Method for forming and applying an oxygenated machining fluid

Abstract

The present invention describes a chemically-assisted machining process that converts conventional lubricant chemistries to produce reactive oxygenated species that accelerate the formation of friction-reducing boundary layer lubrication during cutting operationstermed Ozonolytic Machining. The new type of cooling-lubricant chemistry is based on chemical reactions between unsaturated bio-based oils and alcohols, and other types of machining lubricants, containing carbon-carbon double or triple bonds, with ozone gas to form variously reacted or polymerized ozonidestermed super-oxygenated fluids, oils or alcohols, aldehydes or ketones, sulfurized ozonides and super-oxygenated gels.

Claims

1. A method for machining a workpiece employing an oxygenated lubricant aerosol with a metalworking tool, the steps comprising: a. reacting ozonated gas with an unsaturated liquid lubricant containing a dye to form an oxygenated lubricant, which contains reactive ozonide and ozone-reacted dye; b. monitoring and controlling oxygenation level in said oxygenated lubricant by color change; c. injecting said oxygenated lubricant into a compressed gas stream to form the oxygenated lubricant aerosol; d. applying said oxygenated lubricant aerosol on the workpiece; and e. simultaneously performing a machining process on the workpiece with the metalworking tool; whereby the oxygenated lubricant aerosol containing the reactive ozonide lowers friction during the machining of the workpiece.

2. The method of claim 1 wherein the reacting ozonated gas is further defined by: contacting a predetermined amount of the unsaturated liquid lubricant, which contains the dye, with a predetermined amount of the ozonated gas, having a concentration between 0.2 mg/hour and 15000 mg/hour of ozone, at a temperature of between 20 degrees C. and 30 degrees C. and at a pressure of between 1 atm and 150 atm.

3. The method of claim 1 wherein said unsaturated liquid lubricant is at least one of synthetic oil, natural oil, bio-based oil, soybean oil, castor oil, olive oil, rapeseed oil, jatropha oil, corn oil, safflower oil, long-chain alcohol, oleyl alcohol or ricinoleyl alcohol.

4. The method of claim 1 wherein said unsaturated liquid lubricant is modified with sulfur-containing organic and inorganic compounds, fluorine-containing organic compounds, corrosion prevention agents, viscosity modifiers, dimethyl sulfoxide (DMSO), or dimethyl sulfone (DMSO2).

5. The method of claim 1 wherein the reacting of said unsaturated liquid lubricant with the ozonated gas in the presence of deionized water and surfactant to form the oxygenated lubricant as a microemulsion.

6. The method of claim 1 further comprising sparging said oxygenated lubricant with compressed air, nitrogen or carbon dioxide for a predetermined period of time, after reacting the ozonated gas with the unsaturated liquid lubricant, to remove residual, unreacted ozone gas.

7. The method of claim 1 wherein the compressed gas stream comprises a cold compressed gas stream.

8. The method of claim 1 wherein said oxygenated lubricant aerosol is applied in the workpiece as a spray-at-tool, spray-through-spindle, or spray-through-tool configuration for stationary and portable machining and metalworking systems and tools.

9. The method of claim 1 wherein said machining process comprises turning, grinding, dicing, drilling, milling, broaching, reaming, and stamping; the metalworking tool comprises at least one of coated and uncoated carbide, steel, and ceramic drills, inserts, saws, grinding and cutting wheels; and tool coatings comprise TiN, TiAlN, or TiAlNWCC; and the workpiece comprises metals, ceramics, plastics, glasses, or composites.

10. The method of claim 1 wherein a source of oxygen gas for reacting the ozonated gas with the unsaturated liquid lubricant, which contains the dye, is derived from a semi-permeable gas membrane.

