ABSTRACT
The results of systematic studies on the surface energy γ and its polar γP and dispersion γD components of statistical copolymers of styrene and butadiene, acrylonitrile and butadiene, and butyl acrylate and vinyl acetate, with regard to their thermal prehistory, are generalized. Along with copolymers, the surfaces of their composing homopolymers were examined. We obtained the energy characteristics of the adhesive surfaces of copolymers that contacted with air, high-energy aluminium Al (γ = 160 mJ/m2), and the low-energy substrate surface of polytetrafluoroethylene F4 (PTFE) (γ = 18 mJ/m2). The surfaces of copolymers in contact with air, aluminium, and PTFE were investigated for the first time. It was found that the surface energy of these copolymers tended to occupy an intermediate value between the surface energy of the homopolymers. The additive nature of the change in the surface energy of the copolymers with their composition, as previously established in the works of Wu, extends to the dispersive component of the free surface energy γD and the critical surface energy γcr, according to Zisman. It was shown that a significant influence on the adhesive activity of copolymers was exerted by the substrate surface upon which the adhesive was formed. Thus, for the butadiene-nitrile copolymer (BNC) samples formed in contact with a high-energy substrate, their surface energy growth was associated with a significant increase in the polar component of the surface energy γP from 2 mJ/m2 for the samples formed in contact with air, to an increase from 10 to 11 mJ/m2 for the samples formed in contact with Al. The reason why the interface influenced the change in the energy characteristics of the adhesives was the selective interaction of each macromolecule fragment with the active centres of the substrate surface. As a result, the composition of the boundary layer changed and it became enriched with one of the components. The structure of such layers is nonequilibrium. The thermal annealing of copolymers in the mode of a stepwise temperature increase led to a convergence in the values of γ, asymptotically tending to the value characteristic of the surface of the copolymers formed in air. The activation energies for the processes of the conformational rearrangements of the macromolecules in the surface layers of the copolymers were calculated. It was found that the conformational rearrangements of the macromolecules in the surface layers occurred as a result of the internal rotation of the functional groups that determined the polar component of the surface energy.
ABSTRACT
From the examples of three and four-component polymer-polymer systems characterized by amorphous separation, an original technique for determining the pair parameters of interaction between components based on the sorption isotherms of common solvent vapor, particularly water vapor, has been developed. The possibility of calculating thermodynamic characteristics of multicomponent polymer compositions with specific interactions of functional groups from experimentally obtained sorption isotherms is shown. An algorithm for calculating pair interaction parameters, estimating concentration dependences of chemical potential and Gibbs free energy of mixing, and predicting the phase state of polymer mixtures was presented for the first time for such systems. The technique was tested on the example of systems poly(N-vinylpyrrolidone) (PNVP)-polyethylene glycol (PEG), PNVP-PEG-Poly(acrylic acid) (PAA), poly(N-vinylcaprolactam) (PNVCL)-PEG, and polyvinyl alcohol (PVA)-PEG.
ABSTRACT
The sorption-diffusion characteristics of rigid-chain glassy polymers based on polyheteroarylenes (PHAs) have been studied in a wide interval of relative humidity and temperatures of thermal treatment of the polymer sorbents. Experimental data on water vapor sorption for polynaphthoyleneimidobenzimidazole (PNIB) and its copolymers with different chemical nature have been obtained. Water diffusion coefficients have been calculated, and parameters of their concentration and temperature dependences have been determined. It was found that water molecules sorbed by PNIB and its copolymers are strongly bounded. Water mobile and cluster states depend on the structure of macromolecules and thermal prehistory of polymer sorbents. It is shown that the translational coefficients of water diffusion for all PHAs are in the range from 10-9 to 10-8 cm2/s. The diffusion coefficients also increase slightly with temperature increasing, and their general dependence on temperature is satisfactorily described by the Arrhenius equation. The average activation energy of water diffusion varies from 24.3 to 25.9 kJ/mol. The hydrate numbers of rigid-chain PHAs functional groups have been determined. The above-mentioned results allow us to predict the sorption properties of heterocyclic macromolecular sorbents with complex chain architecture.
ABSTRACT
The results ofthe sorption properties of cellulose acetate (CA) with different degrees of substitution (SD) are summarised. It has been shown that the sorption capacity of CA in water vapour decreases naturally with increasing content of acetate groups in monomeric units of cellulose ethers. The experimental isotherms are analysed according to the double sorption model. Hydrate numbers of hydroxyl and acetate groups were determined. The paired parameters of the Flory-Huggins interaction were calculated. It is shown that the decrease of the Langmuir component is due to the replacement of hydroxyl groups by ester groups, whose local sorption capacity by water vapour is lower than the sorption capacity of OH groups. In the area of high humidity, there is an increase in vacancy sizes due to plasticisation of the sorbents.
