Additive manufacturing of sensors

Abstract

A method of additive manufacturing a sensor is provided. The method comprises providing a working electrode and a reference electrode, wherein the reference electrode and the working electrode comprise a conductive agent composition; and delivering a film agent composition onto the reference electrode to form a film, wherein the film formed on the reference electrode is an ion saturated film. In addition, a system for an additive manufacturing sensor is provided. The system includes a receiving region configured to receive an electrode; a film head for delivering a film agent composition onto the electrode through the nozzle; the container carrier is connected to the membrane head; a drive arm configured to drive the film head at least above the receiving area; and a film head actuator configured to feed a film agent composition to the nozzle. Further, a method of additive manufacturing the sensor assembly is provided.

Description

[0001] This application claims the benefit of European Patent Application EP22382764.3, filed on August 5, 2022.

[0002] The present disclosure relates to systems and methods for additive manufacturing sensors. Additionally, the present disclosure relates to systems and methods for additive manufacturing sensor assemblies. Background Art

[0003] Sensors can be at least partially based on a membrane (ion-selective membrane or ion-saturated membrane). The membrane can be formed on the electrodes of the sensor by dropcasting a membrane agent composition. Dropcasting is typically a manual process in which droplets are cast onto a substrate by an operator. Thus, the reproducibility of at least these sensors highly depends on the skill or ability of the operator to properly dropcast the membrane agent composition onto the electrodes of the sensor each time dropcasting is performed. In particular, dropcasting can involve a labor-intensive process, which may limit the scalability of sensor manufacturing.

[0004] Moreover, there are very few parameters that can be controlled in dropcasting. Typically, only the volume of the membrane agent composition delivered to the electrodes is controlled. By only controlling the volume of the membrane agent composition delivered to the electrodes, the reproducibility of the membrane agent composition delivered to the electrodes may be low. Thus, the formed membrane may be sensitive to the coffee ring effect and may not have a constant thickness. Consequently, the manufactured sensors may have poor performance or may even be defective.

[0005] Sensing devices for monitoring, for example, water quality, blood, and saliva can include sensors to determine characteristics of interest, such as redox, pH, free chlorine, conductivity, and temperature. Typically, only a single characteristic of interest is measured at a time. If multiple characteristics must be measured, the sensing device has a stack of several sensors (e.g., a redox sensor, a pH sensor, a free chlorine sensor, a conductivity sensor, and a temperature sensor).

[0006] For pH detection, the current state-of-the-art glass electrodes are large, fragile, and expensive. Glass electrodes require calibration and cleaning of the electrodes between each measurement. Thus, the current state-of-the-art glass electrodes are not suitable for portable applications.

[0007] In addition, free chlorine is typically determined by an optical method that involves adding N,N - diethyl - p - phenylenediamine (DPD) and detecting a color change in a fluid sample. The detection of free chlorine may involve a reaction between the amine group of DPD and chlorine, which produces a pink - colored compound. The color change is detected by an optical system. The optical system uses DPD to perform spectral analysis on the fluid sample. However, such an optical system is bulky and is operated in a laboratory. Therefore, the optical method for determining free chlorine is complex, expensive, not suitable for portable applications, and not suitable for continuous monitoring. In the best - case scenario, each sampled fluid sample is monitored.

[0008] In summary, in order to detect two or more features of interest, the sensing device can stack several sensors to form a sensor assembly. Thus, the sensing device can include, for example, a glass electrode for pH sensing; a light source, a cuvette, DPD, a photodetector, and a free - chlorine detection circuit. Therefore, the sensing device is bulky and may not be suitable for portable applications.

[0009] Examples of the present disclosure seek to at least partially reduce one or more of the above - mentioned problems. Summary of the Invention

[0010] In one aspect, a system for additive manufacturing of sensors is provided. The system includes a receiving area configured to receive an electrode; a membrane head for delivering a membrane agent composition onto the electrode through a nozzle. In particular, the membrane head includes a connection port to receive an outlet end portion of a container for storing the membrane agent composition. In addition, the system includes a container carrier configured to hold the container by a carrier end portion of the container. The container carrier is connected to the membrane head. Further, the system includes a drive arm configured to drive the membrane head at least above the receiving area; and a membrane head actuator configured to feed the membrane agent composition to the nozzle, wherein the membrane head actuator is in fluid communication with the connection port.

[0011] By the action of the container carrier, the configuration of the membrane head and the container allows for efficient feeding of the membrane agent composition from the outlet end portion of the container to the membrane head through the connection port.

[0012] In this configuration, the outlet end portion of the container is connected to the connection port of the membrane head. Thus, the membrane agent composition is fed directly to the membrane head. There is no intermediate connector such as a feed pipe between the container and the membrane head. Therefore, the compounds of the membrane agent composition cannot react with the feed pipe and inherently dissolve and / or deform at least a portion of the feed pipe. A deformed or abnormally shaped feed pipe will inherently cause pressure changes, which may alter the reproducibility of the formed membrane. Since there is no intermediate connector, pressure changes in the steps can be reduced or even avoided. In this way, the reproducibility of the formed membrane can be improved. In addition, this configuration can avoid replacing a damaged feed pipe, thereby avoiding interruption of the subsequent manufacturing process.

[0013] In addition, since there is no feed pipe, there is no need to fill the feed pipe to feed the membrane head. In accordance with this aspect, there is no feed pipe connecting the container and the membrane head. Thus, through the action of the container carrier, the configuration of the membrane head and the container can reduce the amount of the membrane agent composition used. Therefore, the manufacturing process can be more efficient, and the cost of manufacturing the sensor can be reduced.

[0014] In some instances, the container carrier can include a carrier arm. In these instances, the carrier arm can include a hollow portion configured to receive at least the carrier end portion of the container. The carrier arm can engage at least the carrier end portion of the container. Thus, the container carrier can hold the container through, for example, the hollow portion, through the carrier end portion of the container. Accordingly, the proper placement of the container relative to the membrane head can be improved.

[0015] In some instances, the membrane head can have an overall elongated configuration, thereby defining a longitudinal axis of the membrane head, and the container can be configured such that a container longitudinal axis is defined from the carrier end portion to the outlet end portion. In these instances, the container carrier can be configured to hold the container in a manner that defines an angle between the longitudinal axis of the membrane head and the longitudinal axis of the container. Thus, when the carrier arm engages at least the carrier end portion of the container, the angle can be maintained. Accordingly, an inappropriate angle between the connection port of the membrane head and the outlet end portion of the container can be avoided. Thus, through the action of the container carrier, leakage of the membrane agent composition can be avoided. In addition, through the action of the container carrier, the connection between the container and the membrane head can have lower vibration sensitivity, such as when the container carrier moves.

[0016] Since the membrane agent composition is delivered by the membrane head, the parameters of delivery are no longer limited to the volume of the membrane agent composition; rather, there can be multiple parameters to control the delivery of the appropriate membrane agent composition onto the electrode substrate. The multiple parameters can include, for example, pressure; delivery speed; membrane agent composition feed rate; and the distance between the nozzle outlet and the electrode substrate. By controlling the increased number of parameters, the delivered membrane agent composition can form a film with a constant thickness on the electrodes provided on the electrode substrate. Accordingly, the manufactured sensor can have improved performance.

[0017] Due to the synergistic effect resulting from the direct connection between the container and the membrane head and the use of the membrane head, the above parameters can be controlled even more precisely. This may contribute to the delivery of the membrane by additive manufacturing.

[0018] In other aspects, a method of additive manufacturing a sensor is provided. The method includes providing a working electrode and providing a reference electrode. The reference electrode and the working electrode comprise a conductive agent composition. The method includes delivering a membrane agent composition onto the reference electrode to form a film, wherein the film formed on the reference electrode is an ion-saturated film.

[0019] Thus, since the ion-saturated membrane is saturated with a specific ion, the potential of the reference electrode can be maintained stable at a predetermined reference electrode potential.

[0020] In some examples, the first reference electrode can be made of a first conductive ink. In some of these examples, the first conductive ink can include at least one of silver and silver chloride.

[0021] According to this aspect, providing an electrode (e.g., a working electrode or a reference electrode) can include an electrode substrate that includes electrodes (e.g., a first reference electrode; a second reference electrode; a first working electrode; a second working electrode; a third working electrode; and a counter electrode), or delivering a conductive agent composition onto the electrode substrate by additive manufacturing to form electrodes (e.g., a first reference electrode; a second reference electrode; a first working electrode; a second working electrode; a third working electrode; and a counter electrode).

