Additive Manufacturing of Sensors

Abstract

A method for additively manufacturing a sensor is provided. The method includes providing a working electrode and a reference electrode, where 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, where the film formed on the reference electrode is an ion-saturated film. Additionally, a system for additively manufacturing a sensor is provided. The system includes a receiving area configured to receive the electrode, a film head for delivering the film agent composition onto the electrode through a nozzle, a container carrier attached to the film head, a drive arm configured to drive the film head over at least the receiving area, and a film head actuator configured to supply the film agent composition to the nozzle. Further, a method for additively manufacturing a sensor assembly is provided.

Description

[Technical Field]

[0001] This application claims the benefit of European Patent Application Publication No. 223827643, filed August 5, 2022.

[0002] FIELD OF THE DISCLOSURE The present disclosure relates to systems and methods for additively manufacturing sensors. Further, the present disclosure relates to systems and methods for additively manufacturing sensor assemblies. [Background technology]

[0003] The sensor can be based at least in part on a membrane (an ion-selective membrane or an ion-saturated membrane). The membrane can be formed on the sensor's electrodes by drop-casting a coating composition. Drop-casting is often a manual process in which an operator casts drops onto a substrate. Therefore, at least, the reproducibility of these sensors depends heavily on the operator's skill or ability to properly drop-cast the coating composition onto the sensor's electrodes with each drop-cast. In particular, drop-casting can involve a labor-intensive process, which can limit the scalability of sensor manufacturing.

[0004] Furthermore, drop casting has very few controlled parameters. Typically, only the volume of the film composition delivered to the electrode is controlled. Controlling only the volume of the film composition delivered to the electrode can result in low reproducibility of the film composition delivered to the electrode. Therefore, the formed film may be susceptible to the coffee ring effect and may not have a consistent thickness. This can result in poor performance or even failure of the fabricated sensor.

[0005] For example, a sensing device for monitoring water quality, blood, or saliva may include sensors for determining characteristics of interest, such as redox, pH, free chlorine, conductivity, and temperature. Typically, only one characteristic of interest is measured at a time. If various characteristics must be measured, the sensing device may have 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 sensing, state-of-the-art glass electrodes are bulky, fragile, and expensive. Glass electrodes require calibration and cleaning between each measurement. As a result, state-of-the-art glass electrodes are not suitable for portable applications.

[0007] Free chlorine is also often measured using optical techniques that involve adding N,N-diethyl-p-phenylenediamine (DPD) and detecting a color change in a fluid sample. Detection of free chlorine can involve the reaction of chlorine with the amine groups of DPD, which produces a pink compound. The color change is detected by an optical system that uses DPD to perform a spectral analysis of the fluid sample. However, this optical system is large and operates in a laboratory. As a result, optical methods for determining free chlorine are complex, expensive, and not suitable for portable use or continuous monitoring. At best, monitoring is performed on each collected fluid sample.

[0008] In summary, to detect two or more characteristics of interest, a sensing device may stack several sensors to form a sensor assembly. Thus, a sensing device may include, for example, a glass electrode for pH detection; a light source, a cuvette, a DPD, a photodetector, and circuitry for free chlorine detection. As a result, the sensing device may be bulky and unsuitable for portable use.

[0009] Examples of the present disclosure seek to at least partially reduce one or more of the aforementioned problems. Summary of the Invention [Means for solving the problem]

[0010] In one aspect, a system for additively manufacturing a sensor is provided. The system includes a receiving area configured to receive an electrode and a film head for delivering a film agent composition onto the electrode through a nozzle. In particular, the film head includes a connection port for receiving an outlet end of a container for storing the film agent composition. The system further includes a container carrier configured to hold the container via the carrier end of the container. The container carrier is attached to the film head. The system further includes a drive arm configured to drive the film head over at least the receiving area and a film head actuator configured to supply the film agent composition to the nozzle, the film head actuator being in fluid communication with the connection port.

[0011] The configuration of the membrane head with the container by the action of the container carrier allows for efficient delivery of the membrane agent composition from the outlet end of the container to the membrane head via the connection port.

[0012] In this configuration, the outlet end of the container is connected to the connection port of the membrane head. Therefore, the membrane agent composition is directly supplied to the membrane head. There is no intermediate connector, such as a supply tube, between the container and the membrane head. As a result, the compounds of the membrane agent composition cannot react with the supply tube and essentially dissolve and / or deform the supply tube, at least partially. A deformed or misshaped supply tube can essentially induce pressure changes, potentially altering the reproducibility of the formed membrane. Because there is no intermediate connector, pressure changes during the process can be reduced or even avoided. In this way, the reproducibility of the formed membrane can be improved. Additionally, this configuration avoids the need to replace damaged supply tubes and the resulting interruption of the manufacturing process.

[0013] Furthermore, since there is no supply pipe, there is no need to fill the supply pipe to supply the membrane head. According to this embodiment, there is no supply pipe for connecting the container to the membrane head. Therefore, the configuration of the membrane head with the container by the action of the container carrier can reduce the amount of membrane agent composition used. As a result, the manufacturing process can be made more efficient and the cost of manufacturing the sensor can be reduced.

[0014] In some examples, the container carrier may include a carrier arm. In these examples, the carrier arm may include a hollow portion configured to receive at least the carrier end of the container. The carrier arm may engage at least the carrier end of the container. Thus, the container carrier can hold the container via the carrier end of the container, for example, by the hollow portion. As a result, proper placement of the container relative to the film head can be improved.

[0015] In some examples, the membrane head may have a generally elongated configuration such that a membrane head longitudinal axis is defined, and the container may be configured such that a container longitudinal axis is defined from the carrier end to the outlet end. In these examples, the container carrier may be configured to hold the container such that an angle is defined between the head longitudinal axis and the container longitudinal axis. As a result, the angle can be maintained when the carrier arm engages with at least the carrier end of the container. Thus, a mismatch angle between the connection port of the membrane head and the outlet end of the container can be avoided. As a result, leakage of the membrane agent composition can be avoided by the action of the container carrier. Furthermore, the connection between the container and the membrane head can be less susceptible to vibrations caused by the action of the container carrier, for example, when the container carrier moves.

[0016] Because the film composition is delivered by the film head, the delivery parameters are no longer limited to the volume of the film composition, and there can be multiple parameters for controlling the appropriate delivery of the film composition onto the electrode substrate.The multiple parameters can include, for example, pressure; delivery rate; film composition supply rate; and the distance between the nozzle outlet and the electrode substrate.By controlling an increased number of parameters, the delivered film composition can form a film with a consistent thickness on the electrode provided on the electrode substrate.As a result, the performance of the manufactured sensor can be improved.

[0017] The above parameters can be controlled even more precisely due to the direct connection between the container and the membrane head and the synergistic effect of using the membrane head, which can be useful for delivering membranes by additive manufacturing.

[0018] In a further aspect, a method for additively 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 the film agent composition onto the reference electrode to form a film, wherein the film formed on the reference electrode is an ion-saturated film.

[0019] Therefore, since the ion-saturated membrane is saturated with a particular ion, the potential of the reference electrode can remain stable at a predetermined reference electrode potential.

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

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

[0022] Because the sensor membrane is additively manufactured, the membrane is no longer drop-cast manually by an operator, but rather by a system for additively manufacturing sensors. Therefore, the reproducibility of the manufactured sensor does not depend on the operator's skill or ability to properly drop-cast the membrane onto the sensor electrode, but on controlled parameters (e.g., pressure; surface tension; delivery rate; membrane composition feed rate; nozzle temperature; bed temperature; and the distance between the nozzle outlet and the electrode substrate). As a result, membrane reproducibility can be improved.

