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The liquid-to-solid phase transition is a complex process that is difficult to investigate experimentally with sufficient spatial and temporal resolution. A key aspect of the transition is the formation of a critical seed of the crystalline phase in a supercooled liquid, that is, a liquid in a metastable state below the melting temperature. This stochastic process is commonly described within the framework of classical nucleation theory, but accurate tests of the theory in atomic and molecular liquids are challenging. Here, we employ femtosecond x-ray diffraction from microscopic liquid jets to study crystal nucleation in supercooled liquids of the rare gases argon and krypton. Our results provide stringent limits to the validity of classical nucleation theory in atomic liquids, and offer the long-sought possibility of testing nonclassical extensions of the theory.

Here, we present a detailed description of the in situ isothermal crystallization of poly(trimethylene 2,5-furandicarboxylate)(PTF) as revealed by real-time Fourier transform infrared spectroscopy (FTIR) and grazing incidence wide-angle X-ray scattering (GIWAXS). From FTIR experiments, the evolution of hydrogen bonding with crystallization time can be monitored in real time, while from GIWAXS, crystal formation can be followed. Density functional theory (DFT) calculations have been used to simulate FTIR spectra for different theoretical structures, enabling a precise band assignment. In addition, based on DFT ab initio calculations, the influence of hydrogen bonding on the evolution with crystallization time can be understood. Moreover, from DFT calculations and comparison with both FTIR and GIWAXS experiments, a crystalline structure of poly(trimethylene 2,5-furandicarboxylate) is proposed. Our results demonstrate that hydrogen bonding is present in both the crystalline and the amorphous phases and its rearrangement can be considered as a significant driving force for crystallization of poly(alkylene 2,5-furanoate)s., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In the present study, a fully plant-based sustainable copolyester series, namely poly(butylene 2,5-furandicarboxylate)- block -poly(caprolactone)s (PBF- block -PCL)s were successfully synthesized by melt polycondensation combining butylene 2,5-furandicarboxylate with polycaprolactone diol (PCL) at different weight ratios. Differential scanning calorimetry (DSC) showed that only PBF underwent melting, crystallization from the melt, and cold crystallization. Thermogravimetric analysis (TGA) revealed outstanding thermal stability, exceeding 305 °C, with further improvement in thermal and thermo-oxidative stability with increasing PCL content. Broadband dielectric spectroscopy (BDS) revealed that at low temperatures, below the glass transition ( T g ) all copolyesters exhibited two relaxation processes ( β 1 and β 2 ), whereas the homopolymer PBF exhibited a single β -relaxation, which is associated with local dynamics of the different chemical bonds present in the polymer chain. Additionally, it was proved that an increase in PCL content affected the dynamics of the chain making it more flexible, thus providing an increase in the value of the room temperature free volume fractions ( f v ) and the value of elongation at break. These effects are accompanied by a decrease in hardness, Young's modulus, and tensile strength. The described synthesis enables a facile approach to obtain novel fully multiblock biobased copolyesters based on PBF and PCL polyesters with potential industrial implementation capabilities.

In this work, the formation of laser-induced periodic surface structures (LIPSS) on the surfaces of thin films of poly(ethylene terephthalate) (PET) and PET reinforced with expanded graphite (EG) was studied. Laser irradiation was carried out by ultraviolet (265 nm) and near-infrared (795 nm) femtosecond laser pulses, and LIPSS were formed in both materials. In all cases, LIPSS had a period close to the irradiation wavelength and were formed parallel to the polarization of the laser beam, although, in the case of UV irradiation, differences in the formation range were observed due to the different thermal properties of the neat polymer in comparison to the composite. To monitor the modification of the physicochemical properties of the surfaces after irradiation as a function of the laser wavelength and of the presence of the filler, different techniques were used. Contact angle measurements were carried out using different reference liquids to measure the wettability and the solid surface free energies. The initially hydrophilic surfaces became more hydrophilic after ultraviolet irradiation, while they evolved to become hydrophobic under near-infrared laser irradiation. The values of the surface free energy components showed changes after nanostructuring, mainly in the polar component. Additionally, for UV-irradiated surfaces, adhesion, determined by the colloidal probe technique, increased, while, for NIR irradiation, adhesion decreased. Finally, nanomechanical properties were measured by the PeakForce Quantitative Nanomechanical Mapping method, obtaining maps of elastic modulus, adhesion, and deformation. The results showed an increase in the elastic modulus in the PET/EG, confirming the reinforcing action of the EG in the polymer matrix. Additionally, an increase in the elastic modulus was observed after LIPSS formation.

We report on the preparation of micropatterned functional surfaces produced by inducing an out-of-plane deformation on elastic substrates and fixing these by creating a rigid oxidized top layer. Specifically, the elastic substrate used was Polydimethylsiloxane (PDMS) and the rigid layer on top was created by ozonation of this material. We evidenced that the surface pattern formed is directly dependent on the pressure applied, the mechanical properties of the elastic substrate and on the dimensions and shape of the mask employed to define the exposed and non-exposed areas. In addition to the pattern formed, another interesting aspect is related to the ozone diffusion within the material. Softer PDMS enables more efficient diffusion and produced a thicker oxidized layer in comparison to rigid PDMS. Finally, a simulation was carried out using the distribution of Von Misses stresses of a solid plate to understand the conditions in which the applied force resulted in the rupture of the rigid oxidized layer under a permanent deformation.

