Nucleation and overgrowth of PE on PTFE/iPP interfaces

Using an experimental setup with a three‐phase intersecting boundary of PTFE/PE/iPP, the nucleation power of PTFE compared to iPP on the PE was studied by TEM. It was found that the nucleation of the PE on the PTFE interface started at a higher temperature than epitaxial nucleation of the PE onto the iPP interface. During cooling of the melt, the growth direction of the PE crystalline lamellae changes in a continuous manner from the transcrystallization direction of the PTFE/PE interface into the heteroepitaxial “crosshatched” orientation of the iPP/PE interface. A (still highly speculative) self‐assembly of the PE macromolecules at the respective interface just in front of the actual crystallization edge is used to explain this observed phenomenon. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 80–83, 2000     

Nanometer‐scale surface modification by polymerization of tetrafluoroethylene on polymer substrates in supercritical fluoroform

Surface penetrated polymerization of tetrafluoroethylene (TFE) was carried out on a polycarbonate (PC) plate in supercritical fluoroform (scCHF₃). Since the high diffusiveness is one of peculiar features of supercritical fluids, TFE monomers and initiators (perfluorinated benzoyl peroxide) could penetrate into the surface of polymer substrates and be photo‐polymerized. After washing physisorbed homopolymers on the surface, polytetrafluoroethylene (PTFE) was found to penetrate into 50–800 nm depth from the surface and covered the PC surface in the proportion of 85%. The surface coverage density and the penetration depth could be controlled by adjusting of the pressure of scCHF₃. The TFE‐penetrated polymerization could be applied for various polymer plates such as polyethylene, polystyrene, polypropylene, poly(ethylene terephthalate), and polyimide. In addition to polymer plates, this technique could be applied to a cellulose paper, a nylon textile, and a porous PC membrane. The PTFE‐penetrated nylon textile showed a high resistance for washing test with detergents, compared with the commercial fluoropolymer‐sprayed nylon textile. The PTFE‐penetrated porous PC membrane showed high oxygen permeability (P/P = 5.2), compared with that of the untreated PC membrane (P/P = 3.5) in gas permeation experiments of O₂ and N₂. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1577–1585, 2008     

FTIR spectroscopy of monomolecular layers and multilayers of organic molecules on solid substrates

A method for measuring grazing incidence reflection spectra of monomolecular organic layers is presented which involves the use of a stepmotor-driven translation stage to alternately measure the covered and uncovered part of a metal substrate and averaging of the spectra from several such cycles. The method is applied to Langmuir-Blodgett films of poly(octadecylmethacrylate).     

Effect of the initial matrix material on the structure of radiation‐grafted ion‐exchange membranes: Wide‐angle and small‐angle X‐ray scattering studies

Seven different fluoropolymer films were used as matrix materials for radiation‐grafted ion‐exchange membranes. The crystallinity and preferred orientation of these membranes were studied with wide‐angle X‐ray scattering, and the lamellar structure of the membranes was examined with small‐angle X‐ray scattering. The crystallinity of poly(vinylidene fluoride) (PVDF)‐based matrix materials varied between 57 and 40%, and the crystallinity of the sulfonated samples varied between 34 and 23%. The lamellar periods of PVDF‐based matrix materials were about 115 Å, and the lamellar periods of poly(ethylene‐alt‐tetrafluoroethylene) and poly(tetrafluoroethylene‐co‐hexafluoropropylene) were 250 and 212 Å, respectively. When the samples were grafted, the lamellar periods increased. Correlation function analysis showed very clearly that the long‐range order decreased because of grafting and sulfonation processes. For those samples that showed good proton conductivity, the lamellar period also increased because of sulfonation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1539–1555, 2002     

Poly(tetrafluoroethylene) Film Surface Functionalization with 2‐Bromoisobutyryl Bromide as Initiator for Surface‐Initiated Atom‐Transfer Radical Polymerization

A PTFE film surface was modified using a combined plasma/ozone‐activated process. The modified PTFE film was further reacted with 2‐bromoisobutyryl bromide to incorporate ATRP initiators in the film surface. Surface‐initiated ATRP on PTFE films was performed using sodium styrene sulfate as a monomer. The poly(sodium styrene sulfate) chain length grafted onto PTFE film surfaces increased with increasing reaction time. Analysis using X‐ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy and a contact angle analyzer gave evidence of the success of the PTFE surface modifications.

