`
`
`
`
`
`I 1111111111111111 lllll lllllll llll llll lllll 111111111111111 lll111111111111111
`
`
`
`
`
`
`
`
`
`US00RE45415E
`
`c19) United States
`(10) Patent Number: US RE45,415 E
`
`c12) Reissued Patent
`
`(45) Date of Reissued Patent:
`Mar.17,2015
`Senkiw
`
`
`
`(54)FLOW-THROUGH OXYGENATOR
`
`205/701, 628,633,742,756,757;
`
`
`
`22/192, 321.7, 1; 119/263
`
`
`
`
`See application file for complete search history.
`(75)Inventor: James Andrew Senkiw, Minneapolis,
`
`MN(US)
`
`(56)
`
`
`
`(73)Assignee: Oxygenator Water Technologies, Inc.,
`
`St. Louis Park, MN (US)
`
`
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`(21)Appl. No.: 13/247,2 41
`
`(22)Filed:Sep.28,2011
`
`
`
`4,071,447 A 1/1978 Ramirez
`
`
`4,179,347 A 12/1979 Krause et al.
`
`(Continued)
`
`FOREIGN PATENT DOCUMENTS
`
`EP
`GB
`
`0723936 A2 7 /1996
`1 522 188 * 8/1978
`
`(Continued)
`
`OTHER PUBLICATIONS
`
`
`Related U.S. Patent Documents
`
`Reissue of:
`
`(64)Patent No.:7,670,495
`Mar. 2, 2010 Issued:
`
`Appl. No.:
`12/023,431
`Filed:
`Jan.31,2008
`U.S. Applications:
`"Effect of Oxygenated Water on the Growth & Biomass Develop­
`
`
`
`
`(60)Division of application No. 10/732,326, filed on Dec.
`
`
`ment of Seedless Cucumbers and Tomato Seedlings under Green­
`10, 2003, now Pat. No. 7,396,441, which is a continu­
`
`
`
`house Conditions", Project Report: Seair Diffusion Systems,
`
`
`ation-in-part of application No. 10/372,017, filed on
`
`
`
`
`[Online]. Retrieved from the Internet: <URL: http://www.seair.ca/
`
`Feb. 21, 2003, now Pat. No. 6,689,262.
`
`
`Pages/pdfs/DrMirzaReport.pdf>, (2003), 5 pgs.
`(Continued)
`
`(60) Provisional application No. 60/358,534, filed on Feb.
`
`
`
`
`22, 2002.
`
`(51)Int. Cl.
`C02F 1148
`
`(2006.01)
`(2006.01)
`C02F 1100
`(Continued)
`
`- Walter D Griffin
`
`Primary Examiner
`
`
`- Cameron J Allen
`
`Assistant Examiner
`
`
`
`
`Woessner, P.A.
`
`(74)Attorney, Agent, or Firm - Schwegman Lundberg &
`
`(57)
`
`ABSTRACT
`
`(52)U.S. Cl.
`An oxygen emitter which is an electrolytic cell is disclosed.
`
`
`
`USPC ...... 210/739; 204/157.15; 204/245; 204/232;
`
`
`
`
`
`
`
`
`W hen the anode and cathode are separated by a critical dis­
`
`
`
`204/628; 204/600; 210/600; 210/243; 210/153;
`
`
`
`
`tance, very small micro bubbles and nanobubbles of oxygen
`
`422/22; 422/186; 422/186.04
`
`
`
`are generated. The very small oxygen bubbles remain in
`
`suspension, forming a solution supersaturated in oxygen. A
`
`( 58)Field of Classification Search
`
`
`flow-through model for oxygenating flowing water is dis­
`
`
`
`
`USPC .......... 210/739, 746, 748.01, 748.16, 748.15,
`
`
`
`
`closed. The use of supersaturated water for enhancing the
`
`
`210/748.17, 748.19, 749,757,167.21;
`
`
`
`growth of plants is disclosed. Methods for applying super­
`
`
`422/22, 27, 28, 129, 186, 186.04,
`
`
`
`
`saturated water to plants manually, by drip irrigation or in
`
`
`422/186.03, 186.07, 186.01, 186.1, 186.15,
`
`
`
`
`hydroponic culture are described. The treatment of waste
`
`422/186.16, 186.21, 616, 243, 305, 308;
`
`
`water by raising the dissolved oxygen with the use of an
`
`204/155, 157.15, 157.5, 164,176,178,
`
`oxygen emitter is disclosed.
`
`204/450, 554,193,194,260,272,280,277,
`
`204/278.5, 287, 288, 288.1, 288.2, 230.2;
`
`1 6 Claims, 8 Drawing Sheets
`
`8
`
`6
`
`2
`
`4
`
`Tennant Company
`Exhibit 1001
`
`

