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Project “Investigation of phase transitions in liquid media using acoustoelectronic methods and the development of new sensors of physical quantities on this basis”

RSF project No. 20-19-00708 (2020-2024) “Investigation of phase transitions in liquid media using acoustoelectronic methods and the development of new sensors of physical quantities on this basis.”

Head: Doctor of Physico-mathematical Sciences Kuznetsova I.E.

Report for 2022-2024

With the help of a developed and created multimode experimental sample based on 128 YX lithium niobate, the probing of the tested liquid and ice was carried out by a set of acoustic waves, the sensory properties of which varied due to different propagation directions, mode number and plate thickness. Experiments have shown that in most cases, the transition of water from a liquid to a solid state is accompanied by an increase in insertion losses and positive values of response changes, which change with the frequency (number) of the mode. The maximum response values among different piezo plates and acoustic channels vary widely – from 14 to 42 dB. The minimum response values are at the level of 1-3 dB.

A method of multiparametric characterization of microliter volume liquid media, as well as their phase transitions of the first kind, has also been developed. The method is based on the use of fundamental properties of bulk acoustic waves. These transversely polarized waves can propagate only in solid media, and with longitudinal polarization they can pass through both solid and liquid media at different speeds and absorption. The developed method made it possible to determine seven acoustic parameters of the liquid in one measurement cycle. Namely, the absorption coefficient, the temperature coefficient of velocity, the temperature coefficient of delay, density, the coefficient of thermal expansion, the elastic modulus of the liquid and its temperature coefficient. The method was tested on the example of petroleum jelly oil containing activated carbon nanoparticles and SPAN80. The same method was also used to characterize the liquid-ice phase transition, determine the Poisson’s ratio and the velocity of the surface acoustic wave in ice, as well as analyze the homogeneity of the ice that occurs. The temperature range of measurements is 20-+90C, the frequency of the acoustic wave is 13 MHz.

As a result of the work carried out on the study of liquid-ice and ice-liquid phase transitions using bulk acoustic waves, a new experimental research technique has been developed. It is based on the fundamental properties of bulk acoustic waves – the ability of transverse vibrations to propagate only in solids and the dependence of the velocity of longitudinal waves on the aggregate state of matter (liquid or solid). For the first time, the process was recorded not by changing the velocity and/or absorption of acoustic waves, as is done in most acoustic sensors, but by changing the delay time of waves propagating from the emitter to the receiver. It turned out that this acoustic parameter is ideally suited for studying liquid-ice phase transitions because it weakly depends on temperature, but strongly on the aggregate state of the propagation medium. Using the developed techniques and laboratory prototypes, the velocities and absorption coefficients of bulk acoustic waves in water and ice at frequencies 1-37 MHz were measured. An experimental technique has also been developed and a prototype acoustic sensor has been created to study liquid-ice and ice-liquid phase transitions for two different liquids simultaneously using two bulk acoustic waves. It is based on the use of a bar of crystalline quartz oriented along the Y axis. Piezoelectric transducers on its surface excited quasi-longitudinal and quasi-transverse volume waves in it, the directions of energy flows of which are directed in different directions relative to the wave normal and formed angles with it of +23 degrees and -23 degrees, respectively. This made it possible to separate the beams of two OAVs in quartz and use each of them to probe its cuvette with its own liquid. The efficiency of the method was confirmed for two ice samples obtained from distilled water and an aqueous solution of NaCl. As a result of the work carried out, the possibility of using several bulk acoustic waves probing different areas of the ice sample to detect the uniformity of ice in its thickness was shown.

As part of the development of a technique for controlling the properties of a liquid under supercritical conditions in a sealed volume, calculations of the phase velocity of acoustic waves in plates in contact with an inviscid, non-conductive liquid at various values of its elastic modulus, depending on water pressure, at temperatures of 20C-80C were carried out. A decrease in the density of the liquid with increasing temperature was also taken into account. Previously, it was found that with a decrease in temperature, the velocity of acoustic waves in the LiNbO3 piezoelectric plate increases. This is due to the fact that as the temperature decreases, the effective modulus of elasticity of lithium niobate increases, while the density also increases, but not so significantly. Together, a decrease in temperature leads to an increase in the wave velocity. As for the structure of the “piezoelectric plate-a layer of water”, here the phase velocity of acoustic waves decreases with decreasing temperature. This is due to the fact that the effect of reducing the velocity of acoustic waves in a liquid with a decrease in temperature prevails over the effect of increasing the velocity of acoustic waves in a piezo plate. Taking into account the pressure, it was shown that a greater change in the phase velocity occurs with smaller plate thicknesses. A change in temperature in this case leads to a slight increase in the velocity of this wave. The analysis showed that from a technological point of view, it would be more practical to use bulk acoustic waves to implement a technique for controlling the properties of a liquid under critical conditions. An adhesive has been determined that can withstand heating of an airtight capsule up to 350C. As a result, the frequency dependence of the insertion losses of the longitudinal bulk acoustic wave on the temperature (20-200C) was obtained when alcohol is in a sealed chamber. It was found that with increasing temperature and, consequently, pressure inside the sealed capsule, the frequency of the acoustic wave decreases, which corresponds to a decrease in the wave velocity. The magnitude of the insertion loss for the signal increases, which indicates an increase in the attenuation of the acoustic wave with increasing temperature. The results obtained correspond to the known physical data. As a result of the experiments, the possibility of creating an acoustic method based on the use of bulk acoustic waves to control the physical parameters of a liquid in a critical condition was demonstrated.

