The present application relates to conductivity probes and more particularly to a wipeable conductivity probe for use in environmental water quality testing.
Fouling is a major problem on instruments used in long term submersion studies, such as oceanographic or other under water studies. These studies usually involve deploying multi-parameter devices for long periods of time (i.e., a year or more). The fouling, for example, may include the growth of algae or fungal slimes and grasses or hard shelled barnacles. One example of a water quality measurement device that employs a brush and wiper to wipe the probes is disclosed in commonly assigned U.S. Pat. No. 6,779,383.
Conductivity probes for use in water quality measurements have often been constructed from a small non-conductive tube having large flat electrodes at each end. The tube shape isolates a fluid volume that can enter the tube from either end. Based on the distance between the electrodes, the tube volume, and the measured resistance, the conductivity of a fluid in the tube can be determined. It will be apparent that the tubular design of these probes is not amenable to wiping. Over time, biological growth will occur within the tube and the conductivity measurements may no longer be reliable.
One aspect of the invention is a conductivity probe or sensor for use in environmental or water quality monitoring applications in which the probe isolates a volume of fluid but has an open construction that is accessible to wiping elements that can wipe organic foulants from the probe surfaces. The conductivity probe can be designed to be insertable into a water quality monitoring sonde as known in the art.
In one embodiment, the conductivity probe includes a forked electrode support. The forked electrode support being at an end of the conductivity probe. The forked electrode support includes first and second opposing arms or prongs that are separated by a slot and support a plurality of electrodes. In one embodiment, first and second electrodes are embedded in the first arm and third and fourth electrodes are embedded in the second arm. The first and second arms are designed so that they form an electrical conductivity cell by retaining a predetermined volume of fluid within the slot such that the conductivity of the fluid retained within the slot can be determined accurately. In one embodiment, the first electrode is a hollow cylindrical electrode and the second electrode is a rod electrode concentrically located within the first electrode and the third electrode is a hollow cylindrical electrode and the fourth electrode is a rod electrode concentrically located within the third electrode.
In another embodiment, the conductivity sensor is coupled with a reciprocating or rotating wiper assembly to form a wipeable conductivity sensor assembly. The wiper assembly includes a wiper element that travels through the slot in the forked electrode support and removes contaminants that form or accumulate in the slot that may affect the characteristics of the cell, more particularly, on the electrodes, the floor of the slot, and on the first and second arms.
Another aspect of the invention is a process of manufacturing the conductivity sensor, in particular, a process for making the forked electrode support and the opposing arm.
In one embodiment, the process includes providing a preform electrode element that is machineable to form two sets of concentric electrodes, which each comprise at least two concentric electrodes separated from one another by a gap to electrically insulate the electrodes, in which the alignment of portions that will form first and second electrodes relative to portions that will form third and fourth electrodes is fixed, encasing the preform electrode element in a plastic or ceramic material to form an encased preform electrode body, forming a slot in the encased preform electrode body by removing a portion of the plastic or ceramic material and a portion of the preform electrode element. The slot divides a portion of the encased preform electrode body into a first support and a secondsupport, wherein the first support includes a first set of concentric electrodes and the second support includes a second set of concentric electrodes that are aligned opposite one another to define a conductivity cell of a pre-determined volume.
The process may include surrounding the plastic member containing the preform electrode element with an outer housing. The outer housing can be a protective layer covering the electrode leads and may be made of an anti-fouling material.
In another embodiment, the process includes providing a first set of concentric electrodes and a second set of concentric electrodes and providing a forked electrode support that has first and second opposing arms spaced apart to provide a slot therebetween. The first opposing arm includes a first receptacle for receiving the first set of concentric electrodes and the second opposing arm includes a second receptacle for receiving the second set of concentric electrodes. The process includes placing the first and second sets of concentric electrodes into their respective receptacles and bonding the forked electrode support to each of the first and the second set of concentric electrodes with a watertight seal. This process may also include applying sealing glass to each mating surface of the first and second receptacles and the first and second set of concentric electrodes to seal the electrodes of each concentric electrode set to one another and to the forked electrode support when the electrode support is a ceramic material.