`

`US RE45,415 E
`Page 2
`
`Int. Cl.
`C02F 1/02
`C02F [/04
`
`(51)
`
`(56)
`
`(2006.01)
`(2006.01)
`
`References Cited
`
`6,524,475 B1
`2/2003 Herrington et al.
`6,689,262 B2*
`2/2004 Senkiw ...................... 204/278.5
`
`7,396,441 B2 *
`7/2008 Senkiw .........
`204/278
`
`7,628,912 B2 * 12/2009 Yamasaki et al.
`............. 210/150
`2002/0074237 A1
`6/2002 Takesako et al.
`2003/0091469 A1 *
`5/2003 Kondo et al.
`................... 422/23
`2003/0164306 A1
`9/2003 Senkiw
`2004/0118701 A1*
`6/2004 Senkiw ......................... 205/633
`
`2006/0054205 A1*
`3/2006 Yabe et al.
`.................... 134/184
`2006/0150491 A1
`7/2006 Senkiw
`2007/0187262 A1*
`8/2007 Field et a1.
`2008/0202995 A1
`8/2008 Senkiw
`
`.................... 205/742
`
`FOREIGN PATENT DOCUMENTS
`
`GB
`KR
`W0
`WO
`WO
`WO
`
`8/1978
`1522188 A
`940003935 a1 * 12/1991
`WO 99/39561
`8/1999
`WO-9939561 A1
`8/1999
`WO-0189997 A2
`11/2001
`WO-03072507 A1
`9/2003
`
`............. A01K 63/04
`
`OTHER PUBLICATIONS
`
`Mohyuddin Mirza et al., “Effect of Oxygenated Water on the
`Growth & Biomass Development of Seedless Cucumbers and
`Tomato Seedlings under Greenhouse Conditions,” Seair Diffusion
`Systems, 2003, 5 pages, www.seair.ca.
`
`* cited by examiner
`
`U.S. PATENT DOCUMENTS
`*
`
`>>>>>>>>>>>>>>>
`
`4,219,417
`4,225,401
`4,252,856
`4,257,352
`4,587,001
`5,015,354
`5,049,252
`5,148,772
`5,336,399
`5,389,214
`5,500,131
`5,534,143
`5,728,287
`5,982,609
`6,110,353
`6,171,469
`6,296,756
`6,315,886
`6,328,875
`6,394,429
`6,419,815
`6,478,949
`
`8/1980
`9/1980
`2/1981
`3/1981
`5/1986
`5/1991
`9/1991
`9/1992
`8/1994
`2/1995
`3/1996
`7/1996
`3/1998
`11/1999
`8/2000
`1/2001
`10/2001
`11/2001
`12/2001
`5/2002
`7/2002
`11/2002
`
`Ramirez ....................... 2 10/707
`DiVisek et a1.
`Sara
`Habegger
`Cairns et al.
`Nishiki et al.
`Murrell
`......................... 204/268
`Kirschbaum
`Kajisono .................. 210/170.02
`Erickson et al.
`205/701
`
`Metz ............................. 2 10/705
`Portier et al.
`Hough et al.
`Evans
`Hough
`Hough et al.
`Hough et a1.
`Zappi
`Zappi et al.
`Gafian-Calvo
`Chambers ..................... 205/628
`Hough et al.
`
`................. 205/744
`
`

`

`US. Patent
`
`Mar. 17, 2015
`
`Sheet 1 of8
`
`US RE45,415 E
`
` Fig13
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`
`
`
`
`
`
`
`
`
`

`

`US. Patent
`
`Mar. 17, 2015
`
`Sheet 2 of 8
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`US RE45,415 E
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`HBWIL GTHOHLNOS dWEll
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`
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`

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`US. Patent
`
`Mar. 17, 2015
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`Sheet 3 of8
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`US RE45,415 E
`
`THERMISTOR
`
`
`
`TEMP
`
`SENSOR
`
`
`
`
`
` TIMER CONTROL
`
`CATHODE
`CIRCUIT
`
`
`
`fig 3
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`

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`US. Patent
`
`Mar. 17, 2015
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`Sheet 4 of8
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`US RE45,415 E
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`£251.41
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`

