Abstract:

This article is a review of the Mn+1AXn phases (“MAX phases”, where n = 1, 2 or 3), their MXene derivatives and the reinforcement of polymers with these materials. The MAX phases are a class of hexagonal-structure ternary carbides and nitrides (“X”) of the transition metal (“M”) and the A-group element. The unique combination of chemical, physical, electrical and mechanical properties that combine the characteristics of metals and ceramics is of interest to researchers in the MAX phases. For example, MAX phases are typically resistant to oxidation and corrosion, elastic, but at the same time, they have high thermal and electrical conductivity and are machinable. These properties stem from an inherently nanolaminated crystal structure, with Mn+1Xn slabs intercalated with pure A-element layers. To date, more than 150 MAX phases have been synthesized. In 2011, a new family of 2D materials, called MXene, was synthesized, emphasizing the connection with the MAX phases and their dimension. Several approaches to the synthesis of MXene have been developed, including selective etching in a mixture of fluoride salts and various acids, non-aqueous etching solutions, halogens and molten salts, which allows the synthesis of new materials with better control over the chemical composition of their surface. The use of MAX phases and MXene for polymer reinforcement increases their thermal, electrical and mechanical properties. Thus, the addition of fillers increases the glass transition temperature by an average of 10%, bending strength by 30%, compressive strength by 70%, tensile strength up to 200%, microhardness by 40%, reduces friction coefficient and makes the composite material self-lubricating, and 1 % wt. MAX phases increases thermal conductivity by 23%, Young’s modulus increases. The use of composites as components of sensors, electromagnetic protection, wearable technologies, in current sources, in aerospace and military applications, etc. are proposed.

Key words: MAX phase, MXene, nanolaminate, oxygen-free ceramics, polymer, composite material, nanocomposite.

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Abstract:

This article is devoted to the study of the influence of the chemical nature of the components of polyurethane matrices (PU) on their optical and viscoelastic properties in order to obtain polymer materials that combine several different functional properties: high transparency, effective UV protection and high damping ability. PU matrices with different chemical structures of diisocyanate (aliphatic (hexamethylene diisocyanate) or aromatic (toluylene diisocyanate)) and oligodiol (oligoether (oligooxypropylene glycol) or oligoester (oligodiethylene glycol adipate)) blocks were synthesized. PU matrices with different molecular weights of ester (800 and 1500) were synthesized too. It was established that all PU matrices have a fairly high (~90 %) transmission coefficient in the range of visible wavelengths and UV blocking. However, the range of UV absorption significantly depends on the PU components. Matrices based on aliphatic diisocyanate absorb UV up to 250–280 nm. The UV absorption of PU matrices based on aromatic diisocyanate, regardless of the nature of their oligoester component and its molecular weight, undergoes a shift to the long-wavelength region – up to 300–400 nm, which is due to the presence of aromatic rings. For PUs with an aromatic component, the highest absorption in the UV region is observed for PUs based on oligoesters, which is explained by the greater absorption ability of ester groups relative to ether ones. It was found that PU matrix based on oligoester has better elastic properties, but the PU matrix based on oligoether is characterized by a wider temperature range of effective damping. The replacement of aliphatic diisocyanate with an aromatic one shifts the area of effective damping of PU material towards positive temperatures. Therefore, by changing the nature of PU components, as well as the molecular weight of the PU oligoester component, it is possible to obtain transparent materials with a wide temperature range of effective damping in combination with high protection against UV radiation.

Key words: polyurethane, ultraviolet protection, damping ability, viscoelastic properties, transparency.

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Abstract:

Modification of tubular ceramic membranes made of clay minerals, which were obtained by slip casting (produced by the Dumansky Institute of Colloid Chemistry and Water Chemistry of the National Academy of Sciences of Ukraine) was carried out. The membranes were modified with pyrocarbon, which was obtained by carbonization of a precursor – poly(urethane urea)s. The carbonization precursor was synthesized from polyisocyanate (average functionality 2.7) and laprol grade 5003, which was introduced into the membrane by impregnation of the corresponding solutions in ethylacetate. When laprol reacts with polyisocyanate, three-dimensional polyurethane is formed. Since undried reagents were used, water entered the pores of the membrane, which reacted with the NCO groups of the polyisocyanate to form polyurea. The parallel course of these reactions leads to the formation of poly(urethane urea)s in the pores of the membrane. Carbonization was carried at 800 °C in an argon flow. The apparent density and open porosity of the membranes were determined by CCl4 uptake. After modification, the open porosity of the membrane decreased from 29.9 to 27.3 %, the apparent density increased from 1.86 to 1.87 g/cm3. The composition and structure of the membranes were studied by X-ray diffraction analysis and SEM. It is shown that the obtained modifier is pyrocarbon – the relative intensity of reflexes increases at 26,0 – 26,4 and 41,3 and 44,2° 2Θ. Pyrocarbon covers the surface of the pores with a continuous layer, and there are also three-dimensional formations of various shapes and sizes from several nm to several microns. Testing of modified membranes was carried out by water purification from direct scarlet dye and from Ca2+ of calcium chloride using the baromembrane method at a working pressure of 0.7 MPa. The unmodified membrane does not retain direct scarlet dye and Ca2+ at all. Tests of modified membranes have shown that the membranes acquire ultrafiltration properties. The retention factor (R) for direct scarlet dye is 100 % and 25 % for Ca2+.

