Stress-induced birefringence in elastomers doped with ferrofluid magnetic particles: Mechanical and optical investigation

Magnetic nanoparticles from magnetic colloidal suspensions were incorporated in the urethane/urea elastomer (PU/PBDO) by adding to the prepolymers solution in toluene diverse amounts of magnetite grains. It is shown that ferrofluid grains can be efficiently incorporated into the elastomer according to this procedure. Mechanical and optical experiments performed show that the elastomer preparation procedure (casting) introduces a structural anisotropy on the optically isotropic sample. This fact is put in evidence by the measurements of the Young's moduli and orientation of the sample's optical axis under stress. The dependence of the phase shift of both the pure and ferrofluid-doped elastomer samples under strain is linear, and the strain-optic coefficient is show to be linear with the ferrofluid concentration.     

Self-organization of triblock copolymer patterns obtained by drying and dewetting

Self-organized block copolymer structures derived from dewetting of thin films are becoming important in nanotechnology because of the various spontaneous and regular sub-micrometric surface patterns that may be obtained. Here, we report on the self-organization of a poly(styrene)-b-poly(ethene-co-butene-1)-b-poly(styrene) triblock copolymer during drying of its solution over a mica substrate. Regular submicrometric arrangements with long-range order were formed at critical polymer concentrations, consisting of parallel ribbons and hexagonal arrays of dots (droplets). This variety of highly ordered structures is explained by the interplay between forming mechanisms, mainly due to “fingering instabilities” at the three-phase line of the copolymer solution during drying. The thickness of the structures was “quantized” due to the microphase separation of the block copolymer. The formation of hexagonal patterns may be attributed to Marangoni instability at the liquid film surface prior to dewetting.     

Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via photo-initiated graft polymerization of poly(ethylene glycol)

Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) copolymer biomedical elastomer was covalently grafted with poly(ethylene glycol) methyl ether methacrylate (PEGMA) via a photo-initiated graft polymerization technique. The surface graft polymerization of SEBS with PEGMA was verified by ATR-FTIR and XPS. Effect of graft polymerization parameters, i.e., monomer concentration, UV irradiation time and initiator concentration on the grafting density was investigated. Comparing with the virgin SEBS film, the PEGMA-modified SEBS film presented an enhanced wettability and a larger surface energy. Besides, the surface grafting of PEGMA imparted excellent anti-platelet adhesion and anti-protein adsorption to the SEBS surface.     

Surface characteristics of UV-irradiated polyurethane elastomers extended with α, ω-alkane diols

Polyurethane elastomers (PUEs) based on 4,4′-diphenylmethane diisocyanate (MDI), poly (?-caprolactone) (PCL) and extended with series of chain extender (CE) were synthesized via two step polymerization technique. The synthesized samples were irradiated for 50, 100 and 200 h in an UV exposure unit as such the spectral distribution of the light is good match for terrestrial solar radiation. The modifications in the chemical structures of the PU before and after irradiation were characterized using Fourier transform infrared (FT-IR) technique. The effect of irradiation time and chain extenders length on surface properties were studied and investigated. Photo-oxidation of PU surface leads to fast increase in surface free energy and its polar component. Simultaneously, the work of water adhesion to polymer increases significantly during UV-irradiation. The higher changes in surface properties, observed by water absorption (%), equilibrium degree of swelling, as well as monitored by ATR-FT-IR and contact angle measurement, were found for the PU samples extended with higher number of methylene unit and irradiation time.     