As a result of the work, the following articles were published:

  1. Агейкин Н.А., Анисимкин В.И., Воронова Н.В., Смирнов А.В. Анализ радиационного поглощения акустических волн Лэмба в пластинах, нагруженных невязкой непроводящей жидкостью// Радиотехника и электроника, 2023, том 68, № 10, с. 1030–1034, 10.31857/S0033849423100029 (Ageikin N.A., Anisimkin V.I., Voronova N.V., Smirnov A.V. Analysis of Radiation Absorption of Acoustic Lamb Waves in Plates Loaded with Inviscid Nonconducting Liquid// Journal of Communications Technology and Electronics, 2023, Vol. 68, No. 10, pp. 1243–1247, 10.1134/S1064226923100029)
  2. Smirnov A., Anisimkin V., Voronova N., Kashin V., Kuznetsova I. Multi-Parameter Characterization of Liquid-to-Ice Phase Transition Using Bulk Acoustic Waves// Sensors, 2024, 24, 4010, 10.3390/s24124010.
  3. Anisimkin V.I., Voronova N.V., Shamsutdinova E.S., Smirnov A., Datsuk E., Kashin V., Kolesov V., Filippova N., Kotsyurbenko O., Kuznetsova I. Determination of acoustic properties of paraffin oil mixed with activated coal nanoparticles or SPAN80 using only BAW time delay measurement// Sensors and Actuators A: Physical, 2024, 379, 115893, 10.1016/j.sna.2024.115893
  4. Smirnov A., Anisimkin V., Ageykin N., Datsuk E., Kuznetsova I. Influence of Lamb wave anisotropy on detection of water-to-ice phase transition// Sensors, 2024, v.24, 7969, 10.3390/s24247969
  5. Агейкин Н.А., Анисимкин В.И., Воронова Н.В., Тельминов О.А., Шамин Е.С. Получение и обработка акустических откликов волн Лэмба в датчиках водных растворов базовых вкусов. РЭНСИТ: Радиоэлектроника. Наносистемы. Информационные технологии, 2024, 16(3), c. 325-330 (Ageikin N.A., Anisimkin V.I., Voronova N.V., Telminov O.A., Shamin E.S. Measurement and processing of the acoustic Lamb wave responses towards water solutions of basic flavors . Radioelektronika, Nanosistemy, Informacionnye Tehnologii, 2024, 16(3), pp.325-330e.) 10.17725/rensit.2024.16.325
  1. Анисимкин В.И., Колесов В.В., Кузнецова И.Е. Исследование фазового перехода вода-лед-вода при помощи акустических волн в тонких пьезоэлектрических пластинах// Труды Всерос. конф. с межд. участием «II Лавёровские чтения – Арктика: актуальные проблемы и вызовы», 13-17 ноября 2023, Архангельск, Россия, с. 13-16
  2. Анисимкин В.И., Воронова Н.В., Кузнецова И.Е., Осипенко В.А., Смирнов А.В. Датчики оледенения на основе акустических волн Лэмба// Труды XХXV сессии РАО, 13-17 февраля 2023 г., г. Москва, АЕ, с.599-604, 10.34756/GEOS.2023.17.38503
  3. Анисимкин В.И., Воронова Н.В., Кузнецова И.Е., Смирнов А.В. Ультразвуковой датчик агрегатного состояния вещества // XXVII международная научная конференция «Волновая электроника и инфокоммуникационные системы» (WECONF-2024), 03-07.06.2024, С.-Петербург, с. 4-8
  4. Воронова Н.В., Анисимкин В.И., Кузнецова И.Е., Смирнов А.В., Горнев Е.С. Акустический датчик оледенения на эллиптических, сдвиговых и продольных волнах пьезоэлектрической пластины//XXVII международная научная конференция «Волновая электроника и инфокоммуникационные системы» (WECONF-2024), 03-07.06.2024, С.-Петербург, с.46-51
  5. Анисимкин В.И., Шамсутдинова Е.С. Кузнецова И.Е. Акустические температурные коэффициенты суспензий на основе вазелинового масла // LXVIII Международная научная конференция «Актуальные проблемы прочности» Витебск, Беларусь,  27-31 мая 2024, с.266-268 .
  6. Анисимкин В.И., Кузнецова И.Е., Колесов В.В. Акустоэлектронные датчики фазовых переходов// 9th Int. Conf. On Physical Electronics, Tashkent, Uzbekistan, Oct. 3-4, 2024, 78-79
  7. Шамсутдинова Е.С., Смирнов А.В., Анисимкин В.И. Исследование фазовых переходов водных растворов хлоридов с помощью объемных волн// Труды 34 Межд. Конф. «СВЧ-техника и телекоммуника-ционные технологии», 8-14 сент. 2024, Севастополь, Россия, 2024, вып.4, с.206-207.
  8. Кузнецова И.Е., Шамсутдинова Е.С., Анисимкин В.И. Акустические методы контроля характеристик проводящих полимеров, композитов и дисперсий// Тезисы Всероссийской научно-технической конференции с международным участием «Сопряженные проводящие полимеры и продукты на их основе: методы синтеза и технологии применения», 05-07.06.2024, Ижевск, с.18-20