11. A method for machining a workpiece employing an oxygenated lubricant aerosol with a metalworking tool, the steps comprising: a. reacting ozonated gas with an unsaturated liquid lubricant to form an oxygenated lubricant containing reactive ozonide; b. wherein oxygenation level in said oxygenated lubricant is monitored and controlled by a viscosity sensor or a digital timer; c. injecting said oxygenated lubricant into a compressed gas stream to form the oxygenated lubricant aerosol; d. applying said oxygenated lubricant aerosol on the workpiece; and e. simultaneously performing a machining process on the workpiece with the metalworking tool; whereby the oxygenated lubricant aerosol containing the reactive ozonide lowers friction during the machining of the workpiece.

12. The method of claim 11, wherein the oxygenated lubricant has a measurable ozonide level between 0.1 percent and 10 percent.

13. The method of claim 11 wherein said unsaturated liquid lubricant is at least one of synthetic oil, natural oil, bio-based oil, soybean oil, castor oil, olive oil, rapeseed oil, jatropha oil, corn oil, safflower oil, long-chain alcohol, oleyl alcohol or ricinoleyl alcohol; the unsaturated lubricant is modified with sulfur-containing organic and inorganic compounds, fluorine-containing organic compounds, corrosion prevention agents, viscosity modifiers, dimethyl sulfoxide (DMSO), or dimethyl sulfone (DMSO2).

14. The method of claim 11 wherein the reacting of said unsaturated liquid lubricant with the ozonated gas in the presence of deionized water and surfactant to form the oxygenated lubricant as a microemulsion.

15. The method of claim 11 wherein the compressed gas stream comprises a cold compressed gas stream.

16. A method for machining a workpiece employing an oxygenated lubricant aerosol with a metalworking tool, the steps comprising: a. sparging an unsaturated liquid lubricant with an ozonated gas to form an oxygenated lubricant containing reactive ozonide; said oxygenated lubricant having a measurable ozonide level between 0.1 percent and 10 percent; b. wherein oxygenation level in said oxygenated lubricant is monitored and controlled by a digital timer or a viscosity sensor; c. injecting said oxygenated lubricant into a compressed gas stream to form the oxygenated lubricant aerosol; d. applying said oxygenated lubricant aerosol on the workpiece; and e. simultaneously performing a machining process on the workpiece with the metalworking tool; whereby the oxygenated lubricant aerosol containing the reactive ozonide lowers friction during the machining of the workpiece.

17. The method of claim 16 wherein said unsaturated liquid lubricant is at least one of synthetic oil, natural oil, bio-based oil, soybean oil, castor oil, olive oil, rapeseed oil, jatropha oil, corn oil, safflower oil, long-chain alcohol, oleyl alcohol or ricinoleyl alcohol; the unsaturated lubricant is modified with sulfur-containing organic and inorganic compounds, fluorine-containing organic compounds, corrosion prevention agents, viscosity modifiers, dimethyl sulfoxide (DMSO), or dimethyl sulfone (DMSO2).

Description

(1) Other objects and features of the invention will be evident hereinafter by reference to the following figures.

(2) FIG. 1Diagram depicting a generalized oxygenated machining fluid composition triangle.

(3) FIG. 2Chemical reaction diagram describing the intermediate ozonides and oxyanions used to oxygenate exemplary bio-based oil used in the present invention.

(4) FIG. 3Chemical reaction diagram describing the formation of trioxalane (an ozonide) and reduction of same.

(5) FIG. 4Chemical reaction diagram showing a conceptualized reaction of oxyanion by-products of ozonolysis of bio-based oils with an exemplary (and optional) sulfurizing compound.

(6) FIG. 5Chemical reaction diagram depicting conceptualized reactions of ozone, carbon-carbon double bonds and organic sulfur to form super-oxygenated (and sulfurized) bio-oils and bio-alcohols.

(7) FIG. 6Diagram showing the general progression of the reaction of ozone with an unsaturated hydrocarbon to form super-oxygenated fluids or a super-oxygenated gel.

(8) FIG. 7Related to FIG. 6, a table showing the general reaction time of the reaction of ozone with an unsaturated hydrocarbon to produce a level of saturation (i.e., oxygenation) in super-oxygenated fluids or a super-oxygenated gel.

(9) FIG. 8Diagram showing the increase of viscosity due to the reaction of ozone with an unsaturated hydrocarbon.