[0023] Furthermore, additive manufacturing of sensors may allow for more control over parameters than drop casting for delivering the coating composition onto the electrode. Thus, by increasing the controlled parameters, the formed coating can have a substantially constant thickness on the electrode. As a result, the performance of additively manufactured sensors can be improved.

[0024] According to this aspect, the sensor including the membrane is additively manufactured, which can improve the scalability of manufacturing sensors with membranes, thereby reducing the cost and time to manufacture the sensor.

[0025] In a further aspect, a method for additively manufacturing a sensor assembly is provided. The method includes providing a first sensor on an electrode substrate, the first sensor being 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 spray-coating an IrOX agent composition onto the first working electrode, wherein the first reference electrode and the IrOX spray-coated first working electrode form a second sensor on the electrode substrate, the second sensor being a pH sensor.

[0026] In some examples, the sensor assembly additively manufactured on the electrode substrate may include at least one of a redox sensor, a membrane-based pH sensor, a pH sensor based on an IrOX agent composition, a chlorine sensor, a conductivity sensor, and a temperature sensor. The sensor assembly may include two or more of the above-mentioned sensors. As a result, since the sensor assembly includes two or more sensors delivered on the same electrode substrate, the sensor assembly may be suitable for portable applications.

[0027] In a further aspect, 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 the method according to the examples disclosed herein or a sensor assembly obtained by the method according to the examples disclosed herein. Furthermore, the structure can include an inlet channel, an outlet channel, and a detection chamber in fluid communication with the inlet channel and the outlet channel. Furthermore, the microfluidic device can be connected to the sensor such that the detection chamber is fluidly connected to an electrode of the sensor or an electrode of the sensor assembly. This can provide a rapid point-of-care analysis device.

[0028] The term "additive manufacturing" can refer to an automated process in which successive layers are delivered onto a manufacturing substrate. Automated processes may include screen printing, 3D screen printing, spray coating, binder jetting, material jetting, and material extrusion.

[0029] The term "structure" may be understood as a spatial pattern along three different directions (i.e., x, y, z) in three-dimensional space, which may be any suitable spatial arrangement, such as, for example, a layer, a wafer, a cube, a cone, a cylinder, a disk, 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 the first component (eg, solids) relative to the total weight of the second component (eg, ink).

[0031] Non-limiting examples of the present disclosure are described below with reference to the accompanying drawings. [Brief explanation of the drawings]

[0032] [Figure 1a] FIG. 10 schematically depicts a block diagram of a method for additively manufacturing a sensor according to an example of the present disclosure. [Figure 1b] FIG. 10 schematically depicts a block diagram of a method for additively manufacturing a sensor according to an example of the present disclosure. [Figure 2] FIG. 10 schematically depicts a block diagram of a method for additively manufacturing a sensor according to an example of the present disclosure. [Figure 3] FIG. 1A is a block diagram of a conductive track fabrication according to an example of the present disclosure. [Figure 4] FIG. 1 shows a schematic block diagram of a spray coating of a platinum agent composition according to an example of the present disclosure. [Figure 5] FIG. 1 is a block diagram of a spray coating of an IrOX agent composition according to an example of the present disclosure. [Figure 6] FIG. 1 is a schematic block diagram of injection of a gold nanoparticle agent composition according to an example of the present disclosure. [Figure 7a] FIG. 10 is a diagram that schematically illustrates a sensor assembly comprising an additively manufactured sensor according to an example of the present disclosure. [Figure 7b] FIG. 7b is a schematic representation of the sensor assembly of FIG. 7a with conductive tracks according to an example of the present disclosure. [Figure 8] FIG. 1 illustrates a cross-sectional view of a system for additively manufacturing a sensor according to an example of the present disclosure. [Figure 9] FIG. 1 is a schematic diagram of a system for additively manufacturing a sensor according to an example of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0033] In these figures, the same reference numbers are used to indicate corresponding elements.

[0034] The method examples disclosed herein are not constrained to any particular order.

[0035] 1a shows a schematic block diagram 100 of a method for additively manufacturing a sensor. The sensor membrane may be according to any of the examples disclosed herein. The method may be performed by a system for additively manufacturing a sensor according to any of the examples disclosed herein.

[0036] Throughout this specification, the term "additive manufacturing" may be understood as an automated process in which successive layers are delivered onto a production substrate.

[0037] In some examples, additive manufacturing of the present disclosure may be selected from screen printing, 3D screen printing, spray coating, binder jetting, material jetting (e.g., inkjet), and material extrusion.

[0038] In FIG. 1a, electrodes are provided at block 110. Providing the electrodes may include an electrode substrate including 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 may be provided on or within the electrode substrate by additive manufacturing or another manufacturing process. For example, the provided electrodes may be screen-printed electrodes.

[0039] 1b schematically depicts a block diagram of a method for additively manufacturing a sensor 100 according to one example of the present disclosure. In FIG. 1b, providing an electrode at block 110 may include delivering a conductive agent composition onto an electrode substrate by additive manufacturing to form the electrode (see block 112). In this example, providing the electrode at block 110 further includes curing the conductive agent composition at block 114. Curing may be performed by heating the conductive agent composition, for example, in an oven.

[0040] In summary, providing an electrode can include an electrode substrate that includes the electrode, or can include delivering a conductive agent composition onto an electrode substrate to form the electrode.

[0041] Any electrode provided by an electrode substrate that includes the electrode or by a conductive agent composition delivered onto the electrode substrate to form the electrode includes a conductive agent composition.

[0042] The conductive agent composition may include a conductive compound selected from at least one of silver, carbon, a carbon allotrope, and copper. In particular, the conductive compound may have 1 to 4 valence electrons. Furthermore, the conductive agent composition may include a solids content of 10 to 90 wt %, specifically 20 to 80 wt %, more specifically 30 to 70 wt %, of the total weight of the ink.

[0043] 1a and 1b, in block 120, a membrane agent composition is delivered onto an electrode to form a membrane. The membrane agent composition is delivered by additive manufacturing. The membrane agent composition can vary depending on the characteristics of the membrane to be formed. The characteristics can be related to the membrane's function, such as ion saturation or ion selectivity.

[0044] In some examples, the filming agent composition may be delivered to form a film on a reference electrode or may be delivered to form a film on a working electrode.

[0045] In some examples, the formed film may be an ion-saturated film. The ion-saturated film may be saturated with a specific ion. In these examples, the film-forming composition that forms the ion-saturated film may include a polymer, a solvent, and a specific ionic compound. In particular, the polymer may be polyvinyl butyral (PVB). The solvent may be methanol. The specific ionic compound may be Cl. - In these instances, the film characteristics formed may be configured to be saturated with ions.

[0046] In some examples, the membrane formed may be an ion-selective membrane. The ion-selective membrane may be based on an ionophore. An ionophore is a lipophilic complexing agent that can reversibly bind to a specific ion. In the case of an ion-selective membrane, selectivity may depend, for example, on the free energy of transfer of the specific ion from the fluid sample to the ion-selective membrane; the complex formation constant between the specific ion and the ionophore; and / or the concentration of the membrane compound in the membrane. In these examples, the membrane agent composition forming the ion-selective membrane may include a polymer, a solvent, an ionophore compound, an additive, and a plasticizer. In particular, the polymer may be polyvinyl chloride (PVC), the solvent may be tetrahydrofuran (THF), the ionophore compound may be tri-n-dodecylamine (TDDA), and the additive may be an anionic additive such as potassium tetrakis(4-chlorophenyl)borate (KTpClPB). Since TDDA is a hydrogen-selective ionophore, the membrane formed from the membrane agent composition may selectively select hydrogen ions (e.g., H+ ) can be selective for

[0047] In some instances, the concentration of the anionic additive, ie, KTpClPB, can alter the ion selectivity of a membrane that can be formed from the membrane agent composition.

