How Confinement Affects the Nucleation, Crystallization, and Dielectric Relaxation of Poly(butylene succinate) and Poly(butylene adipate) Infiltrated within Nanoporous Alumina Templates.

This work describes the successful melt infiltration of poly(butylene succinate) (PBS) and poly(butylene adipate) (PBA) within 70 nm diameter anodic aluminum oxide (AAO) templates. The infiltrated samples were characterized by SEM, Raman, and FTIR spectroscopy. The crystallization behaviors and crystalline structures of both polymers, bulk and confined, were analyzed by differential scanning calorimetry (DSC) and grazing incidence wide angle X-ray scattering (GIWAXS). DSC revealed that a change in the nucleation process occurred from heterogeneous nucleation for bulk samples to homogeneous nucleation for infiltrated PBA and to surface-induced nucleation for infiltrated PBS. GIWAXS results indicate that PBS nanofibers crystallize in the α-phase, as well as their bulk samples. However, PBA nanofibers crystallize just in the ß-phase, whereas PBA bulk samples crystallize in a mixture of α- and ß-phases. The crystal orientation within the pores was determined, and differences between PBS and PBA were also found. Finally, broadband dielectric spectroscopy was applied to study the segmental dynamics for bulk and infiltrated samples. The glass temperature was found to significantly decrease in the PBS case upon infiltration, while that of PBA remained unchanged. These differences were correlated with the higher affinity of PBS to the AAO walls than PBA, in accordance with their nucleation behavior (surface-induced versus homogeneous nucleation, respectively).

Gecko-like Branched Polymeric Nanostructures from Nanoporous Templates.

Here, we report a simple method to produce hierarchically shaped polymeric one-dimensional nanostructures. More specifically, dual-sized polymer nanowires are fabricated employing multibranched anodic aluminum oxide templates. By fine selection of the anodization conditions, we achieve branched nanopores having a first segment of 400 nm in diameter from which seven further 55 nm in diameter pores arise. Wetting of such nanopores with polymer melts-for example, poly(ε-caprolactone) and polystyrene-allows for the nanomolding of their respective inverse nanostructures, that is, dual-sized multibranched polymer nanowires that, when supported on a flat surface, strongly resemble the spatulae of geckos' toes. The structural features of the dual-sized polymer nanostructures, namely, crystalline phase, crystallinity, texture, and so on, are furthermore characterized and interpreted within the context of polymer phase transitions in confined media. Our work presents a readily applicable approach to produce soft nanomaterials of high morphological complexity, thereby with promising implications in the nanotechnology area, for example, in biomimetic solid adhesion.

Quantitative Nanomechanical Properties of Multilayer Films Made of Polysaccharides through Spray Assisted Layer-by-Layer Assembly.

Nanomechanical properties of alginate/chitosan (Alg/Chi) multilayer films, obtained through spray assisted layer-by-layer assembly, were studied by means of PeakForce quantitative nanomechanical mapping atomic force microscopy (PF-QNM AFM). Prepared at two different alginate concentrations (1.0 and 2.5 mg/mL) and a fixed chitosan concentration (1.0 mg/mL), Alg/Chi films have an exponential growth in thickness with a transition to a linear growth toward a plateau by increasing the number of deposited bilayers. Height, elastic modulus, deformation, and adhesion maps were simultaneously recorded depending on the number of deposited bilayers. The elastic modulus of Alg/Chi films was found to be related to the mechanism of growth in contrast to the adhesion and deformation. A comparison of the nanomechanical properties obtained for non-cross-linked and thermally cross-linked Alg/Chi films revealed an increase of the elastic modulus after cross-linking regardless alginate concentration. The incorporation of iron oxide nanoparticles (NPs), during the spray preparation of the films, gave rise to nanocomposite Alg/Chi films with increased elastic moduli with the number of incorporated NPs layers. Deformation maps of the films strongly suggested the presence of empty spaces associated with the method of preparation. Finally, adhesion measurements point out to a significant role of NPs on the increase of the adhesion values found for nanocomposite films.

Thermally-induced softening of PNIPAm-based nanopillar arrays.