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`US. Patent
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`Mar. 17, 2015
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`Sheet 5 0f8
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`US RE45,415 E
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`US. Patent
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`Mar. 17, 2015
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`Sheet 6 of 8
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`US RE45,415 E
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`US. Patent
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`Mar. 17, 2015
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`Sheet 7 0f8
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`US RE45,415 E
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`US. Patent
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`Mar. 17, 2015
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`Sheet 8 of 8
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`US RE45,415 E
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`

`1
`FLOW-THROUGH OXYGENATOR
`
`US RE45,415 E
`
`2
`
`Matter enclosed in heavy brackets [ ] appears in the
`original patent but forms no part of this reissue specifica-
`tion; matter printed in italics indicates the additions
`made by reissue; a claim printed with strikethrough indi-
`cates that the claim was canceled, disclaimed, or held
`invalid by a prior post-patent action or proceeding.
`
`RELATED APPLICATIONS
`
`This application is a division of application Ser. No.
`10/732,326 filed Dec. 10, 2003 now US. Pat. No. 7,396,441,
`which in turn is a continuation-in—part of application Ser. No.
`10/372,017, filed Feb. 21, 2003, now U.S. Pat. No. 6,689,262,
`which claims the benefit of U.S. Provisional Application No.
`60/358,534, filed Feb. 22, 2002, each ofwhich is hereby fully
`incorporated herein by reference.
`
`FIELD OF THE INVENTION
`
`This invention relates to the electrolytic generation of
`microbubbles of oxygen for increasing the oxygen content of
`flowing water. This invention also relates to the use of super-
`oxygenated water to enhance the growth and yield of plants.
`The flow-through model is useful for oxygenating water for
`hydroponic plant culture, drip irrigation and waste water
`treatment.
`
`BACKGROUND OF THE INVENTION
`
`Many benefits may be obtained through raising the oxygen
`content of aqueous media. Efforts have been made to achieve
`higher saturated or supersaturated oxygen levels for applica-
`tions such as the improvement of water quality in ponds,
`lakes, marshes and reservoirs, the detoxification of contami-
`nated water, culture of fish, shrimp and other aquatic animals,
`biological culture and hydroponic culture. For example, fish
`held in a limited environment such as an aquarium, a bait
`bucket or a live hold tank may quickly use up the dissolved
`oxygen in the course of normal respiration and are then sub-
`ject to hypoxic stress, which can lead to death. A similar effect
`is seen in cell cultures, where the respiring cells would benefit
`from higher oxygen content of the medium. Organic pollut-
`ants from agricultural, municipal and industrial facilities
`spread through the ground and surface water and adversely
`affect life forms. Many pollutants are toxic, carcinogenic or
`mutagenic. Decomposition of these pollutants is facilitated
`by oxygen, both by direct chemical detoxifying reactions or
`by stimulating the growth of detoxifying microflora. Con-
`taminated water is described as having an increased biologi-
`cal oxygen demand (BOD) and water treatment is aimed at
`decreasing the BOD so as to make more oxygen available for
`fish and other life forms.
`
`The most common method of increasing the oxygen con-
`tent of a medium is by sparging with air or oxygen. While this
`is a simple method, the resulting large bubbles produced
`simply break the surface and are discharged into the atmo-