The following detailed description will illustrate the general principles of the invention, examples of which are additionally illustrated in the accompanying drawings. In the drawings, like reference numbers indicate identical or functionally similar elements.
In one embodiment, as shown in
The first and second electrodes 18, 19 together are a predetermined distance apart from the third and fourth electrodes 28, 29. The electrodes 18, 19, 28, 29 are used to measure the conductivity of a volume of fluid that is temporarily retained within slot 14 by applying a known AC voltage and observing the resultant AC current, which is proportional to the conductivity in the volume of fluid that is within the slot 14. The measured electrical conductivity is related to the effective path length (l) and the effective cross-sectional area (A) of the volume of fluid measured. The effective path length and area determine the cell constant (K) of the sensor: K=l/A. The cell constant determines the sensitivity of the sensor, and accordingly the specific electronic component values necessary to result in a certain circuit output signal for a given actual conductivity of the fluid. The apparent conductivity as seen by the circuit equals the actual conductivity of the fluid divided by K. Since temperature affects the conductivity measurement, a temperature probe 31 may be included in the electrode conductivity sensor 10. In
Slot 14 is wide enough and shaped to receive a wiper element 22 passing therethrough to remove debris from the slot 14 and/or the electrodes 18, 19, 28, 29, the arms 16, 17 and the floor 21 of the electrode support 12. Slot 14 needs to be kept free of foulants because the buildup of foulants such as scale or organic growth inside the slot will change its geometry and hence affect the calibration of the conductivity sensor 10. It is important that the slot 14 retain a stable or substantially constant volume of water (or analyte) during and after calibration for accurate measurements. Accordingly, the slot 14 should be small enough that surrounding conditions such as turbulence do not disturb the volume of water that is resident in the slot during the conductivity measurement. Otherwise it may be difficult to obtain reproducible measurements. In one embodiment, the slot is about 0.58 cm wide (0.23 in) and about 1.27 cm long (0.5 in) in an electrode support that is about 1.59 cm in diameter (0.625 in). In another embodiment, the slot may be about 0.25 cm (0.10 in) to about 2.5 cm (1.0 in) wide and about 0.64 cm (0.25 in) to about 3.8 cm (1.5 in) deep, and the electrode support may be about 0.51 cm (0.20 in) to about 5.08 cm (2.00 in) in diameter.
In one embodiment, the first and second electrodes 18, 19 and the third and fourth electrodes 28, 29 define separate sets of electrodes that each include one drive electrode and one sense electrode. A drive electrode imparts an AC current across the conductivity cell and a sense electrode detects the voltage across the cell. As shown in
In one embodiment, the conductivity sensor 10, as shown in
In another embodiment, as shown in
In one embodiment, the wiping mechanism 20 may be coupled to a wiping controller 38 to control the timing of the passing or movement of the wiper element 22 through slot 14. The wiping controller 38 may be programmable. In one embodiment, the wiping controller 38 controls the movement of the wiper element 22 so that the wiper element 22 passes through slot 14 at a selected repeating time interval. The time interval may be consistent or may be varied. In another embodiment, the wiping controller 38 controls the movement of the wiper element 22 so that the wiper element 22 passes through slot 14 prior to the conductivity sensor 10 measuring the conductivity of the fluid within slot 14. The wiping controller may be a component of a probe that includes the wiping mechanism 20 or of a sonde that is connected to the wiping mechanism 20.
In one embodiment, the wipeable conductivity sensor assembly may include a stand or holder for holding the conductivity sensor 10 and the wiping mechanism 20 in place within the fluid, whether the fluid is still or moving. In another embodiment, the conductivity sensor may be mounted within a multi-probe assembly or sonde as illustrated in U.S. Pat. No. 6,779,383 and wiped with a wiper element that cleans not only the conductivity sensor but other sensors in the probe. Thus, one embodiment of the invention is the sensor itself having the open electrode design and another embodiment is the combination of the sensor and the wiper element. A further embodiment is the sonde described in U.S. Pat. No. 6,779,383 modified to include the conductivity sensor disclosed herein.
