Real Time Monitoring of the Precipitation of Calcium Oxalate by Using Corrosion Resistant Magnetoelastic Resonance Sensors

Abstract

Magnetoelastic sensors are typically amorphous ferromagnetic ribbons in which mechanical and magnetic properties are coupled, so an acoustic wave can be excited in these materials by the application of an alternating magnetic field and detected by the magnetic changes induced in it. The magnetoelastic ribbon can enter in resonance at certain frequencies of excitation, compatible with the dimensions and elastic properties of the material. These resonance frequencies are sensitive to different external parameters, which can be used to design different types of sensors [1], in particular, differences in ribbon mass loading cause a shift of the resonance frequency of the sensor. This sensitivity and its ability to query and detect remotely, made these devices especially interesting for sensing biological and chemical agents.In the present work, we have used magnetoelastic sensors to monitor the precipitation reaction of calcium oxalate crystals (CaC2O4), one of the most common minerals which form calcifications in the urinary track. The formation of these crystals was measured in real-time by tracking the changes in the resonant frequency of the sensor, which decreases as the precipitate is deposited on its surface (Figure 1), changing its total mass [2]. Previous works by Bouropoulos et al. have used magnetoelastic sensors based on the commercial material Metglas® 2826 for monitoring the kinetics of different precipitation reactions [3]; in this work a different amorphous ferromagnetic alloy ((Fe-Cr)-Based metallic glass of composition Fe73Cr5Si10B12) that has shown to have an improved corrosion resistance has been used [4]. This composition contains a small amount of chromium that allows the formation of a passivation layer on the material, thus favoring its corrosion-resistant behavior, which allows it to be used in biomimetic environments without any pre-treatment of its surface and avoid possible changes in the resonance frequency due to the corrosion of the ribbon. The precipitation reaction of calcium oxalate was carried out by mixing equal parts of solutions at the same concentration of oxalic acid and calcium chloride, and the formation of the insoluble salt crystals was monitored in a 500 s time interval. Solutions of different concentration (1, 5, 10, 30, 50 and 100 mM) were used in order to observe its effect on the rate of reaction (Figure 1).In addition, the monitoring of the reaction was complemented with the numerical fittings of the obtained resonance curves (Figure 2) to an analytical expression that describes the behavior of the resonance [5]. These numerical fittings improve the observation of the temporal evolution of the different parameters that characterize the response of the sensor (such as the resonance frequency, the damping parameters or the quality factor Q), and can be used to monitor the precipitation reaction, since in addition to a decrease in the resonance frequency, the deposition of calcium oxalate crystals on the ribbon causes an increase in the damping experienced by the sensor and therefore, a decrease in its quality factor. The numerical fittings made allowed to obtain this quality factor of the sensor with more accuracy than with traditional methods, which are unreliable when working with damped signals, such as when the sensor is immersed in a liquid and subject to mass loads. In addition, these fittings allow to get rid of the noise associated with the experimental measurements, which facilitates the calibration and use of the sensor. These fittings allow to follow the evolution of the precipitation reaction of calcium oxalate in a more reliable, precise and noiseless way. **