polymer films and has a direct impact on the photocurrent generation by organic solar cell devices. However, very little is known about the material properties controlling the lifetimes of singlet excitons, with most of our knowledge originating from studies of small organic molecules. Herein, we provide a brief summary of the nature of the excited states in conjugated polymer films and then present an analysis of the singlet exciton lifetimes of 16 semiconducting polymers. The exciton lifetimes of seven of the studied polymers were measured using ultrafast transient absorption spectroscopy and compared to the lifetimes of seven of the most common photoactive polymers found in the literature. A plot of the logarithm of the rate of exciton decay vs. the polymer optical bandgap reveals a medium correlation between lifetime and bandgap, thus suggesting that the Energy Gap Law may be valid for these systems. This therefore suggests that small bandgap polymers can suffer from short exciton lifetimes, which may limit their performance in organic solar cell devices. In addition, the impact of film crystallinity on the exciton lifetime was assessed for a small bandgap diketopyrrolopyrrole co-polymer. It is observed that the increase of polymer film crystallinity leads to reduction in exciton lifetime and optical bandgap again in agreement with the Energy Gap Law. Full article

A series of iminopyridine ligated Co(II) (1a–7a) and Ni(II) (1b–7b) complexes were synthesized. The structures of complexes 3a, 4a, 5a, 7a, 5b, and 6b were determined by X-ray crystallographic analyses. Complex 3a formed a chloro-bridged dimer, whereas 4a, 5a, and 7a, having a substituent (4a, 5a: CH₃; 7a: Br) at the 6-position of pyridine, producing the solid structures with a single ligand coordinated to the central metal. The nickel atom in complex 5b features distorted trigonal-bipyramidal geometry with one THF molecule ligating to the metal center. All the complexes activated by ethylaluminum sesquichloride (EASC) were evaluated in 1,3-butadiene polymerization. The catalytic activity and selectivity were significantly influenced by the ligand structure and central metal. Comparing with the nickel complexes, the cobalt complexes exhibited higher catalytic activity and cis-1,4-selectivity. For both the cobalt and nickel complexes, the aldimine-based complexes showed higher catalyst activity than their ketimine counterparts. Full article

Solution-processed bulk heterojunction solar cells have experienced a remarkable acceleration in performances in the last two decades, reaching power conversion efficiencies above 10%. This impressive progress is the outcome of a simultaneous development of more advanced device architectures and of optimized semiconducting polymers. Several chemical approaches have been developed to fine-tune the optoelectronics and structural polymer parameters required to reach high efficiencies. Fluorination of the conjugated polymer backbone has appeared recently to be an especially promising approach for the development of efficient semiconducting polymers. As a matter of fact, most currently best-performing semiconducting polymers are using fluorine atoms in their conjugated backbone. In this review, we attempt to give an up-to-date overview of the latest results achieved on fluorinated polymers for solar cells and to highlight general polymer properties’ evolution trends related to the fluorination of their conjugated backbone. Full article

Precise control of the energy levels in a conjugated polymer is the key to allowing their exploitation in optoelectronic devices. The introduction of spirocycles into conjugated polymers has traditionally been used to enhance their solid state microstructure. Here we present a highly novel method of energetic tuning through the use of electronically active spirocyclic systems. By modifying the size and oxidation state of a heteroatom in an orthogonal spirocycle we demonstrate energetic fine tuning in both the absorption and emission of a conjugated polymer. Furthermore, the synthesis of highly novel triplet-decker spirocyclic conjugated polymers is presented. This new method of energetic manipulation in a conjugated polymer paves the way for future application targeted synthesis of polymers with electronically active spirocycles. Full article

