PERSPEKTIVNYE MATERIALY
2021, no. 8
Solvatochromic effects in absorption and luminescence
spectra and stability of emission quantum yield
of carbon nanoparticles (part II)
S. A. Kazaryan, V. N. Nevolin, S. Kh. Pilosyan
Have been investigated and analyzed the spectroscopic features of the solvatochromic effects of absorption and luminescence bands, as well as the parameters of the quantum yield of emission (QYE) of proton and aprotic solutions of carbon nanoparticles (CNPs) synthesized by microwave radiation from a mixture of citric acid and urea. It was found that the QYE of particle has an exponential dependence on the polarity and the sum of the acidity and basicity of the solvents. The influence of hydrogen bonding and interaction of particles with electromagnetic radiation on the parameters of solvatochromic effects of absorption bands, luminescence and QYE of nanoparticles is studied. Within the framework of the models of Lippert – Mataga, Bilot – Kavsky, Liptai, McRae, Kamlet – Taft, Catalan and by the method of linear regression analysis, it was established that the solvatochromic effects of CNPs, in addition to universal interactions, also largely depend on specific interactions. An increase in the polarity and the sum of the acidity and basicity of the solvents creates a hypsochromic shift of the absorption band at 410 nm and a bathochromic shift of the green luminescence band of CNPs. It is shown that the optical centers of green emission are localized on the surfaces of the particles. A model of the energy levels of the centers of green emission of particles is proposed, and it is established that the dipole moment of the excited state of the centers is greater than the dipole moment of the ground state.
Keywords: luminescence of nanoparticles, fluorescence of nanoparticles, carbon nanoparticles, emission quantum yield of the nanoparticles, synthesis of carbon nanoparticles, solvatochromic effect of nanoparticle, dipole moments of nanoparticles, Stokes shift.
DOI: 10.30791/1028-978X-2021-8-5-21
Kazaryan Samvel —Lebedev Physical Institute of Russian Academy of Science (Leninsky prospect 53, 119991, Moscow, Russia), PhD (Phys-Math), head of the department, specialist in the field of luminescence of semiconductors, diamonds, nanosized carbons, as well as technology for the synthesis of nanoporous materials and electrochemical supercapacitors. E-mail: skazaryan.fian@gmail.com.
Nevolin Vladimir —Lebedev Physical Institute of Russian Academy of Science (Leninsky prospect 53, 119991, Moscow, Russia), Dr Sci (Phys-Math), professor, chief researcher, specialist in the field of physics of thin-film structures. E-mail: nevolin@sci.lebedev.ru.
Pilosyan Sergey — Lebedev Physical Institute of Russian Academy of Science (Leninsky prospect 53, 119991, Moscow, Russia), highly qualified senior researcher, specialist in the field of physics of thin films, technology of semiconductor and high-temperature ceramic materials. E-mail: pilosyans@lebedev.ru.
Reference citing
Kazaryan S.A., Nevolin V.N., Pilosyan S.Kh. Sol'vatohromnye effekty v spektrah pogloshcheniya i lyuminescencii i stabil'nost' kvantovogo vyhoda emissii uglerodnyh nanochastic (chast' II). [Solvatochromic effects in absorption and luminescence spectra and stability of emission quantum yield of carbon nanoparticles (part II)]. Perspektivnye Materialy — Advanced Materials (in Russ), 2021, no. 8, pp. 5 – 21. DOI: 10.30791/1028-978X-2021-8-5-21
Study of rheological and structural properties
of modified carboxymethyl cellulose solutions
using cross-linking agents based on substituted oxyranes
A. N. Venzhik, D. A. Nikolaev, I. V. Romanova
Modified carboxymethyl cellulose (CMC) biopolymer materials are widely used in various fields of medicine. For different medical purpose and therapeutic goals it is required to regulate the degree of biodegradation of implanted biopolymers by synthesizing modified gels using substituted oxiranes cross-linkers — 1,4-butanediol diglycidyl ether (BDDE) and polyethylene glycol diglycidyl ether (PEGDE). However, a high cost of the ones determine actual the investigation of new crosslinking agents that will be more cheaper and at the same time will not require a change in the technological process. So, the crosslinking agent polypropylene glycol diglycidyl ether (PPGDE) was chosen. In this work the rheological and structural properties of modified CMC gels with a new crosslinking agent - polypropylene glycol diglycidyl ether (PPGDE) — were investigated and compared with the properties of both unmodified CMC and modified CMC using BDDE and PEGDE. It is shown the modified samples have a 2 – 3 times higher viscosity in comparison with unmodified CMC. The sample modified with PPGDE showed high viscosity and shear force, however, the difference in the ones compared to other samples is small. The modification degree of all gels is similar, but the cross-linking degree of PPGDE is practically absent. However, due to the low degree of crosslinking in the rest of the samples, this parameter does not effect on the viscosity of the solution. The cytotoxicity of all gels was also tested, which confirmed their low toxicity. Thus, gels using a new cross-linking agent — PPGDE — exhibit similar properties with both BDDE and PEGDE, which makes it possible to predict other properties and effects in practical use.