Floor 21a, shown in
Floor 21b, shown in
Floor 21d, shown in
In one embodiment, the electrode support 12 is manufactured initially with a preform electrode element 60 (
Referring now to
The first electrode end 76 is connected to a first lead 66 and the second electrode end 77 is connected to a second lead 68. The first end 83 of rod 82 is connected to a third lead 86 and the second end 84 of rod 82 is connected to a fourth lead 88. The four leads, 66, 68, 86, 88 are coupled to the conductivity drive circuitry depicted as the ‘conductivity controller’ 32 in
The first and second electrode ends 76, 77 may each include a recess 90, 92 in their outer generally cylindrical surfaces. The recesses 90, 92 are areas where molded material can embed itself for a stronger more resilient connection to the electrodes 76, 77. In one embodiment, the recesses 90, 92 may be continuous or discontinuous annular recesses. During molding, the molding material also embeds itself between the rod 82 and the concentric generally cylindrical electrode ends 76, 77 as seen in
The arms 79, 80 may each include an alignment feature for aligning the preform electrode element 60 in a mold. The alignment feature may be holes 96, 98, or pins, notches, or the like that hold the preform electrode element 60 in place while another material is molded over and/or around it, for example by injection molding.
Referring now to
The preform electrode element 60′ is generally dumb-bell shaped with an arm 178, rod, bar, or the like integrally connecting the first and second cylindrical electrode ends 176, 177. The first cylindrical electrode end 176 is connected to a first lead 166 and the second cylindrical electrode end 177 is connected to a second lead 168. Rod 182 is connected to a third lead 186 and rod 182′ is connected to a fourth lead 188. The four leads, 166, 168, 186, 188 are coupled similarly to that described above for preform electrode element 60.
The first and second cylindrical electrode ends 176, 177 may each include a recess 190, 192 in their outer cylindrical surfaces for a stronger more resilient connection of molded material to the cylindrical electrodes. The preform electrode element 60′ may include an alignment feature such as a hole, pin, notch, or the like to hold the preform electrode element 60′ in place while another material is molded over or to it, for example by injection molding. The injected material will also embed itself between the rods 182, 182′ and the cylindrical electrode ends 176, 177. The material between the rods and the cylindrical electrode ends electrically insulates these electrodes from one another.
Referring to
Still referring to
The electrically insulating material may be a plastic, ceramic, or a resin. In an embodiment where the plastic material is being used to encase the preform electrode element, the step of encasing 104 may include the step 111 of injection molding the plastic over the preform electrode element.
In an embodiment where the ceramic material is being used to encase the preformed electrode element, the process may include the step 113 of providing a ceramic body having a bore extending through the body traverse to the longitudinal axis thereof and the step of encasing 104 may include the step 115 of applying a sealing glass to the external surface of the preform electrode element and assembling it into the bore of the ceramic body and heating the assembly to bond it together. The step 115 may also include filling the gap between the electrodes in each set of concentric electrodes with the sealing glass before heating.
Now referring to
This process provides a watertight electrode support 12 with a plurality of electrodes that are electrically insulated from each other by the material filling the gap between the two electrodes in each arm of the electrode support. This process is superior to prior art methods because it results in more closely aligned electrodes that oppose one another across the slot. The assembled electrode support 12 as well as the entire conductivity sensor 10 is a sealed body for underwater use. The assembly may be watertight even up to about 6000 meters and/or 10,000 psi.
The preform electrode element may be a non-corrosive material since it will be exposed to water or other fluids for extended periods of time while taking measurements. For example, the preform electrode element, may be or include at least one of titanium, nickle, preferably nickle 200, or a nickel-chromium alloy, such as an INCONEL® commercially available from Special Metals Corporation, preferably INCONEL® 600. INCONEL® 600 is a nonmagnetic, nickel-based high temperature alloy possessing an excellent combination of high strength, hot and cold workability, and resistance to ordinary forms of corrosion. Any other material with similar properties to INCONEL® 600 may be used. The preform electrode element may also be made from or include graphite or graphite-impregnated resins and plastics.