This article presents an experimental study on the relaxation dynamics of a series of random copolymers based on bio-friendly comonomers with interesting gas barrier properties. We analyze the relaxation response in the glassy and ultraviscous regime of poly (trimethylene furanoate/sebacate) random copolymers via dielectric spectroscopy. We report lower values of dynamic fragility [a dimensionless index introduced in 1985 (Angell, Relaxations in Complex Systems, 1985)] in comparison to popular polyesters widely used in industry, such as poly (ethylene terephthalate), suggesting that the amorphous phase of these furanoate-based polyesters adopt an efficient chain packing. This is consistent with their low permeability to gases. We also discuss on different equations (phenomenological and theory-based approaches) for fitting the temperature-evolution of the alpha relaxation time., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. The handling editor GG declared a past co-authorship with the authors AZ, AnS, TE, and MG., (Copyright © 2022 Sanz, Linares, García-Gutiérrez, Nogales, Paszkiewicz, Zubkiewicz, Szymczyk and Ezquerra.)

We reported on the interaction between poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) and high-boiling-point additives in PEDOT:PSS aqueous dispersions and in the final polymer films with the aim of stablishing correlations between the structure of both inks and solid thin films. By Small-Angle X-ray Scattering (SAXS) using synchrotron radiation, it was found that the structural changes of dispersions of PEDOT:PSS with high-boiling-point additives can be explained as a two-step mechanism depending on the additive concentration. A compaction of PEDOT:PSS grains was observed at low concentrations while a swelling of the grains together with a phase segregation between PEDOT and PSS segments was evidenced at larger concentrations. Thin films' morphology and structure were investigated by atomic force microscopy (AFM) and synchrotron Grazing Incidence Wide-Angle X-ray Scattering (GIWAXS) respectively. Our two-step model provides an explanation for the small and sharp domains of PEDOT:PSS thin films observed for low-additive concentrations (first step) and larger domains and roughness found for higher-additive concentrations (second step). A reduction of the ratio of PSS in PEDOT:PSS thin films upon the presence of additives was also observed. This can be related to a thinning of the PSS shells of PEDOT:PSS grains in the dispersion. The results discussed in this work provide the basis for a controlled tuning of PEDOT:PSS thin films structure and the subsequent electrical properties.

Laser-based methods have demonstrated to be effective in the fabrication of surface micro- and nanostructures, which have a wide range of applications, such as cell culture, sensors or controlled wettability. One laser-based technique used for micro- and nanostructuring of surfaces is the formation of laser-induced periodic surface structures (LIPSS). LIPSS are formed upon repetitive irradiation at fluences well below the ablation threshold and in particular, linear structures are formed in the case of irradiation with linearly polarized laser beams. In this work, we report on the simple fabrication of a library of ordered nanostructures in a polymer surface by repeated irradiation using a nanosecond pulsed laser operating in the UV and visible region in order to obtain nanoscale-controlled functionality. By using a combination of pulses at different wavelengths and sequential irradiation with different polarization orientations, it is possible to obtain different geometries of nanostructures, in particular linear gratings, grids and arrays of nanodots. We use this experimental approach to nanostructure the semiconductor polymer poly(3-hexylthiophene) (P3HT) and the ferroelectric copolymer poly[(vinylidenefluoride-co-trifluoroethylene] (P(VDF-TrFE)) since nanogratings in semiconductor polymers, such as P3HT and nanodots, in ferroelectric systems are viewed as systems with potential applications in organic photovoltaics or non-volatile memories.

An accurate knowledge of the parameters governing the kinetics of block copolymer self-assembly is crucial to model the time- and temperature-dependent evolution of pattern formation during annealing as well as to predict the most efficient conditions for the formation of defect-free patterns. Here, the self-assembly kinetics of a lamellar PS-b-PMMA block copolymer under both isothermal and non-isothermal annealing conditions are investigated by combining grazing-incidence small-angle X-ray scattering (GISAXS) experiments with a novel modelling methodology that accounts for the annealing history of the block copolymer film before it reaches the isothermal regime. Such a model allows conventional studies in isothermal annealing conditions to be extended to the more realistic case of non-isothermal annealing and prediction of the accuracy in the determination of the relevant parameters, namely the correlation length and the growth exponent, which define the kinetics of the self-assembly.

We report the study of the formation of Laser Induced Periodic Surface Structures (LIPSS), with UV femtosecond laser pulses (λ = 265 nm), in free-standing films of both Poly(trimethylene terephthalate) (PTT) and the composite PTT/tungsten disulfide inorganic nanotubes (PTT-WS 2 ). We characterized the range of fluences and number of pulses necessary to induce LIPSS formation and measured the topography of the samples by Atomic Force Microscopy, the change in surface energy and contact angle using the sessile drop technique, and the modification in both Young's modulus and adhesion force values with Peak Force-Quantitative Nanomechanical Mapping. LIPSS appeared parallel to the laser polarization with a period close to its wavelength in a narrow fluence and number of pulses regime, with PTT-WS 2 needing slightly larger fluence than raw PTT due to its higher crystallinity and heat diffusion. Little change was found in the total surface energy of the samples, but there was a radical increase in the negative polar component (γ-). Besides, we measured small variations in the samples Young's modulus after LIPSS formation whereas adhesion is reduced by a factor of four. This reduction, as well as the increase in γ-, is a result of the modification of the surface chemistry, in particular a slight oxidation, during irradiation., Competing Interests: The authors declare no conflict of interest.

Crystallization is a fundamental process in materials science, providing the primary route for the realization of a wide range of new materials. Crystallization rates are also considered to be useful probes of glass-forming ability 1-3 . At the microscopic level, crystallization is described by the classical crystal nucleation and growth theories 4,5 , yet in general solid formation is a far more complex process. In particular, the observation of apparently different crystal growth regimes in many binary liquid mixtures greatly challenges our understanding of crystallization 1,6-12 . Here, we study by experiments, theory and computer simulations the crystallization of supercooled mixtures of argon and krypton, showing that crystal growth rates in these systems can be reconciled with existing crystal growth models only by explicitly accounting for the non-ideality of the mixtures. Our results highlight the importance of thermodynamic aspects in describing the crystal growth kinetics, providing a substantial step towards a more sophisticated theory of crystal growth.