The surface properties of soft nanostructured hydrogels are crucial in the design of responsive materials that can be used as platforms to create adaptive devices. The lower critical solution temperature (LCST) of thermo-responsive hydrogels such as poly(N-isopropylacrylamide) (PNIPAm) can be modified by introducing a hydrophilic monomer to create a wide range of thermo-responsive micro-/nano-structures in a large temperature range. Using surface initiation atom-transfer radical polymerization in synthesized anodized aluminum oxide templates, we designed, fabricated, and characterized thermo-responsive nanopillars based on PNIPAm hydrogels with tunable mechanical properties by incorporating acrylamide monomers (AAm). In addition to their LCST, the incorporation of a hydrophilic entity in the nanopillars based on PNIPAm has abruptly changed the topological and mechanical properties of our system. To gain an insight into the mechanical properties of the nanostructure, its hydrophilic/hydrophobic behavior and topological characteristics, atomic force microscopy, molecular dynamics simulations and water contact angle studies were combined. When changing the nanopillar composition, a significant and opposite variation was observed in their mechanical properties. As temperature increased above the LCST, the stiffness of PNIPAm nanopillars, as expected, did so too, in contrast to the stiffness of PNIPAm-AAm nanopillars that decreased significantly. The molecular dynamics simulations proposed a local molecular rearrangement in our nanosystems at the LCST. The local aggregation of NIPAm segments near the center of the nanopillars displaced the hydrophilic AAm units towards the surface of the structure leading to contact with the aqueous environment. This behavior was confirmed via contact angle measurements below and above the LCST.

New Double-Infiltration Methodology to Prepare PCL-PS Core-Shell Nanocylinders Inside Anodic Aluminum Oxide Templates.

Melt nanomolding of core-shell nanocylinders of different sizes, employing anodic aluminum oxide (AAO) templates, is reported here for the first time. The core-shell nanostructures are achieved by a new melt double-infiltration technique. During the first infiltration step, polystyrene (PS) nanotubes are produced by an adequate choice of AAO nanopore diameter size. In the second step, PCL is infiltrated inside the PS nanotubes, as its melting point (and infiltration temperature) is lower than the glass transition temperature of PS. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) measurements verified the complete double-infiltration of the polymers. Differential scanning calorimetry (DSC) experiments show that the infiltrated PCL undergoes a confined fractionated crystallization with two crystallization steps located at temperatures that depend on which surface is in contact with the PCL nanocylinders (i.e., alumina or PS). The melt double-infiltration methodology represents a novel approach to study the effect of the surrounding surface on polymer crystallization under confinement.

Slow dynamics of nanocomposite polymer aerogels as revealed by X-ray photocorrelation spectroscopy (XPCS).

We report on a novel slow dynamics of polymer xerogels, aerogels, and nanocomposite aerogels with iron oxide nanoparticles, as revealed by X-ray photon correlation spectroscopy. The polymer aerogel and its nanocomposite aerogels, which are porous in nature, exhibit hyper-diffusive dynamics at room temperature. In contrast, non-porous polymer xerogels exhibit an absence of this peculiar dynamics. This slow dynamical process has been assigned to a relaxation of the characteristic porous structure of these materials and not to the presence of nanoparticles.

Polymerization within Nanoporous Anodized Alumina Oxide Templates (AAO): A Critical Survey.

In the last few years, the polymerization of monomers within the nanocavities of porous materials has been thoroughly studied and developed, allowing for the synthesis of polymers with tailored morphologies, chemical architectures and functionalities. This is thus a subject of paramount scientific and technological relevance, which, however, has not previously been analyzed from a general perspective. The present overview reports the state of the art on polymerization reactions in spatial confinement within porous materials, focusing on the use of anodized aluminum oxide (AAO) templates. It includes the description of the AAO templates used as nanoreactors. The polymerization reactions are categorized based on the polymerization mechanism. Amongst others, this includes electrochemical polymerization, free radical polymerization, step polymerization and atom transfer radical polymerization (ATRP). For each polymerization mechanism, a further subdivision is made based on the nature of the monomer used. Other aspects of "in situ" polymerization reactions in restricted AAO geometries include: conversion monitoring, kinetic studies, modeling and polymer characterization. In addition to the description of the polymerization process itself, the use of polymer materials derived from polymerization in AAO templates in nanotechnology applications, is also highlighted. Finally, the review is concluded with a general discussion outlining the challenges that remain in the field.