The preform electrode element may be formed into its preform design by metal-injection molding and/or by turning and/or machining it. Metal-injection molding is a process that begins by mixing a metal powder with a thermoplastic binder to produce a homogeneous feedstock, often with approximately 60 volume % metal powder and 40 volume % binders. The feedstock is placed into an injection molder and molded to form a net shape green part. After injection molding, two thermal processes occur. First, the binder is removed from the green part via an evaporative process called “debinding.” Second, after debinding, the part is sintered to form a high-density metal part. Sintering occurs at high temperatures, up to 2300° F. (1260° C.), near the melting point of the metal, under a dry H2 atmosphere or inert gas atmosphere. During sintering, the part will shrink isotropically to form a dense shape. Since, the complex shape of the molded part is retained through the process, close tolerances in the as-sintered part can be achieved. Other variations to this process may be used. Alternately, the preform electrode element may be formed by pressed powder sintering or investment casting.
The electrically insulating material for encasing the preform electrode element may be an engineering thermoplastic material with good material strength that lends itself to having the slot formed therein. The thermoplastic may be water, corrosion, and/or chemically resistant, and electrically insulating. Applicants have found that a superior watertight bond is formed between the preform electrode element and the plastic material when the coefficient of thermal expansion (CTE) of each material is generally similar. Likewise, minimizing the material expansion difference between the preform electrode element and the plastic material is beneficial for the dimensional stability of the conductivity cell (the cell constant). The watertight bond is important since the conductivity sensor is often used under water at significant depths and experiences increased pressure as it descends. If a gap occurs between the electrodes and the plastic material water may be able to enter the conductivity sensor and damage its electrical components.
The thermoplastic material may an acetal, acrylic, acrylonitrile-butadiene-styrene terpolymer, a polyamide, a polycarbonate, a polyetherimide, a polyphenylene ether, a polyphenylene sulfide, a polysulfone, or a thermoplastic poyester. In one embodiment the thermoplastic material is an imide, and is preferably a glass-filled imide. The imide may be a 30% glass-filled polyamide-imide resin such as TORLON® 5030 available from Solvay Advanced Polymers, L.L.C. or a 40% glass-filled polyetherimide such as ULTEM® 2400 available from SABIC Innovative Plastics.
The plastic member encases the preform electrode element as shown in
In an alternate embodiment, the electrically insulating member includes a resin. The resin may be a polyester resin, an epoxy resin, and combinations thereof, but is not limited thereto. Other electrically insulating resins are known in the art and may be equally applicable.
The outer housing may define the outer surface of the conductivity sensor 10 or at least the outer surface of the electrode support 12. In one embodiment, the outer housing surrounds the length of the electrode support and/or the conductivity sensor without covering the first end and/or the second end of the conductivity sensor. The outer housing 64 may be a sheet that is wrapped around the plastic member 62 encasing the preform electrode element and sealed to form the casing or a housing that is fitted over the plastic member. The outer housing may be bonded to the plastic member, for example with an adhesive. The adhesive may be any adhesive that can form a strong bond that is watertight, for example an epoxy. Alternately, the housing may be the die that the plastic member and preform electrode element are molded together in such that the housing is integral with the plastic member encasing the preform electrode element. The housing may be a hollow cylindrical sleeve or any other shape and/or design to match the design of the electrode support.
The outer housing may be a metal and/or an anti-biofouling material. The metal may be water resistant and corrosion resistant. For example the casing may be titanium, stainless steel, nickel, copper, and alloys thereof. In one embodiment, the casing is titanium. In another embodiment, the casing is an antifouling copper-nickle alloy with a high copper content. For example, the antifouling copper-nickle alloy may be a 90-10 CuNi alloy or a 70-30 CuNi alloy.
The portion of the preform electrode element and plastic member removed to form slot 14, see
Furthermore, as shown in
Referring now to
The process of manufacturing the ceramic electrode support 312 of
The ceramic body 240 may be a machineable ceramic, in particular a machineable ceramic that includes aluminum oxide. In one embodiment, the ceramic body may be a machineable glass-ceramic. Suitable machineable ceramic is available under the trade mark MACOR®. The ceramic body may be available as rod stock that is cut and machined to include the slot and the first and second receptacle for the sets of electrodes or a bore that receives a preform electrode element.