Structure Development and Interfacial Interactions in Flexible Polyurethane Foam-Layered Silicate Nanocomposites

Unmodified Na-montmorillonite (MMT) was swollen in a polyol/water mixture using an ultrasound technique. Polyurethane (PU) foam nanocomposites were formed via reaction of these polyol/water/Na-MMT mixtures with toluene diisocyanate (TDI). Forced-adiabatic attenuated total reflectance FTIR spectroscopy was used to determine the kinetics of both the PU copolymerisation and of the microphase separation between poly(ether-urethane) soft segments and polyurea hard segments. Consumption of TDI during the initial stages of the copolymerisation was accelerated significantly by the addition of ≤10 wt% Na-MMT. The initial rate of formation of urea groups also increased significantly upon addition of Na-MMT, but at reaction times >100 s a significant retardation occurred in the development of hydrogen bonding within the urea groups of the hard-segment phase that was recovered only after 1000 s. The reasons for this extensive disruption in structure development were investigated using flow microcalorimetry (FMC), diffuse reflectance Fourier-transform infrared spectroscopy (DRIFTS), and wide angle X-ray scattering (WAXS) to monitor the adsorption process and any chemical reaction between hydrated Na-MMT and a model monoisocyanate; 4-ethylphenyl isocyanate (4-EPI). DRIFTS spectra of 4-EPI adsorbed on Na-MMT revealed urea groups, indicating formation of N,N′-bis(4-ethylphenyl) urea. FMC indicated that a significant quantity of this urea formed at the surface and then desorbed. In addition, DRIFTS spectra indicated that the 4-EPI reacted with hydroxyl groups present at the edges of the silicate platelets to form urethane linkages. Thus, in a PU-foam reaction mixture, the water will tend to associate with the Na-MMT, either within the galleries or on the surfaces of silicate lamellae. Upon reaction with isocyanate, the presence of the Na-MMT both promotes the formation of urea and generates urethane linkages between silicate lamellae and the polyurethane.     

Photoelectrochemical properties of transparent multilayer films via electrostatic alternating assembly of titanate nanotubes and methylpyridinium porphyrin cobalt

Transparent multilayer films of titanate nanotubes (TNTs) and meso-tetrakis (N-methylpyridinium-4-yl) porphyrin cobalt (CoTMPyP) (TNTs/CoTMPyP)_n were fabricated by the layer-by-layer self-assembly based on TNTs and CoTMPyP in the aqueous solution. The CoTMPyP molecules as an organic “spacer” and a sensitizer were confirmed to play important roles in the performance improvement of TNTs by comparing with the TNTs multilayer films fabricated with poly(diallyldimethylammonium chloride) (PDDA) as the interlayer. The optical absorption and photocurrent output of the resulting (TNTs/CoTMPyP)_n films increased consecutively with the number of the TNTs/CoTMPyP bilayer. The optical and thermal stabilities of the (TNTs/CoTMPyP)₁₂ films were evaluated under UV light irradiation and heat treatment, respectively. The results showed that the UV light irradiation and heat treatment had obvious influences on the photoelectrochemical performance of the resulting films.     

Polymer Surface Functionalization Using Plasma,Ultraviolet and Synchrotron Radiation

Polyurethane (PU) and polystyrene (PS) films were functionalized by ultraviolet (UV) or selective synchrotron radiations (SR) in the presence of reactive gases. The UV-PU results were compared with lowpressure plasma treatments of the same films. Oxygen or acrylic acid vapours (AA) were used as reactive gases. X-ray photoelectron spectroscopy measurements of UV modified films in the presence of oxygen or AA matched the RF-plasma treatments results. It is shown that COO and C=O functional groups were incorporated at the polymer surface efficiently with both methodologies. In addition, near-edge X-ray absorption fine structure showed that a thin film of poly(acrylic acid) is formed over the PU and PS films during the UV irradiation in the presence of AA vapours. These results resemble previous AA low-power plasma treatments. PU and PS films were also selectively functionalized by SR using oxygen as reactive gas. Surface concentrations of COO and C=O functional groups were enhanced by C_1s → σ* _C–C excitation after irradiation and oxygen introduction. This efficient surface functionalization was clearly observed in PS films which do not have CO and COO groups in their molecular structure. Excitations involving transitions to π* orbital (π*_C=C, π*_C=O) led to much lower functionalization efficiency. The SR results can be explained by taking into account previous photon stimulated ion desorption studies of polymers. SR results may open new ways to functionalize polymer surfaces selectively and efficiently.     