[0048] In some of these examples, suitable plasticizers may include at least one of bis(2-ethylhexyl) sebacate (DOS), 2-nitrophenyl octyl ether (NPOE), ortho-nitrophenyl octyl ether (o-NPOE), tris(2-ethylhexyl) phosphate, dibutyl sebacate, dioctyl sebacate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate, dioctylphenyl phosphonate, and mixtures thereof. The type of plasticizer used in the membrane can be selected based on the polymer composition. In these examples, the plasticizer may be present in an amount of 40-80% (by weight), specifically 50-70% (by weight), and more specifically about 66% (by weight). In these examples, characteristics of the membrane formed may include ion selectivity.

[0049] The film agent composition can be prepared using any suitable technique for preparing a film agent composition, for example, by dissolving the compounds of the film agent composition in a solvent such as methanol or tetrahydrofuran. Other solvents or mixtures of solvents may also be used. The film agent composition can be delivered by a system for additively manufacturing a sensor according to any of the examples disclosed herein. The formed film can be dried at ambient temperature.

[0050] For example, an ion-saturated membrane can be formed by dissolving PVB (61 wt%) in 5 mL of methanol. NaCl (39 wt%) can be added to the mixture. The total weight of the membrane composition can be 645 g.

[0051] For example, an ion-selective membrane can be formed by dissolving 5 mL of a membrane agent composition of PVC (32.4 wt%), o-NPOE (66 wt%), and KTpClPB (0.6 wt%) in THF. TDDA (1 wt%) can be added to this mixture. The total weight of the membrane agent composition can be 370 g.

[0052] FIG. 2 schematically depicts a block diagram 200 of a method for additively manufacturing a sensor according to an example of the present disclosure.

[0053] 2, the electrode substrate on which the electrodes are to be provided is pre-treated. In block 202, the electrode substrate may undergo a surface treatment prior to block 110. The surface treatment may be performed prior to block 110, for example, to at least partially prevent shrinkage of the electrode substrate when the conductive agent composition is cured. In some examples, the electrode substrate may not undergo a surface treatment prior to block 110.

[0054] During curing, for example, the shape of the delivered conductive agent composition or the additionally delivered drug composition may change. The additionally delivered drug composition may be any drug composition further delivered to the electrode. To avoid incorrect shape, the electrode substrate may be heated at a predetermined temperature for a predetermined time before delivering the conductive agent composition or the additional drug composition. The electrode substrate may be heated at a predetermined temperature depending on the maximum curing temperature of the conductive agent composition or the additional drug composition delivered to the electrode substrate. The predetermined time may be the time during which the conductive agent composition or the additional drug composition with the highest curing temperature is heated. For example, the conductive agent composition delivered in block 110 may be cured by heating the delivered conductive agent composition at 130°C for 30 minutes. In this example, if an additional drug composition is present, the additional drug composition may be cured by heating the delivered conductive agent composition at 140°C for 30 minutes. Therefore, in this example, the surface treatment may include heating the electrode substrate at 140°C for 30 minutes, which is the highest curing temperature between the curing temperatures of the conductive agent composition and the additional drug composition. In this example, the predetermined time may be 30 minutes, since it is the time related to the maximum curing temperature.

[0055] Depending on the material of the electrode substrate, the surface treatment may be selected from at least one of a heat treatment, an oxygen plasma, and delivery of a dielectric composition onto the electrode substrate. Thus, as the material of the electrode substrate varies, the surface treatment applied to the electrode substrate prior to block 110 may vary.

[0056] In some examples, the electrode substrate may be a polymer. In these examples, the polymer may undergo a heat treatment in block 204 prior to block 110 (which may be delivering the conductive agent composition onto the electrode substrate). The polymer may be selected from at least one of polyethylene terephthalate (PET); polyethylene naphthalate (PEN); polyimide such as Kapton; polycarbonate (PC); poly(methyl methacrylate) (PMMA); thermoplastic polyurethane (TPU); and paper.

[0057] In some examples, the electrode substrate may be a metal or a woven material. In these examples, the metal or woven material may undergo a heat treatment in block 204 before block 110, followed by delivery of a dielectric agent composition to at least a portion of the electrode substrate in block 208 before block 110 (which may be delivery of a conductive agent composition onto the electrode substrate). Note that the dielectric agent composition may then be cured by heating or exposure to electromagnetic radiation. The dielectric agent composition may be exposed to heating or electromagnetic radiation depending on its composition.

[0058] In some examples, the electrode substrate may be an oxide or ceramic material, which may be subjected to an oxygen plasma treatment in block 206 prior to block 110 (which may be delivering the conductive agent composition onto the electrode substrate).

[0059] In summary, with reference to Figures 1a-1b and / or 2, a film can be additively deposited onto an electrode that includes a conductive agent composition.

[0060] In some examples, the conductive agent composition may include a first conductive ink. The first conductive ink may include at least one of silver and silver chloride. When the provided electrode includes the first conductive ink, the provided electrode may include a first reference electrode and / or a second reference electrode.

[0061] In some examples, the conductive agent composition may include a second conductive ink. The second conductive ink may include at least one of amorphous carbon, carbon black, and graphite. When the provided electrodes include the second conductive ink, the provided electrodes may include a counter electrode, a first working electrode, and / or a second working electrode.

[0062] In some examples, the conductive agent composition may include a third conductive ink. The third conductive ink may include silver. When the provided electrodes include the third conductive ink, the provided electrodes may include a silver reference electrode and / or a silver working electrode, which may be made of silver.

[0063] In some of these examples, with reference to the description of FIG. 1b and / or FIG. 2, delivering the conductive agent composition may include delivering at least one of a first conductive ink including at least one of silver and silver chloride; a second conductive ink including at least one of amorphous carbon, carbon black, and graphite; and a third conductive ink such that an electrode is formed.

[0064] Additionally, the conductive agent composition delivered onto the electrode substrate may be cured as described above in the discussion of block 114 of FIG. 1b.

[0065] The first conductive ink may be cured by heating the first conductive ink at 130° C. for 30 minutes.

[0066] The second conductive ink may be cured by heating the second conductive ink at 130° C. for 30 minutes.

[0067] The third conductive ink may be cured by heating the third conductive ink at 130° C. for 30 minutes.

[0068] Thus, the electrode substrate may include at least one of a first reference electrode, a second reference electrode, a counter electrode, a first working electrode, a second working electrode, and a third working electrode.

[0069] In some instances, the surface of the electrode substrate may be completely covered by the formed electrodes.

[0070] In some instances, the formed electrode may cover a portion of the surface of the electrode substrate.

[0071] Figure 3 schematically illustrates a block diagram 300 of conductive track fabrication according to an example of the present disclosure. The features of Figure 3 can be described in combination with any of the features of the examples shown in Figures 1-2. The example method shown in Figures 1-2 may or may not further include features of the example of Figure 3.

[0072] 3, the method for additively manufacturing a sensor includes screen printing conductive tracks onto an electrode substrate at block 302. In some examples, the screen printing may be performed by a pneumatic screen printer, specifically a pneumatic flat screen printer.