     

Surface‐initiated atom transfer radical polymerization from porous poly(tetrafluoroethylene) membranes using the C?F groups as initiators

This work reports the surface‐initiated atom transfer radical polymerization (ATRP) from hydrogen plasma‐treated porous poly(tetrafluoroethylene) (PTFE) membranes using the C? F groups as initiators. Hydrogen plasma treatment on PTFE membrane surfaces changes their chemical environment through defluorination and hydrogenation reactions. With the hydrogen plasma treatment, the C? F groups of the modified PTFE membrane surface become effective initiators of ATRP. Surface‐initiated ATRP of poly(ethylene glycol) methacrylate (PEGMA) is carried out to graft PPEGMA chains to PTFE membrane surfaces. The chain lengths of poly(PEGMA) (PPEGMA) grafted on PTFE surfaces increase with increasing the reaction time of ATRP. Furthermore, the chain ends of PPEGMA grown on PTFE membrane surfaces then serve as macroinitiators for the ATRP of N‐isopropylacrylamide (NIPAAm) to build up the PPEGMA‐b‐PNIPAAm block copolymer chains on the PTFE membrane surfaces. The chemical structures of the modified PTFE membranes are characterized using X‐ray photoelectron spectroscopy. The modification increases the surface hydrophilicity of the PTFE membranes with reductions in their water‐contact angles from 120° to 60°. The modified PTFE membranes also show temperature‐responsive properties and protein repulsion features owing to the presence of PNIPAAM and PPEGMA chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2076–2083, 2010     

Polymer brushes on hydrogen-terminated silicon substrates via stable Si—C bond

A universal and straightforward method for the preparation of polymer brushes via the formation of Si-C bond on silicon substrates through the UV-induced photopolymerization is demonstrated.     

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     

Immobilization of silver nanoparticles into POEGMA polymer brushes as SERS‐active substrates

Surface‐enhanced Raman scattering (SERS) has attracted a great deal of interest during the past four decades and emerged as an ultrasensitive optical technique for chemical and biomedical analysis. It is widely accepted that the facile fabrication of SERS substrates with high activity and good reproducibility is of crucial importance for their applications. Herein, we report on a fast and robust method for the synthesis and immobilization of silver nanoparticles (AgNPs) into poly(oligo(ethylene glycol) methacrylate) (POEGMA) brushes under mild conditions without using any reducing agents. POEGMA brushes of different chain lengths were synthesized directly on silicon wafers by surface‐initiated atom transfer radical polymerization with various reaction time. X‐ray photoelectron spectroscopy and field emission scanning electron microscope measurements indicated that the AgNPs were firmly and homogeneously embedded into POEGMA brushes. The resulting POEGMA–AgNP hybrid films were employed as SERS substrates for the detection of 4‐aminothiophenol, giving rise to an enhancement factor of up to 1.9 × 10⁶. The influence of the POEGMA's chain length on SERS performance was also investigated. Copyright © 2016 John Wiley & Sons, Ltd.     

Nanocellulose Polymer Composites as Innovative Pool for (Bio)Material Development

Summary: Using a “never-dried” procedure (according to Figure 4) shaped bacterial nanocellulose (BC, 1% cellulose, 99% water) has been modified by the formation of BC-polymer composites. For this purpose, acrylate and methacrylate monomers and methacrylate crosslinkers were photopolymerized inside an ethanol-swollen nanofiber network. Using the ethanol as solvent and as confirmed by model reactions the synthetic polymer (SP) part of the composites is constructed of crosslinked polymers (number of repeating units in the range of 500). As part of ongoing work on the development of (bio)materials from the innovative pool of BC composites these investigations are recently directed towards the creation of collagen-like materials. Thus, for these purposes, mainly water absorption capacity, strength, and elasticity have to be controlled, whilst still retaining essential features of BC like shape, nanofiber network, pore system, and proved biocompatibility. Using acrylic acid, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone as acrylate monomers and triethylene glycol dimethacrylate and 1,4-butandiol dimethacrylate as crosslinkers of different concentrations either a filling of the pores or a coating of the fibers in the BC nanocomposites could be achieved. The small cellulose content of the composites significantly increases the water absorption value and the strength of the material as well as the ability of re-swelling in the case of fiber coated composites. Sample 12 is an optimized BC-SP composite regarding important properties of hyaline cartilage like Young's modulus in the range of 5–20 MPa using the well-known Simplex-method.     

Annealing Effect on Electrospun Polymer Fibers and Their Transformation into Polymer Microspheres

Electrospinning is a simple and convenient technique to produce polymer fibers with diameters ranging from several nanometers to a few micrometers. Different types of polymer fibers have been prepared by electrospinning for various applications. Among different post‐treatment methods of electrospun polymer fibers, the annealing process plays a critical role in controlling the fiber properties. The morphology changes of electrospun polymer fibers under annealing, however, have been little studied. Here we investigate the annealing effect of electrospun poly(methyl methacrylate) (PMMA) fibers and their transformation into PMMA microspheres. PMMA fibers with an average size of 2.39 μm are first prepared by electrospinning a 35 wt% PMMA solution in dimethylformamide. After the electrospun fibers are thermally annealed in ethylene glycol, a non‐solvent for PMMA, the surfaces of the fibers undulate and transform into microspheres driven by the Rayleigh instability. The driving force of the transformation process is the minimization of the interfacial energy between the polymer fibers and ethylene glycol. The sizes of the microspheres fit well with the theoretical predictions. Longer annealing times are found to be required at lower temperatures to obtain the microspheres.     