[0022] Since the membrane of the sensor is additively manufactured, the membrane is no longer manually drop-cast by an operator, but by a system for additive manufacturing of the sensor. Thus, the reproducibility of the manufactured sensor does not depend on the skill or ability of the operator to perform the appropriate drop-casting of the membrane onto the electrodes of the sensor, but on controlled parameters (e.g., pressure; surface tension; delivery speed; membrane agent composition feed rate; nozzle temperature; bed temperature; and the distance between the nozzle outlet and the electrode substrate). Thus, the reproducibility of the membrane can be increased.

[0023] Furthermore, additive manufacturing of the sensor can allow for controlling more parameters than drop-casting to deliver the membrane agent composition onto the electrodes. Thus, by increasing the controlled parameters, the formed membrane can have a substantially constant thickness on the electrodes. Thus, the performance of the additively manufactured sensor can be improved.

[0024] According to this aspect, a sensor including a membrane is additively manufactured. The scalability of manufacturing a sensor including a membrane can be improved. Thus, the cost and time for manufacturing the sensor can be reduced.

[0025] In other aspects, a method of additive manufacturing a sensor assembly is provided. The method includes providing a first sensor on an electrode substrate, wherein the first sensor is manufactured using an additive manufacturing method according to any of the examples disclosed herein; providing a first reference electrode on the electrode substrate; and providing a first working electrode on the electrode substrate. The method further includes spraying an IrOX reagent composition onto the first working electrode, wherein the first reference electrode and the IrOX-sprayed first working electrode form a second sensor on the electrode substrate, and the second sensor is a pH sensor.

[0026] In some instances, a sensor assembly additively manufactured on an electrode substrate may include at least one of the following: a redox sensor; a membrane-based pH sensor; a pH sensor based on an IrOX reagent composition; a chlorine sensor; a conductivity sensor; and a temperature sensor. The sensor assembly may include two or more of the above sensors. Thus, the sensor assembly may be suitable for portable applications since it includes two or more sensors delivered onto the same electrode substrate.

[0027] In other aspects, a method for manufacturing a microfluidic device is provided. The method includes providing a microfluidic device including a structure; and connecting the microfluidic device to a sensor obtained by a method according to the examples disclosed herein, or to a sensor assembly obtained by a method according to the examples disclosed herein. Further, the structure may include an inlet channel, an outlet channel, and a detection chamber in fluid communication with the inlet channel and the outlet channel. Additionally, the microfluidic device may be connected to the sensor such that the detection chamber is in fluid connection with an electrode of the sensor or an electrode of the sensor assembly. Thus, a rapid point-of-care analysis device may be provided.

[0028] The term "additive manufacturing" may refer to an automated process of delivering successive layers on a manufacturing substrate. The automated process may include screen printing; 3D screen printing; spraying; binder jetting; material jetting; and material extrusion.

[0029] The term "structure" may be understood as a spatial model along three different dimensions (i.e., x, y, z) of three-dimensional space, which may be any suitable spatial arrangement, such as a layer, a wafer, a cube, a cone, a cylinder, a disc, a hexagonal prism, a triangular prism, a pentagonal prism, a tetrahedron, an octahedron, a sphere, and any combination thereof.

[0030] The term "wt%" may be used to refer to the weight percentage of a first component (e.g., solid content) relative to the total weight of a second component (e.g., ink). BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Non-limiting examples of the present disclosure will be described below with reference to the drawings, wherein:

[0032] Figure 1a A block diagram schematically showing a method for additively manufacturing a sensor according to an example of the present disclosure;

[0033] Figure 1b A block diagram schematically showing a method for additively manufacturing a sensor according to an example of the present disclosure;

[0034] Figure 2 A block diagram schematically showing a method for additively manufacturing a sensor according to an example of the present disclosure;

[0035] Figure 3 A block diagram schematically showing the manufacture of a conductive track according to an example of the present disclosure;

[0036] Figure 4 A block diagram schematically showing the spraying of a platinum reagent composition according to an example of the present disclosure;

[0037] Figure 5 A block diagram schematically showing the spraying of an IrOX reagent composition according to an example of the present disclosure;

[0038] Figure 6 A block diagram schematically showing the jetting of a gold nanoparticle reagent composition according to an example of the present disclosure;

[0039] Figure 7a A sensor assembly including an additively manufactured sensor according to an example of the present disclosure;

[0040] Figure 7b Schematically showing an example of the present disclosure including a conductive track Figure 7a of the sensor assembly;

[0041] Figure 8 A cross-sectional view of a system for additively manufacturing a sensor according to an example of the present disclosure; and

[0042] Figure 9 A schematic view of a system for additively manufacturing a sensor according to an example of the present disclosure. Specific Embodiments

[0043] In these figures, the same reference numerals are used to denote matching elements.

[0044] Examples of the methods disclosed herein are not limited to a particular order.

[0045] Figure 1a A block diagram 100 of a method for additively manufacturing a sensor is schematically shown. The film of the sensor can be according to any example disclosed herein. The method can be implemented by a system for additively manufacturing a sensor according to any example disclosed herein.

[0046] Throughout the specification, the term "additive manufacturing" can be understood as an automated process in which successive layers are delivered onto a manufacturing substrate.

[0047] In some examples, the additive manufacturing of the present disclosure can be selected from screen printing; 3D screen printing; spraying; binder jetting; material jetting (e.g., inkjet); and material extrusion.

[0048] In Figure 1a, electrodes are provided in block 110. Providing the electrodes may include an electrode substrate that includes electrodes (e.g., a first reference electrode; a second reference electrode; a first working electrode; a second working electrode; a third working electrode; and a counter electrode). The electrode substrate may include one or more electrodes that can be provided on or within the electrode substrate by additive manufacturing or another manufacturing method. For example, the provided electrodes may be screen-printed electrodes.

[0049] Figure 1b FIG. 100 is a block diagram schematically showing a method of additive manufacturing a sensor according to an example of the present disclosure. In Figure 1b , providing the electrodes at block 110 may include delivering a conductive agent composition onto the electrode substrate by additive manufacturing to form the electrodes, see block 112. In this example, providing the electrodes at block 110 includes additionally curing the conductive agent composition at block 114. Curing can be carried out, for example, by heating the conductive agent composition in an oven.

[0050] In summary, providing the electrodes may include an electrode substrate that includes the electrodes, or delivering a conductive agent composition onto the electrode substrate to form the electrodes.

[0051] The electrodes provided by the electrode substrate including the electrodes or the electrodes provided by delivering a conductive agent composition onto the electrode substrate to form the electrodes contain the conductive agent composition.

[0052] The conductive agent composition may include at least one conductive compound selected from the following: such as silver; carbon; carbon allotropes; and copper. In particular, the conductive compound may have one to four valence electrons. In addition, the conductive agent composition may contain a solids content of 10 wt% to 90 wt% of the total weight of the ink; specifically 20 wt% to 80 wt% of the solids content; more specifically 30 wt% to 70 wt% of the solids content.

[0053] Referring to Figure 1a and Figure 1b , at block 120, a membrane agent composition is delivered onto the electrodes to form a membrane. The membrane agent composition is delivered by additive manufacturing. The membrane agent composition may vary according to the characteristics of the membrane to be formed. The characteristics may be related to the function of the membrane, for example, ion-saturated or ion-selective.

[0054] In some examples, the membrane agent composition may be delivered onto a reference electrode to form a membrane; or onto a working electrode to form a membrane.

[0055] In some instances, the formed membrane can be an ion-saturated membrane. The ion-saturated membrane can be saturated with specific ions. In these instances, the film-forming composition for forming the ion-saturated membrane can comprise a polymer; a solvent; and a specific ionic compound. In particular, the polymer can be polyvinyl butyral (PVB); the solvent can be methanol; and the specific ionic compound can be NaCl, such that the ion-saturated membrane is saturated with Cl - ions. In these instances, the characteristics of the membrane to be formed can include being ion-saturated.