Keywords:carboxymethylcellulose, crosslinked gel, implantable materials, chemical crosslinking of polymers, biopolymer compositions.
DOI: 10.30791/1028-978X-2021-8-22-32
Venzhik Anton — JSC “Medtekhnoproekt” (Moscow, 143026, Innovatsionnyy tsentr Skolkovo, Bol’shoj bul’var St., 42/1), the chief technologist, specialist in synthesis and investigation of biopolymer composition for medical uses. E-mail: a.venzhik@medtp.ru.
Nikolaev Denis — JSC “Medtekhnoproekt” (Moscow, 143026, Innovatsionnyy tsentr Skolkovo, Bol’shoj bul’var St., 42/1), chief product officer, specialist in macromolecular compounds. E-mail: d.nikolaev@medtp.ru.
Romanova Irina — JSC “Medtekhnoproekt” (Moscow, 143026, Innovatsionnyy tsentr Skolkovo, Bol’shoj bul’var St., 42/1), CEO, specialist in biomedical technologies. E-mail: i.romanova@medtp.ru.
Reference citing
Venzhik A.N., Nikolaev D.A., Romanova I.V. Issledovanie reologicheskih i strukturnyh svojstv rastvorov modificirovannoj karboksimetilcellyulozy s ispol'zovaniem sshivayushchih agentov na osnove zameshchennyh oksiranov [Study of rheological and structural properties of modified carboxymethyl cellulose solutions using cross-linking agents based on substituted oxyranes]. Perspektivnye Materialy — Advanced Materials (in Russ), 2021, no. 8, pp. 22 – 32. DOI: 10.30791/1028-978X-2021-8-22-32
Influence of titanic substrate temperature
on phase structure
of a plasma hydroxyapatite coating
T. R. Chueva, N. V. Gamurar, V. I. Kalita, D. I. Komlev,
A. A. Radyuk, V. S. Komlev,
A. Yu. Teterina, V. F. Shamray, A. B. Mikhailova
Plasma coatings of hydroxyapatite (HA) were formed on Ti substrates in modes to obtain high mechanical properties, structural stability, and phase composition. Preheating the titanium substrate to 550 °C increases the content of the HA phase in the coating to 92 % and its equilibrium, there is no local thermal effect of heat release at 723 °C, as in the case of a coating sprayed onto an unheated substrate in DSC studies, there is no halo in the X-ray diffraction pattern in the region of the main reflections GA. Hydrothermal treatment (HTT) of the HA coating at 650 °C increases the HA content to 98%, regardless of the temperature of the preheating of the Ti substrate. Regardless of the state of the coatings, there is a gradual release of heat in DSC studies in the range of 450 – 1000 °C, which increases after hydrothermal treatment. This phenomenon requires additional research. The crystallite size in the sprayed coatings, 42.1 – 43.1 nm, increases after HTT to 64.4 – 68.3 nm and is comparable to the crystallite size in the sprayed powder, 57.4 nm. After HTT of coating, the tricalcium phosphate phase is absent.
Keywords: hydroxyapatite, plasma coatings, hydrothermal treatment, differential scanning calorimetry.
DOI: 10.30791/1028-978X-2021-8-33-43
Chueva Tat`iana — Baikov Institute of Metallurgy and Material Science RAS (Moscow, 119334, Leninsky Prospect, 49), researcher, specialist in differential scanning calorimetry. E-mail: chueva.tr@gmail.com.
Gamurar Nadezhda — Baikov Institute of Metallurgy and Material Science RAS (Moscow, 119334, Leninsky Prospect, 49), PhD (Eng), senior researcher, specialist in the field of differential scanning calorimetry. E-mail: kurakova_n@mail.ru.
Kalita Vasilii — Baikov Institute of Metallurgy and Materials Sciences RAS (Moscow, 119334, Leninsky Prospect, 49), Dr Sci (Eng), head of laboratory, specialist in the field of plasma spraying. E-mail: vkalita@imet.ac.ru.
Komlev Dmitry — Baikov Institute of Metallurgy and Materials Sciences RAS (Moscow, 119334, Leninsky Prospect, 49), PhD, leading researcher, specialist in the field of plasma spraying. E-mail: imet-lab25@yandex.ru.
