RSF project No. 20-19-00708 (2020-2022) “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 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:
- 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
- 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
- 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
- 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
- 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)