[0056] In some instances, the formed membrane can be an ion-selective membrane. The ion-selective membrane can be based on an ionophore. An ionophore is a lipophilic complexing agent capable of reversibly binding specific ions. For an ion-selective membrane, its selectivity can depend on, for example, the free energy of transfer of a specific ion from a fluid sample to the ion-selective membrane; the complex formation constant between the specific ion and the ionophore; and / or the concentration of the film-forming compound in the membrane. In these instances, the film-forming composition for forming the ion-selective membrane can comprise a polymer, a solvent, an ionophore compound, an additive, and a plasticizer. In particular, the polymer can be polyvinyl chloride (PVC), the solvent can be tetrahydrofuran (THF), the ionophore compound can be tri-n-dodecylamine (TDDA), and the additive can be an anionic additive such as potassium tetrakis(4-chlorophenyl)borate (KTpClPB). Since TDDA is a hydrogen-selective ionophore, the membrane that can be formed from the film-forming composition can be selective for hydrogen ions (e.g., H + ).

[0057] In some instances, the concentration of the anionic additive, i.e., KTpClPB, can change the ion selectivity of the membrane formed from the film-forming composition.

[0058] In some of these instances, suitable plasticizers can include at least one of the following: bis(2-ethylhexyl) sebacate (DOS); 2-nitrophenyl octyl ether (NPOE); o-nitrophenyl octyl ether (o-NPOE); tris(2-ethylhexyl) phosphate; dibutyl sebacate; dioctyl sebacate; bis(2-ethylhexyl) adipate; bis(2-ethylhexyl) phthalate; dioctyl phenylphosphonate; and mixtures thereof. The type of plasticizer used in the membrane can be selected considering the composition of the polymer. In these instances, the plasticizer can be present in an amount of 40 wt% to 80 wt%, specifically 50 wt% to 70 wt%, more specifically about 66 wt%. In these instances, the characteristics of the membrane to be formed can include being ion-selective.

[0059] The film composition can be prepared using any suitable technique for preparing a film composition, for example, by dissolving the compounds of the film composition in a solvent such as methanol or tetrahydrofuran. Other solvents or solvent mixtures can be used. The film composition can be delivered by a system for additive manufacturing sensors according to any of the examples disclosed herein. The formed film can be dried at ambient temperature.

[0060] For example, an ion-saturated film can be formed from the following film composition: Dissolve PVB (61 wt%) in 5 mL of methanol. NaCl (39 wt%) can be added to the mixture. The total weight of the film composition can be 645 g.

[0061] For example, an ion-selective film can be formed from the following film composition: Dissolve PVC (32.4 wt%); o-NPOE (66 wt%); and KTpClPB (0.6 wt%) in 5 mL of THF. TDDA (1 wt%) can be added to the mixture. The total weight of the film composition can be 370 g.

[0062] Figure 2 A block diagram 200 of a method for additive manufacturing a sensor according to an example of the present disclosure is shown respectively.

[0063] In Figure 2 this example, the electrode substrate providing the electrode is pretreated. At block 202, the electrode substrate can be surface-treated prior to block 110. Surface treatment can be performed prior to block 110 to at least partially avoid shrinkage of the electrode substrate when, for example, the conductive agent composition cures. In some examples, prior to block 110, the electrode substrate may not be surface-treated.

[0064] During curing, the shape of, for example, a delivered conductive agent composition or other delivered reagent composition can change. The other delivered reagent composition can be any reagent composition that is otherwise delivered onto the provided electrode. To avoid abnormal shapes, before delivering the conductive agent composition or other reagent composition, the electrode substrate can be heated at a predetermined temperature for a predetermined time. The electrode substrate can be heated at the predetermined temperature, which depends on the highest curing temperature of the conductive agent composition or other reagent composition to be delivered onto the electrode substrate. The predetermined time can be the time during which the conductive agent composition or other reagent composition can be heated to have the highest curing temperature. For example, the conductive agent composition delivered at block 110 can be cured by heating the delivered conductive agent composition at 130 °C for 30 minutes. In this example, the other reagent composition can be cured by heating the other reagent composition at 140 °C for 30 minutes. Thus, in this example, the surface treatment can include heating the electrode substrate at 140 °C for 30 minutes, which is the highest curing temperature between the curing temperature of the conductive agent composition and the curing temperature of the other reagent composition. In this example, the predetermined time can be 30 minutes because this is the time associated with the highest curing temperature.

[0065] Depending on the material of the electrode substrate, the surface treatment can be selected from at least one of the following: heat treatment, oxygen plasma, and delivering a dielectric agent composition onto the electrode substrate. Thus, if the material of the electrode substrate changes, the surface treatment applied to the electrode substrate before block 110 can change.

[0066] In some examples, the electrode substrate can be a polymer. In these examples, before block 110, the polymer can be heat treated at block 204 (which can be delivering the conductive agent composition onto the electrode substrate). The polymer can be selected from at least one of the following: polyethylene terephthalate PET; polyethylene naphthalate PEN; polyimide, such as Kapton; polycarbonate PC; polymethyl methacrylate PMMA; thermoplastic polyurethane TPU; and paper.

[0067] In some examples, the electrode substrate can be a metallic material or a textile material. In these examples, before block 110, the metallic material or textile material can be heat treated at block 204, and then a dielectric agent composition can be delivered onto at least a portion of the electrode substrate at block 208 before block 110 (which can be delivering the conductive agent composition onto the electrode substrate). Note that the dielectric agent composition can thereafter be cured by heating or exposure to electromagnetic radiation. The dielectric agent composition can be heated or exposed to electromagnetic radiation depending on its composition.

[0068] In some instances, the electrode substrate can be an oxide material or a ceramic material. In these instances, at block 206 before block 110, the oxide material or ceramic material can be treated with oxygen plasma (which can be delivering a conductive agent composition onto the electrode substrate).

[0069] In summary, referring Figures 1a to 1b and / or Figure 2 , a film can additionally be deposited onto the electrode comprising the conductive agent composition.

[0070] In some instances, the conductive agent composition can include a first conductive ink. The first conductive ink can comprise at least one of silver and silver chloride. When the provided electrode comprises the first conductive ink, the provided electrode can include a first reference electrode and / or a second reference electrode.

[0071] In some instances, the conductive agent composition can include a second conductive ink. The second conductive ink can comprise at least one of amorphous carbon, carbon black, and graphite. When the provided electrode comprises the second conductive ink, the provided electrode can include a counter electrode and / or a first working electrode and / or a second working electrode.

[0072] In some instances, the conductive agent composition can include a third conductive ink. The third conductive ink can comprise silver. When the provided electrode comprises the third conductive ink, the provided electrode can include a silver reference electrode and / or a silver working electrode, which can be made of silver.

[0073] In some of these instances, referring Figure 1b and / or Figure 2 to the description of, delivering the conductive agent composition can include delivering at least one of the following: a first conductive ink having at least one of silver and silver chloride; a second conductive ink having at least one of amorphous carbon, carbon black, and graphite; and a third conductive ink to form an electrode.

[0074] Furthermore, as described in the description at block 114 above Figure 1b , the conductive agent composition delivered onto the electrode substrate can be cured.

[0075] The first conductive ink can be cured by heating the first conductive ink at 130 °C for 30 minutes.

[0076] The second conductive ink can be cured by heating the second conductive ink at 130 °C for 30 minutes.

[0077] The third conductive ink can be cured by heating the third conductive ink at 130 °C for 30 minutes.

[0078] Thus, the electrode substrate can include at least one of the following: a first reference electrode, a second reference electrode, a counter electrode, a first working electrode, a second working electrode, and a third working electrode.

[0079] In some instances, the surface of the electrode substrate can be completely covered by the formed electrode.

[0080] In some instances, the formed electrode can cover a portion of the surface of the electrode substrate.

[0081] Figure 3 FIG. 300 schematically shows a block diagram of the manufacturing of a conductive track according to an example of the present disclosure. Figure 3 The features of can be described in combination with the features of any of the examples shown in FIGS. 1 to Figure 2 The features of any of the examples shown in FIGS. 1 to Figure 2 The examples of the method shown can also include or not include Figure 3 the features of the examples.

[0082] In Figure 3 the example of, the method of additive manufacturing a sensor includes screen printing a conductive track on an electrode substrate at block 302. In some instances, the screen printing can be performed by a pneumatic screen printer, specifically by a pneumatic flat screen printer.

[0083] The conductive track can comprise a conductive compound selected from at least one of the following: such as silver, carbon, carbon allotropes, and copper. As described above, the conductive compound can have one to four valence electrons. In Figure 3 this example of, the conductive track comprises silver.

