Multi-Parameter Characterization of Liquid-to-Ice Phase Transition Using Bulk Acoustic Waves.

The detection of the liquid-to-ice transition is an important challenge for many applications. In this paper, a method for multi-parameter characterization of the liquid-to-ice phase transition is proposed and tested. The method is based on the fundamental properties of bulk acoustic waves (BAWs). BAWs with shear vertical (SV) or shear horizontal (SH) polarization cannot propagate in liquids, only in solids such as ice. BAWs with longitudinal (L) polarization, however, can propagate in both liquids and solids, but with different velocities and attenuations. Velocities and attenuations for L-BAWs and SV-BAWs are measured in ice using parameters such as time delay and wave amplitude at a frequency range of 1-37 MHz. Based on these measurements, relevant parameters for Rayleigh surface acoustic waves and Poisson's modulus for ice are determined. The homogeneity of the ice sample is also detected along its length. A dual sensor has been developed and tested to analyze two-phase transitions in two liquids simultaneously. Distilled water and a 0.9% solution of NaCl in water were used as examples.

Acoustic Waves in Piezoelectric Layered Structure for Selective Detection of Liquid Viscosity.

The acoustic waves of higher orders propagating in a layered structure consisting of a silicon plate coated with piezoelectric ZnO and/or AlN films were used for the development of a sensor with selective sensitivity to liquid viscosity η in the range of 1-1500 cP. In that range, this sensor possessed low sensitivity to liquid conductivity σ and temperature T in the ranges of 0-2 S/m and 0-55 °C, respectively. The amplitude responses insensitive to the temperature instead of the phase were used to provide the necessary selectivity. The sensor was based on a weak piezoactive acoustic wave of higher order. The volume of the probes sufficient for the measurements was about 100 µL. The characteristics of the sensors were optimized by varying the thicknesses of the structure layers, number of layers, wavelength, wave propagation direction, and the order of the acoustic waves. It was shown that in the case of the layered structure, it is possible to obtain practically the same selective sensitivity toward viscosity as for acoustic waves in pure ST, X quartz. The most appropriate waves for this purpose are quasi-longitudinal and Lamb waves of higher order with in-plane polarization. It was found that for various ranges of viscosity η = 1-20 cP, 20-100 cP, and 100-1500 cP, the maximum sensitivity of the appropriate wave is equal to 0.26 dB/cP, 0.087 dB/cP, and 0.013 dB/cP, respectively. The sensitivity of the waves under study toward the electric conductivity of the liquid is much less than the sensitivity to liquid viscosity. These two responses become comparable only for very small η < 2 cP. The waves investigated have shown no temperature responses in contact with air, but in the presence of liquid, they increase depending on liquid properties. The temperature dependence of liquid viscosity is measurable by the same sensors. The results obtained have shown the possibility of designing acoustic liquid viscosity sensors based on multilayered structures. The set of possible acoustic waves in layered structures possesses modified propagation characteristics (various polarization, phase velocities, electromechanical coupling coefficients, and attenuations). It allows choosing an optimal acoustic wave to detect liquid viscosity only.

Langmuir-Blodgett Films with Immobilized Glucose Oxidase Enzyme Molecules for Acoustic Glucose Sensor Application.

In this work, a sensitive coating based on Langmuir-Blodgett (LB) films containing monolayers of 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) with an immobilized glucose oxidase (GOx) enzyme was created. The immobilization of the enzyme in the LB film occurred during the formation of the monolayer. The effect of the immobilization of GOx enzyme molecules on the surface properties of a Langmuir DPPE monolayer was investigated. The sensory properties of the resulting LB DPPE film with an immobilized GOx enzyme in a glucose solution of various concentrations were studied. It has shown that the immobilization of GOx enzyme molecules into the LB DPPE film leads to a rising LB film conductivity with an increasing glucose concentration. Such an effect made it possible to conclude that acoustic methods can be used to determine the concentration of glucose molecules in an aqueous solution. It was found that for an aqueous glucose solution in the concentration range from 0 to 0.8 mg/mL the phase response of the acoustic mode at a frequency of 42.7 MHz has a linear form, and its maximum change is 55°. The maximum change in the insertion loss for this mode was 18 dB for a glucose concentration in the working solution of 0.4 mg/mL. The range of glucose concentrations measured using this method, from 0 to 0.9 mg/mL, corresponds to the corresponding range in the blood. The possibility of changing the conductivity range of a glucose solution depending on the concentration of the GOx enzyme in the LB film will make it possible to develop glucose sensors for higher concentrations. Such technological sensors would be in demand in the food and pharmaceutical industries. The developed technology can become the basis for creating a new generation of acoustoelectronic biosensors in the case of using other enzymatic reactions.