This work reports a study on the influence of graphene oxide (GO) and reduced graphene oxide (rGO) on the functional properties of poly(trimethylene terephthalate)-block-poly(caprolactone) (PTT- block -PCL-T) (75/25 wt.%/wt.%) copolymer, obtained from dimethyl terephthalate (DMT), 1,3-biopropanediol and polycaprolactone diol (PCL) via in situ polymerization. The article presents, if and how the reduction of graphene oxide, in comparison to the non-reduced one, can affect morphological, thermal, electrical and mechanical properties. SEM examination confirms/reveals the homogeneous distribution of GO/rGO nanoplatelets in the PTT- block -PCL-T copolymer matrix. More than threefold increase in the value of the tensile modulus is achieved by the addition of 1.0 wt.% of GO and rGO. Moreover, the thermal conductivity and thermal stability of the GO and rGO-based nanocomposites are also improved. The differential scanning calorimetry (DSC) measurement indicates that the incorporation of GO and rGO has a remarkable impact on the crystallinity of the nanocomposites (an increase of crystallization temperature up to 58 °C for nanocomposite containing 1.0 wt.% of GO is observed). Therefore, the high performances of the PTT- block -PCL-T-based nanocomposites are mainly attributed to the uniform dispersion of nanoplatelets in the polymer matrix and strong interfacial interactions between components.

Broadband dielectric spectroscopy has been used to characterize in deep the relaxation behavior of novel bio-based aliphatic-aromatic block copolymers based on poly(butylene terephthalate) (PBT) and poly(lactic acid) (PLA). The results indicate that the copolymerization decreases the ability to crystallize of the resulting block copolymer. The [Formula: see text] relaxation of the block copolymers is consistent with this fact exhibiting initially the characteristics features of an amorphous polymeric material cold crystallizing upon heating. The cold crystallization can be easily visualized by dielectric spectroscopy by a discontinuous and abrupt change of the shape parameters of the [Formula: see text] relaxation. The sub-glass dynamics of the block copolymers is complex and be ascribed to a [Formula: see text] relaxation composed of two local modes, [Formula: see text] and [Formula: see text], which can be assigned to the relaxation in PBT of the bond between the ester oxygen and the aliphatic carbon and to the bond between the aromatic ring carbon to the ester carbon, respectively. With increasing amount of the PLA block the crystallinity decreases as well as the activation energy of the [Formula: see text] mode approaching the expected value for amorphous PBT. On the contrary, the activation energy for the [Formula: see text] exhibits an unexpected increase as the amount of PLA increases. This effect has been explained by considering that at lower temperatures the [Formula: see text] mode of PBT is the more significant while at higher temperatures the [Formula: see text] relaxation of the PLA block becomes the dominant one.

Ordered and homogeneous laser-induced periodic surface structures (LIPSS) could be fabricated in poly(3-hexyl thiophene):[6,6]-phenyl C71-butyric acid methyl ester (P3HT:PC 71 BM) blends by using wavelengths in the ultraviolet (UV) range (266 nm). The absorption coefficient of PC 71 BM, which is maximum in its UV⁻Visible absorption spectrum around 266 nm, enhanced the overall absorption of the blend. In addition, PC 71 BM itself was capable of developing homogeneous LIPSS by laser irradiation at λ laser = 266 nm. Therefore, we proposed that the synergistic effect of PC 71 BM on the LIPSS formation in P3HT:PC 71 BM (1:1) was due to a templating effect for the LIPSS formation of the PC 71 BM itself, which added to the overall increment of the absorption of the blend. LIPSS formation at ambient conditions in this wavelength range led to chemical modification of both P3HT and PC 71 BM, which rendered to non-conducting samples. Irradiation in vacuum significantly reduced radiation damage, rendering to the characteristic electrical conductivity pattern observed in P3HT LIPSS samples irradiated in the visible range. This effect could be of potential interest in order to obtain LIPSS in low absorbing polymers.

The chemical structure-dynamics relationship for poly(trimethylene 2,5-furanoate) and poly(trimethylene 1,4-cyclohexanedicarboxylate) was investigated via dielectric spectroscopy and compared with that of poly(trimethylene terephthalate) in order to evaluate the impact on the subglass dynamics of the chemical nature of the ring. Further comparison was accomplished with the neopentyl glycol containing counterparts: poly(neopentyl 2,5-furanoate) and poly(neopentyl 1,4-cyclohexanedicarboxylate). Our study reveals a multimodal nature of the subglass β process. For the more flexible polymers (containing cyclohexane rings) three modes for the β process were detected. The faster mode was assigned to the relaxation of the oxygen linked to the aliphatic carbon, the slower one to the link between the aliphatic ring and the ester group, and the third mode to the aliphatic ring. For stiffer polymers (containing aromatic rings), the local modes appear more coupled. This effect is more evident in the polymers with the furan ring where essentially a single β mode can be resolved.

In this work we report a broad scenario for the patterning of semiconducting polymers by laser-induced periodic surface structures (LIPSS). Based on the LIPSS formation in the semicrystalline poly(3-hexylthiophene) (P3HT), we have extended the LIPSS fabrication to an essentially amorphous semiconducting polymer like poly[N-90-heptadecanyl-2,7-carbazole-alt-5,5-(40,70-di-2-thienyl-20,10,30-benzothiadiazole)] (PCDTBT). This polymer shows a good quality and well-ordered nanostructures not only at the 532 nm laser wavelength, as in the case of P3HT, but also at 266 nm providing gratings with smaller pitch. In addition, we have proven the feasibility of fabricating LIPSS in the P3HT/PCDTBT (1:1) blend, which can be considered as a model bulk-heterojunction for all-polymer solar cells. In spite of the heterogeneous roughness, due to phase separation in the blend, both P3HT and PCDTBT domains present well-defined LIPSS as well as a synergy for both components in the blend when irradiating at wavelengths of 532 and 266 nm. Both, P3HT and PCDTBT in the blend require lower fluence and less pulses in order to optimize LIPSS morphology than in the case of irradiating the homopolymers separately. Near edge X-ray absorption fine structure and Raman spectroscopy reveal a good chemical stability of both components in the blend thin films during LIPSS formation. In addition, scanning transmission X-ray spectro-microscopy shows that the mechanisms of LIPSS formation do not induce a further phase segregation neither a mixture of the components. Conducting atomic force microscopy reveals a heterogeneous electrical conductivity for the irradiated homopolymer and for the blend thin films, showing higher electrical conduction in the trenches than in the ridge regions of the LIPSS.