“Elastic” fluctuation-induced effects in smectic wetting films

The Li-Kardar field theory approach is generalized to wetting smectic films and the “elastic” fluctuation-induced interaction is obtained between the external flat bounding surface and distorted IA (isotropic liquid-smectic A) interface acting as an “internal” (bulk) boundary of the wetting smectic film under the assumption that the IA interface is essentially “softer” than the surface smectic layer. This field theory approach allows calculating the fluctuation-induced corrections in Hamiltonians of the so-called “correlated” liquids confined by two surfaces, in the case where one of the bounding surfaces is “rough” and with different types of surface smectic layer anchoring. We obtain that in practice, the account of thermal displacements of the smectic layers in a wetting smectic film reduces to the addition of two contributions to the IA interface Hamiltonian. The first, so-called local contribution describes the long-range thermal “elastic” repulsion of the fluctuating IA interface from the flat bounding surface. The second, so-called nonlocal contribution is connected with the occurrence of an “elastic” fluctuation-induced correction to the stiffness of the IA interface. An analytic expression for this correction is obtained.     

The role of photoelectronic processes in the formation of a fluorescent plume by 248-nm laser irradiation of single crystal NaNO3

 Visible fluorescent “plumes” are readily produced when nominally transparent ionic materials are exposed to pulsed UV laser irradiation. Over a wide range of laser fluences where plumes are observed, however, the photon and electron densities are inadequate to support multiphoton ionization and inverse bremsstrahlung, which are often used to explain plasma production and excitation of atomic spectral lines. We present evidence that the great majority of charged particles (electrons and positive ions) comprising the plume at the onset of formation in defect-laden NaNO₃ are emitted directly from the surface. A model is described wherein the required electron energy to excite and eventually ionize neutral atoms is provided by electrostatic interactions in the expanding plume. The time evolution of the “overlap” between the expanding charge cloud and thermally emitted neutrals accounts for the time evolution of the atomic line emissions after the laser pulse. Received: 15 August 1996/Accepted: 16 August 1996     

Comment on “The properties of free polymer surfaces and their influence on the glass transition temperature of thin polystyrene films” by J.S. Sharp,J.H. Teichroeb and J.A. Forrest

Sharp, Teichroeb and Forrest [J.S. Sharp, J.H. Teichroeb, J.A. Forrest, Eur. Phys. J. E 15, 473 (2004)] recently published a viscoelastic contact mechanics analysis of the embedment of gold nanospheres into a polystyrene (PS) surface. In the present comment, we investigate the viscoelastic response of the surface and conclude that the embedment experiments do not support the hypothesis of a liquid surface layer of sufficiently reduced “rheological temperature” to explain reports of very large reductions in the glass temperature of freely standing ultrathin polystyrene films. We also report some errors and discrepancies in the paper under comment that resulted in an inability to reproduce the reported calculations. We present our findings of error in a spirit of clarifying the problem of embedment of spheres into surfaces and in order that others can understand why they may not reproduce the results reported by Sharp, Teichroeb and Forrest. In the comment, we also examine the effects of the magnitude of the forces that result from the polymer surface-nanosphere particle interactions on the viscoelastic properties deduced from the embedment data and we provide a comparison of apparent surface or “rheological” temperature vs. experimental temperature that indicates further work needs to be performed to fully understand the surface embedment experiments. Finally, we comment that the nanosphere embedment measurements have potential as a powerful tool to determine surface viscoelastic properties.     

The influence of UV irradiation on surface composition of collagen/PVP blended films

The surface chemical composition and surface properties of collagen/poly(vinyl pyrrolidone) (PVP) blended films before and after UV irradiation (λ = 254 nm) were investigated using X-ray Photoelectron Spectroscopy (XPS), FTIR-ATR spectroscopy and Atomic Force Microscopy (AFM).The XPS results showed that collagen is enriched on the surface of the collagen/PVP blend. The surface composition of the collagen film was changed more by UV irradiation than the surface composition of the collagen/PVP blend.FTIR-ATR spectra showed that the positions of the amide bands in collagen are more altered after UV irradiation than those for the collagen/PVP blends.AFM images showed that the collagen surface is ordered contrary to PVP. The blend surface was similar to the pure collagen surface and confirms that there is more collagen present at the surface (higher concentration of collagen at the surface compared to PVP). UV irradiation caused only the small changes in the surface morphology of the collagen/PVP films. All of the results confirm that the surface of the collagen/PVP blend is more photoresistant than collagen.     