[0073] The conductive tracks may include a conductive compound selected from at least one of silver, carbon, a carbon allotrope, and copper. As noted above, the conductive compound may have one to four valence electrons. In this example of FIG. 3, the conductive tracks include silver.

[0074] In block 304, the screen-printed conductive tracks on the electrodes can be cured by heating the screen-printed conductive tracks and exposing the screen-printed conductive tracks to electromagnetic radiation. The screen-printed conductive tracks 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 in the wavelength range of 240 nm to 270 nm. In some examples, the electromagnetic radiation source can have a peak emission wavelength in this range. However, in other examples, the electromagnetic radiation source can have a peak emission wavelength outside this range. Even if the peak emission wavelength is outside the range, the electromagnetic radiation source can still generate radiation in the 240 nm to 270 nm range sufficient to heat the conductive track composition.

[0075] In some examples, the electromagnetic radiation source may include a UV light emitting diode (LED), a mercury lamp, etc. In some examples, the electromagnetic radiation source may include a UV-LED that emits a central emission wavelength of 200 nm to 420 nm, particularly 240 nm to 270 nm.

[0076] The rate at which the evaporable solvent evaporates from the screen-printed conductive tracks can be related to the intensity of the applied electromagnetic radiation. For example, lower intensities can be associated with rapid evaporation, while higher intensities can be associated with longer evaporation. The intensity can be adjusted by selecting an electromagnetic radiation source with the desired power, or by adjusting the power density of the electromagnetic radiation source, etc.

[0077] In summary, in the example of Figure 3, the electrodes are connected to electrical contacts via conductive tracks.

[0078] Referring to the description of Figures 1-3, the electrode substrate may include one or more electrodes, for example, 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] To obtain a sensor, the film may be delivered onto one or more electrodes, and / or an additional pharmaceutical composition may be delivered onto one or more electrodes. In both cases, the film and the additional pharmaceutical composition may be delivered onto a cured electrode (i.e., an electrode that has been cured in advance, or an electrode that has been cured after the conductive agent composition has been delivered onto the electrode substrate).

[0080] The following figures and examples are intended to illustrate how sensors or sensor assemblies (e.g., redox sensors, pH sensors, chlorine sensors, conductivity sensors, temperature sensors) can be obtained by at least partially applying the methods disclosed in the description of Figures 1-3. Also, 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).

[0081] Figure 4 shows a schematic block diagram 400 of a method for spray coating a platinum agent composition according to one example of the present disclosure. The features of Figure 4 can be described in combination with any of the features of the examples shown in Figures 1-3. The example method shown in Figures 1-3 may or may not further include features of the example of Figure 4.

[0082] In Figure 4, a platinum agent composition is spray coated onto the first working electrode in block 402. In this example, the additional drug composition can be a platinum agent composition.

[0083] In some examples, spray coating may be performed using pressurized gas, such as air, at a flow rate of 50 to 1000 μl / min, specifically 100 to 800 μl / min, and more specifically 200 to 700 μl / min.

[0084] At block 404, the delivered platinum agent composition is cured by heating the platinum agent composition at 80° C. for 10 minutes.

[0085] In this example of FIG. 4, the platinum agent composition may be a carbon-supported platinum composition with 3% platinum by weight.

[0086] It should be noted that the curing parameters (e.g., heating temperature; and the time for which the platinum agent composition is heated) may vary depending on the platinum agent composition. In some instances, the curing parameters may differ from those described above.

[0087] Below are some examples of sensors. The sensors described below may be combined into a sensor assembly. A first sensor, a second sensor, etc. may be additively manufactured on the same electrode substrate of the sensor assembly. Additively manufacturing a first sensor on an electrode substrate does not preclude additively manufacturing additional sensors (e.g., a second sensor, a third sensor, a fourth sensor, etc.) on the same electrode substrate. The sensors additively manufactured on the same electrode substrate may be selected from at least one of a redox sensor, a pH sensor, a chlorine sensor, a conductivity sensor, and a temperature sensor. Thus, the following sensors are not mutually exclusive.

[0088] An example of a redox sensor: The platinum agent composition can be spray coated onto a first working electrode, and the film agent composition can be delivered to a first reference electrode to form a film, resulting in a redox sensor, which can be a potentiometric sensor.

[0089] In these examples, the membrane formed on the first reference electrode is an ion-saturated membrane. The ion-saturated membrane can be manufactured according to the examples disclosed in the description of Figures 1a and 1b. The ion-saturated membrane can be saturated with chloride ions so that the potential of the Ag / AgCl reference electrode (i.e., the first reference electrode) can remain stable at a predetermined reference electrode potential. Therefore, the ion-saturated membrane can maintain a substantially constant concentration of chloride ions in contact with the Ag / AgCl reference electrode.

[0090] An example of a pH sensor: If the membrane formed on the Ag / AgCl reference electrode (i.e., the first reference electrode) can be an ion-saturated membrane, a pH sensor can be obtained. The membrane formed on the first working electrode can be an ion-selective membrane that can be selective for hydrogen ions. The pH sensor can also be a potentiometric sensor.

[0091] According to the example disclosed in the description of Figures 1a and 1b, the first working electrode may be made of a second conductive ink, which may include at least one of amorphous carbon, carbon black, and graphite.

[0092] On the other hand, an ion-saturated membrane can be manufactured according to the example disclosed in the description of Figures 1a and 1b. The ion-saturated membrane can be saturated with chloride ions so that the potential of the Ag / AgCl reference electrode can remain stable at a predetermined reference electrode potential. Therefore, the ion-saturated membrane can maintain a substantially constant concentration of chloride ions in contact with the Ag / AgCl reference electrode.

[0093] Alternatively, ion-selective membranes can be produced according to the examples disclosed in the description of Figures 1a and 1b. In these examples, the membranes formed from the membrane agent compositions selectively react with hydrogen ions (e.g., H + ) can be selective for

[0094] FIG. 5 shows a schematic block diagram 500 of spray coating an IrOX agent composition according to one example of the present disclosure.

[0095] 1a and 1b, the second working electrode may be made of a second conductive ink, which may include at least one of amorphous carbon, carbon black, and graphite.

[0096] 5, an IrOX agent composition is spray coated onto the second working electrode in block 502. In this example, the additional agent composition can be an IrOX agent composition.

[0097] In some examples, spray coating may be performed using pressurized gas such as air at a flow rate of 50 to 1000 μl / min, specifically 100 to 800 μl / min, and more specifically 200 to 700 μl / min.

[0098] In block 504, the delivered IrOX agent composition is cured by heating the IrOX agent composition at 80° C. for 10 minutes.

[0099] The IrOX agent composition may include an iridium oxide compound, a solvent, and an ion-conducting polymer. The ion-conducting polymer may be an organic fluorinated polymer selected from a homopolymer, a copolymer, a multicomponent polymer, or a combination thereof. In some examples, the ion-conducting polymer is a fluorinated polymer, particularly a fluorinated polymer having sulfonic acid moieties, preferably a sulfonated tetrafluoroethylene-based fluoropolymer or a perfluorosulfonic acid (PFSA) polymer, more preferably a tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octene sulfonic acid polymer or copolymer. In some of these examples, the fluorinated polymer may be a compound of formula (I): [ka] In the formula, n and m are integers greater than 1. Furthermore, the compound of formula (I) contains 800 to 1400 equivalents.