(10) FIG. 9Diagram showing the application of super-oxygenated and optionally electrostatically charged machining fluids as a spray (MQL or Flood) into a conceptualized cutting zone.

(11) FIG. 10Related to FIG. 9, a diagram showing the conceptualized reactions of super-oxygenated and (optionally) sulfurized machining fluid constituents with reactive metal surfaces.

(12) FIG. 11Schematic showing an exemplary MQL system for producing and applying in-situ super-oxygenated machining fluids.

(13) FIG. 11aSchematic showing the use of a membrane to selectively generate an oxygen rich or nitrogen rich gas stream for use with the present invention.

(14) FIG. 12Schematic showing an exemplary MQL system for producing and applying in-situ super-oxygenated machining fluids.

(15) FIG. 13Schematic showing an exemplary MQL system for producing and applying in-situ super-oxygenated machining fluids.

(16) FIG. 14Schematic showing an exemplary MQL applicator for transporting, forming and projecting an electrostatically-charged super-oxygenated machining fluid spray.

(17) FIG. 15Schematics showing exemplary coaxial and coaxial-Coanda nozzles for forming and projecting super-oxygenated machining fluid sprays.

(18) FIG. 16Schematic showing an exemplary ozonation system for producing a super-oxygenated machining gel or concentrate.

(19) FIG. 17Tables showing three types of exemplary oxygenated machining fluid compositions for use with the present invention.

(20) FIG. 18Schematic showing an exemplary MQL system for producing and applying in-situ super-oxygenated machining fluids.

DETAILED DESCRIPTION OF INVENTION

(21) FIG. 1 is a diagram depicting a generalized oxygenated machining fluid composition triangle. Referring to FIG. 1, exemplary compositions generated in-situ and applied in accordance with the present invention comprise combinations of ozone (2) and unsaturated bio-based compounds (4), and optionally organic sulfur compounds (6) as extreme pressure adjuncts, to form exemplary functional groups such as trioxalane (8) derived from the reaction of ozone (2) with the carbon-carbon double bonds contained on unsaturated hydrocarbons. Exemplary unsaturated hydrocarbons for use with the present invention are preferably natural or bio-based oils or alcohols. Preferred machining oils may include soybean oil, castor oil, olive oil, rapeseed oil, jatropha oil, corn oil, safflower oil, including commercial machining fluid formulations derived from same, among many others. Preferred machining fluid alcohols comprise long chain alcohols derived from bio-based oils, for example oleyl alcohol and ricinoleyl alcohol, among others. Optional organic sulfur compounds for use in the present invention include dimethyl sulfoxide (DMSO) and dimethyl sulfone (DMSO.sub.2), a natural and safe organic sulfur compound. Other types of additives not shown in FIG. 1 may be used with instantaneous oxygenated compositions of the present invention, including anti-foaming agents, dispersants, surfactants, extreme pressure agents such as fluorinated materials, water and carbon dioxide, among other beneficial machining process adjuncts. Thus the present invention provides a novel method for forming and delivering an instantaneous MQL (air-oil aerosol) or flood composition comprising highly reactive organic oxygen bearing fluids and dissolved ozone, dissolved oxygen, and additional beneficial and engineered chemistries which include organic sulfur.

(22) FIG. 2 is a diagram describing the intermediate ozonides and oxyanions used to oxygenate exemplary bio-based oil used in the present invention. Referring to FIG. 2, the reaction of ozone with the carbon-carbon double bond (10) of the oleate fatty acid backbone of soybean oil results in the rapid formation of primary and reactive ozonide structure (12), which rapidly breaks up into oxyanions (14) and into a secondary ozonide structure called trioxalane (16). It is this unstable compound that is used as a source of reactive oxygen in the present invention. Now referring to FIG. 3, the carbon-carbon double bonds (18), present at one or more locations on the unsaturated fatty acid segments of bio-based oils, are reacted with ozone in the present invention to form a (time/ozone-concentration) controllable fraction of trioxalane (20) in-situ. As shown in FIG. 3, ozonide-based fluids are too unstable to economically produce, transport and store commercially because they readily reacts with moisture, heat, light and particles to form various carbonyl by-products (22). However it is this reactivity that is the basis for improved cutting zone oxygenation and machinability in the present invention due to the presence of all of these reactive elements during a cutting operation.