An unconventional strategy is proposed that takes advantage of localized high-deformation areas, referred to as folded wrinkles, to produce microstructured elastic surfaces with precisely controlled pattern dimensions and chemical distribution. For that purpose, elastic PDMS substrates were prestretched to a different extent and oxidized in particular areas using a mask. When the stretching was removed, the PDMS substrate exhibited out-of-plane deformations that largely depend on the applied prestretching. Prestretchings below 100% lead to affine deformations in which the treated areas are buckled. On the contrary, prestretchings above ε >100% prior to surface treatment induce the formation of folded wrinkles on those micrometer-size ultraviolet-ozone (UVO) treated areas upon relaxation. As a result, dual periodic wrinkles were formed due to the alternation of highly deformed (folded) and low deformed (buckled) areas. Our strategy is based on the surface treatment at precise positions upon prestretching of the elastic substrate (PDMS). Additionally, this approach can be used to template the formation of wrinkled surfaces by alternating lines of folded wrinkles (valleys) and low-deformed areas (hills). This effect allowed us to precisely tune the shape and distribution of the UVO exposed areas by varying the prestretching direction. Moreover, the wrinkle characteristics, including period and amplitude, exhibit a direct relation to the dimensions of the patterns present in the mask.

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.

We describe the conditions for optimal formation of laser-induced periodic surface structures (LIPSS) over poly(3-hexylthiophene) (P3HT) spin-coated films. Optimal LIPSS on P3HT are observed within a particular range of thicknesses and laser fluences. These conditions can be translated to the photovoltaic blend formed by the 1:1 mixture of P3HT and [6,6]-phenyl C 71 -butyric acid methyl ester (PC 71 BM) when deposited on an indium tin oxide (ITO) electrode coated with (poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS). Solar cells formed by using either a bilayer of P3HT structured by LIPSS covered by PC 71 BM or a bulk heterojunction with a P3HT:PC 71 BM blend structured by LIPSS exhibit generation of electrical photocurrent under light illumination. These results suggest that LIPSS could be a compatible technology with organic photovoltaic devices.

Amyloid fibrils are exceptionally stable oligomeric structures with extensive, highly cooperative H-bonding networks whose physical origin remains elusive. While nonpolar systems benefit from both H-bonds and hydrophobic interactions, we found that highly polar sequences containing glutamine and asparagine amino acid residues form hyperpolarized H-bonds. This feature, observed by density functional theory calculations, encodes the origin of these polar oligomers' high stability. These results are explained in a theoretical model for complex amyloid assembly based on two different types of cooperative effects resulting from highly delocalized electrons, one of which is always present in both polar and hydrophobic systems. Experimental electric conductivity measurements, ThT fluorescence enhancement, and NMR spectroscopy support this proposal and reveal the conditions for disassembly.

Polymer ferroelectric laser-induced periodic surface structures (LIPSS) have been prepared on ferroelectric thin films of a poly(vinylidene fluoride-trifluoroethylene) copolymer. Although this copolymer does not absorb light at the laser wavelength, LIPSS on the copolymer can be obtained by forming a bilayer with other light-absorbing polymers. The ferroelectric nature of the structured bilayer was proven by piezoresponse force microscopy measurements. Ferroelectric hysteresis was found on both the bilayer and the laser-structured bilayer. We show that it is possible to write ferroelectric information at the nanoscale. The laser-structured ferroelectric bilayer showed an increase in the information storage density of an order of magnitude, in comparison to the original bilayer.

The formation of laser-induced periodic surface structures (LIPSS) on model spin-coated polymer films has been followed in situ by grazing incidence small-angle X-ray scattering (GISAXS) using synchrotron radiation. The samples were irradiated at different repetition rates ranging from 1 up to 10 Hz by using the fourth harmonic of a Nd:YAG laser (266 nm) with pulses of 8 ns. Simultaneously, GISAXS patterns were acquired during laser irradiation. The variation of both the GISAXS signal with the number of pulses and the LIPSS period with laser irradiation time is revealing key kinetic aspects of the nanostructure formation process. By considering LIPSS as one-dimensional paracrystalline lattice and using a correlation found between the paracrystalline disorder parameter, g, and the number of reflections observed in the GISAXS patterns, the variation of the structural order of LIPSS can be assessed. The role of the laser repetition rate in the nanostructure formation has been clarified. For high pulse repetition rates (i.e., 10 Hz), LIPSS evolve in time to reach the expected period matching the wavelength of the irradiating laser. For lower pulse repetition rates LIPSS formation is less effective, and the period of the ripples never reaches the wavelength value. Results support and provide information on the existence of a feedback mechanism for LIPSS formation in polymer films.

We have investigated the use of tightly focused, temporally shaped femtosecond (fs)-laser pulses for producing nanostructures in two dielectric materials (sapphire and phosphate glass) with different characteristics in their response to pulsed laser radiation. For this purpose, laser pulses shaped by third-order dispersion (TOD) were used to generate temporally asymmetric excitation pulses, leading to the single-step production of subwavelength ablative and subablative surface structures. When compared to previous works on the interaction of tightly focused TOD-shaped pulses with fused silica, we show here that this approach leads to very different nanostructure morphologies, namely, clean nanopits without debris surrounding the crater in sapphire and well-outlined nanobumps and nanovolcanoes in phosphate glass. Although in sapphire the debris-free processing is associated with the much lower viscosity of the melt compared to fused silica, nanobump formation in phosphate glass is caused by material network expansion (swelling) upon resolidification below the ablation threshold. The formation of nanovolcanoes is a consequence of the combined effect of material network expansion and ablation occurring in the periphery and central part of the irradiated region, respectively. It is shown that the induced morphologies can be efficiently controlled by modulating the TOD coefficient of the temporally shaped pulses.