`sphere. Attempts have been made to reduce the size of the
`bubbles in order to facilitate oxygen transfer by increasing the
`total surface area of the oxygen bubbles. U.S. Pat. No. 5,534,
`143 discloses a microbubble generator that achieves a bubble
`size of about 0.10 millimeters to about 3 millimeters in diam-
`eter. U.S. Pat. No. 6,394,429 (“the ’429 patent”) discloses a
`device for producing microbubbles, ranging in size from 0.1
`
`5
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`to 100 microns in diameter, by forcing air into the fluid at high
`pressure through a small orifice.
`When the object of generating bubbles is to oxygenate the
`water, either air, with an oxygen content ofabout 21%, or pure
`oxygen may be used. The production of oxygen and hydrogen
`by the electrolysis ofwater is well known. A current is applied
`across an anode and a cathode which are immersed in an
`aqueous medium. The current may be a direct current from a
`battery or an AC/DC converter from a line. Hydrogen gas is
`produced at the cathode and oxygen gas is produced at the
`anode. The reactions are:
`
`AT THE CATHODE:
`AT THE ANODE:
`NET REACTION:
`
`4H2O + 46’ —> 4OH’ + 2H2
`2H2O —> 02 + 4H+ + 46’
`6H2O —> 4OH’ + 4H+ ++ 2H2 + 02
`
`286 kilojoules of energy is required to generate one mole of
`oxygen.
`The gasses form bubbles which rise to the surface of the
`fluid and may be collected. Either the oxygen or the hydrogen
`may be collected for various uses. The “electrolytic water”
`surrounding the anode becomes acidic while the electrolytic
`water surrounding the cathode becomes basic. Therefore, the
`electrodes tend to foul or pit and have a limited life in these
`corrosive environments.
`Many cathodes and anodes are commercially available.
`U.S. Pat. No. 5,982,609 discloses cathodes comprising a
`metal or metallic oxide of at least one metal selected from the
`group consisting of ruthenium,
`iridium, nickel,
`iron,
`rhodium, rhenium, cobalt, tungsten, manganese, tantalum,
`molybdenum,
`lead,
`titanium, platinum, palladium and
`osmium. Anodes are formed from the same metallic oxides or
`metals as cathodes. Electrodes may also be formed from
`alloys of the above metals or metals and oxides co-deposited
`on a substrate. The cathode and anodes may be formed on any
`convenient support in any desired shape or size. It is possible
`to use the same materials or different materials for both elec-
`trodes. The choice is determined according to the uses. Plati-
`num and iron alloys (“stainless steel”) are often preferred
`materials due to their inherent resistance to the corrosive
`electrolytic water. An especially preferred anode disclosed in
`U.S. Pat. No. 4,252,856 comprises vacuum deposited iridium
`oxide.
`Holding vessels for live animals generally have a high
`population of animals which use up the available oxygen
`rapidly. Pumps to supply oxygen have high power require-
`ments and the noise and bubbling may further stress the
`animals. The available electrolytic generators likewise have
`high power requirements and additionally run at high volt-
`ages and produce acidic and basic water which are detrimen-
`tal to live animals. Many of the uses of oxygenators, such as
`keeping bait or caught fish alive, would benefit from portable
`devices that did not require a source of high power. The need
`remains for quiet, portable, low voltage means to oxygenate
`water.
`
`It has also been known that plant roots are healthier when
`oxygenated water is applied. It is thought that oxygen inhibits
`the growth of deleterious fungi. The water sparged with air as
`in the ’429 patent was shown to increase the biomass of
`hydroponically grown cucumbers and tomatoes by about
`1 5%.
`
`The need remains for oxygenator models suitable to be
`placed in-line in water distribution devices so as to be applied
`to field as well as hydroponic culture.
`
`SUMMARY OF THE INVENTION
`
`This invention provides an oxygen emitter which is an
`electrolytic cell which generates very small microbubbles
`
`

