Polymers, Volume 6, Issue 1 (January 2014) – 15 articles , Pages 1-263

Polymers is instituting an annual award to recognize outstanding papers in the area of polymer science published in Polymers. We are pleased to announce the first “Polymers Best Paper Award” for 2014. Nominations were selected by the Editor-in-Chief and Editorial Board members of Polymers from all papers published in 2010. The awards are issued to reviews and articles respectively. [...] Full article

Drug delivery systems (DDS) are able to deliver, over long periods of time, therapeutic concentrations of drugs requiring frequent administration. Two classes of DDS are available, biodegradable and non-biodegradable. The larger non-biodegradable implants ensure long-term delivery, but require surgical interventions. Biodegradable biomaterials are smaller, injectable implants, but degrade hydrolytically and release drugs in non-zero order kinetics, which is inefficient for long-term sustained drug release. Biodegradable poly(ester amides) (PEAs) may overcome these difficulties. To assess their ocular biocompatibility and long-term behavior, PEA fibrils were analyzed in vitro and in vivo. In vitro, incubation in vitreous humor changes to PEA structure, suggests degradation by surface erosion, enabling drug release with zero order kinetics. Clinical and histological analysis of PEA fibrils implanted subconjunctivally and intravitreally showed the absence of an inflammatory response or other pathological tissue alteration. This study shows that PEA fibrils are biocompatible with ocular environment and degrade by surface erosion. Full article

Two amphiphilic block copolymers using hydrophobic poly(ε-caprolactone) (PCL) and hydrophilic poly(ethylene glycol) (PEG) were successfully synthesized. One of them is an (A-b-B)₄ type star polymer [(PCL-b-PEG)₄] and the other one is a Y-shaped PEG–(PCL)₂. A star-shaped polymer (PCL-b-PEG)₄ was prepared by ring-opening polymerization (ROP) of ε-caprolactone continued by click reaction of (PCL-azide)₄ and PEG-alkyne. The synthesis of Y-shaped PEG–(PCL)₂ block copolymer was carried out via Diels-Alder click reaction of a furan protected maleimide end-functionalized PEG (PEG-MI) with an anthracene end-functionalized PCL following the ROP of ε-caprolactone. The characterization of micelles is carried out using both materials in aqueous media as drug delivery vehicles, which showed satisfying results and enhanced the cytotoxic effect of the anti-cancer drug vinorelbine (VLB). However, micelles consisted of Y-shaped unimers were found to be more convenient for delivery of hydrophobic drugs such as VLB because they formed in lower concentration, carrying a higher amount of drugs and owing a monomodal distribution. We concluded that the free tails of hydrophobic chains in Y-shaped block copolymer facilitate the assembly of amphiphilic material in water to form micelles. Full article

Polyester dendrimers have been shown to be outstanding candidates for biomedical applications. Compared to traditional polymeric drug vehicles, these biodegradable dendrimers show excellent advantages especially as drug delivery systems because they are non-toxic. Here, advances on polyester dendrimers as smart carriers for drug delivery applications have been surveyed. Both covalent and non-covalent incorporation of drugs are discussed. Full article

Polyethylene glycol (PEG) at the moment is considered the leading polymer for protein conjugation in view of its unique properties, as well as to its low toxicity in humans, qualities which have been confirmed by its extensive use in clinical practice. Other polymers that are safe, biodegradable and custom-designed have, nevertheless, also been investigated as potential candidates for protein conjugation. This review will focus on natural polymers and synthetic linear polymers that have been used for protein delivery and the results associated with their use. Genetic fusion approaches for the preparation of protein-polypeptide conjugates will be also reviewed and compared with the best known chemical conjugation ones. Full article

An analytical approach with the help of numerical simulations based on the equivalent constraint model (ECM) was proposed to investigate the progressive failure behavior of symmetric fiber-reinforced composite laminates damaged by transverse ply cracking. A fracture criterion was developed to describe the initiation and propagation of the transverse ply cracking. This work was also concerned with a statistical distributions of the critical fracture toughness values with due consideration given to the scale size effect. The Monte Carlo simulation technique coupled with statistical analysis was applied to study the progressive cracking behaviors of composite structures, by considering the effects of lamina properties and lay-up configurations. The results deduced from the numerical procedure were in good agreement with the experimental results obtained for laminated composites formed by unidirectional fiber reinforced laminae with different orientations. Full article

Examination of thermal degradation of natural and synthetic lacquer films by pyrolysis-gas chromatography with mass spectrometry (Py-GC/MS) is reviewed. Due to the instantaneous heating decomposition, side reactions of internal or intermediate samples hardly occur, and the pyrolysis products can be retrieved without any change. Py-GC/MS has been used to analyze the composition of insoluble polymers and investigate degradation of resin materials. Lacquer film is a cross-linked polymer that is insoluble in any solvent. The aim of this review is to describe the application of Py-GC/MS to the analysis of lacquer, including natural lacquer saps, synthetic lacquer derivatives, and their films. After analyzing the chemical structures of the specific pyrolysis products by mass spectrometry, the lacquer tree species and growing region can be determined. These results have great significance for the protection and restoration of lacquer-coated cultural treasures. Full article