The sealing glass may be any commercially available or after developed metal-ceramic paste that can fuse the plurality of electrodes to the ceramic body. Preferably the sealing glass forms a water tight and electrically insulating seal between the electrodes and the ceramic body. The sealing glass may a powder, paste, granulate, or preform. When the sealing glass is a powder it is mixed with an appropriate solvent to form a paste that can be painted, spread, or sprayed onto the parts. Sealing glass is commercially available from Schott Electronic Packaging.
The appropriate sealing glass depends on the materials being joined, the required temperature profile, and the coefficient of thermal expansion. The coefficient of thermal expansion as discussed above is an important factor. For matched seals, the coefficient of thermal expansion of the glass is matched as closely as possible to those of the sealing partners. When the electrodes are titanium and the ceramic is MACOR®, then the sealing glass should be suitable for fusing titanium to MACOR®.
The parts after being coated with the sealing glass are assembled and heated to the temperature for fusing the parts together. Sealing glass typically has a processing temperature of 800-1000° C. When the sealing glass is fusing titanium and MACOR®, the assembled electrode support is heated to about 1000° C.
In an alternate embodiment, the first electrode pair 316 and the second electrode pair 318 may be formed from a preform electrode element, such as either of the preform electrode elements 60, 60′ of
As explained above, sealing glass may be used to seal the preform electrode element to the ceramic body.
Now referring to
For the embodiments having a ceramic body, the difference between the ceramic body's coefficient of thermal expansion and that for the preformed electrode may be about 10% or less, preferably about 5% or less, or more preferably about 1% or less. This provides a superior watertight bond between the ceramic and the preformed electrode and helps prevent the ceramic from cracking.
At any time after insertion of the preform electrode element 460 additional lead wires, like lead wires 460, 468 shown in
For any of the above conductivity electrodes that includes a preform electrode element with a conically-shaped gap between the electrodes, like that shown in
Now referring to
The electrode support 512 may include a temperature sensor 531 positioned in slot 514. The temperature sensor 531 is mounted in a bore 570 in the plastic material 562. The temperature sensor 531 may include protrusions 578 on is exterior surface of the end received in the bore 570 to connect the sensor to the bore or to enhance bonding between the sensor and the plastic. The protrusions 578 may be threading, annular protruding rings, or any other pattern of protrusions suitable to connect or enhance bonding of the sensor to the plastic material. Preferably, a watertight seal is present between the temperature sensor 531 and the bore 570.
The bore 570 may be formed when the plastic 562 is injection molded or may be formed after molding using known machining, etching, boring, etc. techniques. Extending from the end of the temperature sensor 531 received in bore 570 is an electrical lead 532. The electrical lead 532 can be connected to a circuit such as the main circuit board housed with a probe body.
The plastic material 562 may be a suitable plastic, such as those described above. The plastic material 562 is preferably over-molded onto a connecting ring 565. The connecting ring 565 has a central annular sleeve 590, an integral upper annular sleeve 592 defining the first end 595 of the connecting ring and an integral lower annular sleeve 594 defining the second end 596 of the connecting ring. Both the upper annular sleeve 592 and the lower annular sleeve 594 have a smaller outer diameter compared to the central annular sleeve 590. Accordingly, a first annular step 584 is formed where the upper annular sleeve 592 meets the central annular sleeve 590 and a second annular step 564 is formed where the lower annular sleeve 594 meets the central annular sleeve 590. The first annular step 584 can be a seat or stop for the over-molded plastic 562 and the second annular stop 564 can be a seat or stop that mates against an end of a probe body, like those described in commonly assigned U.S. patent application Ser. No. 12/773,995, PROBE AND PROCESS OF ASSEMBLING SAID PROBE, (the “ASSEMBLING application”) filed May 5, 2010 and incorporated herein by reference in its entirety. The connecting ring 565 may be a welding ring that can be laser welded to a probe body as disclosed in ASSEMBLING application.
The upper annular sleeve 592 may include one or more protrusions 574, for example continuous or discontinuous annular rings or any other pattern of protrusions suitable to enhance adhesion of the plastic material to the upper annular sleeve of the connecting ring. In an alternate embodiment, the upper annular sleeve 592 may be scored or have recessed groves to enhance adhesion. The height H1 of the upper annular sleeve 592 is preferably greater than the height H2 of the central annular sleeve 590. This provides for a larger surface area for over-molding the plastic and enables the connecting ring to support the plastic material and the electrodes.
The connecting ring 565 is preferably a metal ring. The metal for the ring may be any suitable metal for underwater use and in forming a water tight seal when affixed to a probe body. Suitable metals includes those described above for the housing 64 of
For a titanium connecting ring, Applicants have found that improved adhesion to the over-molded plastic is achieved when the titanium is silanized prior to the over-molding step. The titanium is silanized using know techniques and commercially available silane coupling agents. The appropriate choice of silanes, solvents, and other conditions depend upon the system in question, and are described by the silane coupling agent's manufacturer's literature, such as Advanced Polymer, Inc., Mitsubishi International Corporation, Momentive Performance Materials, Power Chemical Corporation, Gelest, Inc., and texts on the subject (“Silane Coupling Agents” by Edwin Pleuddemann; Plenum Press, New York, 1982, incorporated herein by reference in their entirety).
The upper annular sleeve 592 or the entire connecting ring 565 may be silanized. Any suitable silane may be used that can act as a coupling agent between the plastic material 562 and the metal of the connecting ring 565. When the connecting ring is titanium and the plastic is a glass-filled imide resin, the silane coupling agent is preferably an amino silane, and more preferably a primary amino silane. In one embodiment, the silane is Gamma-aminopropyltrimethoxy silane.
Other silane coupling agents and methods of silanation are disclosed in U.S. Pat. No. 5,622,782, International Published Application WO 99/20705, U.S. Patent Application Publication No. 2003/0113523, and an article by J. Matinlinna, M. Ozcan, L. Lassila, and P. Vallittu on “the effect of a 3-methacryloxypropyltrimethoxysilane and vinyltriisopropoxysilane blend and tris(3-trimethoxysilylpropyl)isocyanurate on the shear bond strength of composite resin to titanium metal” (Dental Materials, Vol. 20, Issue 9, pgs. 804-813), all of which are incorporated herein by reference in their entirety.
Silanes can be applied with various methods such as solution treatment or bulk deposition for particulates, or chemical vapor deposition when a monolayer deposition is desirable. Deposition from aqueous alcohol solutions is the most facile method for preparing silylated surfaces. A 95% ethanol-5% water solution is adjusted to pH 4.5-5.5 with acetic acid. Silane is added with stirring to yield a 2% final concentration. Five minutes should be allowed for hydrolysis and silanol formation. Large objects are dipped into the solution, agitated gently, and removed after 1-2 minutes. They are rinsed free of excess materials by dipping briefly in ethanol. Cure of the silane layer is for about 5-10 min. at 110° C. or 24 hours at room temperature (<60% relative humidity).
Deposition from aqueous solution can also be employed. The silane is dissolved at 0.5-2.0% concentration in water. For less soluble silanes, 0.1% of a nonionic surfactant is added prior to the silane and an emulsion rather than a solution is prepared. The solution is adjusted to pH 5.5 with acetic acid. The solution is either sprayed onto the substrate or employed as a dip bath. Cure is at 110-120° C. for 20-30 minutes. Stability of aqueous silane solutions varies from 2-12 hours for the simple alkyl silanes. Poor solubility parameters limit the use of long chain alkyl and aromatic silanes by this method. Distilled water is not necessary, but water containing fluoride ions must be avoided.
It will be appreciated that while the invention has been described in detail and with reference to specific embodiments, numerous modifications and variations are possible without departing from the spirit and scope of the invention as defined by the following claims.
The present application claims the priority benefit of U.S. provisional patent application Ser. No. 61/187,768, filed on Jun. 17, 2009, which is expressly incorporated by reference herein in its entirety.
Number | Date | Country | |
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61187768 | Jun 2009 | US |