Key words: ceramic membranes, polyisocyanate, laprol, pyrocarbon, water purification ultrafiltration.

REFERENCES

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Abstract:

Using X-ray diffraction data the short-range ordering was analyzed of the plant polysaccharide konjac glucomannan (KGM) and glycopolymers of different composition based on KGM and ε-caprolactam blocked isocyanates in the presence of saturated water vapor both for moistened and dried systems. The decrease in the values of the Breg’s period corresponding to the average distances between atoms and atomic groups in saturated water vapor is shown for glycopolymers placed under normal conditions. It was found that when the crosslinked KGM based glycopolymers are moistened, a secondary maximum is observed on the diffractograms, which corresponds to the ordering of the polysaccharide chains in the transverse direction. This secondary maximum was observed on the diffractograms of uncrosslinked KGM, but was absent on the initial diffractograms of crosslinked samples. This secondary maximum does not appear again on the diffractograms of dried glycopolymer samples. The influence of moisturizing-drying processes on the structuring and moisture content in polysaccharide and glycopolymers is analyzed. The results of WAXS correlate with thermogravimetry data on changes in the ability of KGM and KGM-based glicopolymers to retain moisture in humidified and dried systems. Using a nitroxyl paramagnetic probe, it has been demonstrated that the increase in molecular mobility of glycomolymers based on konjac glucomannan under the influence of low molecular weight plasticizer does not depend on isocyanate used. This effect allows correlating the irreversible effect of swelling and subsequent drying on the characteristics of these KGM-based systems with the achievement of macrochains of the polymer more equilibrium conformations due to increasing molecular mobility in the presence of moisture.

Key words: polysaccharide, blocked isocyanate, moisture, X-ray diffraction, thermogravimetry, paramagnetic probe.

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6. Kozak N., Hubina A. Polyglucanurethanes: cross-linked polyurethanes based on microbial exopolysaccharide xanthan, Chapter 19. In book: Polyurethane., Zafar F., Sharmin E. (Ed), Croatia: InTech, 2012: 431–447. http://dx.doi.org/10.5772/48007.

7. Didenko K.S., Kozak N.V., Bortnitskyi V.S., Komliakova O.M., Klepko V.V., Rukhailo M.V. The influence of structure and functionality of ε- caprolactam blocked isocyanates on their thermal properties (in Ukrainian), Ukr.Chem.J. 2016, 82:110–116.

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11. Kozak N.V., Didenko K.S., Nesin S.D. The influence of plasticizer on dynamic characteristics and shortrange ordering of crosslinked glycopolymers based on water-soluble polysaccharides, Polym.J.(Ukr.), 2020, 42: 191–198. https://doi.org/10.15407/polymerj.42.03.191.

12. Pаt UA № 61307 A method for the preparation of blocked isocyanate product. Kozak N.V., Kosyanchuk L.F., Nizelʹsʹkyy Yu.M., Lipatov Yu.S., Nesterenko H.M., Nasvit Ya.O. Publ. 15.11. 2005.

13. Pаt UA № 115033, The method of obtaining sorbents for phenol based on crosslinked water-soluble polysaccharides Didenko K. S., Kozak N.V. Publ. 27.03.2017.

14. Pаt UA №80118, Blocked isocyanates as saccharide sorbents cross-linker Kozak N.V., Didenko K. S. Publ.13.05.2013.

15. Kozak N.V, Didenko K.S., Klepko V.V., Dmytrieva N.V.,Bortnytskii V.I. The interaction of the blocked polyisocyanate with konjac glucomanan (in Ukrainian),Ukr.Chem.J., 2014, 80: 119–123.

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Abstract:

The synthesis and physico-chemical properties of chemically cross-linked hydrogels based on polyacrylamide and chitosan, which form interpenetrating polymer networks, are considered in the work. The strategy of obtaining cross-linked networks of both polyacrylamide and polyacrylamide grafted on chitosan by radical polymerization was used. The equilibrium swelling properties, which depend on the pH value of the solution and the composition of the gels, were studied. The chemical structure of the obtained hydrogels was characterized by IR spectroscopy.

Key words: chemically cross-linked hydrogels, interpenetrating polymer networks, chitosan.REFERENCES

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3. Myung D., Waters D., Wiseman M., Duhamel P.E., Noolandi J., Ta C.N., Frank C. W. Progress in the development of interpenetrating polymer network hydrogels. Polym. Adv. Technol., 2008, 19: 647–657. https://doi.org/10.1002/pat.1134.