Features of the Formation of Sensitive Films Based on Mycelium of Higher Fungi for Surface and Plate Acoustic Waves Gas Sensors.

A comparative analysis of the responses of two types of acoustic waves (surface SAW and plate APW) with close frequencies and the same type of waves (SAW) with different frequencies toward various liquid vapors (water, acetone, ethanol) was carried out in this paper. Two types of films based on mycelium of higher fungus Ganoderma lucidum (Curtis) P. Karst (G. lucidum) prepared by various methods were used as sensitive coatings. These films were based on G. lucidum mycelium ethanolic (48% v/v) homogenizate (MEGl) and extract (EGl). A film deposition procedure compatible with acoustic devices technology was developed. Various piezoelectric substrates (YX-LiNbO3, 128 YX-LiNbO3) were used for appropriate acoustic delay lines production. It was found that additional SAW and APW attenuation associated with the appearance of mycelium films on the surface of the acoustic waveguide is two times greater for MEGL than for EGL films in the frequency range of 20-80 MHz The changes in acoustic wave amplitude and phase due to vapor absorption were measured and compared with each other, taking into account the differences in geometry of the samples. It was found that the phase response of the SAW delay lines with EGL films is three times higher than one with the presence of MEGL films for water and ethanol vapors. The films used are demonstrated good reproducibility and long-term stability for at least 2 months. Based on the results obtained, it was concluded that MEGl film is not appropriate for use in high frequency SAW delay lines as a sensitive coating. However, both types of the films (MEGl and EGl) could be used as sensitive coatings for low frequency SAW and APW sensors based on corresponding delay lines. Additionally, it was found that the films used are not sensitive to acetone vapor. As a result of the work carried out, a technique for creating sensitive films based on the mycelium of higher fungi compatible with the planar technology of acoustoelectronic delay lines was developed. The possibility of using such films for the development of gas SAW and APW sensors was shown.

Multimode Design and Piezoelectric Substrate Anisotropy Use to Improve Performance of Acoustic Liquid Sensors.

Using acoustic wave modes propagation in piezoelectric plates loaded with conductive liquids, peculiarities of the mode-liquid acoustoelectric interaction are studied. It is found that (i) in contrast to bulk and surface acoustic waves propagating in piezoelectric semiconductors, the acoustoelectric attenuation of the modes is not symmetric in respect to its maximum, (ii) a large increase in attenuation may be accompanied by a small decrease in phase velocity and vice versa, (iii) the peculiarities are valid for "pure" (without beam steering) and "not pure" (with beam steering) modes, as well as for modes of different orders and polarizations, and (iv) conductivity of test liquid increases electromagnetic leakage between input and output transducers, affecting results of the measurements. To decrease the leakage, the liquid should be localized between transducers, outside the zone over them. If so, the mode sensitivity may be as large as 8.6 dB/(S/m) for amplitude and 107°/(S/m) for phase. However, because of comparable cross-sensitivity towards viscosity and dielectric permittivity, modes with selective detection of liquid conductivity are not found.

Selective Detection of Liquid Viscosity Using Acoustic Plate Waves with In-Plane Polarization.