[0084] At block 304, the screen printed conductive track on the electrode can be cured by heating the screen printed conductive track and exposing the screen printed conductive track to electromagnetic radiation. The screen printed conductive track can be heated by exposure to electromagnetic radiation. The electromagnetic radiation can be provided by any type of electromagnetic radiation source that generates electromagnetic radiation having a wavelength of 240 nm to 270 nm. In some instances, the electromagnetic radiation source can have a peak emission wavelength within this range. However, in other instances, the electromagnetic radiation source can have a peak emission wavelength outside this range. Even if the peak emission wavelength is outside this range, the electromagnetic radiation source can still generate sufficient radiation having a wavelength of 240 nm to 270 nm to heat the conductive track composition.

[0085] In some instances, the electromagnetic radiation source can include a UV light emitting diode (LED), a mercury lamp, etc. In some instances, the electromagnetic radiation source can include a UV-LED that emits a central emission wavelength of 200 nm to 420 nm, specifically 240 nm to 270 nm.

[0086] The rate at which the evaporable solvent evaporates from the screen-printed conductive tracks may be related to the intensity of the applied electromagnetic radiation. For example, a lower intensity may involve rapid evaporation, while a higher intensity may involve more persistent evaporation. The intensity can be adjusted by selecting an electromagnetic radiation source with a desired power, or by adjusting the power density of the electromagnetic radiation source, etc.

[0087] In summary, in Figure 3 the example of

[0088] Referring to FIGS. 1 to Figure 3 as described, the electrode substrate may include one or more electrodes, such as a first reference electrode, a second reference electrode, a counter electrode, a first working electrode, a second working electrode, and a third working electrode.

[0089] To obtain a sensor, a film may be delivered onto one or more electrodes, and / or other reagent compositions may be delivered onto one or more electrodes. In both cases, the film and other reagent compositions may be delivered onto the cured electrodes (i.e., providing pre-cured electrodes, or the formed electrodes cured after the conductive agent composition is delivered onto the electrode substrate).

[0090] The following drawings and examples are intended to explain how to obtain a sensor or a sensor assembly (such as a redox sensor, a pH sensor, a chlorine sensor, a conductivity sensor, and a temperature sensor) by at least partially applying the methods disclosed in the description of FIGS. 1 to Figure 3 In addition, two or more sensors may be obtained on the same electrode substrate. The two or more sensors may be the same sensor (e.g., a first redox sensor and a second redox sensor) or different sensors (e.g., a redox sensor and a pH sensor).

[0091] Figure 4 FIG. 400 schematically shows a block diagram of spraying a platinum reagent composition according to an example of the present disclosure. Figure 4 The features of Figure 3 may be described in combination with the features of any example shown in FIGS. 1 to Figure 3 The examples of the methods shown in FIGS. 1 to Figure 4 may or may not also include the features of the example of

[0092] In Figure 4 , in block 402, the platinum reagent composition is sprayed onto the first working electrode. In this example, the other reagent composition may be the platinum reagent composition.

[0093] In some instances, spraying can be performed by using a pressurized gas, such as air with a flow rate of 50 μL / min to 1000 μL / min; specifically, air with a flow rate of 100 μL / min to 800 μL / min; more specifically, air with a flow rate of 200 μL / min to 700 μL / min.

[0094] At block 404, the delivered platinum reagent composition is cured by heating the platinum reagent composition at 80 °C for 10 minutes.

[0095] In Figure 4 instances, the platinum reagent composition can be a platinum-on-carbon composition containing 3 wt% platinum.

[0096] It can be noted that the curing parameters (e.g., heating temperature; and time for heating the platinum reagent composition) can vary depending on the platinum reagent composition. In some instances, the curing parameters can be different from the above parameters.

[0097] Some instances of the sensor are shown below. The sensors described below can be combined in a sensor assembly. The first sensor, the second sensor, etc. can be additively manufactured on the same electrode substrate of the sensor assembly. Additive manufacturing of the first sensor on the electrode substrate does not exclude additive manufacturing of additional sensors (e.g., the second sensor, the third sensor, the fourth sensor, etc.) on the same electrode substrate. The sensors additively manufactured on the same electrode substrate can be selected from at least one of the following: a redox sensor, a pH sensor, a chlorine sensor, a conductivity sensor, and a temperature sensor. Thus, the following sensors are not mutually exclusive.

[0098] Redox sensor according to an example:

[0099] If the platinum reagent composition is sprayed onto the first working electrode and the membrane agent composition is delivered onto the first reference electrode to form a membrane, a redox sensor can be obtained. The obtained redox sensor can be a potentiometric sensor.

[0100] In these instances, the membrane formed on the first reference electrode is an ion-saturated membrane. The ion-saturated membrane can be manufactured according to the instances disclosed in Figure 1a and Figure 1b descriptions. The ion-saturated membrane can be saturated with chloride ions such that the potential of the Ag / AgCl reference electrode (i.e., the first reference electrode) can be maintained stable at a predetermined reference electrode potential. Thus, the ion-saturated membrane can keep the concentration of chloride ions in contact with the Ag / AgCl reference electrode substantially constant.

[0101] pH sensor according to an example:

[0102] When the film formed on the Ag / AgCl reference electrode (i.e., the first reference electrode) can be an ion-saturated film, a pH sensor can be obtained; and the film formed on the first working electrode can be an ion-selective film selective to hydrogen ions. The pH sensor can be a potentiometric sensor.

[0103] According to Figure 1a and Figure 1b the examples disclosed in the description of, the first working electrode can be made of a second conductive ink. The second conductive ink can include at least one of amorphous carbon, carbon black, and graphite.

[0104] On the one hand, the ion-saturated film can be manufactured according to Figure 1a and Figure 1b the examples disclosed in the description of. The ion-saturated film can be saturated in chloride ions so that the potential of the Ag / AgCl reference electrode can be maintained stable at a predetermined reference electrode potential. Therefore, the ion-saturated film can keep the concentration of chloride ions in contact with the Ag / AgCl reference electrode substantially constant.

[0105] On the other hand, the ion-selective film can be manufactured according to Figure 1a and Figure 1b the examples disclosed in the description of. In these examples, the film that can be formed from the film-forming composition can be selective to hydrogen ions (e.g., H + ).

[0106] Figure 5 FIG. 500 schematically shows a block diagram of spraying an IrOX reagent composition according to an example of the present disclosure.

[0107] According to Figure 1a and Figure 1b the examples disclosed in the description of, the second working electrode can be made of a second conductive ink. The second conductive ink can include at least one of amorphous carbon, carbon black, and graphite.

[0108] In Figure 5 , in block 502, the IrOX reagent composition is sprayed onto the second working electrode. In this example, the additional reagent composition can be the IrOX reagent composition.

[0109] In some examples, spraying can be carried out by using a pressurized gas, such as air with a flow rate of 50 μL / min to 1000 μL / min; specifically, air with a flow rate of 100 μL / min to 800 μL / min; more specifically, air with a flow rate of 200 μL / min to 700 μL / min.

[0110] In block 504, the delivered IrOX reagent composition is cured by heating the IrOX reagent composition at 80 °C for 10 minutes.

[0111] The IrOX reagent composition may comprise an iridium oxide compound, a solvent, and an ion-conductive polymer. The ion-conductive polymer may be an organofluorinated polymer selected from homopolymers, copolymers, multi-component polymers, or combinations thereof. In some instances, the ion-conductive polymer is a fluorinated polymer; particularly a fluorinated polymer having sulfonic acid sites; preferably a sulfonated tetrafluoroethylenebased fluoropolymer or a perfluorosulfonic acid (PFSA) polymer; more preferably a tetrafluoroethylene-perfluoro-3,6-dioxaoct-4-ene sulfonic acid polymer or copolymer. In some instances of these instances, the fluorinated polymer may be a compound of formula (I):

[0112]

[0113] where n and m are integers greater than 1. Additionally, the compound of formula (I) has an equivalent weight of from 800 to 1400.

[0114] Additionally, the iridium oxide compound may be IrO x , where x is equal to 2 or x is greater than 2. Additionally, the solvent may be a solvent that does not oxidize the IrO x compound and dilutes the fluorinated polymer to obtain a viscosity and surface tension compatible with the delivery method (e.g., spraying). For example, the viscosity and surface tension may be altered such that the IrOX reagent composition can be sprayed using a pressurized gas such as air at a predetermined flow rate. In some instances of these instances, the solvent may include propan-2-ol.

