Surface morphology and amide concentration depth profile of aminolyzed poly(ethylene terephthalate) films

Surface of biaxially oriented poly(ethylene terephthalate) films was chemically modified by exposure to ethylenediamine (EDA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) for different treatment times. Variable angle attenuated total reflection Fourier transform infrared (ATR‐FTIR) spectroscopy was used in conjunction with weight loss measurements, scanning electron microscopy (SEM), and atomic force microscopy to establish the surface modification and to draw the depth profile of the newly created species, with emphasis on amide group. A clear differentiation was found between the effects of the three amines studied: EDA produces the highest amidation degree but, because of its deep penetration into the film, leads to delamination of rather thick layers, TETA reacts at and near surface and develops surface cracks without delamination, and TEPA is the mildest reactant, generating amide groups on the surface without visible deterioration of the sample. It was proved that the amide II absorption band became weaker with increasing analyzed depth, with a pronounced heterogeneity near the surface. SEM micrographs showed the development of cracks onto the surface at longer aminolysis time, which allowed a better understanding of ATR‐FTIR observations. Assuming an exponential decay for the depth profile spectrally obtained, the surface concentration of amide groups and the decay constant were determined for the amines and reaction times used. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Study on the viscoelastic properties of the epoxy surface by means of nanodynamic mechanical analysis

The viscoelastic properties of the epoxy surface have been investigated by nanodynamic mechanical analysis (nano‐DMA). Both a Berkovich tip and a conospherical tip were used under the condition of different forces (i.e., different penetration depths) in the frequency range of 10–200 Hz. Loss tangent and storage modulus are characteristics that describe the viscoelastic properties. The effect of force frequency, penetration depth, and tip shape on the viscoelastic properties is studied and discussed according to the features of microstructures and mobility of molecular chains. The experimental results show important variations when the penetration depth is shallow (<30 nm). As the depth becomes deeper, the results tend to be stable and become almost constant over 120 nm. The two kinds of indenter tip can cause a slight difference of the storage modulus. A “master curve” of the storage modulus as a function of force frequency is established. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 281–288, 2008     

Effect of the pore surface modification of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes

We have investigated the effect of the surface state and surface treatment of the pores of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes. Shirasu porous glass (SPG) was used as the inorganic substrate, and methyl acrylate was used as the grafting monomer. The grafting rate increased as the density of silanol on the SPG substrate increased. This result suggests that radicals are generated mainly at the silanol groups on the pore surface by plasma irradiation. The SPG substrates were treated with silane coupling agents used to control the mass of organic material bonded to the pore surface. The thickness of the grafted layer became thinner as the mass of organic material bonded to the pore surface of SPG increased. This decrease in the thickness of the grafted layer could be explained by the decrease in the penetration depth of vacuum ultraviolet rays contained in plasma having a wavelength of less than 160 nm that generated radicals in the pores of the substrate. The thickness of the grafted layer inside the SPG substrates could be controlled through the control of the mass of organic material bonded to the pore surface of the SPG substrate. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 846–856, 2006     

Leaching of PVP from polyacrylonitrile/PVP blending membranes: A comparative study of asymmetric and dense membranes

Poly(N‐vinyl‐2‐pyrrolidone) (PVP) has been often used as an additive to improve the structure and performances of asymmetric membrane. In this work, we examined the leaching of PVP from polyacrylonitrile/PVP asymmetric membranes regarding the effect of leaching time, PVP content, and the molecular weight of PVP. Also, comparative studies of dense membranes were performed. It was found that the water contact angle on the dense membrane surface is very low compared with that on the asymmetric membrane surface. Results from X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy‐attenuated total reflection (FTIR‐ATR) showed that more amount of PVP exists at the surface layer of the dense membrane than at the asymmetric one. If the dense membrane was immersed into water for several hours and then dried in the air, the water contact angle increases and closes to that on the asymmetric membrane surface. Although leaching time was extended from 2 h to 15 days, PVP leaches out little from the asymmetric membrane. The leaching of PVP mainly occurs during the phase‐inversion process. Furthermore, the surface features were examined by atomic force microscopy and field emission scanning electron microscopy, respectively. In comparison with PVP K30, more PVP K90 remains in the asymmetric membrane based on the FTIR‐ATR spectra. However, it can be concluded from the results of XPS that at the most outer surface of the asymmetric membrane (e.g., in depth about 1～2 nm), the residual PVP K90 is almost the same with PVP K30. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1490–1498, 2006     