[0100] Furthermore, iridium oxide compounds are known as IrO x and x is equal to 2 or greater than 2. The solvent may also be IrO x The solvent may be a solvent that does not oxidize the compound and dilutes the fluorinated polymer to obtain a viscosity and surface tension that is compatible with the delivery method (e.g., spray coating). For example, the viscosity and surface tension may be adjusted so that the IrOX agent composition is sprayed using a pressurized gas, such as air, at a predetermined flow rate. In some of these examples, the solvent may include propan-2-ol.

[0101] 5, a pH sensor is obtained when the IrOX agent composition is spray coated onto the second working electrode. In this example, the first reference electrode may be an Ag / AgCl reference electrode as described above.

[0102] It should be noted that in some examples, the IrOX agent composition can be used in a method for additively manufacturing a sensor assembly, the method including providing a first sensor on an electrode substrate, the sensor being manufactured using a method for additively manufacturing sensors according to an example of the present disclosure, providing a first reference electrode on the electrode substrate according to an example of the present disclosure, providing a first working electrode on the electrode substrate, and spray coating the IrOX agent composition onto the first working electrode, the first reference electrode and the IrOX spray-coated first working electrode forming a second sensor on the electrode substrate, the second sensor being a pH sensor.

[0103] pH sensors based on IrOX agent compositions can be suitable for obtaining reliable measurements of pH in acidic or basic media. In particular, pH sensors based on IrOX agent compositions can have a pH operating range that includes acidic media (e.g., pH < 4) or basic media (e.g., pH > 10.5).

[0104] The IrOX agent composition has low reactivity with the pH conditions, and therefore can enhance the chemical stability of the pH sensor under the pH conditions of these media.

[0105] In some examples, the IrOX agent compositions may be used in other systems or methods not described in this disclosure.

[0106] An example of a chlorine sensor: Figure 6 shows a schematic block diagram 600 of injection of a gold nanoparticle agent composition according to one example of the present disclosure. The features of Figure 6 can be described in combination with any of the features of the example shown in Figure 5. The example method shown in Figure 5 may or may not further include features of the example of Figure 6.

[0107] 1a and 1b, the second working electrode may be made of a second conductive ink, which may include at least one of amorphous carbon, carbon black, and graphite.

[0108] 6, a gold nanoparticle agent composition can be sprayed onto the second working electrode in block 602. In this example, the additional agent composition can be a gold nanoparticle agent composition.

[0109] At block 604, the delivered gold nanoparticle agent composition can be cured by heating the gold nanoparticle agent composition at 140° C. for 30 minutes.

[0110] The gold nanoparticle composition contains gold particles having a size of 1 nm to 100 nm.

[0111] In Figure 6, a chlorine sensor can be obtained when the gold nanoparticle agent composition can be sprayed onto the second working electrode. In this example, the second reference electrode can be an Ag / AgCl reference electrode as described above. The chlorine sensor can output a signal representative of the presence of free chlorine. The sprayed gold nanoparticle second working electrode can improve the stability of the chlorine sensor over time (e.g., over 12 hours). Therefore, calibration to compensate for changes in the chlorine sensor response over time can be avoided. As a result, the chlorine sensor can be used for continuous measurements.

[0112] It should be noted that in some examples, the gold nanoparticle agent composition can be used in a method for additively manufacturing a sensor assembly, such that a second working electrode sprayed with the gold nanoparticle agent composition and a second reference electrode can form a sensor on an electrode substrate of the sensor assembly, where the sensor is a chlorine sensor.

[0113] Conductivity sensor by example: By delivering a third conductive ink (as described above), a conductivity sensor can be obtained.

[0114] In some examples, the conductivity sensor can include two electrodes including a silver reference electrode made of silver and a silver working electrode made of silver.

[0115] In some examples, the conductivity sensor can include four electrodes, including a first pair of inner electrodes including an inner silver reference electrode and an inner silver working electrode for potentiometric measurements (U) and a second pair of outer electrodes including an outer silver reference electrode and an outer silver working electrode for amperometric measurements (I). In this configuration, conductivity can be measured from the amperometric measurements (I) and the potentiometric measurements (U).

[0116] An example of a temperature sensor: A temperature sensor can be obtained by delivering the conductive agent composition onto an electrode substrate. The temperature sensor can include a resistor formed from the conductive agent composition. In some examples, 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 and second electrical contacts to measure the resistance of the resistor, which can be correlated to temperature.

[0117] The method for additively manufacturing sensors can result in the fabrication of at least one of a redox sensor; and at least a membrane-based pH sensor.

[0118] A method for additively manufacturing a sensor assembly according to an example of the present disclosure can result in manufacturing at least one of a membrane-based pH sensor, a pH sensor based on an IrOX agent composition, a chlorine sensor, a conductivity sensor, and a temperature sensor, as described above.

[0119] The combination of the above-mentioned sensors can be obtained, for example, in the same electrode substrate. Therefore, the combination of the above-mentioned sensors can constitute a sensor assembly. As a result, the sensor assembly can include two or more of the above-mentioned sensors (i.e., a redox sensor, a pH sensor, a chlorine sensor, a conductivity sensor, and a temperature sensor).

[0120] FIG. 7a depicts a sensor assembly 700 comprising an additively manufactured sensor according to an example of the present disclosure.

[0121] In this example of FIG. 7a, the sensor assembly may 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.

[0122] It should be noted that the sensor assembly 700 may include any additively manufactured sensor according to the present disclosure (e.g., a redox sensor, a pH sensor, a chlorine sensor, a conductivity sensor, a temperature sensor), and the sensor assembly includes at least one sensor including a membrane delivered according to one example of the present disclosure.

[0123] FIG. 7b schematically illustrates the sensor assembly 700 of FIG. 7a with conductive tracks according to an example of the present disclosure.

[0124] In this example of Figure 7b, the sensor assembly further comprises conductive tracks, in which the electrodes of redox sensor 702 are connected to redox electrical contacts via redox conductive track 703, the electrodes of pH sensor 704 are connected to pH electrical contacts via pH conductive track 705, the electrodes of chlorine sensor 706 are connected to chlorine electrical contacts via chlorine conductive track 707, the electrodes of conductivity sensor 708 are connected to conductivity electrical contacts via conductivity conductive track 709, and temperature sensor 710 is connected to temperature electrical contacts via temperature conductive track 711.

[0125] According to one aspect, a method for manufacturing a microfluidic device is disclosed. The method includes providing a microfluidic device including a structure. In particular, the structure includes an inlet channel, an outlet channel, and a detection chamber 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 a sensor assembly according to any example of the present disclosure such that the detection chamber is fluidly connected to an electrode of the sensor or an electrode of the sensor assembly.

[0126] In some examples, the structure may include a first member structure and a second member structure. The first member structure may have a transition temperature Tg1 and the second member structure may have a transition temperature Tg2. The transition temperature Tg1 may be higher than the transition temperature Tg2.

[0127] In some examples, the first component structure and / or the second component structure may be a cyclic olefin copolymer (COC).

[0128] When the first and second component structures are joined, a fluid channel may be milled through the second component structure into the first component structure. The fluid channel may include an inlet channel, an outlet channel, and a detection chamber. The detection chamber may be in fluid communication with the inlet channel and the outlet channel.

[0129] The connection between the microfluidic device and the sensor or sensor assembly may be achieved at least in part by fusing the second component structure with the electrode substrate of the sensor or sensor assembly. The second component structure may have a lower transition temperature, such that when a temperature t (Tg1 > t ≥ Tg2) and pressure are applied across the structure (including the first component structure and the second component structure) and the sensor or sensor assembly, the second component structure may at least in part fuse with the electrode substrate, resulting in a microfluidic device.