(23) As described under FIG. 1, optional organic sulfur compounds such as DMSO2 may be dissolved into bio-oil or bio-alcohol to form sulfurized compositions. Returning to the same bio-oil structure depicted under FIG. 2, FIG. 4 describes a conceptualized reaction of oxyanion intermediates with the exemplary DMSO or DMSO2 compounds to form exemplary sulfur-bridged ozonides (24) for use as safe extreme pressure adjuncts in the present invention. Other extreme pressure compounds such as perfluoroalkyl polyether (PFPE) may also be used in compositions of the present invention. Such compounds, in cooperation with oxygen, are required to form suitable metal-oxide/metal-sulfide foundations for proper boundary layer lubrication, for example during the machining of super-hard steels or ceramics.

(24) FIG. 5 summarizes the basic functional group reaction ingredients and resulting instantaneous lubrication by-products used in the present invention. As shown in FIG. 5(A), reactions of ozone (I) and carbon-carbon double bonds (II) produce an ozonide structure (26), for example trioxalane. As shown in FIG. 5(B), reactions of ozone (I), carbon-carbon double bonds (II), and organic sulfur (III) produce a (conceptualized) sulfurized ozonide structure (28), which can be bonded, coordinated or in the vicinity of the ozonide structure.

(25) During the process of oxygenating the oils or alcohols of the present invention, including admixtures as already noted, the oxygenation levels (i.e., formation of trioxalane) in the fluid increases as the ozonide structure replaces carbon-carbon double bonds, up to as high as between 15% and 20% by volume. Referring to FIG. 6, the general progression of the reaction of ozone with unsaturated hydrocarbon chains forms first a range of super-oxygenated fluids (30), followed by saturation and cross-polymerization of ozonide-saturated fatty acid groups to form super-oxygenated gels (32). The amount of time required to oxygenate an oil or alcohol is based on the input ozone concentration and moles of carbon-carbon double bonds in the mixture, with higher ozone concentrations producing more rapid saturation rates.

(26) For example as shown in FIG. 7, diffusing 1000 mg/hour of ozone (as air-ozone) through 250 ml of soybean oil will produce near-maximum oxygenation level (i.e., as trioxalane) of the oil in approximately 120 minutes. Thus a range of super-oxygenated fluids (34) can be developed instantaneously using the present invention. A preferred range of instantaneous super-oxygenation fluid levels for use in most machining applications is between 0 and 5%, which is achieved rather quickly with the reaction of ozone with bio-based fluids (less than 6 minutes of total reaction time). In fact is has been discovered by the present inventor that even trace amounts (less than 2%) of super-oxygenation enhances cutting operations, demonstrated as increased tool life for example. Continuing beyond 120 minutes or more increases cross-linking reactions and polymerization within the super-oxygenated bio-fluid to form super-oxygenated gels (36). This is evidenced by analyzing the viscosity of the bio-fluid during oxygenation, FIG. 8. As shown in FIG. 8, the viscosity of the bio-fluid (i.e., soybean oil) increases (38) during ozonolysis, for example from 60 cP to 80 cP over a period of 420 minutes.

(27) Organic dyes may be also used in machining fluid compositions and ozonolysis reactions of the present invention as a general indicator of oxygenation. For example, an oleic acid and FDA Blue dye (95.5%:0.5% v:v, respectively) mixture was ozonated using the apparatus and method of the present invention. It was observed over time that the bio-based machining fluid color changed from blue to green, green to red, and ultimately to near-colorless (yellowish oil). The color change was a result of the consumption of double bonds in the dye molecules. Thus a spectrophotometer or color chart can be used with a specific dye and dye concentration (having known double-bond concentration) and machining fluid chemistry of the present invention to produce a calibration curvecolor versus apparent level of oxygenation; measured in terms of ozone dose mg/hour, time, and ozonide level. For example, for every 1 mole of double bonds consumed, approximately 3 moles of oxygen (based on the ozonide structure) are produced.