Polymer-tethered ligand–receptor interactions between surfaces

We study the interaction between two parallel surfaces having a polymer-tethered ligand on one and a random distribution of receptors on the other. We examine the interplay between the specific ligand–receptor binding and the conformation degrees of freedom of the polymer tether, and address the difference between the cases of mobile (annealed) and immobile (quenched) receptors. The annealed case is solved exactly and the quenched case is treated by both Monte Carlo direct sampling and an analytical density expansion. The combination of the entropic repulsion due to chain confinement at small surface separations, and the attraction due to ligand–receptor binding which can take place at significant chain stretching, results in a minimum in the interaction free energy. For the same set of parameters, stronger binding is obtained for the annealed case than for the quenched case, reflecting the ability of the mobile receptors to migrate into the region of the ligand. In the quenched case, binding is limited by the availability of receptors within the reach of the ligand; for a given receptor density and binding energy, there exists an optimal chain length that yields the lowest minimum in the interaction free energy for the quenched case. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2621–2637, 2006     

Gas transport in surface‐modified low‐density polyethylene films with acrylic acid as a grafting agent

The modification of polyethylene by the grafting of poly(acrylic acid) onto the surface of one of the faces of low‐density polyethylene films with UV radiation is reported. The transport of oxygen, nitrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, and argon across surface‐modified films containing 3.7% poly(acrylic acid) has been investigated at several temperatures. The layer of poly(acrylic acid) grafted onto the surface of one of the faces of the films reduces the permeability coefficient of the gases by a factor of about 1/6. The sharp drop in the gas permeability as a result of the poly(acrylic acid) layer may arise either from the formation of ordered structures of the grafted chains or from the development of highly crosslinked structures. The values of the polymer–gas enthalpic interaction parameter for the modified film are higher than those for the unmodified one. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2828–2840, 2006     

Synthesis and characterization of a new disubstituted polyacetylene containing indolylazo moieties in side chains

A new disubstituted polyacetylene with indolylazo moieties in its side chains ( 9 ) was synthesized by a post functionalization strategy, which was difficult, or perhaps impossible, to obtain from the direct polymerization of its corresponding monomer. The polymer is soluble in common solvents and thermally stable. The polymer shows good optical transparency with an absorption maximum at 393 nm and a band edge at ～530 nm. Its poled film exhibits a resonant d₃₃ value of 17.9 pm/V and its optical nonlinearity is resistant to thermal decay at up to 147 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5672–5681, 2006     

A surface-induced transition in polymeric nematics

New polymeric liquid crystals can be treated as standard nematic liquid crystals when only their bulk properties are at issue, but they exhibit peculiar surface properties. The most striking one is that biaxial distributions may be induced on a confining surface. On continuously varying the surface anchoring conditions, we find a first-order phase transition from planar to homeotropic alignment in the bulk. Moreover, the decay towards these uniaxial states is radically different in the two cases: it is asymptotically exponential in the former, whereas it happens abruptly at a finite depth in the latter. There is precisely one surface biaxial distribution that induces bistability between these decay modes: it depends on the elastic constants in the Landau-de Gennes free energy functional. The analysis of the model we propose can prove useful in detecting the sign of the difference between splay and bend constants.     

Spectroscopic study of the penetration depth of grafted polystyrene onto poly(tetrafluoroethylene‐co‐perfluoropropylvinylether) substrates. 1. Effect of grafting conditions

This study concerns the radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐perfluoropropylvinylether) (PFA) substrates and the penetration depth of the graft. Grafting was obtained by the simultaneous irradiation method, and the spectroscopic analysis was made with the micro‐Raman technique. Effects of grafting conditions such as the type of solvent, dose rate, and irradiation dose on the grafting yield were investigated. Of the different solvents used, the most efficient in terms of increasing grafting yield were dichloromethane, benzene, and methanol, respectively. A mixture of methanol and dichloromethane used as a solvent for styrene achieved a higher degree of grafting and concentration of grafted polystyrene onto the surface of PFA substrates than solutions of the monomer in the separate solvents. The degree of grafting increased with increasing radiation dose up to 500 kGy, stabilizing above this dose. However, the grafting yield decreased with an increase in the dose rate. The increase in the overall grafting yield was accompanied by a proportional increase in the penetration depth of the grafts into the substrate. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3191–3199, 2002     

Directed assembly of copolymer materials on patterned substrates: Balance of simple symmetries in complex structures