Radiuk Aleksei — Baikov Institute of Metallurgy and Materials Sciences RAS (Moscow, 119334, Leninsky Prospect, 49), junior researcher, specialist in the field of plasma spraying. E-mail: imet-lab25@yandex.ru.
Komlev Vladimir — Baikov Institute of Metallurgy and Materials Sciences RAS (Moscow, 119334, Leninsky Prospect, 49), corresponding member of RAS, Dr Sci (Eng), director of the Institute, specialist in the field of ceramic composite materials.
Teterina Anastasia — Baikov Institute of Metallurgy and Materials Sciences RAS (Moscow, 119334, Leninsky Prospect, 49), PhD, researcher, specialist in the field of ceramic composite materials.
Shamrai` Vladimir — Baikov Institute of Metallurgy and Materials Sciences RAS (Moscow, 119334, Leninsky Prospect, 49), Dr Sci (Phys-Math), chief researcher, specialist of crystal structural research. E-mail: shamray@imet.ac.ru.
Mihai`lova Alexandera — Baikov Institute of Metallurgy and Material Science RAS (Moscow, 119334, Leninsky Prospect, 49), PhD, senior researcher, specialist in the field of X-ray phase analysis. E-mail: sasham1@mail.ru.
Reference citing
Chueva T.R., Gamurar N.V., Kalita V.I., Komlev D.I., Radyuk A.A., Komlev V.S.,
Teterina A.Yu., Shamray V.F., Mikhailova A.B. Vliyanie temperatury titanovoj podlozhki na fazovyj sostav plazmennogo pokrytiya gidroksiapatita [Influence of titanic substrate temperature on phase structure of a plasma hydroxyapatite coating]. Perspektivnye Materialy — Advanced Materials (in Russ), 2021, no. 8, pp. 33 – 43. DOI: 10.30791/1028-978X-2021-8-33-43
Features of thermal expansion of pyrite in air
A. M. Klyushnikov, E. N. Selivanov, S. M. Pikalov
The composition of natural pyrite has been studied by atomic emission spectroscopy, X-ray powder diffraction, scanning electron microscopy, and X-ray energy dispersive spectroscopy. According to high-temperature X-ray powder diffraction data, the phase transformations of the grinded (< 0.1 mm) sample in air were studied. It is shown that heating up to 500 °C leads to its oxidation with the formation of a mixture of magnetite (up to 44.5 wt %) and hematite (up to 55.5 wt %). The low ignition temperature (360 – 400 °C) is explained by the oxidation of impurity sulfur. Using the results of a full-profile analysis of X-ray powder diffraction data performed by the Rietveld method, the parameters of the pyrite unit cell are determined, and the coefficients of thermal expansion of the pyrite are calculated. Empirical equations describing the change in the lattice period of pyrite when heated in air in the range of 20 – 380 °C are proposed. The linear coefficient of the actual thermal expansion (9.72·10–6 °C–1) is close to the known estimates. Above 234 °C, the effect of chemical expansion is noted, which increases the coefficient of thermal expansion up to 62.96·10–6°C–1 near 380 °C. A significant increase in interatomic distances can affect the adsorption capacity of pyrite, which determines its catalytic activity as applied to the decomposition of nitrogen oxides.
Keywords: pyrite, oxidation, unit cell parameters, thermal expansion, coefficient of thermal expansion.
DOI: 10.30791/1028-978X-2021-8-44-54
Klyushnikov Alexander —Institute of metallurgy of the Ural branch of the Russian Academy of Sciences (Amundsen str. 101, Yekaterinburg 620016, Russia), PhD (Eng), senior researcher, specialist in the field of physical chemistry of metallurgical processes. E-mail: amk8@mail.ru.
Selivanov Evgeniy — Institute of metallurgy of the Ural branch of the Russian Academy of Sciences (Amundsen str. 101, Yekaterinburg 620016, Russia), Dr Sci (Eng), chief researcher, specialist in the field of physical chemistry of metallurgical processes. E-mail: pcmlab@mail.ru.
Pikalov Sergej — Institute of metallurgy of the Ural branch of the Russian Academy of Sciences (Amundsen str. 101, Yekaterinburg 620016, Russia), researcher, specialist in the field of X-ray powder diffraction. E-mail: s.pikalov@mail.ru.