[0130] Thus, a fluid sample can be provided to an inlet channel of a microfluidic device, and the provided fluid sample can be contacted with an electrode or membrane. The provided fluid sample can reach the detection chamber by, for example, capillary action, gravity, pumping, etc. Contact between the fluid sample and the electrode or membrane can generate a signal. The signal can represent the presence or absence of a target agent 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.

[0131] FIG. 8 illustrates a cross-sectional view of a system 800 for additively manufacturing a sensor according to an example of the present disclosure.

[0132] The membrane head may have a generally elongated configuration such that a membrane head longitudinal axis 825 is defined. In some examples, the membrane head longitudinal axis 825 may be the same axis as the motor shaft axis.

[0133] In FIG. 8 , an electric motor 810 is operably connected to a film head actuator 822. The electric motor 810 can include a motor shaft defining a motor shaft axis. The motor shaft drives the film head actuator 822. The film head actuator 822 can be an endless screw. The film head actuator 822 can force the film agent composition through a conduit 824 to a nozzle 830. The conduit 824 is in fluid communication with a nozzle having a nozzle outlet 832. The film head actuator 822 can be in fluid communication with a connection port 826 such that the film head actuator 822 can be configured to supply the nozzle 830. Thus, the film agent composition can be delivered onto a receiving area 840 to receive an electrode 850. The electrode 850 can be provided on an electrode substrate (as described above) or can be provided on an electrode substrate with a conductive agent composition delivered to form the electrode (as described above).

[0134] In FIG. 8, the drive arm 900 may be configured to drive the membrane head 820 over at least the receiving area 840, and the membrane head actuator 822 may be configured to supply the membrane agent composition to the nozzle 830.

[0135] Further in FIG. 8, the membrane agent composition may be supplied to membrane head 820 via connection port 826 in fluid communication with conduit 824 and reservoir 860 .

[0136] Thus, the system 800 for additively manufacturing a sensor includes a receiving area 840 configured to receive an electrode 850 and a film head 820 for delivering a film agent composition onto the electrode 850 via a nozzle 830.

[0137] The container 860 may also contain a membrane agent composition to be supplied to the membrane head 820. The container 860 may include an outlet end 870 and a carrier end 880. Accordingly, a container longitudinal axis 865 may be defined from the outlet end 870 to the carrier end 880. The outlet end 870 may be directly connected to the connection port 826.

[0138] Additionally, the carrier end 880 of the vessel may be connected to a vessel actuator 862. The vessel actuator 862 may be configured to apply pressure to the carrier end 880 to deliver the membrane agent composition through the outlet end. In some examples, the system 800 may include a controller configured to control the synchronized operation of the vessel actuator 862 and the membrane head actuator 822.

[0139] 8 , container carrier 890 can have a distal portion 892 and a proximal portion 894. Container carrier 890 can be configured to hold a container via container carrier end 880. Container carrier 890 can be attached to membrane head 820 by proximal portion 894. Container carrier 890 can be configured to hold a container 860 such that an angle 910 is defined between membrane head longitudinal axis 825 and container longitudinal axis 865.

[0140] In some examples, the container carrier 890 includes a carrier arm 896 that is connected to the membrane head 820 via a carrier adapter 898 .

[0141] In some examples, the carrier arm 896 may be hingedly connected to the carrier adapter 898. In this way, the carrier arm 896 can assume different positions relative to the membrane head 820. This can be useful for connecting containers having different shapes or sizes.

[0142] In some examples, the carrier arm 896 may include a hollow portion configured to receive at least the carrier end 880 of the container. The hollow portion may include an opening that can surround the carrier end 880 of the container when the carrier end 880 of the container engages the opening.

[0143] Referring again to container 860, in some examples, container 860 may be a syringe. The syringe may include a barrel having a hollow interior portion; a plunger disposed within the hollow interior portion, the plunger movable along a longitudinal axis of the barrel; the plunger operably connected to container actuator 862; and a syringe outlet in fluid communication with the hollow interior portion. The longitudinal axis of the barrel may be container longitudinal axis 865.

[0144] The reservoir actuator 862 may be configured to drive the plunger to deliver the membrane agent composition from the syringe outlet to the connection port 826 .

[0145] FIG. 9 shows a schematic diagram of a system 990 for additively manufacturing a sensor according to an example of the present disclosure.

[0146] The system 990 may include a first dispensing 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 for curing the delivered conductive agent composition, and a second dispensing unit 996. The second dispensing unit 996 is configured to deliver at least the film agent composition onto the electrode to form a film.

[0147] In some examples, the second delivery unit 996 may include a receiving area 840 configured to receive the electrode 850 and a film head 820 for delivering the film agent composition onto the electrode 850 through the nozzle 830. The film head 820 may include a connection port 826 for receiving the outlet end 870 of a container 860 for storing the film agent composition. Furthermore, the second delivery unit may include a container carrier 890 configured to hold the container 860 via the container carrier end 880. The container carrier 890 may be attached to the film head 820. The system 990 may include a drive arm 900 configured to drive the film head 920 over at least the receiving area 840 and a film head actuator 822 configured to supply the film agent composition to the nozzle 830, the film head actuator 822 being in fluid communication with the connection port. Thus, the second delivery unit 996 may include a system according to the example of FIG. 8.

[0148] In some examples, the system 990 may include an illumination device that emits electromagnetic radiation onto the electrode substrate having wavelengths comprised between 100 nm and 400 nm, which may be useful for curing some curable agent compositions.

[0149] According to one embodiment, an IrOX agent composition is disclosed. The IrOX agent composition comprises an iridium oxide compound, a solvent, and a compound of formula (I): [ka] where n and m are integers greater than 1.

[0150] Although this IrOX agent composition is described in connection with the example systems or methods for additively manufacturing sensors disclosed herein, the IrOX agent composition can be used in other example systems or methods for manufacturing sensors.

[0151] In some examples of this embodiment, the solvent comprises propan-2-ol.

[0152] In some examples of this embodiment, the compound of Formula (I) contains between 800 and 1400 equivalents.

[0153] In some examples of this embodiment, the stoichiometry of the iridium oxide compound is IrO x and x is equal to 2 or x is greater than 2.

[0154] The IrOX agent composition may be spray coated onto a working electrode, which may be suitable for determining pH.

[0155] A suitable system may include a spray coating head for delivering the IrOX agent composition onto the working electrode, which may be disposed on an electrode substrate.

[0156] For completeness, various aspects of the disclosure are set forth in the following numbered clauses.

[0157] 1. A method for additively manufacturing a sensor, the method comprising: providing an electrode, the electrode comprising a conductive agent composition; delivering a film agent composition onto the electrode to form a film; A method comprising:

[0158] 2. Providing an electrode delivering a conductive agent composition onto an electrode substrate to form an electrode; curing the conductive agent composition; 2. The method according to clause 1, comprising:

[0159] 3. Heating the electrode substrate before delivering the conductive agent composition onto the electrode substrate. 3. The method according to clause 2, comprising:

[0160] 4. The method of clause 3, wherein the electrode substrate is heated at a predetermined temperature for a predetermined time.

[0161] 5. The method of clause 3 or 4, wherein the electrode substrate is a polymer.

[0162] 6. The method of clause 5, wherein the polymer is selected from at least one of polyethylene terephthalate (PET); polyethylene naphthalate (PEN); polyimide such as Kapton; polycarbonate (PC); poly(methyl methacrylate) (PMMA); thermoplastic polyurethane (TPU); and paper.