(28) Super-oxygenated fluids of the present invention are useful as MQL and flood cooling-lubricating agents and super-oxygenated gels, including sulfurized compositions, of the present invention are useful for horizontal machining or lubrication applications such as tapping or broaching. As depicted in FIG. 9, super-oxygenated fluids (40), optionally sulfurized super-oxygenated fluids (42), and optionally electrostatically charged fluids of same (44) are projected as MQL or flood sprays into a cutting zone (46) using a propellant gas (48) such as air, ozonated air, or carbon dioxide, to cool and lubricate cut chip (50), cutting tool (52) and grounded workpiece (54). More particularly, the instantaneous super-oxygenated machining fluids of the present invention are used to enhance both cooling and lubrication between the interfacial contact areas bounded by the intersection of the tool face and chip face (56), and flank surface area between tool and workpiece (58). As shown in FIG. 10(A) and FIG. 10(B), bond-breaking reactions between super-oxygenated (60) and (optionally) sulfurized super-oxygenated machining fluid constituents (62), respectively, with juvenile and reactive metal surfaces (64) serve as a critical foundation for allowing the unsaturated bio-based fluids (66) to form beneficial boundary layer lubricating structures on the polar metal surfaces and between the cutting face and flank surface regions (68).

(29) Having thus described the instantaneous oxygenated lubricant formulations and conceptualized reactions of same to for extreme pressure agents and application to cut metal surfaces, following is a discussion of various apparatuses for producing and the applying the present invention in its various aspects as a cooling-lubricating MQL spray.

(30) FIG. 11 is a schematic showing an exemplary MQL system for producing and applying in-situ super-oxygenated machining fluids. The exemplary apparatus of FIG. 11 is useful for producing various levels of oxygenation in a particular machining fluid composition prior to application. As shown in FIG. 11, a source of clean, dry air (70), or other fluid such as carbon dioxide, is used to produce three fluid supply streams as follows; vortex-cooled ozonated air-fluid stream (72), oxygenated fluid air stream (74), and propellant fluid stream (76). It should be noted that a gas membrane filter (available from Parker Filter) may be employed to generate an oxygen-enriched clean, dry air for use with the present invention. Use of oxygen-enriched dry air enhances the performance of both ozonation and fluid oxygenation steps of the present invention.

(31) Regarding vortex-cooled ozonated fluid stream (72); clean, dry air is flowed through a valve (78) and pressure regulator (80), and into the inlet (82) of a vortex tube (84). Said vortex tube converts clean, dry air into a super-cooled fraction (86) and a super-heated fraction (88). A vortex tube supply pressure of between 20 psi and 1000 psi generates ample amounts of cold, clean air for a couple of uses in the present invention. A valve (90) is used to direct the clean, cold air to an ozonator (92) and timer (94) for use in oxygenating bio-fluids (96) to produce super-oxygenated fluids for use in the present aspect of the present invention. Alternatively, dry, cold air (86) may be used via valve (90) and a transfer pipe (98) as a cooling adjunct with the exemplary MQL spray applicator (100) of the present invention. The vortex tube can produce various capacities and temperatures of cold air. This is controlled by adjusting the outlet pressure of regulator (80), to between 20 psi and 1000 psi in cooperation with an adjustment of a small heat waste valve (not shown) located on the hot air discharge side (88) of the vortex tube.