[0115] In Figure 5 instances, when the IrOX reagent composition is sprayed onto a second working electrode, a pH sensor is obtained. In this instance, the first reference electrode may be the Ag / AgCl reference electrode as described above.

[0116] It may be noted that in some instances, the IrOX reagent composition may be used in a method of additive manufacturing a sensor assembly. The method includes providing a first sensor onto an electrode substrate, where the sensor is manufactured using a method of additive manufacturing a sensor according to an instance of the present disclosure, providing a first reference electrode onto the electrode substrate according to an instance of the present disclosure; providing a first working electrode onto the electrode substrate; and spraying the IrOX reagent composition onto the first working electrode, where the first reference electrode and the IrOX-sprayed first working electrode form a second sensor on the electrode substrate, and the second sensor is a pH sensor.

[0117] A pH sensor based on the IrOX reagent composition may be adapted to obtain reliable pH measurements in acidic or alkaline media. In particular, a pH sensor based on the IrOX reagent composition may have a pH working range that includes acidic media (e.g., pH < 4) or alkaline media (e.g., pH > 10.5).

[0118] Due to the low reactivity of the IrOX reagent composition with pH conditions, the IrOX reagent composition can improve the chemical stability of the pH sensor under the pH conditions of these media.

[0119] In some instances, the IrOX reagent composition can be used in other systems or methods not described in the present disclosure.

[0120] Chlorine sensor according to an example:

[0121] Figure 6 FIG. 600 schematically shows a block diagram of a jetting gold nanoparticle reagent composition according to an example of the present disclosure. Figure 6 The features of can be combined Figure 5 with the features of any of the examples shown. Figure 5 Examples of the methods shown may or may not also include Figure 6 the features of the examples of.

[0122] According to Figure 1a and Figure 1b the examples disclosed in the description of, the second working electrode can be made of a second conductive ink. The second conductive ink can include at least one of amorphous carbon, carbon black, and graphite.

[0123] In Figure 6 , at block 602, the gold nanoparticle reagent composition can be jetted onto the second working electrode. In this example, the other reagent composition can be the gold nanoparticle reagent composition.

[0124] At block 604, the delivered gold nanoparticle reagent composition can be cured by heating the gold nanoparticle reagent composition at 140 °C for 30 minutes.

[0125] The gold nanoparticle reagent composition includes gold particles having a size of 1 nm to 100 nm.

[0126] In Figure 6 , when the gold nanoparticle reagent composition can be jetted onto the second working electrode, a chlorine sensor can be obtained. In this example, the second reference electrode can be the Ag / AgCl reference electrode as described above. The chlorine sensor can output a signal representative of the presence of free chlorine. The second working electrode jetted with gold nanoparticles can improve the stability of the chlorine sensor over time (e.g., over 12 hours). Thus, calibration for compensating for the change in the response of the chlorine sensor over time can be avoided. Thus, the chlorine sensor can be used for continuous measurement.

[0127] It can be noted that, in some instances, the gold nanoparticle reagent composition can be used in a method for additive manufacturing of a sensor assembly. Thus, a second working electrode and a second reference electrode ejected with the gold nanoparticle reagent composition can form a sensor on the electrode substrate of the sensor assembly, and the sensor is a chlorine sensor.

[0128] Conductivity sensor according to an example:

[0129] By delivering a third conductive ink (as described above), a conductivity sensor can be obtained.

[0130] In some instances, the conductivity sensor can include two electrodes, which include a silver reference electrode made of silver and a silver working electrode made of silver.

[0131] In some instances, the conductivity sensor can include four electrodes, which include a first pair of internal electrodes, which include an internal silver reference electrode and an internal silver working electrode for potential measurement (U); and a second pair of external electrodes, which include an external silver reference electrode and an external silver working electrode for current measurement (I). In this configuration, the conductivity can be measured by current measurement (I) and potential measurement (U).

[0132] Temperature sensor according to an example:

[0133] A temperature sensor can be obtained by delivering a conductive agent composition onto an electrode substrate. The temperature sensor can include a resistor formed by the conductive agent composition. In some instances, the resistor can have a positive temperature coefficient of resistance. The temperature sensor can include a first electrical contact at a first end of the resistor, a second electrical contact at a second end of the resistor, and a resistance measuring device connected to the first electrical contact and the second electrical contact to measure the resistance of the resistor (which can be associated with temperature).

[0134] The method for additive manufacturing of a sensor can result in the manufacture of at least one of the following: a redox sensor; and a pH sensor based on at least the film.

[0135] According to an example of the present disclosure, the method for additive manufacturing of a sensor assembly can result in the manufacture of at least one of the following: a film-based pH sensor as described above, a pH sensor based on an IrOX reagent composition, a chlorine sensor, a conductivity sensor, and a temperature sensor.

[0136] For example, a combination of the above sensors can be obtained in the same electrode substrate. Thus, the combination of the above sensors can constitute a sensor assembly. Therefore, the sensor assembly can include two or more than two sensors among the above sensors (i.e., redox sensor, pH sensor, chlorine sensor, conductivity sensor, and temperature sensor).

[0137] Figure 7a Represents a sensor assembly 700 that includes an additively manufactured sensor according to an example of the present disclosure.

[0138] In Figure 7a an example, the sensor assembly can be a stack of at least two of a redox sensor 702 according to an example of the present disclosure, a pH sensor 704 according to an example of the present disclosure, a chlorine sensor 706 according to an example of the present disclosure, a conductivity sensor 708 according to an example of the present disclosure, and a temperature sensor 710 according to an example of the present disclosure.

[0139] It can be noted that the sensor assembly 700 can include any additively manufactured sensor according to the present disclosure (e.g., a redox sensor; a pH sensor; a chlorine sensor, a conductivity sensor, and a temperature sensor). The sensor assembly includes at least one sensor that includes a membrane delivered according to an example of the present disclosure.

[0140] Figure 7b Schematically shows Figure 7a the sensor assembly 700 that includes conductive tracks according to an example of the present disclosure.

[0141] In Figure 7b an example, the sensor assembly further includes conductive tracks. In Figure 7b it, the electrodes of the redox sensor 702 are connected to a redox electrical contact through a redox conductive track 703, the electrodes of the pH sensor 704 are connected to a pH electrical contact through a pH conductive track 705, the electrodes of the chlorine sensor 706 are connected to a chlorine electrical contact through a chlorine conductive track 707, the electrodes of the conductivity sensor 708 are connected to a conductivity electrical contact through a conductivity conductive track 709, and the temperature sensor 710 is connected to a temperature electrical contact through a temperature conductive track 711.

[0142] According to one aspect, a method for manufacturing a microfluidic device is disclosed. The method includes providing a microfluidic device that includes a structure. In particular, the structure includes an inlet channel, an outlet channel, and a detection chamber that is in fluid communication with the inlet channel and the outlet channel. The method further includes connecting the microfluidic device to a sensor obtained by a method according to an example of the present disclosure, or to a sensor assembly according to any example of the present disclosure, such that the detection chamber is in fluid connection with the electrodes of the sensor or the electrodes of the sensor assembly.

[0143] In some examples, the structure can include a first member structure and a second member structure. The first member structure can have a glass transition temperature Tg1, and the second member structure can have a glass transition temperature Tg2. The glass transition temperature Tg1 can be higher than the glass transition temperature Tg2.

[0144] In some instances, the first component structure and / or the second component structure can be a cycloolefin copolymer (COC).

[0145] When the first component structure and the second component structure are combined, a fluid channel can be milled through the second component structure and into the first component structure. The fluid channel can include an inlet channel, an outlet channel, and a detection chamber. The detection chamber can be in fluid communication with the inlet channel and the outlet channel.

[0146] Connecting the microfluidic device to a sensor or a sensor assembly can be achieved by at least partially fusing the second component structure with the electrode substrate of the sensor or the sensor assembly. Since the second component structure can have a lower transition temperature, when the temperature t, Tg1 > t ≥ Tg2, and pressure is applied to the structure (including the first component structure and the second component structure) and the sensor or the sensor assembly, the second component structure can be at least partially fused with the electrode substrate. Thus, a microfluidic device can be obtained.