The self-assembly of a lamella-forming blend of a diblock copolymer and its respective homopolymers on periodically patterned substrates is investigated by a concerted experimental and theoretical approach. The substrate pattern consists of square arrays of spots that preferentially attract one component of the blend. The mismatch between the lamellar equilibrium morphology of the copolymer material and the substrate pattern results in the formation of a bicontinuous morphology. At the substrate, a quadratically perforated lamella (QPL) assembles in perfect registry with the substrate pattern. From this, QPL necks emanate and reach the top surface of the film. The detailed structure of these cylindrical nanochannels is analyzed using Voronoi tessellation, orientation correlation functions, and the structure factor of the neck positions on the top surface. The surface morphology is dictated by the antagonism of the square symmetry of the substrate pattern and the tendency of the necks to locally pack in a hexagonal arrangement. The analogy and differences to a system of adsorbed monolayer on corrugated substrates is explored by comparing the arrangement of the necks on the film's top surface with the structure of a soft disk model on a quadratically corrugated substrate. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2589–2604, 2006     

Relation between the adhesion strength and interfacial width for symmetric polystyrene bilayers

Polystyrene (PS) bilayers were prepared and were adhered at a temperature between the surface and bulk glass-transition temperatures for a given time. Then, the interfacial adhesion strength (G_L) was examined with a conventional lap-shear measurement. G_L first increased with increasing adhesion time and then reached a constant value. This result implied that the segments moved across the interface, to a certain depth, even at a temperature below the bulk glass-transition temperature. To confirm this, the interfacial evolution for the PS/deuterated PS bilayers was examined with dynamic secondary-ion mass spectrometry. The G_L value was linearly proportional to the thickness of the interfacial adhesion layer. Finally, we propose a strategy for regulating the adhesion strength based on the chain-end chemistry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3598–3604, 2006     

Fluorescence resonance energy transfer by quencher adsorption into hydrogels containing fluorophores

We synthesized anionic hydrogels containing fluorophores and investigated the adsorption of a cationic quencher having an amino group into hydrogels by fluorescence resonance energy transfer (FRET). FRET from the fluorophore to the quencher in hydrogels was examined by fluorescence intensity and fluorescence decay using a fluorescence spectrophotometer and femtosecond laser spectroscopy. The fluorescence intensity of the fluorophore‐containing hydrogels decreased rapidly with increasing amounts of adsorbed cationic quencher. The fluorescence emission of the fluorophore in the quencher‐adsorbed hydrogels containing fluorophores decayed more rapidly than that of the original hydrogels. The aforementioned result indicates that the fluorescence of the fluorophore‐containing hydrogels is quenched due to FRET from the fluorophore to the quencher as the cationic quenchers can approach the fluorophores in hydrogels by electrostatic interactions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3245–3252, 2006     

Coarse graining in block copolymer films

We present few ordering mechanisms in block copolymer melts in the coarse-graining approach. For chemically homogeneous or modulated confining surfaces, the surface ordering is investigated above and below the order–disorder temperature. In some cases, the copolymer deformation near the surface is similar to the copolymer morphology in bulk grain boundaries. Block copolymers in contact with rough surfaces are considered as well, and the transition from lamellae parallel to perpendicular to the surface is investigated as a function of surface roughness. Finally, we describe how external electric fields can be used to align block copolymer mesophases in a desired direction, or to induce an order–order phase transition, and dwell on the role of mobile dissociated ions on the transition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2725–2739, 2006     

Depth characterization by confocal raman microscopy of oxygen inhibition in free radical photopolymerization of acrylates: Contribution of the thiol chemistry

The oxygen inhibition of acrylate photopolymerization using visible light was depth characterized by confocal Raman microscopy. The sample thickness was found to influence the depth conversion profile. With increasing sample thickness, the conversion at the surface was increased and the oxygen‐affected layer (OAL) decreased, up to a limit where the profiles became independent of the thickness. The addition of a thiol in the acrylate mixture reduced the OAL and the conversion in this region increased. This effect was noticeable even at low concentration of thiol. Real‐time infrared spectroscopy (RT‐FTIR) experiments pointed out that for low thiol content, this beneficial effect is not only attributable to the thiol–ene process—oxygen insensitive—but also to the homopolymerization of acrylates which is enhanced. Homopolymerization and thiyl radical addition were found to have the same impact on the overall mechanism. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Characteristics of polypyrrole electrodeposited onto roughened substrates composed of gold–silver bimetallic nanoparticles