Report for 2020-2022

The project was aimed at the study of phase transitions in liquid media using acoustoelectronic methods and the development of new sensors of physical quantities on this basis. The relevance of the completed project is determined, firstly, by the need to ensure the safety of equipment and people working in extreme climatic conditions, and secondly, by the need to develop new methods for studying the properties of media in a supercritical state. The use of supercritical fluid as a reaction medium is an intensively developing direction in chemistry for obtaining new ultrapure materials, but the physical processes occurring under such conditions are still insufficiently studied.

The scientific novelty of the project was the development of acoustoelectronic methods in relation to the study of the processes of change in the state of aggregation of water and liquids based on it with changes in temperature and pressure and the properties of the underlying surface. The use of these methods made it possible not only to develop prototypes of sensors for the simultaneous monitoring of liquid parameters such as viscosity, conductivity, temperature and density in real time, including for microliter volume liquids, but also to study in more depth the physical processes that occur when the state of aggregation changes. water and liquids based on it in the process of freezing and thawing. The studies carried out made it possible to develop prototypes of glaciation sensors based on piezoelectric structures. In addition, the concept of creating sensors for media in a supercritical state was proposed.

All tasks set in the project were successfully completed. Published 5 articles in foreign and Russian journals included in the WOS and Scopus citation systems, of which 4 articles are in journals of the first quartile Q1.

As a result of the project, the tasks of studying the characteristics of higher-order acoustic waves in piezoelectric plates and structures in contact with polar and non-polar liquids were solved when their state of aggregation changes as a result of temperature changes. Theoretical studies were carried out for plates and structures made of the most commonly used piezoelectric materials (ST,X+90-SiO2, ST,X-SiO2, 36YX+90 LiTaO3, 36YX LiTaO3, YZ LiNbO3, 128YX LiNbO3, 41Y-LiNbO3, 64Y-LiNbO3, ZnO/ Si), as well as for structures based on them, including various types of liquids (distilled H2O, heavy water, aqueous glycerol solutions, aqueous NaCl solutions, motor oil) and ice. On the basis of the obtained theoretical results, the choice of the working wave, frequency and geometry corresponding to the task was carried out. As a result of the project, it was shown that the use of acoustoelectronic methods with a gradual decrease and a gradual increase in temperature near the liquid-ice and ice-liquid phase transitions makes it possible to establish the presence / absence of hysteresis phenomena during these processes, as well as to measure the final temperature of the direct process (complete glaciation liquid) and the initial temperature of the reverse process (the beginning of the melting of the ice sample). In addition, it was shown that such an approach makes it possible to analyze the liquid-ice and ice-liquid phase transitions not only for one-component liquid media, but also for mixtures of liquids, for example, from viscous and electrically conductive components. A distinctive feature of such detection in the latter case is the temperature dependences of the viscosity of individual liquids, which make additional contributions to the resulting acoustoelectronic response.

