This low-cost, miniaturized, multiplexed, and connected platform has been tested and used experimentally as a DIS sensor node on ZigBee mesh. The platform interfaced three DIS sensors at the same time and relayed the information through the Zigbee network for data analysis and storage. Specifically, the platform has been tested for in situ dielectric impedance spectroscopy applications pertaining to fertilizer sensing, touch sensing, and water quality sensing, that find applications in many smart household, building, and industrial environments. To our knowledge, this is the first time a wireless platform, featuring an AD5933 device, was used along with touch and chemical sensors for environmental monitoring. For the sake of care, this warranted comparison with other known and well-calibrated impedance meters, such as the Solartron 1260 Impedance Analyzer [
12], which provides accurate complex impedance measurements in the AC frequency range from 1 Hz to 1 MHz.
3.1. Electro-Chemical Impedance Spectroscopy (EIS) Nitrate Sensors
Fertilizer sensors, such as nitrate sensors, controlled by DIS platforms find many applications in agriculture and allow the feeding of sensor data into online databases for continuous crop monitoring, production optimization, and data storage. A research challenge in this field is focused on the need to develop rapid, reliable, specific, and sensitive methods to detect and monitor these nutrients cost-effectively [
13,
14], while large scale analysis implies improved miniaturization, reduction of analysis time and cost, and wireless connectivity [
15].
The tested nitrate sensor [
4] comprises a set of electrode wires surrounded by an ion selective polymer membrane, as shown in
Figure 5a, and is controlled by the DIS platform described previously. The polymer membrane is inserted into the medium (preferably wet) and interacts locally with the medium under test. This sensor configuration provides two main electrical conduction paths, one within the polymer membrane, and the other into the medium under test, depicted as paths 1 and 2 in
Figure 5b, respectively. It is worth mentioning that both the membrane (path 1) and medium (path 2) are predominantly dielectric materials in nature and therefore exhibited poor DC electrical conductivities. Their electrical properties relate to various delocalized electrical carrier conduction mechanisms at play in non-crystalline materials, such as short-range carrier mobility, defect hopping/trapping, and carrier diffusion, which manifest themselves negligibly in DC but may become significant and easily-measured at AC frequencies in the kHz and MHz range [
4]. Therefore, electrical conductivity measurements of highly resistive materials becomes possible at high AC frequencies, thus bringing the range of measurability within the 10-MΩ impedance sensing limit of the AD5933 device. In this context, the AD5933 device was designed with a 16 MHz oscillator providing the highest frequency range of 5 kHz to 100 kHz [
11], and the equivalent electrical circuit model contained both resistance and reactance (capacitive) elements, which governed carrier mobility at this driving frequency range. Specifically, the electrical circuit model assigned resistances and capacitances related to the nitrate-selective polymer membrane (Path 1: R
1, C
1) and to the non-selective medium under test (Path 2: C
2-CPE
1-CPE
2), which comprised phenomenological constant phase elements (CPE) that account for carrier diffusion mechanisms and electrical double layers.
Figure 5.
(
a) Picture of the EIS nitrate sensor head connected to the DIS platform; and (
b) Schematics of the main electrical conduction paths of the EIS nitrate sensor: one through the polymer membrane and the other throughout the medium under test, with corresponding equivalent electrical circuits [
4].
Figure 5.
(
a) Picture of the EIS nitrate sensor head connected to the DIS platform; and (
b) Schematics of the main electrical conduction paths of the EIS nitrate sensor: one through the polymer membrane and the other throughout the medium under test, with corresponding equivalent electrical circuits [
4].
The polymer membrane is composed of high molecular weight polyvinyl chloride (PVC—from Aldrich) and of a plasticizer bis(2-ethylhexyl) phthalate (BEHP—also from Aldrich). Ion-selectivity is provided by adding two components to the polymer membrane: an ionophore and ionic sites. For the nitrate sensor, the ionophore consisted of tetramethyl cyclotetra-decanato-nickel(II) complex (NiTMTAA), and the ionic site consisted of trioctylmethylammonium chloride (TOMAC—from Aldrich). Both of these have been chosen according to the reversibility, selectivity (>4
, where A
− stands for NO
2−, HPO
42−, SO
42−, or Cl
−) and efficiency reported in previous potentiometric studies [
16]. Together, this polymer membrane composition can be dissolved into tetrahydrofurane and molded into any desired shape prior to drying, which brings mechanical strength, environmental endurance, and abrasion resistance, and which defines a stable baseline of electrical conductivity to the system.