Spectroscopic evidence for radiation-induced crosslinking of poly(tetrafluoroethylene)

Direct spectroscopic evidence for radiation-induced crosslinking of poly(tetrafluoroethylene) (PTFE) is presented for all x-ray and electron dose levels above which it is possible to distinguish between deliberately introduced radiation damage and the x-ray damage inherent in obtaining an x-ray photoelectron spectrum (XPS). The C (1s) spectrum obtained after irradiation with 2 keV electrons for all doses greater than 1 μA-min/cm² consists of a four-peak spectrum identical to that previously obtained for plasma-polymerized tetrafluoroethylene and assigned to carbon atoms with variable numbers of bound F atoms (CF₃, CF₂, CF₁, and CF₀). X-ray irradiated PTFE can be fitted with the same four-peak spectrum. At or below an electron dose level of 1 μA-min/cm², the radiation damage is comparable to that produced by the x-ray dose necessary to obtain an XPS spectrum. The CF₁ and CF₀ components increase with increasing electron dose, and at high electron doses dominate the spectrum. With increasing dose the CF₃ component approaches a constant value while both the CF₂ component and the total F : C ratio decreases. These four components are those expected to result from radiation-induced crosslinking reactions of the polymer and are consistent with previous suggestions that crosslinking is the basis of radiation patterned adhesion to PTFE. © 1993 John Wiley & Sons, Inc.     

Synthetic Uniform Polymers and Their Use for Understanding Fundamental Problems in Polymer Chemistry

Summary: A uniform polymer is a polymer composed of molecules that are uniform with respect to molecular weight and constitution. Besides natural uniform polymers such as nucleic acids and polypeptide, synthetic uniform polymers have been obtained by a variety of approaches. In particular, a combination of living polymerization and supercritical fluid chromatography (SFC) separation is one of the promising ways for the preparation of uniform polymers. End‐functionalized uniform polymers enabled us to prepare uniform polymer architectures such as block, graft, comb, and star polymers. Their use for understanding the fundamental problems in polymer chemistry is discussed; topics include crystallization of polymers, chain conformation in solution, and association of stereoregular polymers in solution.

SFC traces of isotactic PMMA containing an authentic sample of the 45‐mer (a) and of the isolated uniform PMMA of 100‐mer (b).     

Morphology Evolution During Polymer Crystallization Simultaneous Calorimetric and Optical Measurements

The crystallization of the isotactic poly(propylene) (I-PP) has been studied carrying out measurements by means of a special calorimeter connected to a microscope and a digital acquisition system of images. To authors' knowledge, this is the first time that simultaneous calorimetric and optical measurements are carried out on polymers. The analysis of Polarized Optical Microscopy images has allowed the appraisal of nucleation density and growth rate in isothermal and non isothermal conditions. The results obtained in isothermal conditions have been analyzed through the Kolmogoroff model and the crystallinity calculated from the model has been compared with that obtained from the calorimetric measurements.     

Thermal Analysis of the Poly(Siloxane)–Poly(Tetrafluoroethylene) Coating System

Thermal properties of poly(siloxane)–poly(tetrafluoroethylene) (SIL–PTFE) system were investigated, using Perkin Elmer DSC-7 differential scanning calorimeter and TGA-7 thermogravimetric analyzer. For SIL–PTFE compositions, one glass transition temperature T _g has been found, in accordance with the reciprocal rule up to about 40 mass% of PTFE. However, for higher PTFE contents, T _g values about –118 to –112°C were observed that can be ascribed to motions of cross-linked SIL structures. Endo- and exothermic transitions, found in the range from 70 to 290°C, not observed for pure SIL and PTFE components, are considered as specific ones for the SIL–PTFE semi-IPN structures. The SIL–PTFE system, as well as its components, is thermally stable, if degradation reactions are considered; the temperatures of decomposition at the maximum decomposition rate were above 530°C. It has been found that the thermal stability of the SIL–PTFE system is increasing with the increase of the PTFE content. This revised version was published online in August 2006 with corrections to the Cover Date.     

Phase Separation in Aqueous Polymer Solutions as Studied by NMR Methods

Some possibilities of ¹H NMR spectroscopy in investigations of structural-dynamic changes and polymer-solvent interactions during the temperature-induced phase transitions in aqueous polymer solutions are described. Results obtained recently on D₂O solutions of poly(vinyl methyl ether) (PVME), poly(N-isopropylmethacrylamide) (PIPMAm), negatively charged copolymers of N-isopropylmethacrylamide and sodium methacrylate, and PIPMAm/PVME mixtures are discussed. A markedly different rate of dehydration process in dilute solutions on the one hand, and in semidilute and concentrated solutions on the other hand, was revealed from ¹H spin-spin relaxation measurements.     