The dynamics of lower disorder-order temperature diblock copolymer leading to phase separation has been observed by X ray photon correlation spectroscopy. Two different modes have been characterized. A non-diffusive mode appears at temperatures below the disorder to order transition, which can be associated to compositional fluctuations, that becomes slower as the interaction parameter increases, in a similar way to the one observed for diblock copolymers exhibiting phase separation upon cooling. At temperatures above the disorder to order transition TODT, the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chain segments across the interface is the governing dynamics. As the segregation is stronger, the diffusive process becomes slower. Both observed modes have been predicted by the theory describing upper order-disorder transition systems, assuming incompressibility. However, the present results indicate that the existence of these two modes is more universal as they are present also in compressible diblock copolymers exhibiting a lower disorder-order transition. No such a theory describing the dynamics in LDOT block copolymers is available, and these experimental results may offer some hints to understanding the dynamics in these systems. The dynamics has also been studied in the ordered state, and for the present system, the non-diffusive mode disappears and only a diffusive mode is observed. This mode is related to the transport of segment in the interphase, due to the weak segregation on this system.

In this work we present an accurate mapping of the structural order of laser-induced periodic surface structures (LIPSS) in spin-coated thin polymer films, via a microfocus beam grazing incidence small-angle X-ray scattering (μGISAXS) scan, GISAXS modeling, and atomic force microscopy imaging all along the scanned area. This combined study has allowed the evaluation of the effects on LIPSS formation due to nonhomogeneous spatial distribution of the laser pulse energy, mapping with micrometric resolution the evolution of the period and degree of structural order of LIPSS across the laser beam diameter in a direction perpendicular to the polarization vector. The experiments presented go one step further toward controlling nanostructure formation in LIPSS through a deep understanding of the parameters that influence this process.

This work reports on the formation of different types of structures on the surface of polymer films upon UV laser irradiation. Poly(ethylene terephthalate) was irradiated with nanosecond UV pulses at 193 and 266 nm. The polarization of the laser beam and the irradiation angle of incidence were varied, giving rise to laser induced surface structures with different shapes and periodicities. The irradiated surfaces were topographically characterized by atomic force microscopy and the chemical modifications induced by laser irradiation were inspected via micro-Raman and fluorescence spectroscopies. Contact angle measurements were performed with different liquids, and the results evaluated in terms of surface free energy components. Finally, in order to test the influence of surface properties for a potential application, the modified surfaces were used for mesenchymal stem cell culture assays and the effect of nanostructure and surface chemistry on cell adhesion was evaluated.

In this work we report the application of two and three-beam single pulse laser interference lithography to thin polymer films of poly(trimethylene terephthalate) (PTT). By irradiating the sample surface with temporary and spatially overlapped single pulses from two or three coherent beams and changing the angles of incidence, we have accomplished the fabrication of large-area polymer micro and submicrogratings as well as submicrometric cavities arranged in a hexagonal lattice. The characterization of the structures in real space by atomic force microscopy (AFM) and scanning electron microscopy (SEM) has allowed us to determine the formation mechanism of the microgratings to be based on different ablation regimes depending on the local fluence. Moreover, complementary characterization of the submicrometric cavities in reciprocal space by grazing incidence small-angle X-ray scattering (GISAXS) confirms the existence of large areas where two-dimensional order is present. The experiments presented in this work demonstrate the suitability of single pulse laser interference lithography for micro and submicrostructuring polymer films, opening up new possibilities for patterning and paving the way for potential applications where polymer structures are involved.

Transformation of deuterated ethanol from the plastic crystal phase into the monoclinic one is investigated by means of a singular setup combining simultaneously dielectric spectroscopy with neutron diffraction. We postulate that a dynamic transition from plastic crystal to supercooled liquid-like configuration through a deep reorganization of the hydrogen-bonding network must take place as a previous step of the crystallization process. Once these precursor regions are formed, subsequent crystalline nucleation and growth develop with time.

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.

In the present work, we report on the application of optical near fields to nanostructuring of poly(trimethylene terephthalate) (PTT) thin films. By exposure to a single ultraviolet nanosecond laser pulse, the spatial intensity modulation of the near-field distribution created by a silica microsphere is imprinted into the films. Setting different angles of incidence of the laser, elliptical or circular periodic ring patterns can be produced with periods as small as half the laser wavelength used. These highly complex patterns show optical and topographical contrast and can be characterized by optical microscopy (OM) and atomic force microscopy (AFM). We demonstrate the key role of the laser wavelength and coherence length in achieving smooth, extended patterns in PTT by using excimer laser (193 nm) and Nd:YAG laser (266 nm) pulses. Reference experiments performed in Ge2Sb2Te5 (GST) demonstrate that nanopatterning in PTT is triggered by ablation as opposed to GST, in which nanopatterning originates from laser-induced phase change, accompanied by a small topographical contrast. The experiments presented in this work demonstrate the suitability of optical near fields for structuring polymer films, opening up new possibilities for nanopatterning and paving the way for potential applications where optical near fields and polymer nanostructures are involved.