`

`US RE45,415 E
`
`3
`and nanobubbles of oxygen in an aqueous medium, which
`bubbles are too small to break the surface tension of the
`medium, resulting in a medium supersaturated with oxygen.
`The electrodes may be a metal or oxide ofat least one metal
`selected from the group consisting of ruthenium, iridium,
`nickel, iron, rhodium, rhenium, cobalt, tungsten, manganese,
`tantalum, molybdenum, lead, titanium, platinum, palladium
`and osmium or oxides thereof. The electrodes may be formed
`into open grids or may be closed surfaces. The most preferred
`cathode is a stainless steel mesh. The most preferred mesh is
`a {fraction (1/15)} inch grid. The most preferred anode is
`platinum and iridium oxide on a support. A preferred support
`is titanium.
`In order to form microbubbles and nanobubbles, the anode
`and cathode are separated by a critical distance. The critical
`distance ranges from 0.005 inches to 0.140 inches. The pre-
`ferred critical distance is from 0.045 to 0.060 inches.
`Models of different size are provided to be applicable to
`various volumes of aqueous medium to be oxygenated. The
`public is directed to choose the applicable model based on
`volume and power requirements ofproj ected use. Those mod-
`els with low voltage requirements are especially suited to
`oxygenating water in which animals are to be held.
`Controls are provided to regulate the current and timing of
`electrolysis.
`A flow-through model is provided which may be connected
`in-line to a watering hose or to a hydroponic circulating
`system. The flow-through model can be formed into a tube
`with triangular cross-section. In this model, the anode is
`placed toward the outside ofthe tube and the cathode is placed
`on the inside, contacting the water flow. Altematively, the
`anodes and cathodes may be in plates parallel to the long axis
`of the tube, or may be plates in a wafer stack. Altemately, the
`electrodes may be placed in a side tube (“T” model) out of the
`direct flow ofwater. Protocols are provided to produce super-
`oxygenated water at the desired flow rate and at the desired
`power usage. Controls are inserted to activate electrolysis
`when water is flowing and deactivate electrolysis at rest.
`This invention includes a method to promote growth and
`increase yield of plants by application of superoxygenated
`water. The water treated with the emitter of this invention is
`one example of superoxygenated water. Plants may be grown
`in hydroponic culture or in soil. The use of the flow-through
`model for drip irrigation of crops and waste water treatment is
`disclosed.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`FIG. 1 is the O2 emitter of the invention.
`FIG. 2 is an assembled device.
`
`FIG. 3 is a diagram of the electronic controls of the O2
`emitter.
`FIG. 4 shows a funnel or pyramid variation of the O2
`emitter.
`FIG. 5 shows a multilayer sandwich O2 emitter.
`FIG. 6 shows the yield of tomato plants watered with
`superoxygenated water.
`FIG. 7 shows an oxygenation chamber suitable for flow-
`through applications. FIG. 7A is a cross section showing
`arrangement of three plate electrodes. FIG. 7B is a longitu-
`dinal section showing the points of connection to the power
`source.
`
`FIG. 8 is a graph showing the oxygenation of waste water.
`
`DETAILED DESCRIPTION OF THE INVENTION
`
`Definitions
`
`For the purpose of describing the present invention, the
`following terms have these meanings:
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`4
`
`“Critical distance” means the distance separating the anode
`and cathode at which evolved oxygen forms microbubbles
`and nanobubbles.
`
`“Critical distance” means the distance separating the anode
`and cathode at which evolved oxygen forms microbubbles
`and nanobubbles.
`
`“O2 emitter” means a cell comprised of at least one anode
`and at least one cathode separated by the critical distance.
`“Metal” means a metal or an alloy of one or more metals.
`“Microbubble” means a bubble with a diameter less than
`50 microns.
`“Nanobubble” means a bubble with a diameter less than
`
`that necessary to break the surface tension of water.
`Nanobubbles remain suspended in the water, giving the water
`an opalescent or milky appearance.
`“Supersaturated” means oxygen at a higher concentration
`than normal calculated oxygen solubility at a particular tem-
`perature and pressure.
`“Superoxygenated water” means water with an oxygen
`content at least 120% of that calculated to be saturated at a
`temperature.
`“Water” means any aqueous medium with resistance less
`than one ohm per square centimeter; that is, a medium that can
`support the electrolysis ofwater. In general, the lower limit of
`resistance for a medium that can support electrolysis is water
`containing more than 2000 ppm total dissolved solids.
`and
`The present
`invention produces microbubbles
`nanobubbles of oxygen via the electrolysis of water. As
`molecular oxygen radical (atomic weight 8) is produced, it
`reacts to form molecular oxygen, Oz. In the special dimen-
`sions of the invention, as explained in more detail in the
`following examples, O2 forms bubbles which are too small to
`break the surface tension of the fluid. These bubbles remain
`
`suspended indefinitely in the fluid and, when allowed to build
`up, make the fluid opalescent or milky. Only after several
`hours do the bubbles begin to coalesce on the sides of the
`container and the water clears. During that time, the water is
`supersaturated with oxygen.
`In contrast,
`the H2 formed
`readily coalesces into larger bubbles which are discharged
`into the atmosphere, as can be seen by bubble formation at the
`cathode.
`
`The first objective of this invention was to make an oxygen
`emitter with low power demands, low voltage and low current
`for use with live animals. For that reason, a small button
`emitter was devised. The anode and cathode were set at vary-
`ing distances. It was found that electrolysis took place at very
`short distances before arcing ofthe current occurred. Surpris-
`ingly, at slightly larger distances, the water became milky and
`no bubbles formed at the anode, while hydrogen continued to
`be bubbled off the cathode. At distance of 0.140 inches
`between the anode and cathode, it was observed that the
`oxygen formed bubbles at the anode. Therefore, the critical
`distance for microbubble and nanobubble formation was
`determined to be between 0.005 inches and 0.140 inches.
`
`EXAMPLE 1
`
`Oxygen Emitter
`
`As shown in FIG. 1, the oxygen evolving anode 1 selected
`as the most efficient is an iridium oxide coated single sided
`sheet of platinum on a support of titanium (Eltech, Fairport
`Harbor, Ohio). The cathode 2 is a (fraction (1/15)} inch mesh
`(size 8 mesh) marine stainless steel screen. The anode and
`cathode are separated by a non-conducting spacer 3 contain-
`ing a gap 4 for the passage of gas and mixing of anodic and
`cathodic water and connected to a power source through a
`
`

