Simulation of Binodal and Spinodal Curves of Phase State Diagrams for Binary Polymer Systems

A new approach is proposed for simulating binodal and spinodal curves of phase diagrams for binary polymer systems. It is shown that the Flory–Huggins theory makes it possible to predict phase behavior in a wide range of temperatures and concentrations based on limited data on the components’ solubility. The approbation data of the technique are presented in the example of PS–PB and PS–PMMA systems, for which generalized phase diagrams are constructed

Adhesion and Energy Characteristics of Rigid-Chain Polymer Surface: Polyamidoimides

The adhesion characteristics and surface energies of two series of polyamidoimides (PAI) with different molecular weights, monomer unit structures, hinge groups in the main chain of the macromolecules, and thermal prehistory were determined via delamination at 180° and test fluids contact angles. We found that PAI are high-energy polymers, the surface energy of which varies in the range from 32 to 45 mJ/m2. In contrast to flexible-chain polymers, the exponent in the McLeod equation is two, which is due to the flat parallel orientation of the macromolecular chains in the surface layers. The main contribution to the change in surface characteristics of these polymers is the change in the packing density of PAI macromolecules, which is reflected mainly in the change in the polymers’ dispersion component. We found that the adhesion properties of PAI with respect to high- and low-energy substrates are determined mainly by the macromolecules packing density in the surface layers with their conformation state unchanged

Water Sorption by Polyheteroarylenes

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

Spectra of Internal Friction in Polyethylene

The study of spectra of internal friction λ=fT and temperature dependencies of frequency of freely damped ν=fT oscillatory process excited in investigated samples of polyethylene with different degree of crystallinity in the temperature range from −150 °C to +150 °C. It is established that four local dissipative processes of different intensity shown in different temperature intervals are observed on the spectra λ=fT. These are μ, β, α, βk processes. The theoretical analysis of the relationship between the anomalous changes of the vibrational process frequency ν=fT and the shift modulus defect ΔG=fT and the internal friction mechanisms for each of the dissipative loss processes detected on the spectrum λ=fT is carried out. The influence of supramolecular structures on local dissipative βk process in polyethylene is estimated

Abstract P-42: Structure of Hydrogels of an Anionic PolAbstract P-42: Structure of Hydrogels of an Anionic Polysaccharide Studied by Freeze-Fracture Transmission Electron Microscopyysaccharide Studied by Freeze-Fracture Transmission Electron Microscopy

Background: Polysaccharide hydrogels draw attention due to the ability to form mechanically tough gels at low concentrations (typically 1 wt% or lower), combined with biocompatibility and biodegradability. Biopolymer hydrogels can be used as a matrix for cell growth, in order to obtain materials for the replacement of damaged tissues. “Physical” gels with macromolecules cross-linked by dynamic reversible cross-links are of great interest due to their self-healing ability. However, investigation of the native un-perturbed structure of such hydrogels presents a challenge, since they collapse upon drying, and present a difficulty for preparing a thin specimen for cryo-TEM experiments due to very high viscosity. The aim of this work is to study the native structure of hydrogels of an anionic polysaccharide – carboxymethyl hydroxypropyl guar (CMHPG) – cross-linked by borax. Methods: Freeze-fracture transmission electron microscopy (FF-TEM) was conducted on a Phillips EM-301 microscope. A small volume of the sample (100 μl) was put into the copper cell and cooled down by liquid nitrogen, put under vacuum (10−5 torr) at continuous cooling with liquid nitrogen, and fractured. The surface was etched for 10–20 min at 10−5 torr and then replicated by spraying platinum and carbon. Results: The gels have a microphase-separated microstructure – a rather thick (several nm) polymer backbone is seen, which is presumably formed by multiple aggregated macromolecules, and meshes between the backbone do not contain polymer and are filled with solvent. Mesh size determined from the micrographs qualitatively coincides with the value determined from the elastic modulus of the gels. Upon increasing the concentrations of cross-linker, the network becomes denser: the mesh size becomes lower, and the thickness of the backbone increases. Thus, the addition of cross-linker favors the aggregation of polymer chains forming the backbone. Conclusion: It was shown by FF-TEM that cross-linked CMHPG gels have a microphase-separated structure with a dense backbone formed by polymer chains and rather large meshes between them

Phase Equilibrium, Morphology, and Physico-Mechanics in Epoxy–Thermoplastic Mixtures with Upper and Lower Critical Solution Temperatures

The mutual solubility of epoxy oligomer with polysulfone (PSU) and polyethersulfone (PES) was studied by optical interferometry. Additionally, phase diagrams (PDs) were plotted and their evolution during the curing process was shown. The phase structures of modified hardened systems, as well as their tensile strengths, elastic moduli, and crack resistance, have been studied by scanning electron microscopy and physico-mechanical techniques. The effect of initial components’ mutual solubility on the phase structure and, subsequently, on the physico-mechanical properties of the composite material is shown. Differences in the structure and properties of the cured modified compositions depending on the type of PD (with Upper Critical Solution Temperature (UCST) for PSU and Lower Critical Solution Temperature (LCST) for PES) of the initial components are shown

Mechanism of Post-Radiation-Chemical Graft Polymerization of Styrene in Polyethylene

Structural and morphological features of graft polystyrene (PS) and polyethylene (PE) copolymers produced by post-radiation chemical polymerization have been investigated by methods of X-ray microanalysis, electron microscopy, DSC and wetting angles measurement. The studied samples differed in the degree of graft, iron(II) sulphate content, sizes of PE films and distribution of graft polymer over the polyolefin cross section. It is shown that in all cases sample surfaces are enriched with PS. As the content of graft PS increases, its concentration increases both in the volume and on the surface of the samples. The distinctive feature of the post-radiation graft polymerization is the stepped curves of graft polymer distribution along the matrix cross section. A probable reason for such evolution of the distribution profiles is related to both the distribution of peroxide groups throughout the sample thickness and to the change in the monomer and iron(II) salt diffusion coefficients in the graft polyolefin layer. According to the results of electron microscope investigations and copolymer wettability during graft polymerization, a heterogeneous system is formed both in the sample volume and in the surface layer. It is shown that the melting point, glass transition temperature and degree of crystallinity of the copolymer decreases with the increasing proportion of graft PS. It is suggested that during graft polymerization a process of PE crystallite decomposition (melting) and enrichment of the amorphous phase of graft polymer by fragments of PE macromolecules occurs spontaneously. The driving force of this process is the osmotic pressure exerted by the phase network of crystallites on the growing phase of the graft PS

Phase Equilibria and Interdiffusion in Bimodal High-Density Polyethylene (HDPE) and Linear Low-Density Polyethylene (LLDPE) Based Compositions

The compositions based on bimodal high-density polyethylene (HDPE, copolymer of ethylene with hexene-1) and in mixture with monomodal tercopolymer of ethylene with butene-1/hexene-1 (LLDPE, low-density polyethylene) have been studied. Phase equilibrium, thermodynamic parameters of interdiffusion in a wide range of temperatures and ratios of co-components were identified by refractometry, differential scanning calorimetry, optical laser interferometry, X-ray phase analysis. The phase state diagrams of the HDPE—LLDPE systems were constructed. It has been established that they belong to the class of state diagrams of “solid crystal solutions with unrestricted mixing of components”. The paired parameters of the components interaction and their temperature dependences were calculated. Thermodynamic compatibility of α-olefins in the region of melts and crystallization of one of the components has been shown. The kinetics of formation of interphase boundaries during crystallization of α-olefins has been analyzed. The morphology of crystallized gradient diffusion zones has been analyzed by optical polarization microscopy. The sizes of spherulites in different areas of concentration profiles and values of interdiffusion coefficients were determined

Phase Equilibria and Interdiffusion in Bimodal High-Density Polyethylene (HDPE) and Linear Low-Density Polyethylene (LLDPE) Based Compositions

The compositions based on bimodal high-density polyethylene (HDPE, copolymer of ethylene with hexene-1) and in mixture with monomodal tercopolymer of ethylene with butene-1/hexene-1 (LLDPE, low-density polyethylene) have been studied. Phase equilibrium, thermodynamic parameters of interdiffusion in a wide range of temperatures and ratios of co-components were identified by refractometry, differential scanning calorimetry, optical laser interferometry, X-ray phase analysis. The phase state diagrams of the HDPE—LLDPE systems were constructed. It has been established that they belong to the class of state diagrams of “solid crystal solutions with unrestricted mixing of components”. The paired parameters of the components interaction and their temperature dependences were calculated. Thermodynamic compatibility of α-olefins in the region of melts and crystallization of one of the components has been shown. The kinetics of formation of interphase boundaries during crystallization of α-olefins has been analyzed. The morphology of crystallized gradient diffusion zones has been analyzed by optical polarization microscopy. The sizes of spherulites in different areas of concentration profiles and values of interdiffusion coefficients were determined