In this work we present the formation of laser induced periodic surface structures (LIPSS) on spin-coated thin films of several model aromatic polymers including poly(ethylene terephthalate), poly(trimethylene terephthalate) and poly carbonate bis-phenol A upon irradiation with femtosecond pulses of 795 and 265 nm at fluences well below the ablation threshold. LIPSS are formed with period lengths similar to the laser wavelength and parallel to the direction of the laser polarization vector. Formation of LIPSS upon IR irradiation at 795 nm, a wavelength at which the polymers absorb weakly, contrasts with the absence of LIPSS in this spectral range upon irradiation with nanosecond pulses. Real and reciprocal space characterization of LIPSS obtained by Atomic Force Microscopy (AFM) and Grazing Incidence Small Angle X-ray Scattering (GISAXS), respectively, yields well correlated morphological information. Comparison of experimental and simulated GISAXS patterns suggests that LIPSS can be suitably described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice. Fluorescence measurements, after laser irradiation, provide indirect information about dynamics and structure of the polymer at the molecular level. Our results indicate that the LIPSS are formed by interference of the incident and surface scattered waves. As a result of this process, heating of the polymer surface above its glass transition temperature takes place enabling LIPSS formation.

The successful development of ferroelectric polymer devices depends on the effective fabrication of polar ferroelectric crystalline nanostructures. We demonstrate, by scanning X-ray microdiffraction using synchrotron light, the heterogeneous character of high aspect ratio one-dimensional nanoarrays of poly(vinylidene fluoride-co-trifluoroethylene) copolymers supported by a residual polymer film. They were prepared by melt and solution template wetting, using porous anodic aluminum oxide as a template. The spatial evolution of different polymorphs from the mixture of paraelectric and ferroelectric crystal forms (residual film) to the pure ferroelectric form (nanoarray) is evidenced for the samples prepared by solution wetting. However, for samples prepared by melt wetting the ferroelectric phase is exclusively obtained in both the residual film and nanoarray. The crystal nuclei formed in the polymer film connected to the nanoarray play a key role in determining the formation of a crystallinity distribution gradient, where the crystallinity decreases along the first 5-10 microns in the nanorods reaching a steady value afterwards. The minimum decrease in crystallinity is revealed for samples prepared by melt wetting. The results reported in this work endeavour to enhance the understanding of crystallization under confinement for ferroelectric copolymers and reveal the parameters for improving the ferroelectric character of polymer nanostructures.

We report the preparation of semicrystalline polymer nanorods of PTT and of its nanocomposites with SWCNTs by infiltration of the molten polymer into disordered anodic alumina membranes. An accurate study of the crystalline orientation of these systems has been accomplished by means of X-ray microdiffraction. While polymer residual film exhibits isotropic character, edge-on lamellae are formed upon approaching the polymer/membrane interface. This effect might be due to the elongational flow that takes place in the molten state as polymer chains infiltrate the AAO membrane. At the interface, edge-on and flat-on crystalline lamellae coexist as a consequence of the strong interaction between the polymer and the AAO surface. Inside the nanopores, the confined environment induces a kinetic selection of polymer crystals which only allows the growth of crystalline lamellae with its a-axis parallel to that of the pore. In the case of PTT/SWCNT nanocomposites, this effect, in conjunction with the strong interaction between polymer and AAO surface, seems to prevail over the templating effect of the carbon nanotubes and a similar orientation to that of the neat PTT case is observed.

One of the simplest ways to confine polymeric materials is by self-assembling during the crystallization process. The remaining amorphous phase is then constrained by the lamellar crystals. In this manuscript, we aim to shed additional light in the understanding of the amorphous chains dynamics of semicrystalline polymers above the Tg by using incoherent quasielastic neutron scattering QENS in a nanoscopic time scale (10(-9)-10(-10)s) on poly(ethylene terephthalate). The observed dynamics is satisfactorily described by a theoretical model that considers that the proton mobility follows a random jump-diffusion in a restricted environment. We demonstrate that the combination of macroscopic with nanoscopic dynamic tools allows a complete description of the confined dynamics on a paradigmatic semicrystalline polymer like poly(ethylene terephthalate).

We report on the fabrication of gold coated nanostructured polymer thin films and on their characterization as substrates for surface enhanced Raman spectroscopy (SERS). Laser induced periodic surface structures (LIPSS) were obtained on thin polymer films of poly(trimethylene terephthalate) (PTT) upon laser irradiation with the fourth harmonic of a Nd:YAG laser (266 nm, pulse duration 6 ns) resulting in a period close to the incident wavelength. The nanostructured polymer substrates were coated with a nanoparticle assembled gold layer by pulsed laser deposition using the fifth harmonic of a Nd:YAG laser (213 nm, pulse duration 15 ns). Different deposition times resulted in thicknesses from a few nanometres up to several tens of nanometres. Analysis by atomic force microscopy and grazing incident small angle X-ray scattering showed that gold coating preserved the LIPSS relief. The capabilities of the produced nanostructures as substrates for SERS have been investigated using benzenethiol as a test molecule. The SERS signal is substantially larger than that observed for a gold-coated flat substrate. Advantages of this new type of SERS substrates are discussed.

This paper reports a thorough microstructural characterization of glancing angle deposited (GLAD) TiO(2) thin films. Atomic force microscopy (afm), grazing-incidence small-angle x-ray scattering (GISAXS) and water adsorption isotherms have been used to determine the evolution of porosity and the existence of some correlation distances between the nanocolumns constituting the basic elements of the film's nanostructure. It is found that the deposition angle and, to a lesser extent, the film thickness are the most important parameters controlling properties of the thin film. The importance of porosity and some critical dimensions encountered in the investigated GLAD thin films is highlighted in relation to the analysis of their optical properties when utilized as antireflective coatings or as hosts and templates for the development of new composite materials.

Here we present a precise morphological description of laser-induced periodic surface structures (LIPSS) nanofabricated on spin-coated poly(trimethylene terephthalate) (PTT) films by irradiation with 266 nm, 6 ns laser pulses and by using a broad range of fluences and number of pulses. By accomplishing real and reciprocal space measurements by means of atomic force microscopy and grazing incidence wide- and small-angle X-ray scattering respectively on LIPSS samples, the range of optimum structural order has been established. For a given fluence, an increase in the number of pulses tends to improve LIPSS in PTT. However, as the pulse doses increase above a certain limit, a distortion of the structures is observed and a droplet-like morphology appears. It is proposed that this effect could be related to a plausible decrease of the molecular weight of PTT due to laser-induced chain photo-oxidation by irradiation with a high number of pulses. A concurrent decrease in viscosity enables destabilization of LIPSS by the formation of droplets in a process similar to surface-limited dewetting.