`

`US RE45,415 E
`
`5
`connectionpoint 5. FIG. 2 shows a plan view ofthe assembled
`device. The O2 emitter 6 with the anode connecting wire 7 and
`the cathode connecting wire 8 is contained in an enclosure 9,
`connected to the battery compartment 10. The spacer thick—
`ness is critical as it sets the critical distance. It must be of
`
`sufficient thickness to prevent arcing of the current, but thin
`enough to separate the electrodes by no more than 0.140
`inches. Above that thickness, the power needs are higher and
`the oxygen bubbles formed at higher voltage will coalesce
`and escape the fluid. Preferably, the spacer is from 0.005 to
`0.075 inches thick. At the lower limits, the emitter tends to
`foul more quickly. Most preferably, the spacer is about 0.050
`inches thick. The spacer may be any nonconductive material
`such as nylon, fiberglass, Teflon®, polymer or other plastic.
`Because ofthe criticality ofthe space distance, it is preferable
`to have a non-compressible spacer. It was found that Buna,
`with a durometer measure of 60 was not acceptable due to
`decomposition. Viton, a common fluoroelastomer, has a
`durometer measure of 90 and was found to hold its shape well.
`In operation, a small device with an O2 emitter 1 .485 inches
`in diameter was driven by 4AA batteries. The critical distance
`was held at 0.050 inches with a Viton spacer. Five gallons of
`water became saturated in seven minutes. This size is suitable
`
`for raising oxygen levels in an aquarium or bait bucket.
`It is convenient to attach a control circuit which comprises
`a timer that is thermostatically controlled by a temperature
`sensor which determines the off time for the cathode. When
`
`the temperature of the solution changes, the resistance of the
`thermistor changes, which causes an off time of a certain
`duration. In cool water, the duration is longer so in a given
`volume, the emitter generates less oxygen. When the water is
`warmer and therefore hold less oxygen, the duration of off
`time is shorter. Thus the device is self-controlled to use power
`most economically. FIG. 3 shows a block diagram of a timer
`control with anode 1, cathode 2, thermistor temperature sen-
`sor 3, timer control circuit 4 and wire from a direct current
`power source 5.
`
`EXAMPLE 2
`
`Measurement of O2 Bubbles
`
`Attempts were made to measure the diameter of the O2
`bubbles emitted by the device of Example 1. In the case of
`particles other than gasses, measurements can easily be made
`by scanning electron microscopy, but gasses do not survive
`electron microscopy. Large bubble may be measured by pore
`exclusion, for example, which is also not feasible when mea-
`suring a gas bubble. A black and white digital, high contrast,
`backlit photograph of treated water with a millimeter scale
`reference was shot of water produced by the emitter of
`Example 1.About 125 bubbles were seen in the area selected
`for measurement. Seven bubbles ranging from the smallest
`clearly seen to the largest were measured. The area was
`enlarged, giving a scale multiplier of 0.029412.
`Recorded bubble diameters at scale were 0.16, 0.22, 0.35,
`0.51, 0.76, 0.88 and 1.09 millimeters. The last three were
`considered outliers by reverse analysis of variance and were
`assumed to be hydrogen bubbles. When multiplied by the
`scale multiplier, the assumed O2 bubbles were found to range
`from 4.7 to 15 microns in diameter. This test was limited by