Reference citing
Klyushnikov A.M., Selivanov E.N., Pikalov S.M. Osobennosti termicheskogo rasshireniya pirita na vozduhe [Features of thermal expansion of pyrite in air]. Perspektivnye Materialy — Advanced Materials (in Russ), 2021, no. 8, pp. 44 – 54. DOI: 10.30791/1028-978X-2021-8-44-54
Influence of technological conditions
in the formation of electric conducting
thermoplastic polymergraphite composites
V. N. Gorshenev
The article discusses the synthesis and properties of electrically conductive polymer composite materials based on low-ash graphite grade GSM-1, modified with acids using bisulfate technology. Investigations of the influence of such technological methods as pressing and rolling on rollers with a variable gap on the conductivity of composite materials based on thermally expanded graphite and thermally expanded polymer-graphite compositions containing acid-modified graphite have been carried out. It is shown that, by applying to polymer composites the technological methods of thermal expansion, pressing, and rolling on rollers, it is possible, firstly, to combine fillers of different nature, shapes and sizes, and, secondly, to obtain composites with the required conductivity of an electrically conductive polymer composite. The paper shows the advantage of using thermally expanded graphite in comparison with other forms of graphite to obtain highly conductive polymer compositions.
Keywords: graphite, polymer electrically conductive composites, thermally expanded graphite, electrical conductivity.
DOI: 10.30791/1028-978X-2021-8-55-64
Gorshenev Vladimir —Institute of Biochemical Physics named after N.M. Emmanuel of the Russian Academy of Sciences (Kosygina str., 4, 119334, Moscow, Russia), PhD (Phys-Math), senior researcher, specialist in the field of physics of polymers and polymer composites, biopolymer composites for medical purposes. E-mail: gor@sky.chph.ras.ru.
Reference citing
Gorshenev V.N. Vliyanie tekhnologicheskih uslovij pri formirovanii elektroprovodyashchih termoplastichnyh polimergrafitovyh kompozitov [Influence of technological conditions in the formation of electric conducting thermoplastic polymergraphite composites]. Perspektivnye Materialy — Advanced Materials (in Russ), 2021, no. 8, pp. 55 – 64. DOI: 10.30791/1028-978X-2021-8-55-64
Selective hydrogen absorption by Ti – Ni
powder near equiatomic concentration
after a high-intensity mechanical treatment
E. V. Abdulmenova, S. N. Kulkov
The Ti-Ni powder with the composition close to the equiatomic one after its high-intensity mechanical treatment and hydrogenation by electrochemical method were studied. It was shown that the powder in its initial state consists of a mixture of TiNi (austenite, martensite), Ti2Ni, and TiNi3 phases, and after ball milling, an X-ray amorphous phase is formed. It has been shown that the dislocation density estimated from X-ray data after treatment changes differently in all phases: for the Ti2Ni phase it is significantly greater than that for the TiNi and Ni3Ti. It is found that the lattice parameters of the TiNi (austenite) and Ni3Ti phases do not change during electrochemical hydrogenation after treatments and coincide with literature data. The lattice parameter of the Ti2Ni phase increases, which indicates the predominant interaction of hydrogen with the Ti2Ni phase due to the high dislocation density and the content of rather large octahedral / tetrahedral voids. It has been shown that there is an “incubation period” of hydrogenation of the Ti2Ni phase, which attains 90 min for 10 s treatment. It is shown the lattice parameter of the Ti2Ni based phase corresponds to Ti2NiH0.5 and Ti2NiH0.8 hydrides depending on the milling time and hydrogenation time, for example the lattice parameter of theTi2Ni based phase can correspond to Ti2NiH0.5 and Ti2NiH0.8 hydrides after 30 s and 300 s milling after 90 min hydrogenation and correspond to Ti2NiH0.5 after 10 s milling after 140-180 min hydrogenation.
Keywords: Ti – Ni powder, mechanical treatment, electrochemical hydrogenation, hydrogen, lattice parameter, phase composition.
DOI: 10.30791/1028-978X-2021-8-65-73
Abdulmenova Ekaterina — School of Advanced Manufacturing Technologies NR TPU
(30, Lenin Avenue, Tomsk, 634050), postgraduate student, engineer; ISPMS SB RAS (Tomsk, pr. Akademicheskii, 2/4, 634055), engineer of the laboratory of Physics of Nanostructured Functional Materials, specializes in powder metallurgy and X-ray structural analysis. E-mail: Ekaterina.V.Abdulmenova@yandex.ru.
Kulkov Sergei — Institute of Strength Physics and Materials Science of Siberian Branch of Russian Academy of Sciences (ISPMS SB RAS Tomsk, pr. Akademicheskii, 2/4, 634055) Dr Sci (Phys-Math), prof., head of laboratory of Physics of Nanostructured functional materials; School of Advanced Manufacturing Technologies NR TPU (30, Lenin Avenue, Tomsk, 634050), professor, specializes in ceramic and composite materials, X-ray structural analysis, solid state physics. E-mail: kulkov@ms.tsc.ru.