Transformation of deuterated ethanol from supercooled liquid into a plastic crystal or rotator phase is investigated by means of a particular experimental setup combining simultaneously dielectric spectroscopy with neutron diffraction techniques. We demonstrate that, previous to the growth of the bcc lattice of the plastic crystal phase, the formation of a precursor or intermediate phase through a liquid-liquid phase separation takes place. Once this precursor phase is formed, subsequent (plastic) crystalline nucleation and growth is expected to develop.

In this work we evaluate the potential of grazing incidence X-ray scattering techniques in the investigation of laser-induced periodic surface structures (LIPSSs) in a series of strongly absorbing model spin-coated polymer films which are amorphous, such as poly(ethylene terephthalate), poly(trimethylene terephthalate), and poly(carbonate bisphenol A), and in a weaker absorbing polymer, such as semicrystalline poly(vinylidene fluoride), over a narrow range of fluences. Irradiation was performed with pulses of 6 ns at 266 nm, and LIPSSs with period lengths similar to the laser wavelength and parallel to the laser polarization direction are formed by devitrification of the film surface at temperatures above the characteristic glass transition temperature of the polymers. No crystallization of the surface is induced by laser irradiation, and crystallinity of the material prevents LIPSS formation. The structural information obtained by both atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS) correlates satisfactorily. Comparison of experimental and simulated GISAXS patterns suggests that LIPSSs can be well described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice.

Thin films (5-500 nm thick) of the linear aliphatic polyester (3,7) poly(propylene azelate) (PPAz) were prepared by spin-coating of CHCl(3) polymer solutions with different polymer concentrations. The morphology and structure of the spin-coated thin films were investigated by atomic force microscopy (AFM) and by grazing incidence wide-angle X-ray scattering (GIWAXS) techniques. AFM revealed the continuous nature of the flat, spherulitic films which are stable against dewetting even for polymer coatings as thin as 15 nm. GIWAXS patterns revealed a high crystal orientation of the films. A sharp reflection on the meridian whose spacing is related to the polymer chain unit length (c-axis) supports the presence of flat-on lamellae morphology in the whole range of film thicknesses investigated. The flat-on lamellae morphology is also supported by AFM images. A triclinic unit cell with the c*-axis perpendicular to the substrate is proposed for PPAz. The repulsion of the long aliphatic spacer by the Si-substrate is invoked as the main reason for the flat-on morphology observed.

The effect of confinement by crystals on the α relaxation, observed by dielectric broadband spectroscopy, in isotropic as well as in oriented semicrystalline poly(vinilydene fluoride), is analyzed on the basis of a new thermodynamic model. In both samples, it has been found that the average free-energy barrier, ΔF, for conformational rearrangements is of the same order of the dispersion barrier heights, δ(ΔF), around ΔF, i.e., the increase in the barrier height in conformational rearrangement is accompanied by an increase in the heterogeneity of constraining conditions. At a given temperature T, the readjustment free energy is larger in the oriented sample. This fact might be ascribed to either an enhanced effectiveness of confinement in the amorphous region due to the decrease of the amorphous layer thickness in the stacks, or to a change of the mean chain orientation or both. In addition, it is worth noting that in oriented poly(vinilydene fluoride) the regions of cooperative rearrangement are significantly larger. Moreover, independent of orientation, the size of these readjusting regions increase upon decreasing T. This feature, which underlies the Adam-Gibbs approach for liquids, is pointed out for the first time from direct data analysis in the case of confinement enhanced cooperativity. In addition to the above analysis, the samples have been characterized by differential scanning calorimetry, wide angle x-ray scattering, and small angle x-ray scattering.

For the first time, grazing incidence small-angle X-ray scattering (GISAXS) analysis is used to characterize the morphology of TiO(2) thin films grown by glancing angle physical vapor deposition (GLAD). According to cross-section scanning electron microscopy (SEM) images, the films consist of near isotilted TiO(2) columns of different length and width depending on film thickness. The obtained GISAXS patterns show a characteristic asymmetry with respect to the incidence plane, which is associated with the tilted geometry of the TiO(2) columns. The patterns also show the existence of two populations of columns in these GLAD-TiO(2) films. The population of the thinnest columns appears related to the first grown layer and is common for all the films investigated, while the second population of columns grows with the thickness of the films and has been related to wider columns formed by shadowing at the expense of the initially formed columns.

Thin films, with thicknesses from 10 to 400 nm of linear aliphatic polyesters (X, Y), based on propylenediol (X = 3) and on dicarboxylic acid of different chain length (Y = 2, 3, and 4 CH(2) units) were prepared by spin coating of CHCl(3) polymer solutions with different polymer concentrations. Morphology and structure of the spin coated thin films were investigated by atomic force microscopy (AFM) and by grazing incidence X-ray scattering techniques at small, (GISAXS) and wide angles (GIWAXS). AFM revealed a strong dewetting for all three polymers for coatings thinner than 100 nm. The polymer films are clearly semicrystalline for thicknesses higher than 50 nm. GIWAXS of the thicker films revealed their oriented crystalline nature. An edge-on-lamellae morphology is clearly shown by the AFM-phase images even for relatively thin films. SAXS with the beam parallel to the sample plane also support the presence of lamellae perpendicular to the substrate. The use of a mu-beam helped to interpret the GIWAXS patterns and allowed to obtain oriented WAXS patterns from melt solidified filaments. Thus, a crystal chain packing is proposed for the three polymers and consequently the indexing of the observed reflections. Accordingly, the polymer chains lie parallel to the substrate being the bc plane of the monoclinic crystal unit cell parallel to the substrate.