Impedance measurements were performed by immersing the EIS nitrate sensor in 10 mL of KNO
3-containing (Aldrich—selectophore grade) deionized water (18 MΩ·cm) solutions set at 20 °C, room temperature. The sensor was left immersed in the solution for about 5 min to provide enough time for interaction and equilibrium with the ions. After this settling time, the sensor response became time invariant.
Figure 6a shows the impedance spectra of the immersed EIS nitrate sensors through a wide range of nitrate (NO
3−) concentrations, as measured by the Solartron Impedance analyzer, revealing strong dependence on nitrate concentration throughout the range from 0 to 6000 ppm. As expected, the polymer membrane exhibited a negative phase in the impedance spectra indicative of a resistance-capacitance material response (path 1), which, however, became strongly attenuated by the non-selective impedance of the medium at NO
3− concentrations higher than 100 ppm (path 2). The response time of the sensor was measured at about 1 min when the impedance response was dominated by path 1, and about 1 s when dominated by path 2.
The Solartron impedance analyzer measurements have been compared with the DIS platform measurements under the same laboratory conditions, as shown in
Figure 6b. The AD5933 device within the DIS platform exhibited higher measurement errors when operating close to upper or lower frequency limits of 5 kHz and 100 kHz, or when the sensor exhibited an impedance value far from the 200-kΩ calibration resistance. Overall, good agreement in impedance measurements was obtained between the AD5933 and Solartron, to within a ±10% comparative error level, through wide a range of nitrate concentrations. The comparative errors were about ±2% at 200 mV AC amplitude between 0.1 ppm and 100 ppm nitrate, which is the typical measurement range of nitrate sensors for agriculture applications.
3.2. Water Quality Sensors
In addition to being used as nitrate fertilizer sensors for agriculture, the abovementioned EIS nitrate sensors linked with the DIS platform can be used as a basis for water quality sensors, to the extent that these sensors become sensitive to a wide variety of ions in the medium under test when the conductivity of the medium (path 2) dominates the conductivity of the membrane (path 1), which occurs at ion concentrations higher than 100 ppm with the abovementioned sensor design. Water quality is a measure of the condition of water relative to the requirements of human consumption, and it is most frequently used by reference to a set of standards against which compliance can be assessed [
17]. In North America, standards pertaining to the suitability of water for human consumption are usually regulated at the state level, and the following contaminant concentration limits in water may be found: Nitrates (NO
3−) 45 ppm; Chloride (Cl
−) 307 ppm; Sodium (Na
+) 199 ppm; Sulfates (SO
42−) 560 ppm [
18]. Contaminants that may be found at hundreds of ppm concentration in water include inorganic runoffs from agricultural activities (e.g., nitrate, phosphate, potassium), which are a major cause of water pollution in rural areas. The complexity of water quality as a subject is reflected in the many types of measurements of water quality indicators. Measurements commonly made on-site and in direct contact with the water source include temperature, pH, dissolved oxygen, conductivity, oxygen reduction potential (ORP), and turbidity [
19]. Nowadays, citizens demand real-time information about the water they use daily and are drinking. Unfortunately, such information can be very expensive to obtain as water quality is usually sampled and analyzed at certified laboratories requiring water samples to be collected, preserved, transported, and analyzed at diverse locations.
Figure 6.
(a) Nyquist response of the EIS nitrate sensor as measured by the Solartron 1260 Impedance analyzer from 1 Hz to 1 MHz frequency, tested through a wide range of nitrate (NO3−) concentrations; and (b) Comparative EIS nitrate sensor measurement results obtained using the Solartron Impedance analyzer and the DIS Platform featuring an AD5933 device.
Figure 6.
(a) Nyquist response of the EIS nitrate sensor as measured by the Solartron 1260 Impedance analyzer from 1 Hz to 1 MHz frequency, tested through a wide range of nitrate (NO3−) concentrations; and (b) Comparative EIS nitrate sensor measurement results obtained using the Solartron Impedance analyzer and the DIS Platform featuring an AD5933 device.
