Modification of fluoropolymers by means of electron beam irradiation

High molecular weight polytetrafluoroethylene (PTFE) is transformed to free-flowing micropowder by treatment with electron beams. In case of irradiation in presence of air carboxylic acid fluoride groups are incorporated which rapidly hydrolyze to carboxylic groups in the surface-near regions due to atmospheric humidity. These polar groups reduce the hydrophobic and oleophobic properties so much that homogeneous compounding with other materials becomes possible. In addition to PTFE, copolymers of tetrafluoroethylene with hexafluoropropylene (FEP) and perfluoropropylvinylether (PFA) were modified. In case of identical irradiation conditions, the concentration of carboxylic groups is much higher in FEP and PFA than in PTFE, which is due to the lower crystallinity of the copolymers.

Electron beam irradiation of PTFE was performed in vacuum at elevated temperature above the melting point. The changes in the chemical structure were studied. The concentration of CF₃ branches was found to be much higher as compared to room temperature irradiation.

In a practical test PTFE micropowders functionalized by electron irradiation were compounded with epoxy resins, with polyoximethylene and with polyamides. Such compounds are characterized by very good frictional and wearing behaviour in dry-running tests.     

Polyelectrolyte Adsorption on NH3-Plasma-Treated Poly(tetrafluoroethylene-co-hexafluoropropylene)

A two-step procedure for a permanently hydrophilic surface modification of poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP, fluorinated ethylene propylene) was studied. In the first step a cationic polymer surface was created by low-pressure ammonia plasma treatment introducing nitrogen-containing functional groups. Afterwards, the anionic poly(sodium 4-styrenesulfonate) was adsorbed onto the plasma-treated FEP surface. The adsorption was assumed to be controlled by ionic interactions. The modification effects and their long-term behavior were evaluated by means of water contact angle goniometry. Furthermore, electrokinetic measurements and X-ray photoelectron spectroscopy were used for surface characterization.     

BMOA(R,m) and capacity density Bloch spaces on hyperbolic Riemann surfaces

We investigate a number of spaces of functions on Riemann surfaces which are related to Bloch spaces and functions of bounded mean oscillation (BMO). These spaces are defined using properties for the corresponding function spaces on the unit disk in the complex plane, and we show that, in general, different properties lead to different function spaces. We catalogue almost completely the various relationships between these spaces.     

Pre-Irradiation Grafting of Styrene into Modified Fluoropolymers

Summary: The grafting of styrene into commercially available fluoropolymer films by the pre-irradiation method has been investigated. Poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP), poly(tetrafluoroethylene-co-perfluoropropylvinyl ether) (PFA) and poly(tetrafluorethylene-co-ethylene) (ETFE) were chosen as the base polymer material. The influence of the base material, the pre-irradiation dose, and the storage time between the irradiation and the grafting step on the yield of grafting was examined. The base materials were pre-treated by irradiation in the molten state under oxygen-free conditions in order to create branches and cross-links. The effect of pre-treatment on the yield of grafting was studied.     

Modification of perfluorinated polymers by high-energy irradiation

This review surveys about the possibilities for the modification of perfluorinated polymers using high-energy irradiation: degradation, functionalization, branching, and cross-linking. The reaction mechanisms for the different reaction conditions are discussed. Electron irradiation of polytetrafluoroethylene (PTFE) with a very high dose leads to a complete degradation of the macromolecules to low-molecular products. In the presence of oxygen perfluorocarboxylic acids and in an inert atmosphere, mixtures of perfluorinated olefins and paraffins can be obtained. Virgin PTFE is disintegrated by high-energy irradiation in air with a lower dose into a micropowder modified with COOH groups. This powder can be homogeneously incorporated in other polymers. So, the special properties of PTFE can be made effective in these polymers. Micropowders functionalized with COOH groups and polyamides (PA) form by reactive extrusion PTFE-PA blockcopolymers which can be used as slide bearing materials. The copolymers poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) and poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) irradiated in air show a significantly higher degree of COOH functionalization compared with PTFE. Irradiation of molten PTFE in an inert atmosphere leads to formation of different kinds of double bonds, CF₃ side groups, long-chain branches as well as cross-links. Irradiation of PFA in vacuum results in the generation of COF and COOH groups; in molten state also branches and cross-links are formed.The focus of the present paper is on the work that has been carried out at the Institute of Polymer Research Dresden.     