The physical,mechanical, thermal and barrier properties of starch nanoparticle (SNP)/polyurethane (PU) nanocomposite films synthesised by an ultrasound-assisted process

This article reports on the ultrasound-assisted acid hydrolysis for the synthesis and evaluation of starch nanoparticles (SNP) as nanofillers to improve the physical, mechanical, thermal, and barrier properties of polyurethane (PU) films. During the ultrasonic irradiation, dropwise addition of 0.25 mol L^-1 H₂SO₄ was carried out to the starch dispersion for the preparation of SNPs. The synthesized SNPs were blended uniformly within the PU matrix using ultrasonic irradiation (20 kHz, 220 W pulse mode). The temperature was kept constant during the synthesis (4 °C). The nanocomposite coating films were made with a regulated thickness using the casting method. The effect of SNP content (wt%) in nanocomposite coating films on various properties such as morphology, water vapour permeability (WVP), glass transition temperature (Tg), microbial barrier, and mechanical properties was studied. The addition of SNP to the PU matrix increased the roughness of the surface, and Tg by 7 °C, lowering WVP by 60% compared to the PU film without the addition of SNP. As the SNP concentration was increased, the opacity of the film increased. The reinforcement of the SNP in the PU matrix enhanced the microbial barrier of the film by 99.9%, with the optimal content of SNP being 5%. Improvement in the toughness and barrier properties was observed with an increase in the SNP content of the film.     

Thermal conductivity of pressure polymerized C60

60 polymerization in the temperature interval at pressures below by measurements of the time dependence of the thermal conductivity. It has been found at that the polymerization process at is slower than the reverse transformation from “polymeric” to “monomeric” phase at . The thermal conductivity of polymerized C₆₀ was measured in the temperature range and found to increase with increasing temperature, which reflects strong phonon scattering. Both the presence of non-bonded C₆₀ molecules and a high degree of structural disorder in the crystalline lattice of the polymeric phase might be responsible for the behaviour of . The results for are qualitatively similar to those reported previously for C₆₀ polymerized at higher , but an order of magnitude smaller. Received: 20 September 1996/Accepted: 11 November 1996     

Controlled structure and density of “living” polystyrene brushes on flat silica surfaces

Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization. The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution. Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers. Received 20 December 2001     

Hydrophilicity of amorphous TiO2 ultra-thin films

The UV-light-induced hydrophilicity of amorphous titanium dioxide thin films obtained by radio frequency magnetron sputtering deposition was studied in relation with film thickness. The effect of UV light irradiation on the film hydrophilicity was fast, strong and did not depend on substrate or thickness for films thicker than a threshold value of about 12 nm, while for thinner films it was weak and dependent on substrate or thickness. The weak effect of UV light irradiation observed for the ultra-thin films (with thickness less than 12 nm) is explained based on results of measurements of surface topography, UV-light absorption and photocurrent decay in vacuum. Comparing to thicker films, the ultra-thin films have a smoother surface, which diminish their real surface area and density of defects, absorb partially the incident UV light radiation, and exhibit a longer decay time of the photocurrent in vacuum, which proves a spatial charge separation. All these effects may contribute to a low UV light irradiation effect on the ultra-thin film hydrophilicity.     