Using plates of weak piezoeletcric crystal (quartz) loaded with various liquids, it is shown that along with common modes, whose sensitivity towards different liquid parameters comparable with each other, there are some uncommon modes, whose amplitude responses towards viscosity η are much larger than towards temperature T and electric conductivity σ. The search of the modes with the selective properties is accomplished by varying plate thickness h, crystal orientation, wave length λ, and mode order n. It is found that all modes possessing the property are characterized by small surface-normal displacement, avoiding wave radiation into adjacent liquid, large in-plane displacements, enhancing viscous coupling the modes and liquids, and small electro-mechanical constant, reducing electro-acoustic interaction. Basing on the modes, the sensor prototypes with selective operation are developed and tested for η from 1 to 1500 cP, σ from 0 to 1.2 S/m, and t from 0 to 55 °C. Because of operation at ultrasonic frequency (tens MHz) the prototypes have different sensitivities in various η-ranges: 0.3 dB/cP for 1−20 cP, 0.12 dB/cP for 20−100 cP, and 0.015 dB/cP for 100−1500 cP. Viscosity responses of the prototypes become comparable with their electric outputs only for η < 2 cP. Temperature responses are almost zero in air, but when plate is coated with liquid they increase depending on liquid properties, allowing measurements of the temperature dependence of the liquid viscosity.

Langmuir-Blodgett Films of Arachidic and Stearic Acids as Sensitive Coatings for Chloroform HF SAW Sensors.

Properties of the Langmuir-Blodgett (LB) films of arachidic and stearic acids, versus the amount of the films' monolayers were studied and applied for chloroform vapor detection with acoustoelectric high-frequency SAW sensors, based on an AT quartz two-port Rayleigh type SAW resonator (414 MHz) and ST-X quartz SAW delay line (157.5 MHz). Using both devices, it was confirmed that the film with 17 monolayers of stearic acid deposited on the surface of the SAW delay line at a surface pressure of 30 mN/m in the solid phase has the best sensitivity towards chloroform vapors, compared with the same films with other numbers of monolayers. For the SAW resonator sensing using slightly longer arachidic acid molecules, the optimum performance was reached with 17 LB film layers due to a sharper decrease in the Q-factor with mass loading. To understand the background of the result, Atomic Force Microscopy (AFM) in intermittent contact mode was used to study the morphology of the films, depending on the number of monolayers. The presence of the advanced morphology of the film surface with a maximal average roughness (9.3 nm) and surface area (29.7 µm2) was found only for 17-monolayer film. The effects of the chloroform vapors on the amplitude and the phase of the acoustic signal for both SAW devices at 20 °C were measured and compared with those for toluene and ethanol vapors; the largest responses were detected for chloroform vapor. For the film with an optimal number of monolayers, the largest amplitude response was measured for the resonator-based device. Conversely, the largest change in the acoustic phase produced by chloroform adsorption was measured for delay-line configuration. Finally, it was established that the gas responses for both devices coated with the LB films are completely restored 60 s after chamber cleaning with dry air.

The Peculiarities of the Acoustic Waves of Zero-Order Focusing in Lithium Niobate Plate.

In this research, beam focusing in lithium niobate plate was studied for fundamental anti-symmetric (A0) and symmetric (S0) Lamb waves, and the shear-horizontal (SH0) wave of zero-order. Using the finite element method, appropriate configuration of the interdigital transducer with arc-like electrodes was modeled accounting for the anisotropy of the slowness curves and dispersion of the modes in the plate. Profiles of the focalized acoustic beams generated by the proposed transducer were theoretically analyzed. Based on the result of the analysis, relevant delay lines were fabricated and transfer functions (insertion loss) of the line were measured for SH0 wave in YX-lithium niobate plate. Using an electron scanning microscope, distribution of the electric fields of the same wave were visualized. The results of this study may be useful for hybrid devices and sensors combining nano and acoustoelectronic principles.

An Analysis of the Water-to-Ice Phase Transition Using Acoustic Plate Waves.

It is shown that, in spite of the wave radiation into the adjacent liquid, a large group of Lamb waves are able to propagate along piezoelectric plates (quartz, LiNbO3, LiTaO3) coated with a liquid layer (distilled water H2O). When the layer freezes, most of the group's waves increase their losses, essentially forming an acoustic response towards water-to-ice transformation. Partial contributions to the responses originating from wave propagation, electro-mechanical transduction, and wave scattering were estimated and compared with the coupling constants, and the vertical displacements of the waves were calculated numerically at the water-plate and ice-plate interfaces. The maximum values of the responses (20-30 dB at 10-100 MHz) are attributed to the total water-to-ice transformation. Time variations in the responses at intermediate temperatures were interpreted in terms of a two-phase system containing both water and ice simultaneously. The results of the paper may turn out to be useful for some applications where the control of ice formation is an important problem (aircraft wings, ship bodies, car roads, etc.).