The IS nitrate sensor connected to the DIS sensor node on ZigBee mesh provides an affordable in situ measurement technology for water quality sensing. In order to test the suitability of the DIS platform for water quality sensing, a set of water samples have been prepared with known concentrations of nitrate, chloride, sodium and sulfate contaminants. The abovementioned baseline of 45 ppm nitrate (NO
3−), 307 ppm chloride (Cl
−), 199 ppm sodium (Na
+), and 560 ppm sulfate (SO
42−) has been used to define contaminant concentration limit in water, wherein the water samples have been prepared by mixing selected molar quantities of potassium nitrate (KNO
3) (Sigma-Aldrich-ReagentPlus ≥99.0%), potassium sulfate (K
2SO
4) (Sigma-Aldrich, ReagentPlus ≥99.0%), and sodium chloride (NaCl) (EMD chemicals, GR ACS crystals) in deionized water (18 MΩ·cm). Three water samples have been prepared with 0.1×, 1×, and 10× levels of contaminant concentration limit in water, respectively. The DIS platform measurements, along with comparative Solartron impedance analyzer measurements, have been obtained at 20 °C room temperature, at 200 mV AC amplitude, at the AC frequency range from 30 kHz to 55 kHz, and are shown in
Figure 7. Overall, good agreement in impedance measurements was obtained between the DIS platform and the Solartron, to within a ±15% comparative error level in impedance modulus, and the DIS platform signal-to-noise response was sufficiently high to allow a reliable differentiation between varying contaminant concentration levels in water, either below or above the quality limit set by state-level agencies. Although contaminants in water may come with many different ions and with varying relative concentrations, such a DIS platform can be used, for example, as a non-selective distributed sensor for early detections of runoffs from agricultural/industrial activities, where sudden impedance anomalies in water can be detected within seconds and provide a trigger for emergency measures.
Figure 7.
Comparative EIS water quality sensor results obtained using the Solartron Impedance analyzer (solid lines) and the DIS platform (dotted lines), wherein the baseline of 45 ppm nitrate (NO3−), 307 ppm chloride (Cl−), 199 ppm sodium (Na+), and 560 ppm sulfate (SO42−) has been used to define the contaminant concentration limit in water.
Figure 7.
Comparative EIS water quality sensor results obtained using the Solartron Impedance analyzer (solid lines) and the DIS platform (dotted lines), wherein the baseline of 45 ppm nitrate (NO3−), 307 ppm chloride (Cl−), 199 ppm sodium (Na+), and 560 ppm sulfate (SO42−) has been used to define the contaminant concentration limit in water.
3.3. Glass Touchscreen Sensors
The development of glass compounds that transmit both light and electricity represents one of many challenges in the field of materials sciences. Phosphate-based glasses, depending on the glass composition, exhibit high solubility to metallic ions, high chemical and mechanical stability, and high glass transition and crystallization temperatures [
20]; in particular, the phosphate glasses belonging to the AgI-AgPO
3-WO
3 system provide high AC ionic conductivities at room temperature (
i.e., 10
−2 ≥ σ ≥ 10
−3 S·cm
−1) at kHz driving frequencies. This set of attributes are of great interest to science and technology as these glasses may form the basis for electro-optics modulators for telecommunication devices where an electrical field applied to the solid can modulate the phase, the frequency, the amplitude, or the polarization of the incident light passing through the material [
21,
22]. They may also be used as microprobes to measure the electrical activity of neurons in the brain [
23], or integrated into smart textiles to perform radio-frequency emission and electrical interconnect functions [
24].
In this work, the AgI-AgPO
3-WO
3 glass system [
20] and the DIS platform have been used in tandem as the basis for a capacitive touch sensor. Many types of sensors use capacitive sensing, including interface devices, such as trackpads and touchscreens [
25] that can replace mechanical buttons on screens, doors, and windows. These interface devices are generally enabled by the use of conductive specialty thin films (such as Indium-Tin-Oxide, ITO) that tend to be expensive due to containing elements like indium and due to requiring vacuum deposition processes. However, the use of AgI-AgPO
3-WO
3 glasses could open new opportunities for touchscreen devices as they can be manufactured in large float-glass quantities at low cost. For this study, 10 mm diameter, 8 mm thick, 45AgI-(55-
x)AgPO
3-
xWO
3 glass samples, with
x = 0, 12, 15, and 20 mol%, have been used, as pictured in
Figure 8a. Two copper electrodes were pasted on the side of each glass samples using silver paint; the silver paint used consisted of colloidal silver from Pelco
® with a sheet resistance of 0.02–0.05 ohms/sq/mil.
Figure 8b,c illustrate the principle behind glass touchscreens: an object (e.g., finger, conductive stylus) touches the conductive glass and alters the electrical coupling between the two electrodes, creating a grounded path along the touch point, thus changing the overall impedance of the system as recorded through the electrodes. An equivalent electro-static model of the glass touchscreen is illustrated in
Figure 8c, wherein the touch function actuates the grounded state of the glass system.
First, we have investigated the complex impedance of untouched AgI-AgPO
3-WO
3 glasses to characterize the materials under alternate current (AC).
Figure 9a shows the Nyquist complex impedance spectra of 45AgI-(55-
x)AgPO
3-
xWO
3 glass samples with
x = 0, 12, and 20 mol%. The impedance measurements were performed at 22 °C in ambient atmosphere using the Solartron Impedance analyzer. The measured Nyquist profiles are indicative of a resistance-capacitance parallel equivalent electrical circuit behavior [
25] as illustrated in
Figure 8c. The Solartron impedance analyzer measurements have been compared with the DIS platform measurements as shown in
Figure 9b. Overall, good agreement in impedance measurements in the AC frequency range from 30 kHz to 120 kHz was obtained between the DIS platform and Solartron, to within a ±15% comparative error level in impedance modulus.
Figure 8.
(a) Picture of the 45AgI-(55-x)AgPO3-xWO3 glass sample with x = 15 mol%; (b) Representation of the glass touchscreen setup, wherein the copper electrodes were connected to the DIS platform; and (c) equivalent electro-static circuit of the AgI-AgPO3-WO3 glass touchscreen.
Figure 8.
(a) Picture of the 45AgI-(55-x)AgPO3-xWO3 glass sample with x = 15 mol%; (b) Representation of the glass touchscreen setup, wherein the copper electrodes were connected to the DIS platform; and (c) equivalent electro-static circuit of the AgI-AgPO3-WO3 glass touchscreen.
Second, we have investigated the impedance effect of a touched AgI-AgPO
3-WO
3 glass to characterize the materials as the basis of a glass touchscreen.
Figure 10 shows the response of a 45AgI-(55-
x)AgPO
3-
xWO
3 (
x = 15 mol%) glass touchscreen sensor recorded using the DIS platform at an AC frequency of 30 kHz. The DIS platform data acquisition is performed in less than 2 s, consequently the 12-s touches were clearly recorded, with a signal-to-noise ratio exceeding 50, thus demonstrating that the DIS platform can be used for in situ dielectric impedance applications pertaining to touch sensing, enabling advanced touchscreen applications like smart doors and smart windows without the use of expensive specialty thin film coatings on glass.
Figure 9.
(a) Nyquist complex impedance of untouched 45AgI-(55-x)AgPO3-xWO3 glasses, using 200 mV excitation voltage on the Solartron Impedance analyzer from 1 Hz to 1 MHz frequency; and (b) Comparative impedance results obtained using the Solartron Impedance analyzer and the DIS Platform featuring an AD5933 device.
Figure 9.
(a) Nyquist complex impedance of untouched 45AgI-(55-x)AgPO3-xWO3 glasses, using 200 mV excitation voltage on the Solartron Impedance analyzer from 1 Hz to 1 MHz frequency; and (b) Comparative impedance results obtained using the Solartron Impedance analyzer and the DIS Platform featuring an AD5933 device.
Figure 10.
Touch sensing response of a 45AgI-(55-x)AgPO3-xWO3 (x = 15 mol%) glass sample recorded using the DIS platform at an AC frequency of 30 kHz, at 22 °C in ambient atmosphere. The time plot clearly resolves successive 12-s touches applied to the glass, with “touch” corresponding to higher impedance.
Figure 10.
Touch sensing response of a 45AgI-(55-x)AgPO3-xWO3 (x = 15 mol%) glass sample recorded using the DIS platform at an AC frequency of 30 kHz, at 22 °C in ambient atmosphere. The time plot clearly resolves successive 12-s touches applied to the glass, with “touch” corresponding to higher impedance.