Biomaterial immobilization on polyurethane films by XeCl excimer laser processing

The surface chemical modification of polyurethane (PU) films was performed by an UV laser-induced chemical reaction in a polysaccharide solution. This process may be applicable as hydrophilic packaging of implantable medical devices and in vivo sensors. When a PU film in contact with an aqueous alginic acid (AAC) solution was irradiated with a XeCl laser, the PU film turned hydrophilic. Contact angles of water on the film were reduced from 110° to 60°. Since light absorption of the AAC solution at 308 nm was negligibly small, reactive sites were generated solely on the PU surface. There, AAC could be immobilized by chemical bonds thus allowing for a nanometer-scaled grafting of this biomolecule. The mechanism was investigated by surface analyses with Fourier-transform infrared spectroscopy (FT-IR), dye staining, ultraviolet-visible (UV-VIS) spectroscopy, and scanning electron microscopy (SEM) techniques. A one-photon photochemical process could beidentified. Received: 30 June 2000 / Accepted: 4 July 2000 / Published online: 13 September 2000     

Mesoscopic and macroscopic dipole clusters: Structure and phase transitions

A two dimensional (2D) classical system of dipole particles confined by a quadratic potential is studied. This system can be used as a model for rare electrons in semiconductor structures near a metal electrode, indirect excitons in coupled quantum dots etc. For clusters of N ≤ 80 particles ground state configurations and appropriate eigenfrequencies and eigenvectors for the normal modes are found. Monte-Carlo and molecular dynamic methods are used to study the order-disorder transition (the “melting” of clusters). In mesoscopic clusters (N < 37) there is a hierarchy of transitions: at lower temperatures an intershell orientational disordering of pairs of shells takes place; at higher temperatures the intershell diffusion sets in and the shell structure disappears. In “macroscopic” clusters (N > 37) an orientational “melting” of only the outer shell is possible. The most stable clusters (having both maximal lowest nonzero eigenfrequencies and maximal temperatures of total melting) are those of completed crystal shells which are concentric groups of nodes of 2D hexagonal lattice with a number of nodes placed in the center of them. The picture of disordering in clusters is compared with that in an infinite 2D dipole system. The study of the radial diffusion constant, the structure factor, the local minima distribution and other quantities shows that the melting temperature is a nonmonotonic function of the number of particles in the system. The dynamical equilibrium between “solid-like” and “orientationally disordered” forms of clusters is considered.     

Periodic domain structures obtained by growth of LiNbO<Subscript>3</Subscript> crystals doped with gadolinium

The growth of a periodic domain structure in LiNbO₃ crystals doped with gadolinium (Gd, 0.44 wt %) was investigated by special electron beam surface charging in a scanning electron microscope and on a atomic force microscope. Ferroelectric domain boundaries with “tail-to-tail” and “head-to-head” P _s orientations were comparatively analyzed. The domain boundaries had different forms and differed by their physical properties. Micron-size surface crystal regions close to the “tail-to-tail” boundaries were charged slower by electron irradiation and had modified elastic properties. This region was detected by using the lateral force mode of atomic force microscopy. The observed morphology and property features were supposed to be due to different concentration gradients of the Gd impurity and different width of its distribution close to the domain boundaries of different types.     

Critical phenomena at perfect and non-perfect surfaces

The effect of imperfections on surface critical properties is studied for Ising models with nearest-neighbour ferromagnetic couplings on simple cubic lattices. In particular, results of Monte Carlo simulations for flat, perfect surfaces are compared to those for flat surfaces with random, “weak” or “strong”, interactions between neighbouring spins in the surface layer, and for surfaces with steps of monoatomic height. Surface critical exponents at the ordinary transition, in particular ,are found to be robust against these perturbations. Received: 7 October 1997 / Accepted: 19 November 1997     

Transverse Seebeck effect in Bi2Sr2CaCu2O8

2 Cu₃O₇ has been observed in “off-c-axis” grown Bi₂Sr₂CaCu₂O₈ films. The films were prepared by pulsed laser deposition from Bi₂Sr₂CaCu₂O₈ targets and grown with a tilt angle of 10 degrees between the film c-axis and the film surface on off-axis cut SrTiO₃ substrates. From the thermoelectric response upon laser irradiation the anisotropy of the thermopower is estimated. Received: 15 April 1996/ Accepted:19 November 1996