Polymer Mobility Research Articles

Direct enhancement of intercomponent interactions in polyrotaxane and its pronounced effects on glass state properties.

Strong interactions between the host cyclodextrin and the threading guest polymer were introduced by selective modifications to the polymer of a polybutadine-based polyrotaxane. The changes in the intercomponent interactions influenced the mobility of the threading polymer that was confined in the glassy host framework, resulting in different mechanical properties.

Investigation of Dynamic, Mechanical, and Thermal Properties of Calotropis procera Particle‐Reinforced PLA Biocomposites

The thermal behavior of the biodegradable Calotropis procera (CP) particle‐reinforced polylactic acid (PLA) biocomposites was investigated. The injection molding process was used to make the composites, and the CP particle weight percentage was varied during the process (0%, 5%, 10%, 15%, and 20%). The melt flow index, heat deflection temperature, Vicat softening point, and the thermal properties of the composites were determined using dynamic mechanical testing. The results were analyzed and compared to the thermal properties of the neat PLA. The results revealed the increase in thermal stability of the PLA due to the addition of CP particles. The CP particles aided in the restriction of polymer mobility, which elevated the glass transition temperature of the composite. Incorporating CP particles in the PLA can increase the PLA/CP composite utilization in heat dissipation applications.

Dielectric Response Spectroscopy as Means to Investigate Interfacial Effects for Ultra-Thin Film Polymer-Based High NA EUV Lithography.

Extreme ultra-violet lithography (EUVL) is the leading-edge technology to produce advanced nanoelectronics. The further development of EUVL is heavily based on implementing the so-called high numerical aperture (NA) EUVL, which will enable even smaller pitches up to 8 nm half pitch (HP). In anticipation of this high NA technology, it is crucial to assess the readiness of the current resist materials for the high NA regime to comply with the demanding requirements of resolution, line-edge roughness, and sensitivity (RLS). The achievable tighter pitches require lower film thicknesses for both resist and underlying transfer layers. A concern that is tied to the thinning down is the potential change in resist properties and behavior due to the interaction with the underlayer. To increase the fundamental understanding of ultra-thin films for high NA EUVL, a method to investigate the interplay of reduced film thickness and different patterning-relevant underlayers is developed by looking at the glass transition temperature (Tg) of polymer-based resists. To minimize the ambiguity of the results due to resist additives (i.e., photoacid generator (PAG) and quencher), it was opted to move forward with polymer-only samples, the main component of the resist, at this stage of the investigation. By using dielectric response spectroscopy, the results obtained show that changing the protection group of the polymer, as well as altering the polymer film thickness impacts the dynamics of the polymer mobility, which can be assessed through the Tg of the system. Unexpectedly, changing the underlayer did not result in a clear change in the polymer mobility at the tested film thicknesses.

Influence of Alkyl Sidechain Length on Lithium-Ion Conductivity for Polyether Electrolytes

Lithium-ion batteries (LIBs) have been used in various energy devices, from small electronic devices to electric vehicles. However, LIBs have safety concerns, mainly due to the flammable organic solvents used for electrolytes. The development of electrolytes based on flame-retardant materials, including polymer, is one of the potential solutions. Although various polymer electrolytes (PEs) were successfully synthesized, the low lithium-ion (Li+) conductivity hinders its practical application.It is considered that the Li+ conductivity in PEs is determined by two factors; (i) segmental mobility of polymer chains and (ii) Li+ concentration, which is connected to the Li+ mobility and the number of ion carriers, respectively. Most of the PEs failed to meet those requirements, which hinders the improvement of Li+ conductivity. The problem is that the polar groups in the polymer chains tend to actively coordinate with Li+ under high Li+ concentration, which inhibits the mobility of the polymer chains. Also, the Li+-polar group interaction anchors Li+ on the polymer chain, which may also suppress the Li+ conductivity.Therefore, to establish a polymer design strategy, it is necessary to elucidate the factors which affect the interaction between Li+-polar groups and Li+ transportation. Previous studies have focused mainly on the polar properties (e.g., donor number and dielectric constant) of the polymers to understand the interaction between Li+ and polar groups. In contrast, the effect of non-polar groups was often overlooked. Non-polar groups can affect the mobility and polarity of polymers as well as the Li+-polar group interaction, due to its plasticization effect, polarity, and steric hindrance.Here, in this study, we selected polyethers having alkyl sidechains with different lengths (–(CH2)m–H, m = 1, 2, 4, 6, 8, and 12), to clarify the contribution of the non-polar groups on the Li+ conductivity in PEs. Electrochemical impedance spectroscopy revealed that the ionic conductivity (σ) at low temperatures was dominated by glass transition temperature, which correlates with the segmental mobility of polymer chains. Furthermore, σ increase with the increase in the length of the alkyl group due to the internal plasticization effect of the long alkyl groups. On the contrary, the σ at high temperature was mostly determined by salt dissociation capacities of polymers, which tended to increase as the alkyl group became shorter. The Li+ transportation number (t Li+) gradually improved with the extension of the alkyl groups; 0.16 (m = 1) < 0.26 (m = 2) < 0.28 (m = 4) < 0.32 (m = 6) < 0.36 (m = 8) < 0.43 (m = 12). We believe that the gradual changes of t Li+ are due to the low polarity of long alkyl sidechain, giving low dielectric constant and/or low viscous properties. The activation energy of Li+ transportation at the electrode-electrolyte interface (E int) showed a large gap between m =1 and others; E int = 68–82 kJ mol–1 (m = 2, 4, 6, 8, and 12) < E int = 116 kJ mol–1 (m = 1). The coordination number of ether groups (n ether) estimated from ν(COC) intensity of infrared spectra showed a similar trend; n ether = 3.6–4.4 (m ≥ 2) < n ether = 6.2 (m = 1). The interaction between the ether group and Li+ can be affected by the length of alkyl sidechain, and it effectively suppressed for alkyl sidechain of m > 1, probably because of the steric hindrance. Considering the similar trend in both E int and n ether, the amount of ether-Li+ interaction can be a descriptor to determine Li+ transportation at the electrode-electrolyte interface.In summary, the Li+ conductivity, including ionic conductivity (σ) and Li+ transportation number (t Li+) strongly influenced by the properties of the alkyl group, such as the internal plasticization effect and low polarity. The Li+-ether group interaction, which was governed by the steric hindrance of alkyl sidechain, can be a dominant factor for the activation energy of Li+ transportation at the electrode-electrolyte interface (E int). Designing alkyl sidechains is thus a valid strategy to optimize segmental mobility and polarity of the bulk as well as the local interaction at the interface, which leads to the improved Li+ conductivity at bulk and electrode-electrolyte interfaces.

Light-Gated Modulation of Electronic Mobility of a Dihydropyrene-Based Photochromic Coordination Polymer.

Photo-induced modulation of electronic conductance has been achieved by employing an AgI-based two-dimensional coordination polymer (CP) having pyridine-functionalized photochromic dimethyldihydropyrene-cyclophanediene (DHP-CPD) π-switch. Both the coordination polymer and the organic photochromic core were characterized by single-crystal X-ray diffraction studies. The coordination polymer displayed an excellent conductance in the ON state of the switch in the closed form of DHP. Upon exposure to visible light, the π-switch in the CPD form loses its planarity, turning the switch OFF, which is reflected in the drastic reduction of the conductance. Exposure to UV light turns the switch back ON wherein the high electronic conductance of the polymer can be restored.

Comparative Study of Green and Synthetic Polymers for Enhanced Oil Recovery.

Several publications by authors in the field of petrochemical engineering have examined the use of chemically enhanced oil recovery (CEOR) technology, with a specific interest in polymer flooding. Most observations thus far in this field have been based on the application of certain chemicals and/or physical properties within this technique regarding the production of 50–60% trapped (residual) oil in a reservoir. However, there is limited information within the literature about the combined effects of this process on whole properties (physical and chemical). Accordingly, in this work, we present a clear distinction between the use of xanthan gum (XG) and hydrolyzed polyacrylamide (HPAM) as a polymer flood, serving as a background for future studies. XG and HPAM have been chosen for this study because of their wide acceptance in relation to EOR processes. To this degree, the combined effect of a polymer’s rheological properties, retention, inaccessible pore volume (PV), permeability reduction, polymer mobility, the effects of salinity and temperature, and costs are all investigated in this study. Further, the generic screening and design criteria for a polymer flood with emphasis on XG and HPAM are explained. Finally, a comparative study on the conditions for laboratory (experimental), pilot-scale, and field-scale application is presented.

Position-Dependent Diffusion Dynamics of Entangled Polymer Melts Nanoconfined by Parallel Immiscible Polymer Films.

The morphological structure and dynamics of confined polymers adjacent to the polymer-polymer interface have a profound effect on determining the overall physical properties of polymer blends. We measured the diffusion dynamics of poly(methyl methacrylate) (PMMA) melts confined between polystyrene (PS) layers using neutron reflectivity. Combinations of various thicknesses of PMMA and deuterated PMMA (dPMMA) allowed us to experimentally reveal the nonmonotonic behavior of polymer mobility near the PS-PMMA interface. From the neutron reflectivity results, we found that the polymers adjacent to the immiscible polymer-polymer interface showed enhanced diffusion dynamics because of the repulsive interaction between PS and PMMA, whereas the polymer at local regions farther from the interface exhibited reduced dynamics. This is probably due to the nonspherical conformation of PMMA and spatial confinement near the PS-PMMA interface.

Model for athermal enhancement of molecular mobility in solid polymers by light.

Molecular motion in polymers is frozen below the glass transition temperature T_{g} and changes of viscoelastic functions are most spectacular near T_{g}. Exceptional enhancement of molecular mobility and a decrease of polymer viscosity, by several orders of magnitude, down to the viscous flow regime, are observed way below T_{g} by light absorption. Relaxation processes, which take decades to centuries in some high-T_{g} polymers, are reduced to minute timescales by sub-T_{g} light absorption. Here we develop a model for this intriguing albeit spectacular action of light on glass forming materials and we propose experiments to relate light absorption to materials properties. The model provides a solution to a long-lasting problem of how molecular mobility is enhanced in solid polymers by photoisomerization and provides a tool for a better understanding of the relationship between light absorption and material properties and developing photosensitive polymers for light to mechanical energy transduction.

Azaisoindigo-Based Polymers with a Linear Hybrid Siloxane-Based Side Chain for High-Performance Semiconductors Processable with Nonchlorinated Solvents.

Developing nonchlorinated solvent-processed polymeric semiconductors to avoid environmental concerns and health hazards caused by chlorinated solvents is especially urgent. Here, a molecular design strategy, composed of backbone fluorination and side chain optimization, is used for preparing high-solubility and high-performance azaisoindigo-based polymers. The effects of different backbones and side chains on the solubility, film crystallinity, molecular stacking, and charge transport properties are mainly investigated. A long linear hybrid siloxane-based chain (C6-Si7) is chosen to improve the solubility, while the incorporation of fluorine (F) is used to enhance the film crystallinity and charge mobility. By optimizing the backbone and side chain, both solubility and charge mobility of the azaisoindigo-based polymer are significantly improved. As a result, PAIIDBFT-Si films processed with toluene, tetrahydrofuran, ether, and alkanes, achieved charge mobilities of 4.14, 3.78, 2.14, and 2.34 cm2 V-1 s-1, respectively. The current study provides an effective strategy for the design and synthesis of high-performance polymeric semiconductors processed with nonchlorinated solvents.

Multiple conformation locks gift polymer donor high efficiency

Abstract The mechanism that how noncovalent conformation locks (NCLs) to improve the photovoltaic performance of polymer donors was investigated. By developing a model system with three structure-related copolymers W1, W2 and W3, a clear correlation was found between the locking strength in polymer backbone and the photovoltaic performance. W1 with the strongest S⋅⋅⋅O and F⋅⋅⋅H double-side locking gave the highest power conversion efficiency (PCE) of 16.23%, while W2 with a S⋅⋅⋅O single-side locking and W3 with a weakened S⋅⋅⋅O locking caused by Cl–H steric repulsion gave lower PCEs of 11.73% and 0.92%, respectively. With the aid of single crystal X-ray diffraction analysis, density functional theory calculation, grazing-incidence wide-angle X-ray scattering analysis, atomic force microscope study and device characterization, the functions of NCLs in improving the planarity, packing, crystallinity and hole mobility of polymers, as well as the morphology of blend films, were illuminated in detail.

Design Rules to Maximize Charge-Carrier Mobility along Conjugated Polymer Chains.

The emergence of polymeric materials displaying high charge-carrier mobility values despite poor interchain structural order has spawned a renewal of interest in the identification of structure-property relationships pertaining to the transport of charges along conjugated polymer chains and the subsequent design of optimized architectures. Here, we present the results of intrachain charge transport simulations obtained by applying a robust surface hopping algorithm to a phenomenological Hamiltonian parametrized against first-principles simulations. Conformational effects are shown to provide a clear signature in the temperature-dependent charge-carrier mobility that complies with recent experimental observations. We further contrast against molecular crystals the evolution with electronic bandwidth and electron-phonon interactions of the room-temperature mobility in polymers, showing that intrachain charge-carrier mobility values in excess of 100 cm2/(V s) can be achieved through a proper chemical engineering of the backbones.

An experimental study of recovery in embossing of polycarbonate below the glass transition temperature

The hot embossing process is a cost-effective replication technology for the fabrication of polymeric micro/nano-structures. Nevertheless, there is a need to reduce the embossing temperature as industrial applications of the hot embossing process are limited by the high temperature required. For amorphous thermoplastic polymers, the hot embossing process can be conducted below the polymer’s glass transition temperature (Tg), which is promising for many industrial applications. However, it is generally difficult to achieve a high replication fidelity in such a below-Tg embossing process. The large resistance to plastic flow and the significant deformation recovery of the glassy polymer (the amorphous thermoplastic polymer in its glassy state) are two main causes. The problem of plastic flow may be solved by designing and developing a hot embossing system with large force capability, but the recovery problem may not and needs further study. In this research, the recovery of a polycarbonate (PC) glass in the below-Tg embossing process was quantified and investigated systematically. The effects of embossing depth, holding time, temperature, and loading rate on the recovery were discussed and analyzed. The research results reveal that it is the recovery (usually more than 20%) that severely limits the replication fidelity of the below-Tg embossing process. The recovery is strain-dependent due to the strain-dependent chain tension of the PC glass. As the chain tension generated in the strain-hardening region cannot be effectively reduced by increasing the embossing force, holding time, and temperature, the recovery problem poses a great challenge to be overcome. Considering the strain-rate dependence of the segmental mobility of glassy polymers, a strategy of increasing the loading rate to reduce the recovery was proposed and verified. Hence, this research advances our understanding of the below-Tg embossing process and provides new insights into how to improve the hot embossing process.

Comparative removal of Suwannee River natural organic matter and perfluoroalkyl acids by anion exchange: Impact of polymer composition and mobile counterion

Anion exchange resin (AER) adsorption is an established technology for water treatment and groundwater remediation. Two contaminants amenable to AER treatment are natural organic matter (NOM) and per- and polyfluoroalkyl substances (PFAS), specifically anionic perfluoroalkyl acids (PFAAs) such as perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). NOM is ubiquitous in natural waters and is often targeted for removal. PFAS occurrence in water resources is a human health concern. Accordingly, the goal of this research was to provide new insights on the use of AER for water treatment considering separate and combined removal of NOM and PFAAs. Batch experiments were conducted comparing polystyrene and polyacrylic AER in both chloride- and sulfate-forms using natural groundwater spiked with Suwannee River natural organic matter (SRNOM) and/or six PFAAs. The polymer composition of the AER had a significant impact on contaminant removal with polystyrene resin more effective for PFAA removal and polyacrylic resin more effective for SRNOM removal. Both resins had type I quaternary ammonium functional groups; however, the polyacrylic resin had trimethyl ammonium whereas the polystyrene resin had triethyl ammonium. Therefore, the influence of polymer composition could not be isolated conclusively from functional group chemistry. Polystyrene AER showed greater removal of PFAAs with sulfonate than carboxylate head group and 8-carbon than 4-carbon chain length. Removal of SRNOM and PFAAs by both resin polymer compositions were greater when sulfate was the mobile counterion ion than chloride. The results of this research have important implications for using AER for water treatment and remediation. Foremost, polymer composition and mobile counterion form of the resin can be selected to target specific contaminants and maximize contaminant removal. When contaminants have unique interactions with AER such as SRNOM and polyacrylic resin and PFAAs and polystyrene resin, the presence of one contaminant does not impact removal of the other contaminant.

Heterogeneous Solvent Dielectric Relaxation in Polymer Solutions of Water and Alcohols

The dynamics of polymer solutions are heterogeneous. The different molecule sizes and structures cause different mobilities of polymers and solvents. Recently, regarding the heterogeneity of water, two dielectric relaxation processes of water were argued in several supercooled polymer–water mixtures. To investigate whether this is unique to water, we performed broadband dielectric spectroscopy measurements of poly(vinylpyrrolidone)–water (PVP–water), PVP–propylene glycol, PVP–ethylene glycol, and PVP–propanol mixtures with 65 wt% PVP in a temperature range of 123–298 K. For the PVP–water mixture, α-relaxation of PVP and two distinct relaxation processes appeared simultaneously: one was the primary relaxation process of water (fast water process) and the other was the relatively small relaxation process (slow process), at a frequency between that of the α-process of PVP and the fast water process. The strength ratio of the large fast water and small slow processes remained nearly constant in all the temperatures measured. For the PVP–alcohol mixtures, in addition to the α-process of PVP, two or three relaxation processes of alcohol appeared. The primary relaxation process of alcohol above 240 K changed to the small fast secondary process. The small slow processes, which can be recognized below 240 K (the glass transition temperature of the α-process of PVP, Tg,PVP) appears at intermediate frequency between that of the PVP α-process and the primary process of alcohol. The small slow process changed to the primary larger process. The properties of the multiple relaxation processes of solvents below Tg,PVP in PVP–alcohol mixtures are completely different from those in PVP–water mixture.

Preparation of hydrophilic polymeric materials with movable cross-linkers and their mechanical property

Hydrophilic polymeric materials with movable cross-linkers were obtained by the bulk copolymerization of a hydrophilic cyclodextrin monomer (γCDAAmMe) and liquid acrylamide monomers. A 2D 1H-NOESY NMR study revealed that the main chains penetrated the CD ring units, which acted as movable cross-linking points. Copolymerization of γCDAAmMe with N,N-dimethyl acrylamide (DMAA) as a small main chain monomer results in hydrophilic movable cross-linked materials (pDMAA-γCDAAmMe (x)). On the other hand, using 4-acryloylmorpholine (ACMO) or N,N-dimethylaminopropyl acrylamide (DMAPAA) as a bulky main chain monomer disfavours the formation of movable cross-links due to steric hindrance between γCDAAmMe and the side chains. In the water content range of approximately 40–80 wt%, the Young's moduli of pDMAA-γCDAAmMe (1)s are similar to those of pDMAA-MBAAm (1). However, the fracture energy of movable cross-linked materials is higher than that of than materials covalently cross-linked with N,N′–methylenebis(acrylamide) (MBAAm). An addition of water enhanced the mobility of the main chain polymers, allowing the movable cross-linking points.

Polarization Dependence of Charge Conduction in Conjugated Polymer Films Investigated with Time-Resolved Terahertz Spectroscopy.

Room temperature Time-Domain Terahertz (TDS) and Time-Resolved Terahertz (TRTS) spectroscopic methods are employed to measure carrier mobility and charge generation efficiency in thin-film semiconductor polymers. Interrogation of the dependence on excitation and probe polarizations yields insight into the underlying material properties that guide charge transport. We apply THz polarization anisotropy probes to analyze charge conduction in preparations of the copolymer PCDTPT, consisting of alternating cyclopenta-dithiophene (donor) and thiadiazolo-pyridine (acceptor) units. Comparisons are made among films of different ordering and morphology, including aligned films prepared by blade coating, a near isotropic dropcast film, and isotropic liquid dispersion. They are further contrasted with their population dynamics ascertained through transient absorption and the traditional photoconductive polymer poly-3-hexylthiophene (P3HT). Polarization anisotropy is observed as preferential charge conduction along the backbone propagation direction of PCDTPT, with various factors disproportionately influencing directional mobility and charge pair yield. PCDTPT exhibits unexpectedly strong conductivity when isolated in toluene dispersion. Quantitative comparisons yield a better understanding of polaron/free-charge relaxation and transfer mechanisms and illustrate dynamics among photoexcited charge carriers and their motion and diffusion through different material morphologies.

The Effect of Thermomechanical Pretreatment on the Structure and Properties of Lignin-Rich Plant Biomass.

The cooperative thermomechanical properties of plant-derived polymers have been studied insufficiently, although this feedstock has a very high potential. In the present paper, we analyzed the changes in the structure and physicochemical properties of lignin-rich biomass induced by thermomechanical pretreatment. Low-temperature treatment allows one to retain the original supramolecular structure of the cell walls, while an appreciably high disintegration degree is reached. This increases the reactivity of the material in the subsequent heterogeneous reactions. Mechanical pretreatment at medium temperatures (10 °C), when almost all cell wall polymers except for low-molecular-weight lignin are in the glassy state, enhances the mobility of cell wall polymers and causes sufficient cellulose disordering, while the specific surface area is not significantly increased. High-temperature pretreatment of reed biomass is accompanied by pore formation and lignin release from the cell wall structure, which opens up new prospects for using this biomass as a matrix to produce core–shell-structured sorbents of heavy metals. The energy consumed by mechanochemical equipment for the activation of reed biomass was determined.

Synthesis of ionic polymers by free radical polymerization using aprotic trimethylsilylmethyl‐substituted monomers

AbstractAprotic ionic polymers containing trimethylsilylmethyl‐substituted imidazolium structures are synthesized using free radical polymerization of monomers comprising a vinyl group either at the cation or at the anion. Bulk polymerization is used for the room temperature ionic liquid monomer 1‐trimethylsilylmethyl‐3‐vinylimidazolium bis(trifluoromethylsulfonyl)imide. In contrast to this, solution polymerization is applied for 1‐trimethylsilylmethyl‐3‐methylimidazolium p‐styrene sulfonate because this monomer undergoes self‐polymerization during melting at a higher temperature than selected for bulk polymerization. Glass transition temperature (T g) of the ionic polymers and intrinsic viscosity measurements indicate differences between these polymers, which are composed either of a polycation with a trimethylsilylmethyl substituent at each vinylimidazolium segment of the polymer chain and mobile bis(trifluoromethylsulfonyl)imide (NTf2−) anions or a polyanion containing p‐styrene sulfonate segments and mobile 1‐trimethylsilylmethyl‐3‐methylimidazolium cations. The new aprotic ionic polymers containing trimethylsilylmethyl substituents may be interesting for application in adhesive, interlayer and membrane manufacturing.

Role of free volume in molecular mobility and performance of glassy polymers for corrosion-protective coatings

ABSTRACTGlassy polymer coatings on metal substrates rely on their mechanical, physical, and transport properties for corrosion protection. These properties are influenced by free volume between polymer chains that plays a critical role in coating performance. Free volume permits local segmental mobility that affects mechanical properties, such as yield and adhesion, and also permits diffusion of small molecules (water, ions, and oxygen) through the coating to the substrate. Fractional free volume is calculated from the specific volume and Bondi group contribution theory for the occupied volume. Free volume distribution (free volume element size and number) is measured by positron annihilation lifetime spectroscopy (PALS) using the ortho-positronium (oPs) probe, which detects free volume elements in glassy polymer coatings. The oPs probe is sensitive to phenomena that affect both the mechanical and barrier properties of coatings including physical ageing, water sorption, and plasticisation, making PALS a suitable allied testing method for corrosion-protective coatings.

Study of Radiation-Chemical Structuring of Compositions Based on Epoxy Oligomers

The processes of radiation-chemical structuring of modified epoxy acrylic compositions were studied depending on the nature of epoxy oligomers and modifiers. ED-20 and ED-22 grades epoxy oligomers were chosen as epoxidian oligomers; 3,4-epoxyhexahydrobenzal-3,4-epoxy-1,1-bis(hydroxymethyl)cyclohexane (UP-612 grade), 3,4-epoxycyclohexylmethyl-3,3-epoxycyclohexanecarboxylate (UP-632 grade) were chosen as cycloaliphatic oligomers; diethylene glycol diglycidyl ether (DEG) was chosen as aliphatic oligomer. To modify the epoxy oligomers, unsaturated acrylic monomers, such as acrylic acid and methyl acrylic acid ester; aromatic and aliphatic oligoester acrylates, such as α,ω-methacryl(bis-diethylene glycol)phthalate (MDP-1 grade), α,ω-methacryldi(diethyleneglycolphthalate) (MDP-2 grade), α,ω-methacryl(bis-triethyleneglycol)phthalate (MGP-9 grade) and atri-(oxyethylene)-α,ω-dimethacrylate (TGM-3 grade); condensation product of linseed oil dimerized fatty acids and polyethylenepolyamine, such as oligoamide L-20 grade; condensation product of ricinoleic acid, castor oil and maleic anhydride, such as unsaturated polyester PE-220, were used. The thermophysical and relaxation properties of cross-linked polymers, obtained under exposure to γ-radiation of Co60 and electrons accelerated by the absorbed radiation dose of 50–150 kGy at the beam current of 2‑4 mA and electron energy of 240-300 keV, were studied. The distance from the exhaust window of the accelerator to the irradiated surface of the samples was 63-80 mm. The thermophysical properties of the cured polymers were evaluated using thermomechanical studies on a thermomechanograph with the temperature rise of 1о/min and the pressure of 0.54 MPa in the temperature range of 293‑673 K, as well as the differential thermal and thermogravimetric analyzes on a system derivatograph by L. Paulik, R. Paulik, L. Erdei in the temperature range of 293–973 K with the rise rate of 7о/min. The relaxation properties and molecular mobility of the cross-linked polymers were studied by the dielectric method. The dielectric loss tangent was determined in the temperature range of 143‑393K at the frequency of 1 kHz using a digital automatic bridge of alternating current R-589. The test sample temperature was measured using a potentiometer on a copper-constantan thermocouple, which was placed in the measuring cell along with the test sample. The samples were cooled by placing the cell in a vessel with liquid nitrogen. As a result of the studies, the influence of the chemical nature of epoxy oligomers and unsaturated modifiers on the processes of structure formation and molecular mobility of polymers, obtained under conditions of radiation-chemical curing, was established. It was determined, that when modifying epoxy oligomers with acrylic acid, methyl acrylic acid ester, oligoester acrylates of MGP-9 ((α,ω-methacryl(bis-triethyleneglycol)phthalate)) or TGM-3 ((tri-(oxyethyleneglicol)-α,ω-dimethacrylate)) grades, the structuring of compositions, based on the DEG-1 aliphatic epoxy oligomer and UP-612 cycloaliphatic oligomer, was more efficient than the compositions based on unsaturated ETO oligomers grade such as 2-ethylhexylepoxytallate oligomer and epoxidian oligomers of ED-20 and ED-22 grades. It was established, that the modifier oligoamide of L-20 grade, containing primary and secondary amino groups, increased the radiation sensitivity of the compositions, based on epoxidian and cycloaliphatic oligomers, and reduced the inhibitory effect of atmospheric oxygen. The optimal composition and the main technological parameters were determined, what allowed to obtain materials with high physical and mechanical properties and adhesive strength to various metals. The application of the developed materials under industrial conditions will make it possible to organize a continuous high-speed radiation-chemical process for producing polymer coatings on metals, providing improved working conditions, lower energy consumption, as compared to the thermochemical process of the coatings production, and will increase the corrosion resistance of metals.