Confinement effects on the crystallization of poly(ethylene oxide) nanotubes.

In this work, we show the effects of nanoconfinement on the crystallization of poly(ethylene oxide) (PEO) nanotubes embedded in anodized aluminum oxide (AAO) templates. The morphological characteristics of the hollow 1D PEO nanostructures were evaluated by scanning electron microscopy (SEM). The crystallization of the PEO nanostructures and bulk was studied with differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). The crystallization of PEO nanotubes studied by DSC is strongly influenced by the confinement showing a strong reduction in the crystallization temperature of the polymer. X-ray diffraction (XRD) experiments confirmed the isothermal crystallization results obtained by DSC, and studies carried out at low temperatures showed the absence of crystallites oriented with the extended chains perpendicular to the pore wall within the PEO nanotubes, which has been shown to be the typical crystal orientation for one-dimensional polymer nanostructures. In contrast, only planes oriented 33, 45, and 90° with respect to the plane (120) are arranged parallel to the pore's main axis, indicating preferential crystal growth in the direction of the radial component. Calculations based on classical nucleation theory suggest that heterogeneous nucleation prevails in the bulk PEO whereas for the PEO nanotubes a surface nucleation mechanism is more consistent with the obtained results.

A Brief Overview of Polymers Science and Technology, in Spain.

This Special Issue State-of-the-Art on Polymer Science and Technology in Spain is comprised of a collection of 42 publications/contributions related to very different topics undertaken by the numerous research groups working in Spain in Polymer Science and Technology. This monograph collects the contributions of more than 200 different authors from 24 different national Institutions (>30 different centers/departments) from Universities and CSIC centers distributed throughout the whole of Spain. Two-thirds of the contributions to this Special Issue arise from Institutional collaborations, half of which are international collaborations with European research groups and the other half with other international research groups outside Europe including China, Australia or United States of America among others. This brief overview communication provides a general overview of the research lines in Polymer Science and Technology covered in Spain and show most of the representative polymer groups and their distribution throughout Spain. Most of Spanish polymer groups belong to the Grupo Especializado de Polímeros (GEP) being part of the European Polymer Federation (EPF). It also shows how Spanish science about polymers is positioned at European level.

Rheology Applied to Microgels: Brief (Revision of the) State of the Art.

The ability of polymer microgels to rapidly respond to external stimuli is of great interest in sensors, lubricants, and biomedical applications, among others. In most of their uses, microgels are subjected to shear, deformation, and compression forces or a combination of them, leading to variations in their rheological properties. This review article mainly refers to the rheology of microgels, from the hard sphere versus soft particles' model. It clearly describes the scaling theories and fractal structure formation, in particular, the Shih et al. and Wu and Morbidelli models as a tool to determine the interactions among microgel particles and, thus, the viscoelastic properties. Additionally, the most recent advances on the characterization of microgels' single-particle interactions are also described. The review starts with the definition of microgels, and a brief introduction addresses the preparation and applications of microgels and hybrid microgels.

UCST-like hybrid PAAm-AA/Fe3O4 microgels. Effect of Fe3O4 nanoparticles on morphology, thermosensitivity and elasticity.

The incorporation of metal oxide nanoparticles into microgels forming hybrid systems gives additional functionalities to the system and widens the field of potential application in biomedicine, biotechnology, and other fields. In particular, there have been very few investigations regarding UCST-like hybrid microgels. In connection with this, we report the preparation of UCST-like hybrid microgels of magnetite nanoparticles (Fe(3)O(4)) encapsulated in poly(acrylamide-acrylic acid) microgel matrix via an inverse emulsion polymerization method. The key factor in the preparation of hybrid microgels is the need to divide in two the aqueous phase of the emulsion and feed them separately in order to avoid the aggregation of magnetic nanoparticles prior to polymerization reaction. The morphology, size, and spherical shape of hybrid microgels are determined by scanning electron microscopy. The encapsulation of magnetite nanoparticles within the polymer matrix is confirmed by transmission electron microscopy. Dynamic light scattering is employed to study both the swelling UCST-like behavior and the surface charge of the hybrid microgels. Swelling measurements confirm that the incorporation of magnetite does not affect the thermosensitivity of the system. In order to highlight the rheological behavior that can affect the final potential applications of these hybrid systems, a deep study of the viscoelastic properties is carried out by means of an oscillatory rheometer. The dependence of G' and G'' of the microgel dispersions with the frequency suggests a gel-like behavior and hence the occurrence of structural organization. In order to understand this structure formation and the influence of the magnetite in the interaction between hybrid microgels, scaling theory was applied. In terms of rheology, the addition of magnetite leads to a change in the interaction between hybrid microgels giving rise to an increase in the elasticity of the system.