This paper presents a study on the load carrying capacity of reinforced concrete (RC) beams strengthened with externally bonded (EB) carbon fiber reinforced polymer (CFRP) strips prestressed up to 0.6% in strain. At the strip ends, the innovative gradient anchorage is used instead of conventional mechanical fasteners. This method, based on the epoxy resin’s ability to rapidly cure under high temperatures, foresees a sector-wise heating followed by a gradual decrease of the initial prestress force towards the strip ends. The experimental investigation shows a promising structural behavior, resulting in high strip tensile strains, eventually almost reaching tensile failure of the composite strip. Additionally, ductility when considering deflection at steel yielding and at ultimate load is satisfying, too. From a practical point of view, it is demonstrated that premature strip grinding in the anchorage zone is not beneficial. In addition, a non-commercial 1D finite element code has been enlarged to an EB reinforcement with prestressed composite strips. A bilinear bond stress-slip relation obtained in earlier investigations is introduced as an additional failure criterion to the code. The numerical code is able to almost perfectly predict the overall structural behavior. Furthermore, the calculations are used for comparison purposes between an initially unstressed and a prestressed externally bonded composite reinforcement. The increase in cracking and yielding load, as well as differences in structural stiffness are apparent. Full article

Functionalized silica sols were obtained by the hydrolytic condensation of (γ-methacryloxypropyl)trimethoxysilane (MPMS), (γ-glycidyloxypropyl)trimethoxysilane (GPMS) and tetraethoxysilane (TEOS). Three different sols were obtained: MPS (derived from MPMS and TEOS), GPS-MPS (derived from GPMS, MPMS and TEOS), and GPSD (derived from GPMS, TEOS and diglycidyl ether of bisphenol A, DGEBA). These silica sols were mixed with a phenolic resin (PR). Ethylenediamine was used as a hardener for epoxy-functionalized sols and benzoyl peroxide was used as an initiator of the free-radical polymerization of methacrylate-functionalized silica sols. Glass fiber-reinforced composites were obtained from the neat PR and MPS-PR, GPS-MPS-PR and GPSD-PR. The resulting composites were evaluated as ablation resistant materials in an acetylene-oxygen flame. A large increase in the ablation resistance was observed when the PR was modified by the functionalized silica sols. The ablation resistance of the composites decreased as follows: GPSD-PR > MPS-PR > GPS-MPS-PR > PR. Full article

Graphene nanoplatelets (xGnP) were investigated as a novel nano-reinforcement filler in poly(lactic acid)(PLA)/poly(ethylene glycol)(PEG) blends by the melt blending method. PLA was first plasticized by PEG in order to improve its flexibility and thereby overcome its problem of brittleness. Then, xGnP was incorporated into the PLA/PEG blend. The prepared nanocomposites exhibited a significant improvement in tensile properties at a low xGnP loading. The tensile properties demonstrated the addition of 0.3 wt% of xGnP led to an increase of up to 32.7%, 69.5% and 21.9% in tensile strength, tensile modulus and elongation at break of the nanocomposites respectively, compared to PLA/PEG blend. X-ray diffraction (XRD) patterns showed the presence of a peak around 26.5^○ in PLA/PEG/xGnP nanocomposites which corresponds to the characteristic peak of xGnP. The nanocomposites also shows enhanced thermal stability compared with PLA/PEG blend in thermogravimetry analysis (TGA). The enhancement to some extent of the tensile properties of the PLA/PEG/xGnP nanocomposites can be ascribed to the homogeneous dispersion and orientation of the xGnP nanoplatelets in the polymer matrix and strong interfacial interaction between both components. The scanning electron microscopy (SEM) image of PLA/PEG/0.3 wt% xGnP displays good uniformity and more homogenous morphology. Good uniformity of composites indicates a good degree of dispersion of the xGnp and therefore results in good tensile and thermal properties. Full article

This paper investigates the mechanical performance and electrical resistivity of a structural adhesive epoxy enhanced using milled carbon fibre (MCF) as well as the bond performance of carbon fibre reinforced polymers (CFRP) and steel adhesively bonded joints using the enhanced epoxy. The epoxy was enhanced using such MCFs with different weight ratios of 1.5%, 3% and 5%. Tensile experiments were performed on the original and enhanced epoxy specimens according to ASTM D638. More ductile process failure was found for the epoxy after modification and significant improvements of E-modulus and tensile strength were evidenced when the MCF weight ratio was larger than 1.5%. Scanning electron microscopy (SEM) revealed that the failure mechanism of short MCFs pulled out from the epoxy matrix contributed to the enhancement of the mechanical performance of the epoxy. The electrical resistivity of the epoxy with MCF weight ratio of 5% was reduced by at least four orders of magnitude compared to the original epoxy, due to the conductive network formed by MCFs. Steel/CFRP double strap joints (with either CFRP sheets or CFRP laminates) were prepared using the enhanced epoxy and then tested in tension, however no obvious increase in joint stiffness or strength was observed. Full article