An interesting result is the observed effect of increasing the insertion loss of most modes during the formation of ice on the polished surface of the plate, while the same process on the polished plate coated with oil leads to a decrease in the insertion loss of the same modes. It was also shown that for both plate and surface acoustic waves, there is an increase in their amplitude and phase responses on a hydrophilic surface compared to similar responses on surfaces with hydrophobic properties when layers of bound water are deposited on these surfaces from saturated vapor.

As part of the implementation of this project, a prototype of an acoustoelectronic glaciation sensor based on the structure “Si substrate – ZnO film” was developed. A feature of the prototype was the absence of a cuvette for liquid, which excluded its influence on the operation of the prototype. Water was applied to the free silicon surface in such a way as to completely cover the zone between the input and output IDTs, including the area above the transducers. As a result of the measurements, the following results were obtained: the mode response to the water/ice phase transition was 34 dB, the insertion loss measured with a water load was 44 dB. The performance characteristics of the prototype did not change for the weight of the test sample in the range of 500-1000 mg.

A transverse horizontal surface acoustic wave (SH-SAW) sensor has also been proposed to measure the properties of a viscous fluid. A comparison was made of the effect of used motor oil obtained on a scooter driven 6000 km and new motor oil on the characteristics of these surfactants. The thermal effect on the new engine oil was also taken into account. It is shown that a higher frequency SH-surfactant sensor can be used to control the properties of engine oil.

Based on the theoretical analysis, the types of acoustic oscillations (generalized Lamb modes, surface acoustic wave), the propagation directions of these oscillations (along and perpendicular to the crystallographic X axis) and the type of responses (amplitude, phase) to external influences (viscosity, conductivity, liquid temperature) were optimized. , liquid-ice phase transition). To implement a multi-parameter sensor, it was proposed to use Lamb waves at frequencies of 23.9 MHz and 29.77 MHz in a 128YX lithium niobate plate 500 µm thick. The phase velocity of the first wave turned out to be sensitive to the conductivity of the liquid, but weakly sensitive to the viscosity. The attenuation of the second wave turned out to be significant with a change in the viscosity of the liquid, but did not respond to a change in the conductivity of the liquid.

Finally, the work carried out in the project on the study of the effect of water pressure on the characteristics of acoustic waves in piezoelectric plates serves as the initial stage for the development of acoustoelectronic sensors for analyzing the physical processes that occur when applying the methods of supercritical fluids and gases to obtain new types of materials. This approach is fundamentally new for monitoring the processes of obtaining new materials (ceramics, fine-crystalline oxides, carbon materials, etc.) in the process of using supercritical fluid methods. As part of the project, it was proposed to create acoustic sensors operating in extreme conditions of high pressure, high temperatures, aggressive environments, in closed volumes, to use both external devices and those placed inside autoclave reactors. Piezoceramic emitters can be used as external sensors, and delay lines on SAW and waves in plates can be used as sensors placed inside such devices. The main problem in this case will be the shielding of the electrode structure of such sensors from the measured medium. This area of work needs further development.

As a result of the work, the following articles were published:

 

  1. Smirnov A., Anisimkin V., Voronova N., Shamsutdinova E., Li P., Ezzin H., Qian Zh, Ma T., Kuznetsova I. Multimode Design and Piezoelectric Substrate Anisotropy Use to Improve Performance of Acoustic Liquid Sensors. Sensors v.22, p.7231 https://doi.org/10.3390/s22197231 (2022) WOS SCOPUS  Q1  RSCI  
  2. Anisimkin A., Kolesov V., Kuznetsova A., Shamsutdinova E., Kuznetsova I. An Analysis of the Water-to-Ice Phase Transition Using Acoustic Plate Waves. Sensors v.21, #3, p.919 https://doi.org/10.3390/s21030919 (2021) WOS SCOPUS  Q1  RSCI
  3. Anisimkin V.I., Voronova N.V. New modification of the acoustic Lamb waves and its application for liquid and ice sensing. Ultrasonics v.116, p. 106496 https://doi.org/10.1016/j.ultras.2021.106496 (2021) WOS SCOPUS  Q1  RSCI
  4. Kondoh J., Nakayama K., Kuznetsova I. Study of frequency dependence of shear horizontal surface acoustic wave sensor for engine oil measurements. Sensors and Actuators A: Physical v.325, p. 112503 https://doi.org/10.1016/j.sna.2020.112503 (2021) WOS SCOPUS  Q1  RSCI
  5. Anisimkin V.I., Kuznetsova I.E., Shamsutdinova E.S. Specific Features of Detection of Electric Characteristics of Conductive Liquids Using Normal Acoustic Waves. Journal of Communications Technology and Electronics v.67, no.8, p.1022-1029 https://doi.org/10.1134/S1064226922080022 (2022)