`the resolution of the camera and smaller bubbles in the
`
`nanometer range could not be resolved. It is known that white
`light cannot resolve features in the nanometer size range, so
`monochromatic laser light may give resolution sensitive
`enough to measure smaller bubbles. Efforts continue to
`
`5
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`6
`increase the sensitivity of measurement so that sub-micron
`diameter bubbles can be measured.
`
`EXAMPLE 3
`
`Other Models of Oxygen Emitter
`
`Depending on the volume of fluid to be oxygenated, the
`oxygen emitter of this invention may be shaped as a circle,
`rectangle, cone or other model. One or more may be set in a
`substrate that may be metal, glass, plastic or other material.
`The substrate is not critical as long as the current is isolated to
`the electrodes by the nonconductor spacer material of a thick-
`ness from 0.005 to 0.075 inches, preferably 0.050 inches. It
`has been noticed that the flow of water seems to be at the
`
`periphery of the emitter, while the evolved visible bubbles
`(H2) arise at the center of the emitter. Therefore, a funnel or
`pyramidal shaped emitter was constructed to treat larger vol-
`umes of fluid. FIG. 4 is a cross sectional diagram of such an
`emitter. The anode 1 is formed as an open grid separated from
`a marine grade stainless steel screen cathode 2 by the critical
`distance by spacer 3 around the periphery ofthe emitter and at
`the apex. This flow-through embodiment is suitable for treat-
`ing large volumes of water rapidly.
`The size may be varied as required. A round emitter for
`oxygenating a bait bucket may be about 2 inches in diameter,
`while a 3-inch diameter emitter is adequate for oxygenating a
`10 to 40 gallon tank. The live well of a fishing boat will
`generally hold 40 to 80 gallons of water and require a 4-inch
`diameter emitter. It is within the scope of this invention to
`construct larger emitters or to use several in a series to oxy-
`genate larger volumes. It is also within the scope of this
`invention to vary the model to provide for low voltage and
`amperage in cases where the need for oxygen is moderate and
`long lasting or conversely, to supersaturate water very quickly
`at higher voltage and amperage. In the special dimensions of
`the present invention, it has been found that a 6 volt battery
`supplying a current as low as 40 milliamperes is suflicient to
`generate oxygen. Such a model is especially useful with live
`plants or animals, while it is more convenient for industrial
`use to use a higher voltage and current. Table I shows a
`number of models suitable to various uses.
`
`TABLE I
`
`Emitter Model
`
`Gallons
`
`Volts
`
`Amps Max.
`
`Ave Watts
`
`Bait keeper
`Livewell
`OEM2 inch
`Bait store
`Double cycle
`OEM 3 inch
`OEM 4 inch
`Water pail
`Plate
`
`5
`32
`10
`70
`2
`50
`80
`2
`250
`
`6
`12
`12
`12
`12
`12
`12
`24
`12
`
`0.090
`0.180
`0.210
`0.180
`0.180
`0.500
`0.980
`1.200
`5.000
`
`0.060
`0.120
`0.120
`0.180
`0.180
`0.265
`0.410
`1.200
`2.500
`
`0.36
`1.44
`1.44
`2.16
`2.16
`3.48
`4.92
`28.80
`30.00
`
`EXAMPLE 4
`
`Multilayer Sandwich O2 Emitter
`
`An 02 emitter was made in a multilayer sandwich embodi-
`ment. (FIG. 5) An iridium oxide coated platinum anode 1 was
`formed into a grid to allow good water flow and sandwiched
`between two stainless steel screen cathodes 2. Spacing was
`held at the critical distance by nylon spacers 3. The embodi-
`
`