(32) Now referring to the oxygenated fluid air stream (74); clean, dry air is flowed through a valve (102) and pressure regulator (104), and into the inlet (106) of an exemplary eductor tube (108). Said eductor tube (108) uses the flow and pressure of the oxygenated fluid stream inlet (110) to create suction on an eductor inlet (112). Super-oxygenated bio-fluid (96) is suctioned via a tube (114) and filter (116) assembly into the eductor tube (108) via eductor inlet (112) and mixed with the oxygenated fluid stream (110) to form a mixture of clean, dry air and super-oxygenated fluid which is transported via capillary tube (118) and into and coaxially through the exemplary spray applicator (100). The oxygenated air stream flowrate and pressure (and hence suction line super-oxygenated fluid injection flowrate) is controlled by adjusting the outlet pressure of regulator (104), to between 20 psi and 1000 psi in cooperation with an adjustment of a small metering valve (not shown) located on the eductor inlet port (112).

(33) Now referring to propellant fluid stream (76); clean, dry air is flowed through a valve (120) and pressure regulator (122), and into the inlet (124) of an exemplary spray applicator (100). The propellant fluid stream flowrate and pressure is controlled by adjusting the outlet pressure of regulator (122), to between 20 psi and 1000 psi.

(34) Finally, a power supply (126), which is the same HV power supply which is used to generate a corona discharge in the exemplary ozonator (92), is optionally used to power an electrode-in-capillary assembly, described in more detail under FIG. 14 herein, comprising the coaxial capillary tube (118) containing air and super-oxygenated fluids.

(35) All three fluid streams are integrated into a single exemplary coaxial MQL spray applicator as shown with the oxygenated fluid stream line or capillary (118) running coaxially through the interior of a second propellant tube (128). Also shown, adjunct vortex tube cooled air from pipe (114) may be fed coaxially into the spray applicator to provide additional cooling capacity for the super-oxygenated fluid sprays derived from the present invention. Still moreover, the present invention is designed to be used with very high operating spray pressures. Conventional air supplies used for MQL systems generate air pressure in the range of between 10 and 150 psi. An optional gas booster pump (129), for example a Haskel AAD-5, Haskel Pump, Burbank, Calif. may be used to amplify conventional air supplies to between 500 and 1000 psi for use with the present invention. Higher air pressures generate higher vortex cooled air fractions, higher ozone production and ozonide yields/time, and higher fluid spray pressures for better cooling and lubrication action in the cutting zone.

(36) Having thus described the design and operation of an exemplary apparatus for generating and applying oxygenated bio-fluids under FIG. 11, several alternative oxygenating configurations derived from the apparatus of FIG. 11 are discussed under FIGS. 12 and 13. Only aspects relevant to these specific alterations will be discussed with the remaining aspects of these designs considered to be equivalent to those described under FIG. 11.

(37) In certain machining applications, the absence of oxygen in the vicinity of the cut zone is more beneficial. As such, it is an aspect of the present invention to provide controlled levels of oxygen; from near-zero levels to levels well above ambient conditions present in conventional environments and fluids. Referring to FIG. 11a, an optional semi-permeable gas membrane (70a) is used to selectively produce an oxygen-rich or nitrogen-rich gas for use in the present invention. A first 3-way valve (70b) is affixed to the oxygen permeate side and a second 3-way valve (70d) is affixed to the nitrogen permeate side of the exemplary membrane (70a). The valves are operated as a flip-flop circuit (first valve on/second valve off; first valve off/second valve on) to produce either an oxygen-rich stream or a nitrogen-rich stream. When first 3-way valve (70b) is off, oxygen-rich air is bled to the ambient atmosphere through a vent pipe (70c). When second 3-way valve is off, nitrogen-rich air is fed through a vent pipe (70e). When either valve is on, the particular constituent-rich fluid is fed into an optional booster pump (129), and into the exemplary system of the present invention (not shown).

(38) Now referring to FIG. 12, the ozonator (92) may be connected via ozonator outlet pipe (130) to the oxygenated fluid line (132). Using this configuration, the bio-oil suctioned into the eductor (108) via suction line (114) and filter (116) assembly is mixed with ozonated air to form the reactive mixture, and resulting oxygenated by-products, in transit to and through the exemplary capillary (118) coaxial with the spray applicator (100).

(39) Now referring to FIG. 13, the ozonator (92) may be connected via ozonator outlet pipe (134) to the exemplary coaxial spray applicator (134) directly. Using this alternative configuration, the bio-oil suctioned into the eductor (108) via suction line (114) and filter (116) assembly, mixed with oxygenated air, and transported coaxially via capillary tube (118) is mixed with the cold ozonated air from pipe (134) within the air space located from the spray applicator nozzle (136) of exemplary spray applicator (100) to form the reactive mixture, and resulting oxygenated by-products, in transit from the nozzle exit and into the cutting zone.

(40) FIG. 14 is a schematic showing an exemplary MQL applicator for transporting, forming and projecting an electrostatically-charged super-oxygenated machining fluid spray. The apparatus of FIG. 14 also constitutes an alternative means for oxygenating bio-fluids and mixtures, vis--vis in-situ ozonolysis reactions of same. Referring to FIG. 14, a wire electrode (138) connected to a grounded power supply (126) capable generating a voltage somewhere in the range between 5 kV and 40 kV, at a frequency somewhere in the range between 5 kHz and 60 kHz, is positioned coaxially within a dielectric capillary tube (118) constructed of PEEK, Teflon, Nylon etc. The electrode (138) is introduced into said capillary tube (118) using a dielectric connector tee (140) and traverses the entire internal length of the capillary tube (118). The electrode-in-capillary assembly (142) itself is coaxially positioned within a section of flexible stainless steel over-braided Teflon hose propellant line (146), wherein the stainless braided section in connected to the same ground (148) as the power supply (126).

(41) When in operation, the apparatus of FIG. 14 generates an intense radial electrostatic field (150) between the wire electrode surface and grounded propellant line (146), by virtue of dielectric barrier discharge phenomenon also called silent discharge. This electric field ionizes constituents flowing within the capillary, including ionization of oxygen to ozone, and reactions with bio-fluids therein, as well as ionization of propellant gas flowing within the propellant tube (146). The electrode is made to protrude (152) from the capillary tube (118) and nozzle exit (154), and centrally positioned to project an intense electrostatic field into the spray and towards the cutting zone, further ionizing the mixture of oxygenated fluids and propellant gas into charged aerosols (156). Electrostatically charged oxygenated aerosols migrate along electric field and propellant fluid lines toward a grounded cutting zone (158).

(42) FIG. 15 depicts exemplary coaxial and coaxial-Coanda nozzles for use with the present invention to form and project super-oxygenated machining fluid sprays. FIG. 15(A) shows a coaxial spray applicator design with the capillary (118) containing oxygenated fluids carried centrally within a propellant tube (146), and with fluids mixing occurring within the interior of nozzle exit portion (160). An alternative spray applicator scheme involves a Coanda nozzle. FIG. 15(B) depicts a coaxial-Coanda spray applicator design, with the capillary (118) containing oxygenated fluids carried centrally within a propellant tube (146), and with fluids mixing occurring outside the interior of nozzle exit portion (162).

(43) Finally, as described herein, super-oxygenated gels can be derived from the present invention and used as immobile cooling-lubricating gels for applications such as horizontal machining or tapping operations, for example.

(44) In this regard, FIG. 16 gives a schematic showing an exemplary system for producing a super-oxygenated machining gel or concentrate. Referring to FIG. 16, the exemplary oxygenated gel manufacturing system comprises a source of pure oxygen gas (164), through which it is passed through an inlet valve (166) and oxygen gas regulator (168). Regulated oxygen gas flows from regulator (168) into an exemplary air-cooled or water-cooled coaxial corona ozonator (170), commercially available from Plasma Technics Inc., Racine, Wis. Ozonated oxygen at a pressure of between 5 and 100 psi, and 0.1 and 5 lbs Ozone/day, is bubbled into a suitable reactor (172) compatible with ozonated gels (i.e., Teflon) containing one or more bio-fluids and additives (174) as described herein. Said reactor is enclosed with a mixing motor and impeller (176), ventilation system (178), and a chilled water reactor refrigeration system (180). The exemplary system is also equipped with a viscosity sensor (182) and computer control system and software (184), which controls the ozone-enabled gelation process via a control circuit (186) with said air-cooled ozonator (170). The system thus described is operated continuously until the viscosity sensor (182) and software (184) determine endpoint for a pre-determined thickness point within the stirred reactor. Excess oxygenation reactor heat is removed with the chilled water system.

(45) Now referring to FIG. 17, various exemplary oxygenated compositions can be developed using the present invention for use in ozonolytic machining and metalworking operations including turning, drilling, reaming, grinding, dicing, stamping, drawing, forming among many other types of cutting applications where oxygen content control is critical. Referring to FIG. 17, three exemplary classes or types of oxygenated fluids can be created using the present invention, classified as follows:

(46) Type I Oxygenated Bio-Based Fluids (190)

(47) Type II Oxygenated Synthetic Fluids (192)

(48) Type III Oxygenated Microemulsions (194)

(49) Oxygenated bio-based fluids (190) include organic compounds containing one or more double or triple carbon-carbon bonds which can produce super-oxygenated bio-based compounds using the present invention. Exemplary compounds may be derived from solid and semi-solid, dry or wet biological-based substrates including algae, jatropha, canola seeds, soybeans, corn, DDGs, rice bran, wood materials, cellulosic materials, seaweed, among other exemplary biological-based substrates containing oils (natural oleochemicals). Also alcohols, esters and aldehydes derived from bio-based oils containing double or triple bonds may also be used. These include, for example, olive oil, oleyl alcohol, ricinoleyl alcohol, stearic acid, and other unsaturated fatty alcohols and fatty acid esters. These may be used as base stocks, in pure mixtures or in combinations of same. In addition, optional additives may be used to enhance oxygenated machining fluid properties such as extreme pressure capability, anti-corrosiveness, viscosity, cooling capacity, and hydroxyl content; and which generally do not interfere with ozonation reactions of the present invention. In situations where a particular additive would hinder oxygenation reactions of the present invention, it may be added after ozonation reactions. Exemplary optional additives for oxygenated bio-based fluids are described in Table 1.

(50) TABLE-US-00001 TABLE 1 Exemplary (Optional) Additives for Oxygenated Bio-Based Fluids Property Exemplary Additives Extreme Pressure and Molybdenum Disulfide (MoS.sub.2), Dimethyl Anti-Wear Sulfoxide (DMSO), Dimethyl Sulfone (DMSO2), and Polyfluoroalkyl polyether (PFPE) Corrosion Prevention Zinc Dithiophosphate Viscosity Modifiers and 1-Decene, 1-octadecene Diluents Cooling Capacity Dissolved gases: CO.sub.2, N.sub.2, Air Hydroxyl Content 1,2 tetradecanediol

(51) An exemplary bio-based fluid composition for use with the present invention is described in Table 2.

(52) TABLE-US-00002 TABLE 2 Exemplary Oxygenated Bio-Based Fluid Composition Component Percent by Volume Oleic Acid 50% 1-decene 47% 1,2 tetradecanediol 3%

(53) During ozonation reactions using apparatus and processes described in of the present invention, the exemplary composition of Table 2 produces an oxygen-rich mixture of oleyl acid, 1-decene, 1,2 tetradecanediol, oleyl ozonide, decanealdehyde, dissolved ozone and oxygen gases. Residual ozone gas and oxygen gas (free unbound oxygen content) may be discharged from the mixture though the introduction (sparging and pressurization) of pure carbon dioxide or nitrogen gas. This also terminates residual ozonation reactions. For example a mixing and reaction test was performed. The ingredients listed in Table 2 are mixed and are fully miscible with mechanical agitation. An oxygen saturated machining fluid is obtained by ozonolysis using the apparatus and method of the present invention for 16 hours at 250 mg/hour ozone dose rate. There is a strong odor of ozone that is greatly diminished to almost imperceptible by sparging the solution with air for several minutes. The mixture is thicker than the non-ozonated oil which is indicative of ozonide formation and cross-linking.

(54) