This work is devoted to the influence of phosphazene modifiers with different substituents on the curing process, thermal properties and flammability of benzoxazine resin. Novel catalysts with ...m-toluidine substituents were introduced. The catalytic activity of studied phosphazene compounds decreased in the row: hexachlorocyclotriphosphazene (HCP) > tetra m-toluidine substituted phosphazene PN-mt (4) > hexa m-toluidine substituted phosphazene PN-mt (6) > hexaphenoxycyclotriphosphazene (HPP), where HPP is totally inactive. Two types of catalysis: basic and acid were proposed. A brief study of resulting properties of polybenzoxazines was presented. The addition of any studied modifier caused the decrease of glass transition temperature and thermal stability of polymers. The morphology of cured compositions was characterized by matrix-dispersion phase structure. All phosphazene containing polybenzoxazines demonstrated the improved flame resistance.
An epoxy resin modified with polysulfone (PSU) and active diluent furfuryl glycidyl ether (FGE) was studied. Triethanolaminotitanate (TEAT) and iso-methyltetrahydrophthalic anhydride (iso-MTHPA) were ...used as curing agents. It is shown that during the curing of initially homogeneous mixtures, heterogeneous structures are formed. The type of these structures depends on the concentration of active diluent and the type of hardener. The physico-mechanical properties of the hybrid matrices are determined by the structure formed. The maximum resistance to a growing crack is provided by structures with a thermoplastic-enriched matrix-interpenetrating structures. The main mechanism for increasing the energy of crack propagation is associated with the implementation of microplasticity of extended phases enriched in polysulfone and their involvement in the fracture process.
A comparative study of anticorrosive inhibited polymer films on the tungsten surface formed from an aqueous solution of inhibited formulations (INFOR) containing organosilane and corrosion inhibitors ...was carried out by means of the prolonged exposure of a tungsten product in a modifying solution and by the method of cataphoretic deposition (CPD). Depending on the method of forming films on tungsten, the molecular organization of the near-surface layers was studied (ATR-FTIR), and the subprimary structure of the films was explored (TEM). The optimal modes of cataphoresis deposition (CPD duration and current density applied to the sample) for the formation of a protective inhibited polymer film on the tungsten surface were established by means of SEM. The energy and thermochemical characteristics (sessile drop and DSC methods), as well as operational (adhesive behavior) and protective filming ability (EIS and corrosion behavior), according to the method of formation of inhibited polymer film, were determined. Based on the combined characteristics of the films obtained by the two methods and the deposition modes, the CPD method showed better performance than the electroless dipping method.
Currently, there is no quantitative approach for the phase structure of cured thermoplastic systems modified with thermoplastic predicting. To solve this problem, we carried out the first stage of ...the study on a model polycaprolactone-epoxy oligomer (PCL-DGEBA) system. Using differential scanning calorimetry (DSC), refractometry and optical interferometry, a phase diagram for PCL-DGEBA mixtures was constructed, and the Flory-Huggins interaction parameters of PCL-DGEBA mixtures were calculated. The structure of PCL-DGEBA mixtures with different PCL content was analyzed by optical microscopy. The change in the structure formation mechanism with increasing PCL concentration was shown. The diffusion coefficients are calculated by the Motano-Boltzmann method. The values of the apparent activation energy of the viscous flow PCL and of self-diffusion of DGEBA are determined. The obtained data will be used for the in situ curing kinetics and phase equilibria in the diffusion zone investigations in order to develop a quantitative method for predicting the phase structure of cured systems.
The possibility of using thermoplastic polymers in photopolymer compositions for SLA and DLP is discussed in this article. The diffusion and mutual solubility of uncured systems based on tert-butyl ...acrylate (tBA) and ethylene-vinyl acetate copolymers (EVA) or low-density polyethylene (LDPE) were studied. The solubility and diffusion of tBA with EVA containing 7, 20, and 40 wt.% vinyl acetate (VA) and with LDPE in the temperature range 20-75 °C were studied by optical micro-interferometry method. Phase diagrams of LDPE-tBA, EVA-7-tBA, and EVA-20-tBA systems were obtained. It is shown that the compositions are characterized by the phase-state diagrams of amorphous separation with the upper critical solution temperature (UCST). The concentration dependences of the interdiffusion coefficients as well as dependences of the self-diffusion coefficients on VA content and on temperature were plotted. The activation energy of self-diffusion of EVA and LDPE was calculated. It was shown that the most promising tBA modifier is EVA-40, which is completely soluble at all studied temperature ranges. The obtained data on the mixing of the initial components is valuable for further studies of the processes of structure formation during photocuring of compositions, regulation of the phase structure and, as a consequence, the performance characteristics of the 3D printable materials.
Low-temperature properties of high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and their blends were studied. The analyzed low-temperature ...mechanical properties involve the deformation resistance and impact strength characteristics. HDPE is a bimodal ethylene/1-hexene copolymer; LDPE is a branched ethylene homopolymer containing short-chain branches of different length; LLDPE is a binary ethylene/1-butene copolymer and an ethylene/1-butene/1-hexene terpolymer. The samples of copolymers and their blends were studied by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), 13C NMR spectroscopy, and dynamic mechanical analysis (DMA) using testing machines equipped with a cryochamber. It is proposed that such parameters as “relative elongation at break at −45 °C” and “Izod impact strength at −40 °C” are used instead of the ductile-to-brittle transition temperature to assess frost resistance properties because these parameters are more sensitive to deformation and impact at subzero temperatures for HDPE. LLDPE is shown to exhibit higher relative elongation at break at −45 °C and Izod impact strength at −20 ÷ 60 °C compared to those of LDPE. LLDPE terpolymer added to HDPE (at a content ≥ 25 wt.%) simultaneously increases flow properties and improves tensile properties of the blend at −45 °C. Changes in low-temperature properties as a function of molecular weight, MWD, crystallinity, and branch content were determined for HDPE, LLDPE, and their blends. The DMA data prove the resulting dependences. The reported findings allow one to understand and predict mechanical properties in the HDPE–LLDPE systems at subzero temperatures.
To reveal the effect of chlorine substituents in the ring of aromatic amine on the synthesis process of benzoxazine monomer and on its polymerization ability, as well as to develop a fire-resistant ...material, a previously unreported benzoxazine monomer based on 3,3'-dichloro-4,4'-diaminodiphenylmethane was obtained in toluene and mixture toluene/isopropanol. The resulting benzoxazine monomers were thermally cured for 2 h at 180 °C, 4 h at 200 °C, 2 h at 220 °C. A comparison between the rheological, thermal and fire-resistant properties of the benzoxazines based on 3,3'-dichloro-4,4'-diaminodiphenylmethane and, for reference, 4,4'-diaminodimethylmethane was made. The effect of the reaction medium on the structure of the oligomeric fraction and the overall yield of the main product were studied and the toluene/ethanol mixture was found to provide the best conditions; however, in contrast to most known diamine-based benzoxazines, synthesis in the pure toluene is also possible. The synthesized monomers can be used as thermo- and fire-resistant binders for polymer composite materials, as well as hardeners for epoxy resins. Chlorine-containing polybenzoxazines require more severe conditions for polymerization but have better fire resistance.
The development of universal finishing compositions for fibers of various natures is an urgent task for polymer composite materials science. The developed finishes can be used for the fiber ...reinforcement of polymer matrices with a wide range of surface free energy characteristics. Epoxy systems modified with diaminesilane in a wide concentration range were examined by optical interferometry, FTIR spectroscopy, DSC and the sessile drop technique. It was shown that the partial curing of epoxy resin by diaminesilane at room temperature under an inert atmosphere, followed by contact with air, leads to a significant increase of the surface free energy of the system. Varying the concentration of diaminesilane allows us to effectively regulate the surface free energy of the composition. This makes it possible to use fibers finished with epoxyaminosilane compositions in composite materials based on a various thermosetting and thermoplastic binders with a surface tension of up to 75 mJ/m
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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.
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The galvanic replacement (GR) reaction between Fe and Cu in aqueous electroplating solutions typically leads to unsatisfactory adhesion of a Cu coating to the substrates. Here, we ...study the GR process in one of the most promising deep eutectic solvents for electrodeposition – ethaline. We find out that GR deposition of Cu does occur on Fe in ethaline, but it proceeds with a much lower rate as compared to aqueous copper sulphate electrolyte solutions, and forming Cu deposits display rather strong adhesion to Fe substrates. The rate of Cu deposition via the GR reaction is estimated by means of inductively coupled plasma mass spectrometry, whereas the morphology of the sample surface is analyzed using atomic force and scanning electron microscopy. We reveal significant difference in the rate of Cu deposit growth, the character of Fe substrate corrosion, and Cu deposit morphology in the course of GR process in ethaline solutions containing CuCl and CuCl2. In the Cu(I) solution, the GR is characterized by the appearance of pronounced pits on the Fe surface and the nucleation and growth of separate copper crystallites that reach a few micrometers in diameter after 24 h of the reaction. In the case of the Cu(II) solution, relatively uniform copper coatings are formed even after 30 min of the reaction, which leads to deceleration of the GR due to the blocking of the Fe surface undergoing dissolution. Overall, due to the rather low GR reaction rate its effect on the electrochemical deposition of Cu on Fe is negligible. The obtained results allow us to conclude that ethaline-based solutions are promising media for direct copper electrodeposition technology on electronegative metals and alloys.
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