Surface Structure and Stereocomplex Formation of Enantiomeric Polylactide Blends Using Poly(dimethyl siloxane) as a Probe Polymer

In the stereocomplex between enantiomeric poly(l-lactide) (l-PLA) and poly(d-lactide), crystallites formed as a result of stereocomplexation, equimolar l- and d-lactide unit sequences are packed side by side. The stereocomplex exhibits a melting temperature higher by about 50 °C than that of each homopolymer. In this study, we attempt to obtain further insight into the stereocomplex-induced surface structure of enantiomeric PLA blend films. The design of the blend systems is based on principles of surface segregation of multicomponent polymeric systems with a low surface energy, triblock copolymer (l-PLA-b-PDMS-b-l-PLA) of l-PLA and poly-(dimethyl siloxane). (l-PLA-b-PDMS-b-l-PLA/l-PLA) blend films showed the surface segregation of PDMS, regardless of blend composition while the surface composition of PDMS in the (l-PLA-b-PDMS-b-l-PLA/d-PLA) blend films was strongly depended on blend composition or a degree of complexation. These results are likely due to strong interaction between d- and l-lactide unit sequences, which prevents the surface segregation of PDMS.     

Conversion of poly(ethylene‐alt‐tetrafluoroethylene) copolymers into polytetrafluoroethylene by direct fluorination: A convenient approach to access new properties at the ETFE surface

Direct fluorination of poly(ethylene‐alt‐tetrafluoroethylene) copolymer (ETFE) was carried out on commercially available ETFE films with pure fluorine gas at ambient atmosphere. Reaction temperature was either 95 °C or 150 °C and exposure time was 20 hours. Analysis of the fluorinated samples was performed by attenuated total reflection Fourier transform Infrared, confocal micro‐Raman and ¹H and ¹⁹F magic angle spinning nuclear magnetic resonance spectroscopies, scanning electron microscopy, electron diffraction and X‐Ray photoelectron spectroscopies, contact angle determination, atomic force microscopy and nanoindentation measurements, and compared to those of the virgin ETFE copolymer. Integrity of the bulk materials was verified by investigating the thermal behavior of the polymers by thermogravimetric analysis and differential scanning calorimetry. Evidence for the formation of a homogeneous layer of polytetrafluoroethylene with a thickness of several microns at the surface of the copolymers with no degradation of the materials was observed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

The Role of Phase Migration of Carbon Nanotubes in Melt-Mixed PVDF/PE Polymer Blends for High Conductivity and EMI Shielding Applications

In this work, the effects of blend ratio and mixing time on the migration of multi-walled carbon nanotubes (MWCNTs) within poly(vinylidene fluoride) (PVDF)/polyethylene (PE) blends are studied. A novel two-step mixing approach was used to pre-localize MWCNTs within the PE phase, and subsequently allow them to migrate into the thermodynamically favored PVDF phase. Light microscopy images confirm that MWCNTs migrate from PE to PVDF, and transmission electron microscopy (TEM) images show individual MWCNTs migrating fully into PVDF, while agglomerates remained trapped at the PVDF/PE interface. PVDF:PE 50:50 and 20:80 polymer blend nanocomposites with 2 vol% MWCNTs exhibit exceptional electromagnetic interference shielding effectiveness (EMI SE) at 10 min of mixing (13 and 16 dB, respectively-at a thickness of 0.45 mm), when compared to 30 s of mixing (11 and 12 dB, respectively), suggesting the formation of more interconnected MWCNT networks over time. TEM images show that these improved microstructures are concentrated on the PE side of the PVDF/PE interface. A modified version of the “Slim-Fast-Mechanism” is proposed to explain the migration behavior of MWCNTs within the PVDF/PE blend. In this theory, MWCNTs approaching perpendicular to the interface penetrate the PVDF/PE interface, while those approaching in parallel or as MWCNT agglomerates remain trapped. Trapped MWCNTs act as barriers to additional MWCNTs, regardless of geometry. This mechanism is verified via TEM and scanning electron microscopy and suggests the feasibility of localizing MWCNTs at the interface of PVDF/PE blends.     

Tetramethylammonium fluorochromate(VI): a new and efficient oxidant for organic substrates

Tetramethylammonium fluorochromate(VI), (CH₃)₄N⁺CrO₃F⁻ (TMAFC), was prepared and used for quantitative oxidation of several organic substrates. This new compound is more efficient and has certain advantages over similar oxidizing agents in terms of the amount of oxidant and solvent required, short reaction times and high yields.