Hydrothermal reactions of Zn(OAc)₂·2H₂O with flexible bipyridyl benzene ligand and three dicarboxylic derivatives gave rise to four new coordination polymers, [Zn₇(μ₄-O)₂(OAc)₁₀(bpmb)]_n (1), [Zn(5-OH-1,3-BDC)(bpmb)]_n (2), [Zn(1,2-BDC)(bpmb)]_n (3) and [Zn₂(ADB)₂(bpmb)]_n (4) (bpmb = 1,4-bis(pyridine-3-ylmethoxy)benzene, 5-OH-1,3-H₂BDC = 5-hydroxy-1,3-benzenedicarboxylic acid, 1,2-H₂BDC = 1,2-benzenedicarboxylic acid, H₂ADB = 2,2’-azodibenzoic acid). Their structures were characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Compound 1 features a one-dimensional (1D) chain structure based on the rare heptanuclear [Zn₇(μ₄-O)(μ₃-OAc)₂(μ₂-OAc)₈] units. Compound 2 exhibits a novel 2D bilayer structure built from the two parallel 2D (4,4) layers. Compound 3 holds a 2D structure in which the 1,2-BDC ligands work as lockers interlocking 1D [Zn(bpmb)]_n chain. Compound 4 comprises a 3D framework constructed by 2D wrinkled [Zn₂(ADB)₄]_n networks and bpmb linkers with a six-connected pcu net. These results suggest that the motifs of the dicarboxylic ligands have significant effect on the final structures. These compounds exhibited relatively good photocatalytic activity towards the degradation of methylene blue (MB) in aqueous solution under a Xe lamp irradiation. Full article

The aim of the study was to produce 3D sponges based on enzymatically modified lysozyme selected polysaccharides and assess their physicochemical properties. The alginate/chitosan sponges were formed from polymers hydrosols in different proportions at a final concentration of 1% polysaccharides. Hydrosols were modified by lysozyme addition of 1000 U. Hydrosols without or with enzyme were analyzed for their reducing sugar content, rheological properties and ability to scavenge free radicals. Sponges formed from hydrosols were tested for solubility and compressive properties. Only chitosan was hydrolyzed by lysozyme. The morphology of sponges was investigated by scanning electron microscopy (SEM). It was proven that the antioxidant properties of hydrosols are dependent on the concentration of chitosan. It was also shown that the addition of lysozyme negatively affected the free radical scavenging ability of single hydrosols of alginate and chitosan, and their mixtures. The Ostwald de Waele as well as Herschel–Bulkley models of rheological properties fitted the experimental data well (R² is between 0.947 and 1.000). Increase in textural features values of sponges was observed. Sponges with pure alginate and pure chitosan were almost completely soluble. The enzyme addition significantly changed the characteristics of the cross-section structure of sponges, and made the surface smoother. Full article

The analysis of the charge, structure and molecular interactions of/within polymeric substrates defines an important analytical challenge in materials science. Accordingly, advanced electrokinetic methods and theories have been developed to investigate the charging mechanisms and structure of soft material coatings. In particular, there has been significant progress in the quantitative interpretation of streaming current and surface conductivity data of polymeric films from the application of recent theories developed for the electrohydrodynamics of diffuse soft planar interfaces. Here, we review the theory and experimental strategies to analyze the interrelations of the charge and structure of polyelectrolyte layers supported by planar carriers under electrokinetic conditions. To illustrate the options arising from these developments, we discuss experimental and simulation data for plasma-immobilized poly(acrylic acid) films and for a polyelectrolyte bilayer consisting of poly(ethylene imine) and poly(acrylic acid). Finally, we briefly outline potential future developments in the field of the electrokinetics of polyelectrolyte layers. Full article

Poly(2-nonyl-2-oxazoline)₈₀-stat-poly(2-dec-9′-enyl-2-oxazoline)₂₀ and poly(2-dec-9′-enyl-2-oxazoline)₁₀₀ can be synthesized from the cationic ring-opening polymerization of monomers that can be derived from fatty acids from renewable resources. These (co)poly(2-oxazoline)s can be crosslinked with di- and trifunctional mercapto compounds using the UV-induced thiol-ene reaction. The complex permittivity of the corresponding networks increases with the temperature and decreases with the network density. In a frequency range from 10⁻² to 10⁶ Hz and at temperatures ranging from −20 to 40 °C, the changes of the real part of the complex permittivity as well as the loss factor can be explained by interfacial polarization within the material. At a temperature of 20 °C and a frequency of 50 Hz, the permittivity of the crosslinked (co)poly(2-oxazoline)s covers a range from 4.29 to 4.97, and the loss factors are in the range from 0.030 to 0.093. The electrical conductivities of these polymer networks span a range from 5 × 10⁻¹² to 8 × 10⁻⁹ S/m, classifying these materials as medium insulators. Notably, the values for the permittivity, loss factor and conductivity of these copoly(2-oxazoline)s are in the same range as for polyamides, and, hence, these copoly(2-oxazoline)-based networks may be referred to as “green” alternatives for polyamides as insulators in electronic applications. Full article

The preparation and characterization of a novel hybrid material based on the combination of a 2D-layered double hydroxide (LDH) nanosheets and a 1D-coordination polymer (1D-CP) has been achieved through a simple mixture of suspensions of both building blocks via an exfoliation/restacking approach. The hybrid material has been thoroughly characterized demonstrating that the 1D-CP moieties are intercalated as well as adsorbed on the surface of the LDH, giving rise to a layered assembly with the coexistence of the functionalities of their initial constituents. This hybrid represents the first example of the assembly of 1D/2D nanomaterials combining LDH with CP and opens the door for a plethora of different functional hybrid systems. Full article

A novel random copolymer based on donor–acceptor type polymers containing benzodithiophene and dithienosilole as donors and benzothiazole and diketopyrrolopyrrole as acceptors was designed and synthesized by Stille copolymerization, and their optical, electrochemical, charge transport, and photovoltaic properties were investigated. This copolymer with high molecular weight exhibited broad and strong absorption covering the spectra range from 500 to 800 nm with absorption maxima at around 750 nm, which would be very conducive to obtaining large short-circuits current densities. Unlike the general approach using single solvent to prepare the active layer film, mixed solvents were introduced to change the film feature and improve the morphology of the active layer, which lead to a significant improvement of the power conversion efficiency. These results indicate that constructing random copolymer with multiple donor and acceptor monomers and choosing proper mixed solvents to change the characteristics of the film is a very promising way for manufacturing organic solar cells with large current density and high power conversion efficiency. Full article

The copolymer VAMA was synthesized from vinyl acetic and maleic anhydride. A new all-polymeric blend with a high dielectric constant (ε) has been developed by blending polyvinylidene fluoride (PVDF) with vinyl acetic-maleic anhydride modified polyamide (PA66-g-VM). The blend shows high dielectric constants (ε_blend = 20) and excellent mechanical properties. The SEM investigations suggest that the enhanced dielectric behavior originates from significant interfacial interactions between polymers. The XRD demonstrates that the compatibilizer affects the crystalline behavior of each component. Furthermore, the stable dielectric constants of the all-polymeric blends can be tuned by adjusting the content of the compatibilizer. The created high-ε all-polymeric blends represent a novel type of material that is technologically simple, easy to process, and of a relatively high dielectric constant, with application for flexible electronics. Full article

We report on the degradation of organic photovoltaic (OPV) cells in both indoor and outdoor environments. Eight different research groups contributed state of the art OPV cells to be studied at Pomona College. Power conversion efficiency and fill factor were determined from IV curves collected at regular intervals over six to eight months. Similarly prepared devices were measured indoors, outdoors, and after dark storage. Device architectures are compared. Cells kept indoors performed better than outdoors due to the lack of temperature and humidity extremes. Encapsulated cells performed better due to the minimal oxidation. Some devices showed steady aging but many failed catastrophically due to corrosion of electrodes not active device layers. Degradation of cells kept in dark storage was minimal over periods up to one year. Full article