A test of performance of breast MRI interpretation in a multicentre screening study

OBJECTIVES: The aim of this study was to assess the consistency and performance of radiologists interpreting breast magnetic resonance imaging (MRI) examinations. MATERIALS AND METHODS: Two test sets of eight cases comprising cancers, benign disease, technical problems and parenchymal enhancement were prepared from two manufacturers' equipment (X and Y) and reported by 15 radiologists using the recording form and scoring system of the UK MRI breast screening study [(MAgnetic Resonance Imaging in Breast Screening (MARIBS)]. Variations in assessments of morphology, kinetic scores and diagnosis were measured by assessing intraobserver and interobserver variability and agreement. The sensitivity and specificity of reporting performances was determined using receiver operating characteristic (ROC) curve analysis. RESULTS: Intraobserver variation was seen in 13 (27.7%) of 47 of the radiologists' conclusions (four technical and seven pathological differences). Substantial interobserver variation was observed in the scores recorded for morphology, pattern of enhancement, quantification of enhancement and washout pattern. The overall sensitivity of breast MRI was high [88.6%, 95% confidence interval (CI) 77.4-94.7%], combined with a specificity of 69.2% (95% CI 60.5-76.7%). The sensitivities were similar for the two test sets (P=.3), but the specificity was significantly higher for the Manufacturer X dataset (P<.001). ROC curve analysis gave an area under the curve of 0.85 (95% CI 0.79-0.92) CONCLUSIONS: Substantial variation in all elements of the scoring system and in the overall diagnostic conclusions was observed between radiologists participating in MARIBS. High overall sensitivity was achieved with moderate specificity. Manufacturer-related differences in specificities possibly occurred because the numerical thresholds set for the scoring system were not optimised for both equipment manufacturers. Scoring systems developed on one equipment software may not be transferable to other manufacturers.     

Polarization Modulation Effects in Infrared–Infrared Four-Level Double Resonance inCH3F andNH3

The elements of the Jones matrices for an optically pumped sample have been derived and used to predict four-level double resonance absorption coefficients that are functions of the velocity component of the molecules in the direction of the pump beam for different polarizations of the probe beam. When a saturating pump and weak probe are used in four-level double resonance experiments under population modulation conditions, these absorption coefficients are found to depend only on the first three statistical tensor ranks:n= 0 (population), 1 (orientation), and 2 (alignment). It is also found that for polarization modulation experiments with plane-polarized radiation, the absorption coefficient depends only on the alignment of them-state populations. Similarly, for polarization modulation with circularly polarized radiation, the absorption coefficient depends only on the orientation. The theory was used to interpret double-resonance polarization modulation experiments in¹³CH₃F and¹⁵NH₃in order to examine the effects of collisions on the initial anisotropy of the projection ofJon a space-fixedZaxis. The four-level double-resonance lineshapes were fit by least squares to absorption coefficients predicted by the theory. The collisional effects were modeled by a sum of Keilson–Storer collision kernels. The results of the fits were much improved when the value of the effective rate constant for the transfer of then= 0 tensor from the upper level of the pump to the lower level of the probe was larger than the values of the effective rate constants for the transfer of then= 1 and 2 populations. The best ratio of the rate constant forn> 0 to that forn= 0 is about 2/3 for¹³CH₃F and 1/3 for¹⁵NH₃. Additional analysis of the lineshapes showed the importance of long-range dipole–dipole interactions, elastic realignment and reorientation, and V–V mechanisms for collision-induced rotational energy transfer in¹³CH₃F and¹⁵NH₃.