The free-volume depth profile of asymmetric polymeric membrane systems prepared by interfacial polymerization is studied using positron annihilation spectroscopy coupled with a variable monoenergy slow positron beam. Significant variations of S, W, and R parameters from the Doppler broadened energy spectra vs positron incident energy up to 30 keV and orthopositronium lifetime and intensity are observed at different doping times of triethylenetetraamine (TETA) reacting with trimesoyl chloride (TMC) in an interfacial polymerization on modified porous polyacrylonitrile (PAN) asymmetric membrane. The positron annihilation data are analyzed in terms of free-volume parameters as a function of depth from the surface to nano- and micrometer regions of asymmetric membranes. A multilayer structure is obtained in polymerized polyamide (PA) on modified PAN membranes (m-PAN):  a nanometer scale skin polyamide layer, a nanometer to micrometer scale transition layer from dense to porous m-PAN, and the porous m-PAN suppo...

Free-Volume Depth Profile of Polymeric Membranes Studied by Positron Annihilation Spectroscopy: Layer Structure from Interfacial Polymerization

Positron annihilation spectroscopy (PAS) is a novel method that provides molecular-level information about complex macromolecular structure in a manner different from, but complementary to, conventional physical and chemical methodology. This paper presents a perspective of PAS in polymeric systems covering 12 aspects: historical, spacial, spherical quantum model, anisotropic structure, voids, positronium chemistry, time, positron annihilation lifetime spectroscopy and data analysis, variable monoenergetic slow positron beam techniques and depth profiling, elemental analysis, multidimensional instrumentation advances in PAS, and free volume and free-volume theories.

Perspective of Positron Annihilation Spectroscopy in Polymers

The degradation of polymer coating systems due to UV irradiation is studied using positron annihilation spectroscopy. Doppler broadened spectra of positron annihilation are measured as a function of slow positron implantation energy in a series of polymer coating systems which were exposed to UV irradiation for up to 2000 h. The S parameters from the Doppler broadened energy spectra vs positron energy show an increase at very low positron energy (<575 eV) and then a decrease to about 8 keV, followed by a slight increase up to 50 keV. The UV irradiation systematically decreases the S parameter as a function of exposure duration. The significant S parameter decrease is interpreted as the degradation of polymers and the change of the sub-nanometer defect profiles due to UV irradiation. These interpretations are supported by the data from the atomic force microscope, UV absorption, Fourier transform infrared, and profilometry measurements.

Degradation of Polymer Coating Systems Studied by Positron Annihilation Spectroscopy. 1. UV Irradiation Effect

The free volume sizes and distributions and multilayer structures in asymmetric thin layer polyamide membranes in the wet state have been first time measured using the variable monoenergy slow positron beam (VMSPB). This paper presents a newly developed method which combines the technique of plasma-enhanced chemical vapor deposition to form a barrier layer for high-vacuum condition to seal the composite polyamide and of interfacial polymerization between 2-aminoethanethiol (AETH) and trimesoyl chloride (TMC) on the surface of modified asymmetric polyacrylonitrile (mPAN) membrane (AETH-TMC/mPAN), under the wet condition encountered during the pervaporation process in which they are in direct contact with the liquid environment provided by the feed solution. During the VMSPB experiments under a high vacuum, our new method maintained the thin-film composite (TFC) membrane in the wet conditions typically experienced in VMSPB experiments wherein it directly contacts the liquid feed environment, which is essent...

Characterizing Free Volumes and Layer Structures in Asymmetric Thin-Film Polymeric Membranes in the Wet Condition Using the Variable Monoenergy Slow Positron Beam

Positronium annihilation was applied to characterize the nanoporous structure of thin silicon oxide films sputter-deposited at different argon pressures ranging from 0.1 to 2.0 Pa. At higher argon pressures, the 3γ decay probability of ortho-positronium (o-Ps) was substantially enhanced. A comparison of this result with that obtained for capped samples indicated that: (a) 3γ annihilation is due to the intrinsic decay of o-Ps diffusing out from the film into vacuum and (b) films deposited at high argon pressures contain highly connected, open pores. Positron lifetime spectroscopy measurements on the capped films showed that the characteristic size of the pores can be as large as 2.6 nm, depending on the argon pressure.

Nanoporous structure of sputter-deposited silicon oxide films characterized by positronium annihilation spectroscopy

Poly(aryl-ether-ether ketone) (PEEK) films irradiated with 1-MeV and 2-MeV ${\mathrm{O}}^{+}$ ions were exposed to positron beams to measure the positron annihilation Doppler broadening as a function of the positron energy. The annihilation lines recorded at relatively low positron energies were found to become broader with increasing irradiation dose, suggesting that positronium (Ps) formation is inhibited in the damaged regions. The positron data were compared with the results of dynamic hardness and electron-spin-resonance measurements. The slow-positron Doppler broadening technique is found to be a useful means for damage-depth profiling of Ps-forming polymers.

Isao Kojima

Papers

Damage-depth profiling of an ion-irradiated polymer by monoenergetic positron beams.