Polyelectrolyte Multilayer Films Based on Natural Polymers: From Fundamentals to Bio-Applications.

Natural polymers are of great interest in the biomedical field due to their intrinsic properties such as biodegradability, biocompatibility, and non-toxicity. Layer-by-layer (LbL) assembly of natural polymers is a versatile, simple, efficient, reproducible, and flexible bottom-up technique for the development of nanostructured materials in a controlled manner. The multiple morphological and structural advantages of LbL compared to traditional coating methods (i.e., precise control over the thickness and compositions at the nanoscale, simplicity, versatility, suitability, and flexibility to coat surfaces with irregular shapes and sizes), make LbL one of the most useful techniques for building up advanced multilayer polymer structures for application in several fields, e.g., biomedicine, energy, and optics. This review article collects the main advances concerning multilayer assembly of natural polymers employing the most used LbL techniques (i.e., dipping, spray, and spin coating) leading to multilayer polymer structures and the influence of several variables (i.e., pH, molar mass, and method of preparation) in this LbL assembly process. Finally, the employment of these multilayer biopolymer films as platforms for tissue engineering, drug delivery, and thermal therapies will be discussed.

In Situ Synthesis of Poly(butyl methacrylate) in Anodic Aluminum Oxide Nanoreactors by Radical Polymerization: A Comparative Kinetics Analysis by Differential Scanning Calorimetry and 1H-NMR.

In this work, we explore the ability to generate well-defined poly(butyl methacrylate) (PBMA) nanostructures by "in situ" polymerization of butyl methacrylate monomer (BMA). PBMA nanostructures of high and low aspect ratios have been successfully obtained through the free radical polymerization (FRP) of a BMA monomer in anodic aluminum oxide (AAO) nanoreactors of suitable size. A polymerization kinetics process has been followed by differential scanning calorimetry (DSC) and proton Nuclear Magnetic Resonance spectroscopy (1H-NMR).The determination of the kinetics of polymerization through DSC is based on a quick and direct analysis of the exothermic polymerization process, whereas the analysis through 1H-NMR also allows the unambiguous chemical analysis of the resulting polymer. When compared to bulk polymerization, both techniques demonstrate confinement effects. Moreover, DSC and 1H-NMR analysis give the same kinetics results and show a gel-effect in all the cases. The number average molecular weight (Mn) of the PBMA obtained in AAO of 60-300 nm are between 30·103-175·103 g/mol. Even if the Mn value is lower with respect to that obtained in bulk polymerization, it is high enough to maintain the polymer properties. As determined by SEM morphological characterization, once extracted from the AAO nanoreactor, the polymer nanostructures show controlled homogeneous aspect/size all throughout the length of nanopillar over a surface area of few cm2. The Young's modulus of low aspect ratio PBMA nanopillars determined by AFM gives a value of 3.1 ± 1.1 MPa. In this work, a 100% of PBMA polymer nanostructures are obtained from a BMA monomer in AAO templates through a quick double process: 30 min of monomer immersion at room temperature and 90 min of polymerization reaction at 60 °C. While the same nanostructures are obtained by polymer infiltration of PBMA at 200 °C in about 6 h, polymerization conditions are much softer than those corresponding to the polymer infiltration process. Furthermore, the 1H-NMR technique has been consolidated as a tool for studying the kinetics of the copolymerization reactions in confinement and the determination of monomer reactivity ratios.

Novel Hydrogels of Chitosan and Poly(vinyl alcohol) Reinforced with Inorganic Particles of Bioactive Glass.