[0147] Thus, a fluid sample can be provided in the inlet channel of the microfluidic device, where the provided fluid sample can be in contact with an electrode or a membrane. The provided fluid sample can reach the detection chamber by, for example, capillary action, gravity, pumping, etc. The contact between the fluid sample and the electrode or the membrane can generate a signal. The signal can represent: the presence or absence of a target reagent in the fluid sample, and / or the redox potential of the fluid sample, and / or the pH of the fluid sample, and / or the temperature of the fluid sample, and / or the conductivity of the fluid sample.

[0148] Figure 8 A cross-sectional view of a system 800 for additive manufacturing a sensor according to an example of the present disclosure is shown.

[0149] The membrane head can have an overall elongated configuration, thereby defining a membrane head longitudinal axis 825. In some instances, the membrane head longitudinal axis 825 can be the same axis as the motor shaft axis.

[0150] In Figure 8In [the system], the motor 810 is operably connected to the die head actuator 822. The motor 810 may include a motor shaft that defines a motor axis. The motor shaft drives the die head actuator 822. The die head actuator 822 may be an endless screw. The die head actuator 822 may press the medicament composition toward the nozzle 830 through a conduit 824. The conduit 824 is in fluid communication with a nozzle having a nozzle outlet 832. The die head actuator 822 may be in fluid communication with a connection port 826 such that the die head actuator 822 may be configured to feed the nozzle 830. Thus, the medicament composition may be delivered onto the receiving area 840 to receive the electrode 850. The electrode 850 may be provided on the electrode substrate (as described above), or provided by delivering a conductive agent composition onto the electrode substrate to form an electrode (as described above).

[0151] In Figure 8 [the system], the drive arm 900 may be configured to drive the die head 820 at least above the receiving area 840, and the die head actuator 822 may be configured to feed the medicament composition to the nozzle 830.

[0152] In addition, in Figure 8 [the system], the medicament composition may be fed to the die head 820 through a connection port 826 that is in fluid communication with the conductor 824 and the container 860.

[0153] Thus, the system 800 for additive manufacturing of sensors includes a receiving area 840 configured to receive the electrode 850, and a die head 820 for delivering the medicament composition onto the electrode 850 through the nozzle 830.

[0154] In addition, the container 860 may store the medicament composition for feeding the die head 820. The container 860 may include an outlet end portion 870 and a carrier end portion 880. Thus, the longitudinal axis 865 of the container may be defined as extending from the outlet end portion 870 to the carrier end portion 880. The outlet end portion 870 may be directly connected to the connection port 826.

[0155] In addition, the carrier end portion 880 of the container may be connected to a container actuator 862. The container actuator 862 may be configured to apply pressure to the carrier end portion 880 to deliver the medicament composition through the outlet end portion. In some examples, the system 800 may include a controller configured to control the synchronous operation of the container actuator 862 and the die head actuator 822.

[0156] In Figure 8In this case, the container carrier 890 may have a distal portion 892 and a proximal portion 894. The container carrier 890 may be configured to hold the container through the carrier end portion 880 of the container. The container carrier 890 may be connected to the membrane head 820 through the proximal portion 894. The container carrier 890 may be configured to hold the container 860 at an angle 910 that defines the angle between the membrane head longitudinal axis 825 and the container longitudinal axis 865.

[0157] In some instances, the container carrier 890 includes a carrier arm 896, and the carrier arm 896 is connected to the membrane head 820 through a carrier adapter 898.

[0158] In some instances, the carrier arm 896 may be connected to the carrier adapter 898 through a hinge. In this way, the carrier arm 896 can assume different positions relative to the membrane head 820. This helps to connect containers of different shapes or sizes.

[0159] In some instances, the carrier arm 896 includes a hollow portion configured to at least receive the carrier end portion 880 of the container. The hollow portion may include a hole that can surround the carrier end portion 880 of the container when the carrier end portion 880 of the container engages the hole.

[0160] Looking back at the container 860, in some instances, the container 860 may be a syringe. The syringe may include a barrel having a hollow interior; a piston placed in the hollow interior, which can move along the longitudinal axis of the barrel; wherein the piston is operably connected to the container actuator 862; and a syringe outlet in fluid communication with the hollow interior. The longitudinal axis of the barrel may be the container longitudinal axis 865.

[0161] The container actuator 862 may be configured to drive the piston for delivering the film agent composition from the syringe outlet to the connection port 826.

[0162] Figure 9 A schematic diagram of a system 990 for additive manufacturing of sensors according to an example of the present disclosure is shown.

[0163] The system 990 may include a first delivery unit 992 configured to deliver a conductive agent composition onto an electrode substrate to form an electrode. The system 990 may include a curing unit 994 to cure the delivered conductive agent composition; and a second delivery unit 996. The second delivery unit 996 is configured to deliver at least a film agent composition onto the electrode to form a film.

[0164] In some instances, the second delivery unit 996 can include a receiving area 840 configured to receive the electrode 850 and a membrane head 820 for delivering the membrane agent composition onto the electrode 850 through the nozzle 830. The membrane head 820 can include a connection port 826 to receive the outlet end portion 870 of the container 860 so as to store the membrane agent composition. In addition, the second delivery unit can include a container carrier 890 configured to hold the container 860 through the carrier end portion 880 of the container. The container carrier 890 can be connected to the membrane head 820. The system 990 can include a drive arm 900 configured to drive the membrane head 920 at least above the receiving area 840; and a membrane head actuator 822 configured to feed the membrane agent composition to the nozzle 830, wherein the membrane head actuator 822 is in fluid communication with the connection port. Thus, the second delivery unit 996 can include a system according to Figure 8 the examples.

[0165] In some instances, the system 990 can include an illumination device to emit electromagnetic radiation with a wavelength of 100 nm to 400 nm on the electrode substrate. This wavelength is suitable for curing some curable reagent compositions.

[0166] According to one aspect, an IrOX reagent composition is disclosed. The IrOX reagent composition includes: an iridium oxide compound, a solvent; and a compound of formula (I):

[0167]

[0168] where n and m are integers greater than 1.

[0169] Although the IrOX reagent composition has been described in connection with examples of systems or methods for additive manufacturing of sensors as disclosed herein, the IrOX reagent composition can be used in other examples of systems or methods for manufacturing sensors.

[0170] In some examples of this aspect, the solvent includes propan-2-ol.

[0171] In some examples of this aspect, the compound of formula (I) has an equivalent weight of 800 to 1400.

[0172] In some examples of this aspect, the stoichiometry of the iridium oxide compound is IrO x ; where x is equal to 2 or x is greater than 2.

[0173] The IrOX reagent composition can be sprayed onto the working electrode, and the working electrode can be suitable for measuring the pH value.

[0174] A suitable system can include a spray head to deliver the IrOX reagent composition onto the working electrode. The working electrode can be disposed on the electrode substrate.

[0175] For reasons of completeness, various aspects of the present disclosure are set forth in the following numbered clauses:

[0176] 1. A method of an additive manufacturing sensor, the method comprising:

[0177] providing an electrode, wherein the electrode comprises a conductive agent composition; and

[0178] delivering a film agent composition onto the electrode to form a film.

[0179] 2. The method according to clause 1, wherein the providing the electrode comprises:

[0180] delivering a conductive agent composition onto an electrode substrate to form an electrode; and

[0181] curing the conductive agent composition.

[0182] 3. The method according to clause 2, which comprises:

[0183] heating the electrode substrate before delivering the conductive agent composition onto the electrode substrate.

[0184] 4. The method according to clause 3, wherein the electrode substrate is heated at a predetermined temperature for a predetermined time.

[0185] 5. The method according to clause 3 or 4, wherein the electrode substrate is a polymer.

[0186] 6. The method according to clause 5, wherein the polymer is selected from at least one of the following: polyethylene terephthalate PET; polyethylene naphthalate PEN; polyimide, such as Kapton; polycarbonate PC; polymethyl methacrylate PMMA; thermoplastic polyurethane TPU; and paper.

[0187] 7. The method according to any one of clauses 2 to 4, which comprises:

[0188] delivering a dielectric agent composition onto at least a part of the electrode substrate before delivering the conductive agent composition onto the electrode substrate.

[0189] 8. The method according to clause 7, wherein the electrode substrate is a metallic material or a textile material.

[0190] 9. The method according to clause 2, which comprises:

[0191] exposing the electrode substrate to oxygen plasma before delivering the conductive agent composition onto the electrode substrate.