In this work, the characteristics of polypyrrole (PPy) films electrodeposited onto an electrochemically roughened gold substrate with bimetallic silver and gold nanoparticles were first investigated. First, a silver substrate was roughened by a triangular‐wave oxidation–reduction cycle (ORC) in an aqueous solution containing 0.1 M HCl. Subsequently, a gold substrate was roughened by a similar ORC treatment in this used solution. The results revealed that the surface of the roughened gold substrate demonstrated two different kinds of deposition domains because of the modification of silver nanoparticles. Encouragingly, some novel characteristics of PPy deposited onto this substrate were observed, in comparison with those on the roughened gold substrate without the modification of silver nanoparticles. They included a denser and more compact surface morphology, higher oxidation degree, increased conductivity, and improved surface‐enhanced Raman scattering. Furthermore, the nucleation and growth mechanism for PPy electropolymerization on this silver‐modified roughened gold substrate was distinguishable from that on the unmodified one. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2724–2731, 2006     

Small silver particles in glass surface layers produced by sodium-silver ion exchange — their concentration and size depth profile

Small spherical silver particles in a surface layer of commercial flat glass were produced by means of sodium-silver ion exchange. In each volume element of the layer there is a Gaussian distribution of the particle diameters. The mean diameter increases with penetration depth. Within one individual sample it can vary from 4.5 nm immediately at the glass surface up to more than 50 nm at the end of the layer. Due to a special preparation technique the results were gained by microspectrophotometric measurements as well as by investigations carried out with the transmission electron microscope and the electron-probe microanalyzer on one and the same sample always as function of the penetration depth.     

Dynamics of end-grafted polystyrene brushes in theta solvents

The dynamics of the concentration fluctuations in end-grafted polystyrene brushes in a theta solvent (cyclohexane) are probed by evanescent wave dynamic light scattering at different wavevectors q and temperatures. When the solvent quality changes from marginal to poor, the relaxation function C(q, t) exhibits strong effects as compared with the smooth variation of the brush density profile. From a single exponential above 50 °C, C(q, t) becomes a two-step decay function. The fast decay is still assigned to the cooperative diffusion albeit slower than in the good solvent regime whereas the slow nonexponential and nondiffusive process might relate to microsegragated and/or chain dynamics in the present polydisperse brush. The relaxation function of the present three brushes with different grafting density reveals similarities and disparities between wet brushes and semidilute polymer solutions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3590–3597, 2006     

In situ electron spin resonance study of styrene grafting of electron irradiated fluoropolymer films for fuel cell membranes

Three different electron beam irradiated fluoropolymers (ETFE, FEP, and PVDF) as well as their grafting reactions with styrene in different diluents were investigated by means of electron spin resonance (ESR). Depending on the atmosphere during irradiation, ESR spectra of peroxy and alkyl radicals were observed. Radical decay as a function of time and temperature was investigated in the presence and absence of solvent. Grafting levels and number of monomer units per chain were calculated for both types of radicals. Irradiation atmosphere, grafting temperature, and added solvent affect the morphology of the fluoropolymers, in particular the crystalline versus amorphous fractions and their swelling. They thus influence the rate at which the initial radicals at the polymer backbone are reached during the grafting process. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3323–3336, 2006     

Depth profile analysis of polyimide film treated by potassium hydroxide

The structural change in the depth direction of a polyimide (UPILEX‐S) film treated in alkaline solution, which was a representative surface treatment used to form a seed layer for plating and to improve the adhesive strength, was analyzed by means of micro Fourier transform infrared attenuated total reflection (FTIR‐ATR) line analysis with gradient shaving preparation. The polyimide film was treated with KOH. The imide ring opened through the alkaline treatment, and the amide structure and carboxylic acid salt were formed. The attainment depth of this structural change was almost proportional to the treatment time, and it reached about 8 μm after a 30‐min treatment. The degree of structural change through the alkaline treatment was almost constant after it reached a considerably degraded stage, and the chemically changed region penetrated into the inner part of the film from the surface. An intermediate layer before the final degraded stage appeared in the treated layer, and its thickness increased with the treatment time. The region that was changed chemically by the alkaline treatment progressed to the inner part simultaneously and continuously as the treatment time increased. The combined use of gradient shaving preparation and micro FTIR‐ATR line analysis was found to be extremely effective for the depth profiling of organic materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2071–2078, 2003     

Photopolymerization of acrylates without photoinitiators with short‐wavelength UV radiation: A study with real‐time fourier transform infrared spectroscopy

This article reports on the UV photopolymerization of acrylates without photoinitiators. Initiation of the reaction was achieved by direct excitation of the acrylates during irradiation with short‐wavelength UV light by use of the 222‐nm emission of a KrCl^* excimer lamp. The reactivity of various acrylates was studied by real‐time Fourier transform infrared–attenuated total reflection spectroscopy. The rate and the extent of the reaction within the layer were strongly dependent on the depth of penetration of UV light, which was determined by the molar extinction coefficient of the acrylate. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 894–901, 2004