Chitosan (CS) and poly(vinyl alcohol) (PVA) hydrogels, a polymeric system that shows a broad potential in biomedical applications, were developed. Despite the advantages they present, their mechanical properties are insufficient to support the loads that appear on the body. Thus, it was proposed to reinforce these gels with inorganic glass particles (BG) in order to improve mechanical properties and bioactivity and to see how this reinforcement affects levofloxacin drug release kinetics. Scanning electron microscopy (SEM), X-ray diffraction (XRD), swelling tests, rheology and drug release studies characterized the resulting hydrogels. The experimental results verified the bioactivity of these gels, showed an improvement of the mechanical properties and proved that the added bioactive glass does affect the release kinetics.

Effect of Gold Nanoparticles on the Thermosensitivity, Morphology, and Optical Properties of Poly(acrylamide-acrylic acid) Microgels.

Novel positive thermosensitive microgels of poly(acrylamide-acrylic acid) with embedded gold nanoparticles have been synthesized and characterized by means of dynamic light scattering, UV-vis spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy. These systems show temperature (upper critical solution temperature-like volume phase transition) and optical responsiveness making them externally triggered systems.

Structural organization of iron oxide nanoparticles synthesized inside hybrid polymer gels derived from alginate studied with small-angle X-ray scattering.

The structural organization of iron oxide nanoparticles (NPs) obtained through in situ coprecipitation of iron salts in semi-interpenetrating polymer networks (semi-IPNs) constituted of alginate (Alg) and poly(N-isopropylacrylamide) (PNiPAAm) has been investigated by means of small-angle X-ray scattering and transmission electron microscopy. The oxidation reaction was repeated up to two times to increase the amount of iron oxide NPs formed. The results were compared to the synthesis of iron oxide nanoparticles in an alginate solution. It has been demonstrated that the polymeric gel acts as a spatial framework for iron oxide nanoparticles that controls their particle size distribution and that the application of repeating oxidation cycles does not increase the polydispersity of the iron oxide nanoparticles.

A novel organogelator incorporating tert-butyl esters of asparagines.

A novel organogelator based on tert-butyl esters of asparagines has been synthesized and its organogelation abilities have been investigated. The rheological characterization has confirmed the gelation behavior, and its thixotropic properties. Furthermore, the morphological studies performed reveal a spherical structure. Thus, this organogelator can be considered as a new example of the emerging, but still reduced, list of gels with a non-fibrillar assembly.

Neutron scattering study of the dynamics of a polymer melt under nanoscopic confinement.

Poly(ethylene oxide) confined in an anodic aluminum oxide solid matrix has been studied by different neutron scattering techniques in the momentum transfer (Q) range 0.2

Ordered arrays of magnetic polymer-based nanorods by template synthesis.

An ordered array of polymer-based magnetic nanorods has been prepared from poly(vinyl alcohol) solution with dispersed CoFe2O4 nanoparticles by template synthesis using nanoporous anodic alumina. The ordering of the alumina template is transferred to the magnetic nanocomposite in such a way that the magnetic nanorods are located in an orderly fashion. The organic-inorganic nature of the nanorods is proven and their first magnetic characterization reveals a little magnetic anisotropy. The proposed method of synthesis shows a good versatility to obtain ordered magnetopolymeric nanostructures with tailored geometric dimensions which together with their excellent mechanical behaviour open new opportunities of technological applications in the field of magnetic encoding and storage of information.

A Way to Predict Gold Nanoparticles/Polymer Hybrid Microgel Agglomeration Based on Rheological Studies.

In this work, a detailed rheological study of hybrid poly(acrylamide-co-acrylic acid) P(AAm-co-AAc) aqueous microgel dispersions is performed. Our intention is to understand how the presence of gold nanoparticles, AuNP, embedded within the microgel matrix, affects the viscoelastic properties, the colloidal gel structure formation, and the structure recovery after cessation of the deformation of the aqueous microgel dispersions. Frequency sweep experiments confirmed that hybrid microgel dispersions present a gel-like behavior and that the presence of AuNP content within microgel matrix contributes to the elasticity of the microgel dispersions. Strain sweep test confirmed that hybrid microgels aqueous dispersion also form colloidal gel structures that break upon deformation but that can be recovered when the deformation decreases. The fractal analysis performed to hybrid microgels, by applying Shih et al. and Wu and Morbidelli's scaling theories, evidenced that AuNP significantly affects the colloidal gel structure configuration ending up with the formation of agglomerates or microgel clusters with closer structures in comparison to the reference P(AAm-co-AAc) aqueous microgel dispersions.