[0192] 10. The method according to clause 9, wherein the electrode substrate is an oxide material or a ceramic material.

[0193] 11. The method according to any one of clauses 2 to 10, comprising:

[0194] Screen-printing a conductive track onto the electrode substrate.

[0195] 12. The method according to clause 11, wherein the conductive track contains silver.

[0196] 13. The method according to clause 11 or 12, comprising:

[0197] Curing the screen-printed conductive track by:

[0198] Heating the screen-printed conductive track; and

[0199] Exposing the screen-printed conductive track to electromagnetic radiation with a wavelength of 240 nm to 270 nm for 10 seconds.

[0200] 14. The method according to any one of clauses 1 to 13, wherein the conductive agent composition includes a first conductive ink having at least one of silver and silver chloride.

[0201] 15. The method according to clause 14, wherein the electrode includes a first reference electrode.

[0202] 16. The method according to clause 14 or 15, wherein curing the conductive agent composition includes:

[0203] Curing the first conductive ink by heating the first conductive ink at 130 °C for 30 minutes.

[0204] 17. The method according to any one of clauses 1 to 13, wherein the conductive agent composition includes a second conductive ink having at least one of amorphous carbon, carbon black, and graphite.

[0205] 18. The method according to clause 17, wherein the electrode includes a counter electrode and / or a first working electrode and / or a second working electrode.

[0206] 19. The method according to clause 17 or 18, wherein curing the conductive agent composition includes:

[0207] Curing the second conductive ink by heating the second conductive ink at 130 °C for 30 minutes.

[0208] 20. The method according to clause 18 or 19, comprising:

[0209] Spraying a platinum reagent composition onto the first working electrode.

[0210] 21. The method according to clause 20, comprising:

[0211] Curing the platinum reagent composition by heating the platinum reagent composition at 80 °C for 10 minutes.

[0212] 22. The method according to clause 20 or 21, wherein the platinum reagent composition is a platinum-on-carbon composition having 3 wt% platinum.

[0213] 23. The method according to clause 15 and clause 20, comprising obtaining a redox sensor, and wherein the membrane agent composition is delivered onto the first reference electrode to form a membrane.

[0214] 24. The method according to clause 23, wherein the membrane formed on the electrode is an ion-saturated membrane.

[0215] 25. The method according to clause 15, wherein the membrane formed on the electrode is an ion-saturated membrane.

[0216] 26. The method according to clause 18, wherein the membrane formed on the electrode is an ion-selective membrane.

[0217] 27. The method according to clause 25 and clause 26, comprising obtaining a pH sensor.

[0218] 28. A method of additive manufacturing a sensor assembly, comprising:

[0219] Providing a sensor onto an electrode substrate, wherein the sensor is manufactured using the method of additive manufacturing a sensor according to any one of clauses 1 to 27;

[0220] Providing a first reference electrode on the electrode substrate according to clause 15; and

[0221] Spraying an IrOX reagent composition onto a second working electrode provided on the electrode substrate, wherein the provided first reference electrode and the second working electrode sprayed with IrOX form a pH sensor.

[0222] 29. The method according to clause 28, comprising:

[0223] Curing the IrOX reagent composition by heating the IrOX reagent composition at 80 °C for 10 minutes.

[0224] 30. The method according to clause 28 or 29, wherein the IrOX reagent composition comprises:

[0225] An iridium oxide compound;

[0226] A solvent; and

[0227] Compound of formula (I):

[0228]

[0229] wherein n and m are integers greater than 1.

[0230] 31. The method according to any one of clauses 28 to 30, comprising:

[0231] spraying the gold nanoparticle reagent composition onto the second working electrode.

[0232] 32. The method according to clause 31, wherein the gold nanoparticle reagent composition comprises gold particles having a size of 1 nm to 100 nm.

[0233] 33. The method according to clauses 15 and 32, comprising obtaining a chlorine sensor.

[0234] 34. The method according to any one of clauses 1 to 13, wherein the conductive agent composition comprises a third conductive ink containing silver.

[0235] 35. The method according to clause 34, wherein the electrode comprises:

[0236] a silver reference electrode; and

[0237] a silver working electrode.

[0238] 36. The method according to clause 35, comprising obtaining a conductivity sensor.

[0239] 37. A method for manufacturing a microfluidic device, comprising:

[0240] providing a microfluidic device comprising a structure; wherein the structure comprises:

[0241] an inlet channel;

[0242] an outlet channel; and

[0243] a detection chamber that is in fluid communication with the inlet channel and the outlet channel;

[0244] connecting the microfluidic device to a sensor obtained by the method according to any one of clauses 1 to 27, or to a sensor assembly according to any one of clauses 28 to 36, such that the detection chamber is in fluid connection with the electrode of the sensor or the electrode of the sensor assembly.

[0245] 38. A system for additive manufacturing of a sensor, the system comprising:

[0246] a receiving area configured to receive an electrode;

[0247] A membrane head for delivering a membrane agent composition to an electrode through a nozzle, wherein the membrane head includes a connection port for receiving an outlet end portion of a container to store the membrane agent composition;

[0248] A container carrier configured to hold a container by a carrier end portion of the container; the container carrier is connected to the membrane head;

[0249] A drive arm configured to drive the membrane head at least above a receiving area; and

[0250] A membrane head actuator configured to feed the membrane agent composition to the nozzle, wherein the membrane head actuator is in fluid communication with the connection port.

[0251] 39. The system according to clause 38, wherein the container carrier includes a carrying arm, and the carrying arm is connected to the membrane head through a carrier adapter.

[0252] 40. The system according to clause 39, wherein the carrying arm is connected to the carrier adapter through a hinge.

[0253] 41. The system according to clause 39 or 40, wherein the carrying arm includes a hollow portion configured to at least receive the carrier end portion of the container.

[0254] 42. The system according to any one of clauses 38 to 41, wherein the membrane head has a generally elongated configuration, thereby defining a longitudinal axis of the membrane head, and the container is configured such that a container longitudinal axis is defined from the carrier end portion to the outlet end portion; wherein the container carrier is configured to hold the container in a manner that defines an angle between the membrane head longitudinal axis and the container longitudinal axis.

[0255] 43. The system according to any one of clauses 38 to 42, comprising:

[0256] A container actuator configured to apply pressure to the carrier end portion to deliver the membrane agent composition through the outlet end portion;

[0257] wherein the system includes a controller configured to control the synchronous operation of the container actuator and the membrane head actuator.

[0258] 44. The system according to any one of clauses 38 to 43, comprising:

[0259] A conductive agent head for delivering a conductive agent composition to an electrode substrate in a receiving area to form an electrode.

[0260] 45. A sensor assembly comprising at least one of the following:

[0261] A redox sensor according to the method of clause 23;

[0262] A pH sensor for the method according to Clause 27 or 28;

[0263] A chlorine sensor for the method according to Clause 33; and

[0264] A conductivity sensor for the method according to Clause 36.

[0265] 46. A kit, comprising:

[0266] The sensor assembly according to Clause 45; and

[0267] A microfluidic device configured to be connected to the sensor assembly, the microfluidic device comprising a structure; wherein the structure comprises:

[0268] An inlet channel;

[0269] An outlet channel;

[0270] A detection chamber in fluid communication with the inlet channel and the outlet channel; and

[0271] At least one electrode that fluidly connects the detection chamber to the sensor assembly.

[0272] 47. Use of the kit according to Clause 46:

[0273] Wherein a fluid sample is provided in the inlet channel;

[0274] Wherein the provided fluid sample contacts the electrode or the membrane;

[0275] Wherein the contact between the fluid sample and the electrode or the membrane generates a signal;

[0276] Wherein the signal represents:

[0277] The presence of a target reagent; and / or

[0278] The redox potential of the fluid sample; and / or

[0279] The pH value of the fluid sample; and / or

[0280] The temperature of the fluid sample; and / or

[0281] The conductivity of the fluid sample.

[0282] 48. An IrOX reagent composition, comprising:

[0283] An iridium oxide compound;

[0284] A solvent; and

[0285] A compound of formula (I):

[0286]

[0287] wherein n and m are integers greater than 1.

[0288] 49. The IrOX reagent composition according to clause 47, wherein the solvent comprises propan-2-ol.

[0289] 50. The IrOX reagent composition according to clause 48 or 49, wherein the compound of formula (I) has an equivalent weight of 800 to 1400.