This work demonstrates the use of wetting nanoporous alumina template with polymer solution to produce arrays of isolated poly(vinylidene fluoride) (PVDF) ferroelectric gamma-type nanorods supported within a nonpolar alpha-structure film. The method is based upon a crystal phase transition which occurs due to PVDF confinement within alumina nanoporous. The system was studied using scanning X-ray microdiffraction (micro-XRD) that allows the solid-solid phase transition from the alpha-nonpolar crystal form (bulk) to the gamma polar ferroelectric form (nanorod array) to be spatially resolved, as well as providing crystallinity and orientation information. The results reveal that the interaction between polymer chains and the porous membrane's walls imposes a flat-on lamella growth along the nanorrods long axis, while improving crystal orientation.

Integrin alphaIIbbeta3 is the major membrane protein and adhesion receptor at the surface of blood platelets, which after activation plays a key role in platelet plug formation in hemostasis and thrombosis. Small angle neutron scattering (SANS) and shape reconstruction algorithms allowed formation of a low resolution three-dimensional model of whole alphaIIb beta3 in Ca(2+)/detergent solutions. Model projections after 90 degrees rotation along its long axis show an elongated and "arched" form (135 degrees) not observed before and a "handgun" form. This 20-nm-long structure is well defined, despite alphaIIb beta3 multidomain nature and expected segmental flexibility, with the largest region at the top, followed by two narrower and smaller regions at the bottom. Docking of this SANS envelope into the high resolution structure of alphaIIb beta3, reconstructed from crystallographic and NMR data, shows that the solution structure is less constrained, allows tentative assignment of the disposition of the alphaIIb and beta3 subunits and their domains within the model, and points out the structural analogies and differences of the SANS model with the crystallographic models of the recombinant ectodomains of alphaIIb beta3 and alphaV beta3 and with the cryo-electron microscopy model of whole alphaIIb beta3. The ectodomain is in the bent configuration at the top of the model, where alphaIIb and beta3 occupy the concave and convex sides, respectively, at the arched projection, with their bent knees at its apex. It follows the narrower transmembrane region and the cytoplasmic domains at the bottom end. AlphaIIb beta3 aggregated in Mn(2+)/detergent solutions, which impeded to get its SANS model.

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.

The effect of confinement in the segmental relaxation of polymers is considered. On the basis of a thermodynamic model we discuss the emerging relevance of the fast degrees of freedom in stimulating the much slower segmental relaxation, as an effect of the constraints at the walls of the amorphous regions. In the case that confinement is due to the presence of crystalline domains, a quasi-Poissonian distribution of local constraining conditions is derived as a result of thermodynamic equilibrium. This implies that the average free-energy barrier DeltaF for conformational rearrangement is of the same order of the dispersion of the barrier heights, delta(DeltaF) , around DeltaF. As an example, we apply the results to the analysis of the alpha-relaxation as observed by dielectric broad-band spectroscopy in semicrystalline poly(ethylene terephthalate) cold-crystallized from either an isotropic or an oriented glass. It is found that in the latter case the regions of cooperative rearrangement are significantly larger than in the former.

The electrical conductivity of a series of ionomers has been characterized by measuring the electrical conductivity in a relatively broad range of frequencies and temperatures. At low frequencies, the conductivity of the ionomers exhibits a universal Jonscher power law (JPL), and at higher frequencies a nearly constant loss (NCL) behavior. The NCL for the ionomers is qualitatively similar to that observed for other inorganic ionic conductors. However, the magnitude of NCL for ionomers is lower than that observed for inorganic ionic conductors. The analysis of the conductivity master curves suggests that the conduction mechanism, which includes both the NCL and the JPL behaviors, is governed by ion hopping of the mobile ions.

Thin films (9-70 nm) of a series of polymers containing in the main chain dibenzo-18-crown-6 ether unit (DB18C6) linked to an aliphatic spacer of different length (10C and 14C) and nature have been prepared, from chloroform solutions, by spin coating on a silicon substrate. The quality and homogeneity of the polymer coatings was revealed by their reflectivity spectra and atomic force microscopy (AFM). The grazing incidence small-angle X-ray scattering (GISAXS) patterns show an out-of-plane structure correlation (interference maximum near the horizon) of scale size related to the polymer repeating unit length. Above this Bragg reflection, the shape of the scattering observed, in the GISAXS pattern, reveals an orientation of the stacked molecular columns in the coated polymer. A thermal treatment of the samples improves the nanostructure by increasing the lamellar coherence size (in y-direction) as well as the vertical orientation of the molecular columns.

The segmental relaxation in poly(ethylene terephthalate), crystallized from either an isotropic or a cold-drawn glass, is investigated by means of dielectric spectroscopy. It is shown that there exist two distinct alpha relaxation modes: a slow one, characterized by a rather wide frequency interval, and a faster, much narrower one. A simple phenomenological model is developed in order to analyze the polarization autocorrelation functions phi(t)'s associated with these relaxation modes. The model is based on the idea that the growth of crystalline domains causes a progressive confinement of the amorphous regions where, eventually, the observed alpha processes take place. The mechanism of confinement is accounted for by applying to the case of constrained density fluctuations, well known concepts introduced by Adam and Gibbs [J. Chem. Phys. 43, 139 (1965)] concerning the relaxation dynamics in liquids close to the glass transition. Randomness on confining conditions is then introduced, leading to the derivation of analytical expressions which are used afterwards to fit the asymptotic behavior of the phi's for long-time tails. It is found that the slow, broad alpha process takes place in regions where the confining effect of crystals is strong, whereas the amorphous domains relaxing via the fast mode are those where the confinement effect of crystals is weak. The analysis of the phi's by means of this model allows us to relate the fitting exponents to the dispersion in the free energy associated with structural rearrangement.