The failure criteria from rock mechanics, Hoek-Brown and Johnston failure criteria, may be extended and modified to assess the ultimate compressive strength of axially loaded circular fiber reinforced polymer (FRP)-confined concrete columns. In addition to the previously modified Hoek-Brown criterion, in this study, the Johnston failure criterion is extended to scope of FRP-confined concrete, verified with the experimental data and compared with the significant relationships from the current literature. Wide-range compressive strengths from 7 to 108 MPa and high confinement ratios up to 2.0 are used to verify the ultimate strengths in short columns. The results are in good agreement with experimental data for all confinement levels and concrete strengths. Full article

The antioxidant property and other health benefits of the most abundant catechin, epigallocatechin gallate (EGCG), are limited because of poor stability and permeability across intestine. Protecting the EGCG from the harsh gastrointestinal tract (GIT) environment can help to increase its bioavailability following oral administration. In this study, EGCG was loaded to hydrogel prepared from ionic interaction between an optimized concentration of gelatin and γ-polyglutamic acid (γ-PGA), with ethylcarbodiimide (EDC) as the crosslinker. Physicochemical characterization of hydrogel was done using Fourier transform-infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The dependence of the swelling degree (SD) of the hydrogel to the amount of gelatin, γ-PGA, EDC, swelling time and pH was determined. A high SD of the crosslinked hydrogel was noted at pH 4.5, 6.8 and 9.0 compared to pH 7.4, which describes pH-responsiveness. Approximately 67% of the EGCG from the prepared solution was loaded to the hydrogel after 12 h post-loading, in which loading efficiency was related to the amount of EDC. The in vitro release profile of EGCG at pH 1.2, 6.8 and 7.4, simulating GIT conditions, resulted in different sustained release curves. Wherein, the released EGCG was not degraded instantly compared to free-EGCG at controlled temperature of 37 °C at different pH monitored against time. Therefore, this study proves the potential of pH-responsive gelatin-γ-PGA-based hydrogel as a biopolymer vehicle to deliver EGCG. Full article

One of the primary objectives in the design of composite structures is the prevention of premature bond failure. Therefore, the characterization of cohesive behavior is an important field of study in structural engineering. Using fracture mechanics principles, the cohesive behavior of an epoxy bonded coarse silica sand aggregate bond interface is studied in this paper, with a focus on finding a general analytical form of idealizing its behavior when used in a specimen possessing asymmetric and inhomogeneous qualities. Two series of small-scale specimens were experimentally tested under mixed-mode bending (MMB) conditions, where it was found that there was negligible influence exerted on the fracture energy of the interface due to changes in the mixed-mode ratio or initial crack length. Using finite element analysis (FEA) methods, an appropriate bilinear traction-separation model was developed to both validate as well as obtain a set of consistent parameters applicable to all tested specimens. Comparison of the Global Method and the Local Method, used to obtain partitioned Mode I and Mode II fracture energy values from MMB specimens, were made, with the conclusion that both methods are adequate in the calculation of the total fracture energy though the Local Method should be used to obtain accurate partitioned Mode I and Mode II fracture energy values. Idealization of the bond interface using the cohesive parameters derived can be accurately achieved by the use of both contact interactions and cohesive elements in two-dimensional and three-dimensional FE models, though the results obtained using contact interactions would be expected to exhibit greater global stiffness. Full article

The polymorphic phase transformation in the cocrystallization of adefovir dipivoxil (AD) and succinic acid (SUC) was investigated. Inspired by biological and biomimetic crystallization, polymeric additives were utilized to control the phase transformation. With addition of poly(acrylic acid), the metastable phase newly identified through the analysis of X-ray diffraction was clearly isolated from the previously reported stable form. Without additives, mixed phases were obtained even at the early stage of cocrystallization. Also, infrared spectroscopy analysis verified the alteration of the hydrogen bonding that was mainly responsible for the cocrystal formation between AD and SUC. The hydrogen bonding in the metastable phase was relatively stronger than that in the stable form, which indicated the locally strong AD/SUC coupling in the initial stage of cocrystallization followed by the overall stabilization during the phase transformation. The stronger hydrogen bonding could be responsible for the faster nucleation of the initially observed metastable phase. The present study demonstrated that the polymeric additives could function as effective regulators for the polymorph-selective cocrystallization. Full article