4. Ignat L., Stanciu A. Advanced polymers: interpenetrating polymer networks. In Handbook of Polymer Blends and Composites. Ed.: A. K. Kulshreshtha and C. Vasile, Rapra Technology, 2003: 275–280.

5. Wang J.J., Liu F. Enhanced adsorption of heavy metal ions onto simultaneous interpenetrating polymer network hydrogels synthesized by UV irradiation. Polym. Bull., 2013, 70: 1415–1430. https://doi.org/10.1007/s00289-013-0934-z.

6. Chivukula P., Dušek K., Wang D., Duškova-Smrcˇkova M., Kopecˇkova P., Kopecˇek J. Synthesis and characterization of novel aromatic azo bond-containing pH-sensitive and hydrolytically cleavable IPN hydrogels. Biomaterials, 2006, 27: 1140–1151. https://doi.org/10.1016/j.biomaterials.2005.07.020.

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Received 04.07.2022

Abstract:

Developed a new composite material with Dacarbazine based on polyurethane foam (PPUS) The content of the drug substance Dacarbazine (DAC) in the composition was 0.5 wt. % and 1.0 wt.%. PPUS was obtained on the basis of a mixture of oligourethane diisocyanates (OUDIC) synthesized on the basis of 2,4-;2,6-toluene diisocyanate and polyoxypropylene glycols (POPG) MM 1002 and MM 2002 in a ratio of 1:1. Comparative physical and mechanical tests were performed. According to the obtained results, PPUS with DAC in the amount of 1 wt.% have physical and mechanical parameters (σ = 7.8, MPa, ε = 100% and σadhesion = 4.5 MPa), that will meet the requirements for replacement implants for ophthalmology. According to the results of IR spectroscopy, the possibility of chemical immobilization of Dacarbazine on the selected polymeric carrier was established. The thermophysical properties of the synthesized PPUS with Dacarbazine by DSC and TGA methods were studied. It was found that the glass transition temperature (Tg) is practically independent of the content of DAC. Tg PPUS with 0.5 wt.% DAC – (minus) 49.70 °C, Tg PPUS with 1.0 wt.% DAC – (minus) 50.09 °C. According to TGA, the obtained materials are characterized by the same heat resistance characteristics and practically do not depend on the content of DAC. The onset temperature of thermal decomposition (To) is in the range (290,96–298,61) °C and is accompanied by a slight weight loss (0.02–0.04 %). The temperature of maximum decomposition rate (Tmax ) is in the range (331.93–333.95) °C. According to the results of the dynamics of Dacarbazine release study from PPUS samples with a DAC content in the composition of 0.5 and 1.0 wt. % found that the composition of PPUS with a content of DAC 1 wt. % have a higher percentage of medicine, which on day 14 is ~ 64 %. The developed PPUS with Dacarbazine are promising materials for use as implants for ophthalmological surgery.

Key words: polyurethane foam urea, composite material, Dacarbazine, drug release, implant.

REFERENCES

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Abstract:

A number of polyurethane ureas (PUUs) containing 1,8-diamino-3,6-dioxooctane (DOODA) in their structure as a macrochain extender were synthesized with a different molar ratio of 4,4′-diaminodiphenylmethane (DADPh) to DOODA as 30:70; 50:50; 70:30. Synthesized polymers are elastic, transparent films with a thickness of 0.3 mm. According to the results of physical and mechanical tests, the tensile strength of the synthesized PUUs is in the range of (0.7-2.0) MPa, and the relative elongation at break is in the range of (73.9-584.7)%. The best physical and mechanical characteristics have the polymer synthesized with a ratio of DADPh:DOODA as 0.3:0.7 with a tensile strength of 2.0 MPa and a relative elongation of 522%. The formation of PUUs was confirmed by the method of IR-spectroscopy. Thermophysical properties synthesized by DSC, TGA methods were studied. It was established that the glass transition temperature (Tg) in a number of synthesized PUUs with DOODA is in the range from (minus) 18.50 °C to (minus) 34.52 °C. An increase in the content of 1,8-Diamino-3,6-dioxaoctane in the PUUs structure leads to a decrease in Tg and a slight increase in ΔCp during the second heating. According to the TGA, the heat resistance characteristics of the synthesized PUUs depend on the content of DOODA. When entering the structure of the PUUs DOODA, a decrease of the temperature of the start of the decomposition (T0) and the temperature of the maximal speed of the decomposition (Tmax), which is non-linear nature. T0 of the synthesized PUUs is in the range (275.16-289.8)°C and is accompanied by a slight loss of mass (0.007-0.093)%. Synthesized PUUs are heat-resistant to a temperature of 275.16 °C, which makes it possible to carry out dry sterilization of samples without changing their characteristics. Synthesized PUUs are promising materials for the immobilization of medicinal substances for further use in medicine.

Key words: polyurethane, polyurethane urea, 1,8-Diamino-3,6-dioxaoctane, 4,4′- diaminodiphenylmethane.

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