Reference citing
Abdulmenova E.V., Kulkov S.N. Selektivnoe pogloshchenie vodoroda poroshkom Ni – Ti vblizi ekviatomnogo sostava posle ego vysokointensivnoj mekhanicheskoj obrabotki [Selective hydrogen absorption by Ti – Ni powder near equiatomic concentration after a high-intensity mechanical treatment]. Perspektivnye Materialy — Advanced Materials (in Russ), 2021, no. 8, pp. 65 – 73. DOI: 10.30791/1028-978X-2021-8-65-73
Features of pore filling
of track membranes in synthesis
of nanowires of FeNi alloy
I. M. Doludenko
In this work, by the method of matrix synthesis, nanowires were obtained from Fe – Ni alloy with an elemental composition close to permalloy, namely, 20 % iron and 80 % nickel. As a matrix, we used track membranes made of polyethylene terephthalate with pores 100 nm in diameter. Before deposition, the matrix was prepared in a special way to create a continuous contact at the bottom of the pore. The pores of the matrix were filled with metals by electrochemical deposition. The aim of this work was to study the kinetics of nanowire growth and to establish the dependence of the nanowire length on the deposition time. The morphology and geometry of the resulting nanowires were investigated by scanning electron microscopy. It was shown that the growth rate at different stages of filling the pores of the matrix is different, and it changes nonlinearly. The indicators of the current efficiency at various stages of filling the matrix are calculated, the changes in this indicator coincide with the change in the growth rate. Explanations for the nonlinearity of the growth rate are proposed. An equation describing the dependence of the length of medium nanowires on the deposition time is derived by the method of linear interpolation.
Keywords:matrix synthesis, track etched membranes, electrochemical deposition, nanowires, growth kinetics.
DOI: 10.30791/1028-978X-2021-8-74-80
Doludenko Ilia — HSE Univerсity (Moscow, 101000, Myasnitskaya, 20), graduate student; FSRC “Crystallography and Photonics” RAS (119333, Moscow, Leninskiy Prospek, 59), junior researcher, specialist in matrix synthesis, scanning electron microscopy. E-mail:
doludenko.i@yandex.ru.
Reference citing
Doludenko I.M. Osobennosti zapolneniya por trekovyh membran pri sinteze nanoprovolok iz splava FeNi [Features of pore filling of track membranes in synthesis of nanowires of FeNi alloy]. Perspektivnye Materialy — Advanced Materials (in Russ), 2021, no. 8, pp. 74 – 80. DOI: 10.30791/1028-978X-2021-8-74-80
Technique to monitor gate dielectric
of MIS structure
based on high-field charge injection
D. V. Andreev
The paper suggests a novel technique to study charge characteristics and monitor quality of thin dielectric films of MIS structures. The technique is based on a modification of the method of high-field charge injection into dielectric under increasing current. The proposed technique consists in applying of the increasing current stress to MIS structure studied. The technique, besides monitoring parameters characterizing dielectric breakdown, makes possible to monitor change in charge state of the dielectric. In order to implement this, at levels of injection current density when changes in charge state of MIS structure become higher than a threshold levels, a transition to injection with measurement current level (Jm) for a short period of time being made. We choose a value of Jm on the basis of that this level must not significantly influence on the dielectric charge state and transitions to the level must not highly influence on the test procedure. As a result, it is possible to obtain dependencies of voltage across MIS structure on time or value of injected charge at a constant value of the measurement injection current (Jm) for all the range of increasing current stress. From these dependencies we can acquire key parameters characterizing charge effects taking place in MIS structure being under high-field injection of electrons and specifying degradation effects observing in the gate dielectric film.
Keywords: MIS structure, test technique, gate dielectric, injection current, charge accumulation, stress.
DOI: 10.30791/1028-978X-2021-8-81-88
Andreev Dmitrii — The Kaluga branch of Bauman Moscow State Technical University (Kaluga, 248000, Bazhenov str., 2), PhD (Eng), associate professor, specialist in physics of semiconductors and dielectrics. E-mail: dmitrii_andreev@bmstu.ru.
Reference citing
Andreev D.V. Metodika kontrolya podzatvornogo dielektrika MDP-struktur na osnove sil'nopolevoj inzhekcii zaryada [Technique to monitor gate dielectric of MIS structure based on high-field charge injection]. Perspektivnye Materialy — Advanced Materials (in Russ), 2021, no. 8, pp. 81 – 88. DOI: 10.30791/1028-978X-2021-8-81-88