Inkjet Printing of Plate Acoustic Wave Devices.

In the paper, the results of production of Ag inkjet printed interdigital transducers to the acoustic delay line based on Y-cut X-propagation direction of lithium niobate plate for the frequency range from 1 to 14 MHz are presented. Additionally, morphological, structural, and electro-physical characteristics of the obtained electrodes were investigated. Mathematical modeling of the excitation of acoustic waves by these electrode structures was carried out. Comparison of the theoretical results with experimental ones showed their qualitative and quantitative coincidences. It was shown that conventional inkjet printing can replace the complex photolithographic method for production of interdigital transducers for acoustic delay lines working up to 14 MHz. The resulting electrode structures make it possible to efficiently excite acoustic waves with a high value of electromechanical coupling coefficient in piezoelectric plates.

Super high sensitive plate acoustic wave humidity sensor based on graphene oxide film.

The changes of density and elastic modules due to water vapor adsorption are measured for graphene oxide film at room temperature. Dominant mechanism for acoustic wave humidity sensing by the film is shown to be related with variation of its electric conductivity. Basing on the data, super high sensitive humidity sensor employing high-order Lamb wave with large coupling constant, standard lithium niobate plate, and graphene oxide sorbent film is developed. The minimal detectable level of the sensor is as low 0.03% RH, response times are 60/120s, and reproducibility is ±2.5%. The sensor is completely selective towards H2, CO, CH4, NO, O2.

Anisotropy of the acoustic plate modes in ST-quartz and 128°Y-LiNbO(3).

Orientation dependences of the phase velocity vn, coupling coefficient Kn(2), and power flow angle Ψ(n) for zero-order and high-order acoustic modes are calculated numerically in ST-quartz and 128°Y-LiNbO(3) plates with normalized thickness h/λ = 0.1, 0.25, 0.5, 1.0, 1.25, 1.5, and 1.67 (n is the mode order, θ is the angle between propagation direction and the x-axis, h is the thickness, and λ is the wavelength). Results of the calculations are experimentally verified using 128°YLiNbO(3) plates with h/λ = 1.0, 1.67 and θ = 0°, 30°, 60°, 90° as examples.

Sensing properties of the Anisimkin Jr. acoustic modes in uncoated ST-quartz plates.

The Anisimkin Jr. (AN) acoustic plate modes having quasi-longitudinal (QL), quasi-shear-vertical (QSV) and quasi-shear-horizontal (QSH) polarizations are studied experimentally in uncoated ST,X-quartz plates with normalized plate thicknesses h/λ = 1.485 and 1.67 (where h is thickness and λ is wavelength). The sensitivities of the modes toward mass loading (water vapor) are measured at different temperatures in the range 10.6°C to 23°C and compared with that of the Rayleigh SAW. The sensitivity of the same modes toward temperature is measured from 15°C to 85°C and compared with those of the bulk waves propagating in the same direction. Acoustic plate modes with dominant responses toward humidity or temperature are found.

New acoustic plate modes with quasi-linear polarizations.

New acoustic plate modes (APMs) with quasishear- vertical (QSV) and quasi-shear-horizontal (QSH) polarizations are found numerically in piezoelectric, nonpiezoelectric, and isotropic plates with free faces. Experimental verification of the modes is accomplished for ST,X-quartz plate, as an example. Similar to the modes with quasi-longitudinal displacement reported recently, the new counterparts exist when their velocities v(APM) are close to the velocities v(BAW) of the relevant bulk waves, the value of the dispersion slope dv(APM)/d(h/λ) is low enough (dv(APM)/d(h/λ) ~100 m/s, where h is thickness and λ is wavelength), and allowable plate thickness h/λ form a regular succession. All modes with quasi-linear polarization originate from generalized Lamb modes transformed at the aforementioned conditions.

Propagation of the Anisimkin Jr.' and quasi-longitudinal acoustic plate modes in low-symmetry crystals of arbitrary orientation.

The Anisimkin Jr. (AN) acoustic plate mode having dominant and depth-independent longitudinal displacement (u(1) >> u(2), u(3); u(1) ≈ constant) is numerically found in tetragonal 4mm Li(2)B(4)O(7) crystal with one of the low-symmetry orientations (Euler angles 89°, 37°, 104°), as an example. The quasi-longitudinal (QL) modes with dominant and depth-dependent longitudinal displacement (u(1) >> u(2), u(3); u(1) ≠ constant) are experimentally detected along several propagation directions Θ in 128°y-LiNbO(3) plate, where Θ = 0°, 30°, 60°, and 90° with respect to the x-axis. Compared with more symmetrical plate materials and orientations, the displacement profiles of the AN and QL modes in lower-symmetry counterparts are qualitatively the same, but their phase profiles are more complicated. Moreover, like any acoustic wave, all plate modes in anisotropic crystals suffer from beam steering, in general. The power flow angles of the modes propagating in a fixed direction are different and depend on the mode order n.

Acoustic properties of the film/plate layered structure.

A new propagation medium-a layered structure composed of a film and a plate-is suggested and studied, using c-oriented ZnO and AlN films on (001), {100}-Si plate, as two opposite examples of slow-on-fast and fast-on-slow material combinations. For both structures, the modes belonging to Lamb, quasi-longitudinal (QL), and Anisimkin Jr.' (AN) families are found. For each family, the velocities v(n), displacement profiles, and electromechanical coupling coefficients K(n)2 for 4 electrode configurations are numerically calculated by the matrix method as a function of the mode order n = 0 to 8, plate thickness H/λ = 0 to 2.0, and film thickness h/λ = 0.02 to 0.04 (H and h are thicknesses; λ is the wavelength). Some high-order modes in the structure have K(n)2 = 0 for any H/λ, h/λ, and electrode configuration. Other modes possess variable K(n) 2 with a maximum value larger than the coupling coefficient for the Rayleigh SAWs in ZnO and AlN single crystals or layered structures using the same films and semi-infinite silicon substrate. There are also QL-modes having high velocity v(n), large K(n)2, and low propagation loss caused by liquid loading. These modes are well suited for liquid sensors.

General properties of the Anisimkin Jr. plate modes.

Acoustic plate modes of different orders n, having equal velocities v(n) close to that of the longitudinal BAW v(L), are numerically studied in crystals of different symmetries. Three families of the modes with v(n) ≈ v(L), each at relevant plate thickness h/λ = (h/λ)n, are found (h is the thickness, λ is the wavelength): the generalized Lamb mode with comparable longitudinal u1, shear-horizontal u2, and shear-vertical u3 displacements, the Anisimkin Jr. (AN) mode with u1 >> u2 and u3, and u1 ≈ constant ≠ 0 at any depth, and the quasilongitudinal (QL) mode with u1 > u2, and u3, but u1 ≠ constant over the plate thickness. Existence of the families does not depend on anisotropy or piezoelectric properties of the plate, but on the closeness of the mode velocity v(n) to the BAW velocity v(L), the value of the dispersion slope dv(n)/d(h/λ) at v(n) = v(L) and h/λ = (h/λ)n, and the proximity of the plate thickness (h/λ)n supporting the mode, to the thickness (h/λ)R providing transverse BAW resonance between plate faces. The Lamb modes approach v(n) = v(L) at irregular (h/λ)n far from resonance (h/λ)R and at large dv(n)/d(h/λ) ~10(3) m/s. The two other modes are characterized by lower dispersion dv(n)/d(h/λ) ≤ 10(3) m/s and regular (h/λ)n close to the resonance (h/λ)R. Because both modes have small vertical displacement on plate faces and propagate almost entirely within the crystals, they are attractive for liquid sensing.

Attenuation of acoustic normal modes in piezoelectric plates loaded by viscous liquids.

Attenuation cac versus viscosity eta of adjacent liquid is measured for each normal mode n generated in 30 different plates of commercially available, piezoelectric crystals with thickness-to-wavelength ratio in the range h/lamda = 0.6 - 2.5. Two modes with an optimal combination of sensitivity (0.1 dB/mm x cP), insertion loss (<35 dB), and stop-band rejection (>15 dB) are found in liquid-loaded 128 degrees Y,X + 90 degrees - LiNbO3 with h/lamda = 1.67. Both modes are suited for viscosity measurements and other sensing tasks in viscous liquids. They have predominantly longitudinal displacement and large propagation velocity v(n), about 15,000 m/s.