[0290] 51. The IrOX reagent composition according to any one of clauses 48 to 50, wherein the stoichiometry of the iridium oxide compound is IrO x ; where x is equal to 2 or x is greater than 2.

[0291] 52. A method of additive manufacturing a pH sensor, the method comprising:

[0292] providing an electrode, wherein the electrode comprises a conductive agent composition; and

[0293] spraying an IrOX reagent composition onto the electrode.

[0294] 53. The method according to clause 52, wherein the providing the electrode comprises:

[0295] delivering a conductive agent composition onto an electrode substrate to form an electrode; and

[0296] curing the IrOX reagent composition.

[0297] 54. The method according to clause 53, which comprises:

[0298] curing the IrOX reagent composition by heating the IrOX reagent composition at 80 °C.

[0299] 55. The method according to any one of clauses 52 to 54, wherein the IrOX reagent composition comprises:

[0300] an iridium oxide compound;

[0301] a solvent; and

[0302] a compound of formula (I):

[0303]

[0304] wherein n and m are integers greater than 1.

[0305] 56. The method according to any one of clauses 52 to 55, wherein the conductive agent composition comprises a first conductive ink having at least one of silver and silver chloride.

[0306] 57. The method according to clause 56, wherein the electrode comprises a first reference electrode.

[0307] 58. The method according to any one of clauses 52 to 55, wherein the conductive agent composition comprises a second conductive ink having at least one of amorphous carbon; carbon black; and graphite.

[0308] 59. The method according to clause 58, wherein curing the conductive agent composition comprises:

[0309] Curing the second conductive ink by heating the second conductive ink at 130 °C for 30 minutes.

[0310] 60. The method according to clause 58 or 59, wherein the electrode comprises a counter electrode and / or a second working electrode.

[0311] 61. The method according to clause 60, wherein an IrOX reagent composition is sprayed onto the second working electrode.

[0312] 62. A method of additive manufacturing a chlorine sensor, the method comprising:

[0313] Providing an electrode, wherein the electrode comprises a conductive agent composition; and

[0314] Jetting a gold nanoparticle composition onto the electrode.

[0315] 63. The method according to clause 62, wherein providing the electrode comprises:

[0316] Delivering a conductive agent composition onto an electrode substrate to form an electrode; and

[0317] Curing the gold nanoparticle composition.

[0318] 64. The method according to clause 62 or 63, wherein the conductive agent composition comprises a first conductive ink having at least one of silver; and silver chloride.

[0319] 65. The method according to clause 64, wherein the electrode comprises a first reference electrode.

[0320] 66. The method according to clause 62 or 63, wherein the conductive agent composition comprises a second conductive ink having at least one of amorphous carbon; carbon black; and graphite.

[0321] 67. The method according to clause 66, wherein curing the conductive agent composition comprises:

[0322] Curing the second conductive ink by heating the second conductive ink at 130 °C for 30 minutes.

[0323] 68. The method according to clause 66 or 67, wherein the electrode comprises a counter electrode and / or a second working electrode.

[0324] 69. The method according to any one of clauses 62 to 68, wherein the gold nanoparticle composition comprises gold particles having a size of 1 nm to 100 nm.

[0325] 70. A system for additive manufacturing of a sensor, the system comprising:

[0326] A first delivery unit configured to deliver a conductive agent composition onto an electrode substrate to form an electrode;

[0327] A curing unit for curing the delivered conductive agent composition;

[0328] A second delivery unit configured to:

[0329] Provide an electrode, wherein the electrode comprises a conductive agent composition; and

[0330] Deliver a film agent composition onto the electrode to form a film.

[0331] 71. The system according to clause 70, wherein the second delivery unit comprises:

[0332] A receiving area configured to receive an electrode;

[0333] A film head for delivering a film agent composition onto an electrode through a nozzle, wherein the film head has a connection port to receive the outlet end portion of a container, thereby storing the film agent composition;

[0334] A container carrier configured to hold a container through the carrier end portion of the container; the container carrier is connected to the film head;

[0335] A drive arm configured to drive the film head at least above the receiving area; and

[0336] A film head actuator configured to feed the film agent composition to the nozzle, wherein the film head actuator is in fluid communication with the connection port.

[0337] 72. The system according to clause 70 or 71, comprising:

[0338] An illumination device for emitting electromagnetic radiation having a wavelength of 100 nm to 400 nm onto the electrode substrate.

[0339] Although only some examples are disclosed herein, there may be other substitutions, modifications, uses, and / or their equivalents. In addition, all possible combinations of the said examples are covered. Therefore, the scope of the present disclosure should not be limited by the specific examples, but should be determined only by a reasonable interpretation of the appended claims. If reference numerals associated with the drawings are placed in parentheses in the claims, they are merely for the purpose of attempting to increase the understandability of the claims and should not be construed as limiting the scope of the claims.

Claims

1. A method for an additive manufacturing sensor, the method comprising: Providing a working electrode; Providing a reference electrode, wherein the reference electrode and the working electrode comprise a conductive agent composition; And Delivering a membrane agent composition onto the reference electrode to form a membrane, wherein the membrane formed on the reference electrode is an ion-saturated membrane.

2. The method according to claim 1, wherein the conductive agent composition comprises at least one of the following: A first conductive ink having at least one of silver and silver chloride; and A second conductive ink having at least one of amorphous carbon, carbon black, and graphite.

3. The method according to claim 2, wherein the reference electrode comprises a first reference electrode made of the first conductive ink.

4. The method according to claim 2, wherein the working electrode comprises a first working electrode made of the second conductive ink.

5. The method according to claim 4, which comprises: Spraying a platinum reagent composition onto the first working electrode.

6. The method according to claim 2, wherein the reference electrode comprises a first reference electrode made of the first conductive ink; and wherein the working electrode comprises a first working electrode made of the second conductive ink; the method comprises spraying a platinum reagent composition onto the first working electrode such that the additively manufactured sensor is a redox sensor.

7. The method according to any one of claims 1 to 4, the method comprising: Delivering a membrane agent composition onto the working electrode to form a membrane.

8. The method according to claim 7, wherein the membrane formed on the working electrode is an ion-selective membrane.

9. The method according to claim 8, wherein the sensor is a pH sensor.

10. A method for an additive manufacturing sensor assembly, which comprises: Providing a first sensor onto an electrode substrate, wherein the first sensor is manufactured using the method for an additive manufacturing sensor according to any one of claims 1 to 9; Providing a first reference electrode on the electrode substrate; Providing a first working electrode on the electrode substrate; And Spraying an IrOX reagent composition onto the first working electrode, wherein the first reference electrode and the IrOX-sprayed first working electrode form a second sensor on the electrode substrate, and the second sensor is a pH sensor.

11. The method according to claim 10, wherein the IrOX reagent composition comprises: An iridium oxide compound; A solvent; and A compound of formula (I): wherein n and m are integers greater than 1.

12. The method according to claim 10, which comprises: Providing a second reference electrode on the electrode substrate; Providing a second working electrode on the electrode substrate; And Injecting a gold nanoparticle reagent composition onto the second working electrode.

13. The method according to claim 12, Among them, The second working electrode onto which the gold nanoparticle reagent composition is sprayed and the second reference electrode form a third sensor on the electrode substrate, and the third sensor is a chlorine sensor.

14. A method for manufacturing a microfluidic device, which comprises: Providing a microfluidic device comprising a structure; Wherein the structure comprises: Inlet channel; Outlet channel; and Detection chamber, which is in fluid communication with the inlet channel and the outlet channel; Connect the microfluidic device to a sensor obtained by the method according to any one of claims 1 to 9, or to a sensor assembly according to any one of claims 10 to 13, such that the detection chamber is in fluid connection with the electrodes of the sensor or the electrodes of the sensor assembly.

15. A system for additive manufacturing of a sensor, the system comprising: A receiving area configured to receive electrodes; A membrane head for delivering a membrane composition onto the electrodes through a nozzle, wherein the membrane head includes a connection port to receive an outlet end portion of a container for storing the membrane composition; A container carrier configured to hold the container by a carrier end portion of the container; the container carrier is connected to the membrane head; A drive arm configured to drive the membrane head at least above the receiving area; and A membrane head actuator configured to feed the membrane composition to the nozzle, wherein the membrane head actuator is in fluid communication with the connection port.

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