`

`US RE45,415 E
`
`7
`ment illustrated is held in a cassette 4 which is secured by
`nylon bolt 5 with a nylon washer 6. The dimensions selected
`were:
`
`cathode screen
`nylon spacer
`anode grid
`nylon spacer
`cathode screen
`
`0.045 inches thick
`0.053 inches thick
`0.035 inches thick
`0.053 inches thick
`0.045 inches thick,
`
`for an overall emitter thickness of 0.231 inches thick inches.
`
`If a more powerful emitter is desired, it is within the scope
`of this invention to repeat the sequence of stacking. For
`example, an embodiment may easily be constructed with this
`sequence: cathode, spacer, anode, spacer, cathode, spacer,
`anode, spacer, cathode, spacer, anode, spacer, cathode. The
`number of layers in the sandwich is limited only by the power
`requirements acceptable for an application.
`
`EXAMPLE 5
`
`Effect of Superoxygenated Water on the Growth of
`Plants
`
`It is known that oxygen is important for the growth of
`plants. Although plants evolve oxygen during photosynthe-
`sis, they also have a requirement for oxygen for respiration.
`Oxygen is evolved in the leaves of the plants, while often the
`roots are in a hypoxic environment without enough oxygen to
`support optimum respiration, which can be reflected in less
`than optimum growth and nutrient utilization. Hydroponi-
`cally grown plants are particularly susceptible to oxygen
`deficit in the root system. U.S. Pat. No. 5,887,383 describes a
`liquid supply pump unit for hydroponic cultures which attain
`oxygen enrichment by sparging with air. Such a method has
`high energy requirements and is noisy. Furthermore, while
`suitable for self-contained hydroponic culture, the apparatus
`is not usable for field irrigation. In a report available on the
`web, it was shown that hydroponically grown cucumbers and
`tomatoes supplied with water oxygenated with a device simi-
`lar to that described in the ’429 patent had increased biomass
`of about 12% and 17% respectively. It should be noted that
`when sparged with air, the water may become saturated with
`oxygen, but it is unlikely that the water is superoxygenated.
`A. Superoxygenated Water in Hydroponic Culture.
`Two small hydroponic systems were set up to grow two
`tomato plants. Circulation protocols were identical except
`that the 2 1/2 gallon water reservoir for the Control plant was
`eroated with and aquarium bubbler and that for the Test plant
`was oxygenated with a five-inch strip emitter for two minutes
`prior to pumping. The cycle was set at four minutes of pump—
`ing, followed by four minutes of rest. The control water had
`an oxygen content ofabout 97% to 103% saturation, that is, it
`was saturated with oxygen. The test water had an oxygen
`content of about 153% to 165% saturation, that is, it was
`supersaturated. The test plant was at least four times the
`volume of the control plant and began to show what looked
`like fertilizer burn. At that point the fertilizer for the Test plant
`was reduced by half. Since the plants were not exposed to
`natural light but to continuous artificial light in an indoor
`environment without the natural means of fertilization (wind
`and/or insects), the experiment was discontinued after three
`months. At that time, the Test plant but not the Control plant
`had blossomed.
`
`8
`B. Superoxygenated Water in Field Culture.
`A pilot study was designed to ascertain that plants outside
`the hydroponic culture facility would benefit from the appli-
`cation of oxygen. It was decided to use water treated with the
`emitter of Example 1 as the oxygen carrier. Since water so
`treated is supersaturated, it is an excellent carrier of oxygen.
`Tomato seeds (Burpee “Big Boy”) were planted in one-
`inch diameter peat and dirt plugs encased in cheese cloth and
`placed in a tray in a southwest window. Controls were
`watered once a day with tap water (“Control”) or oxygenated
`water (“Test”). Both Controls and Test sprouted at one week.
`After five weeks, the Test plants were an average of 1 1 inches
`tall while the Controls were an average ofnine inches tall. At
`this time, May 10, when the threat of frost in Minnesota was
`minimal, the plants were transplanted to 13 inch diameter
`pots with drainage holes. Four inches of top soil was added to
`each pot, topped off with four inches of Scott’s Potting Soil.
`The pots were placed outside in a sunny area with at least
`eight hours a day of full sun. The plants were watered as
`needed with either plain tap water (Control) or oxygenated
`water (Test). The oxygenated water was produced by use of
`the emitter of Example 1 run for one-halfhour in a five-gallon
`container of water. Previous experiments showed that water
`thus treated had an oxygen content from 160% to 260%
`saturation. The Test plants flowered on June 4, while the
`Controls did not flower until June 18. For both groups, every
`plant in the group first had flowers on the same day. All plants
`were fertilized on July 2 and a soaker hose provided because
`the plants were now so big that watering by hand was diflicult.
`The soaker hose was run for one half to one hour each morn-
`
`ing, depending on the weather, to a point at which the soil was
`saturated with water. One half hour after the soaker hose was
`
`turned off, about 750 ml of superoxygenated water was
`applied to each of the Test plants.
`The Test plants were bushier than the Controls although the
`heights were similar. At this time, there were eight Control
`plants and seven Test plants because one of the Test plants
`broke in a storm. On July 2, the control plants averaged about
`17 primary branches from the vine stem, while the control
`plants averaged about 13 primary branches from the vine
`stem. As the tomatoes matured, each was weighed on a
`kitchen scale at harvest. The yieldhistory is shown in Table 11.
`
`TABLE 11
`
`Control, grams
`tomatoes from eight
`plants/cumulative total
`
`Test, grams
`tomatoes from seven
`plants/cumulative total
`
`240
`180
`905
`410
`3300
`4150
`not weighed
`6435
`
`420
`1325
`1735
`5035
`9175
`15620
`
`400
`2910
`1830
`2590
`2470
`1580
`3710
`8895
`
`3310
`5140
`7730
`10200
`11780
`15490
`243 85
`
`Week of:
`
`July 27
`August 3
`August 10
`August 17
`August 24
`August31
`September 15
`Final Harvest
`September 24
`
`The total yield for the eight Control plants was 15620
`grams or 1952 grams of tomatoes per plant.
`The total yield for the seven Test plants was 24385 grams or
`3484 grams of tomatoes per plant, an increase in yield of
`about 79% over the Control plants.
`FIG. 6 shows the cumulative total as plotted against time.
`No