[0163] 7. Delivering a dielectric agent composition onto at least a portion of the electrode substrate before delivering the conductive agent composition onto the electrode substrate. 5. The method according to any one of clauses 2 to 4, comprising:

[0164] 8. The method of clause 7, wherein the electrode substrate is a metal or a woven material.

[0165] 9. Exposing the electrode substrate to oxygen plasma before delivering the conductive agent composition onto the electrode substrate. 3. The method according to clause 2, comprising:

[0166] 10. The method of clause 9, wherein the electrode substrate is an oxide or ceramic material.

[0167] 11. Screen printing conductive tracks onto the electrode substrate 11. The method of any one of clauses 2 to 10, comprising:

[0168] 12. The method of clause 11, wherein the conductive tracks comprise silver.

[0169] 13. Heating the screen-printed conductive tracks; and Exposing the screen-printed conductive tracks to electromagnetic radiation having a wavelength comprised between 240 nm and 270 nm for 10 seconds Curing the screen printed conductive tracks by 13. The method according to clause 11 or 12, comprising:

[0170] 14. The method of any one of clauses 1-13, wherein the conductive agent composition comprises a first conductive ink comprising at least one of silver and silver chloride.

[0171] 15. The method of clause 14, wherein the electrodes include a first reference electrode.

[0172] 16. Curing the conductive agent composition curing the first conductive ink by heating the first conductive ink at 130°C for 30 minutes; 16. The method according to clause 14 or 15, comprising:

[0173] 17. The method of any one of clauses 1-13, wherein the conductive agent composition comprises a second conductive ink comprising at least one of amorphous carbon, carbon black, and graphite.

[0174] 18. The method of clause 17, wherein the electrodes include a counter electrode and / or a first working electrode and / or a second working electrode.

[0175] 19. Curing the conductive agent composition Curing the second conductive ink by heating the second conductive ink at 130°C for 30 minutes. 19. The method according to clause 17 or 18, comprising:

[0176] 20. Spray coating the platinum agent composition onto the first working electrode. 19. The method according to clause 18 or 19, comprising:

[0177] 21. Curing the platinum agent composition by heating the platinum agent composition at 80°C for 10 minutes. 21. The method of clause 20, comprising:

[0178] 22. The method of clause 20 or 21, wherein the platinum agent composition is a carbon-supported platinum composition containing 3% platinum by weight.

[0179] 23. The method of clauses 15 and 20, comprising obtaining a redox sensor, wherein a film agent composition is delivered onto a first reference electrode to form a film.

[0180] 24. The method of clause 23, wherein the film formed on the electrode is an ion-saturated film.

[0181] 25. The method of clause 15, wherein the film formed on the electrode is an ion-saturated film.

[0182] 26. The method according to clause 18, wherein the membrane formed on the electrode is an ion-selective membrane.

[0183] 27. The method of clauses 25 and 26, comprising obtaining a pH sensor.

[0184] 28. A method of additively manufacturing a sensor assembly, comprising: Providing a sensor on an electrode substrate, the sensor being manufactured using the method for additively manufacturing a sensor according to any one of clauses 1 to 27; providing a first reference electrode on the electrode substrate according to clause 15; spray-coating an IrOX agent composition onto a second working electrode provided on an electrode substrate, where the provided first reference electrode and the IrOX spray-coated second working electrode form a pH sensor; A method comprising:

[0185] 29. Curing the IrOX agent composition by heating the IrOX agent composition at 80°C for 10 minutes. 29. The method of claim 28, comprising:

[0186] 30. The IrOX agent composition is an iridium oxide compound; A solvent; and a compound of formula (I), [ka] 30. The method of clause 28 or 29, wherein n and m are integers greater than 1.

[0187] 31. Spraying the gold nanoparticle agent composition onto the second working electrode. 31. The method of any one of clauses 28 to 30, comprising:

[0188] 32. The method of claim 31, wherein the gold nanoparticle composition comprises gold particles having a size between 1 nm and 100 nm.

[0189] 33. The method of clauses 15 and 32, comprising obtaining a chlorine sensor.

[0190] 34. The method of any one of clauses 1-13, wherein the conductive agent composition comprises a third conductive ink comprising silver.

[0191] 35. The electrode is a silver reference electrode; Silver working electrode and 35. The method of claim 34, comprising:

[0192] 36. The method of clause 35, comprising obtaining a conductivity sensor.

[0193] 37. A method for manufacturing a microfluidic device, comprising: Providing a microfluidic device including a structure, the structure comprising: an inlet channel; An outlet channel; a detection chamber in fluid communication with the inlet channel and the outlet channel; and connecting the microfluidic device with a sensor obtained by the method of any one of clauses 1 to 27 or a sensor assembly according to any one of clauses 28 to 36, such that the detection chamber is fluidly connected to an electrode of the sensor or an electrode of the sensor assembly; A method comprising:

[0194] 38. A system for additively manufacturing a sensor, comprising: a receiving area configured to receive an electrode; a membrane head for delivering a film agent composition onto an electrode through a nozzle, the membrane head comprising a connection port for receiving an outlet end of a container for storing the film agent composition; a container carrier configured to hold a container via a carrier end of the container, the container carrier being attached to the membrane head; a drive arm configured to drive the membrane head over at least the receiving area; a membrane head actuator configured to supply a membrane composition to the nozzle, the membrane head actuator being in fluid communication with the connection port; A system comprising:

[0195] 39. The system of clause 38, wherein the container carrier comprises a carrier arm, and the carrier arm is connected to the membrane head via a carrier adapter.

[0196] 40. The system of clause 39, wherein the carrier arm is hingedly connected to the carrier adapter.

[0197] 41. The system of clause 39 or 40, wherein the carrier arm comprises a hollow portion configured to receive at least the carrier end of the container.

[0198] 42. A system described in any one of clauses 38 to 41, wherein the membrane head has a generally elongated configuration such that a membrane head longitudinal axis is defined, the container is configured such that a container longitudinal axis is defined from the carrier end to the outlet end; and the container carrier is configured to hold the container such that an angle is defined between the head longitudinal axis and the container longitudinal axis.

[0199] 43. A container actuator configured to apply pressure to the carrier end to deliver the membrane composition through the outlet end. Equipped with the system comprising a controller configured to control synchronous operation of the vessel actuator and the membrane head actuator; A system according to any one of clauses 38 to 42.

[0200] 44. A conductive agent head for delivering a conductive agent composition onto an electrode substrate in a receiving area to form an electrode. The system of any one of clauses 38 to 43, comprising:

[0201] 45. A sensor assembly comprising: 24. A redox sensor according to the method of claim 23. 29. A pH sensor according to the method according to clause 27 or 28. a chlorine sensor according to the method described in clause 33, and Conductivity sensor according to the method according to claim 36 a sensor assembly including at least one of:

[0202] 46. A kit comprising: a sensor assembly according to clause 45; 1. A microfluidic device configured to be connected to a sensor assembly, the microfluidic device comprising a structure, the structure comprising: Inlet channel, Exit channel, A detection chamber in fluid communication with the inlet and outlet channels. Including, a microfluidic device, wherein the detection chamber is fluidly connected to at least one electrode of the sensor assembly; Includes a kit.

[0203] 47. Use of a kit according to clause 46, A fluid sample is provided in the inlet channel; contacting the provided fluid sample with the electrode or membrane; Contact between the fluid sample and the electrode or membrane generates a signal; The signal, Presence of targeted agents, and / or the redox potential of the fluid sample, and / or pH of the fluid sample, and / or the temperature of the fluid sample, and / or Conductivity of the fluid sample Represents, use.

[0204] 48. An IrOX agent composition, an iridium oxide compound; A solvent; and a compound of formula (I), [ka] wherein n and m are integers greater than 1.

[0205] 49. The IrOX agent composition according to clause 47, wherein the solvent comprises propan-2-ol.

[0206] 50. The IrOX agent composition according to clause 48 or 49, wherein the compound of formula (I) contains 800 to 1400 equivalents.

[0207] 51. The stoichiometry of iridium oxide compounds is IrO x 51. The IrOX agent composition according to any one of clauses 48 to 50, wherein x is equal to 2 or x is greater than 2.

[0208] 52. A method of additively manufacturing a pH sensor, the method comprising: providing an electrode, the electrode comprising a conductive agent composition; spray coating an IrOX agent composition onto an electrode; A method comprising:

[0209] 53. Providing an electrode delivering a conductive agent composition onto an electrode substrate to form an electrode; curing the IrOX agent composition; 53. The method of claim 52, comprising:

[0210] 54. Curing the IrOX agent composition by heating the IrOX agent composition at 80°C 54. The method of claim 53, including:

[0211] 55. The IrOX agent composition is an iridium oxide compound; A solvent; and a compound of formula (I), [ka] 55. The method of any one of clauses 52 to 54, wherein n and m are integers greater than 1.

[0212] 56. The method of any one of clauses 52-55, wherein the conductive agent composition comprises a first conductive ink comprising at least one of silver and silver chloride.

[0213] 57. The method of clause 56, wherein the electrodes include a first reference electrode.

[0214] 58. The method of any one of clauses 52-55, wherein the conductive agent composition comprises a second conductive ink comprising at least one of amorphous carbon, carbon black, and graphite.

[0215] 59. Curing the conductive agent composition Curing the second conductive ink by heating the second conductive ink at 130°C for 30 minutes. 59. The method of claim 58, including:

[0216] 60. The method of clause 58 or 59, wherein the electrodes include a counter electrode and / or a second working electrode.

[0217] 61. The method of clause 60, wherein the IrOX agent composition is spray coated onto the second working electrode.

[0218] 62. A method of additively manufacturing a chlorine sensor, the method comprising: providing an electrode, the electrode comprising a conductive agent composition; spraying a gold nanoparticle composition onto the electrode; A method comprising:

[0219] 63. Providing an electrode delivering a conductive agent composition onto an electrode substrate to form an electrode; curing the gold nanoparticle composition; 63. The method of claim 62, comprising:

[0220] 64. The method of clause 62 or 63, wherein the conductive agent composition comprises a first conductive ink comprising at least one of silver and silver chloride.

[0221] 65. The method of clause 64, wherein the electrodes include a first reference electrode.

[0222] 66. The method of clause 62 or 63, wherein the conductive agent composition comprises a second conductive ink comprising at least one of amorphous carbon, carbon black, and graphite.

[0223] 67. Curing the conductive agent composition Curing the second conductive ink by heating the second conductive ink at 130°C for 30 minutes. 67. The method of claim 66, comprising:

[0224] 68. The method of clause 66 or 67, wherein the electrodes include a counter electrode and / or a second working electrode.

[0225] 69. The method of any one of clauses 62 to 68, wherein the gold nanoparticle agent composition comprises gold particles having a size between 1 nm and 100 nm.

[0226] 70. A system for additively manufacturing a sensor, comprising: a first delivery unit configured to deliver a conductive agent composition onto an electrode substrate to form an electrode; a curing unit for curing the delivered conductive agent composition; a second delivery unit, providing an electrode, the electrode including a conductive agent composition; Delivering the film agent composition onto the electrode to form a film a second delivery unit configured as follows: A system comprising:

[0227] 71. A second delivery unit: a receiving area configured to receive an electrode; a membrane head for delivering a film agent composition onto an electrode through a nozzle, the membrane head having a connection port for receiving an outlet end of a container for storing the film agent composition; a container carrier configured to hold a container via a carrier end of the container, the container carrier being attached to the membrane head; a drive arm configured to drive the membrane head over at least the receiving area; a membrane head actuator configured to supply a membrane composition to the nozzle, the membrane head actuator being in fluid communication with the connection port; 71. The system of claim 70, comprising:

[0228] 72. A lighting device that emits electromagnetic radiation having a wavelength included in the range of 100 nm to 400 nm onto an electrode substrate 72. The system of clause 70 or 71, comprising:

[0229] While only a few examples are disclosed herein, other alternatives, modifications, uses, and / or equivalents thereof are possible. Moreover, all possible combinations of the described examples are also covered. Therefore, the scope of the present disclosure should not be limited by the specific examples, but should be determined solely by a fair reading of the appended claims. Where reference signs relating to the drawings are placed within parentheses in the claims, they are merely intended to enhance the clarity of the claims and should not be construed as limiting the scope of the claims.

Claims

1. 1. A method of additively manufacturing a 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; 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; A method comprising:

2. The conductive agent composition is a first conductive ink having at least one of silver and silver chloride; and a second conductive ink comprising at least one of amorphous carbon, carbon black, and graphite; The method of claim 1 , comprising at least one of:

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

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

5. spray coating a platinum agent composition onto the first working electrode; The method of claim 4, comprising:

6. 3. The method of claim 2, wherein the reference electrode comprises a first reference electrode made from the first conductive ink and the working electrode comprises a first working electrode made from the second conductive ink, the method comprising spray coating a platinum agent composition onto the first working electrode such that the additively manufactured sensor is a redox sensor.

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

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

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

10. 1. A method of additively manufacturing a sensor assembly, comprising: - providing a first sensor on an electrode substrate, said first sensor being manufactured using a method for additively manufacturing sensors 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; spray-coating an IrOX agent composition onto the first working electrode, wherein the first reference electrode and the IrOX spray-coated first working electrode form a second sensor on the electrode substrate, and the second sensor is a pH sensor; A method comprising:

11. The IrOX agent composition is an iridium oxide compound; a solvent; and a compound of formula (I): 【Chemical 1】 11. The method of claim 10, wherein n and m are integers greater than 1.

12. providing a second reference electrode on the electrode substrate; providing a second working electrode on the electrode substrate; spraying a gold nanoparticle agent composition onto the second working electrode; The method of claim 10, comprising:

13. The second working electrode onto which the gold nanoparticle agent composition is sprayed and the second reference electrode form a third sensor on the electrode substrate, and the third sensor is a chlorine sensor. The method of claim 12.

14. 1. A method for manufacturing a microfluidic device, comprising: Providing a microfluidic device including a structure, the structure comprising: an inlet channel; An outlet channel; a detection chamber in fluid communication with the inlet channel and the outlet channel; and connecting said microfluidic device with a sensor obtained by the method of any one of claims 1 to 9 or a sensor assembly according to any one of claims 10 to 13, so that said detection chamber is fluidly connected to an electrode of the sensor or an electrode of the sensor assembly; A method comprising:

15. 1. A system for additive manufacturing of a sensor, the system comprising: a receiving area configured to receive an electrode; a membrane head for delivering a film agent composition onto the electrode through a nozzle, the membrane head comprising a connection port for receiving an outlet end of a container for storing the film agent composition; a container carrier configured to hold the container via a carrier end of the container, the container carrier being attached to the membrane head; and a drive arm configured to drive the membrane head over at least the receiving area; a membrane head actuator configured to supply the membrane composition to the nozzle, the membrane head actuator being in fluid communication with the connection port; A system comprising:

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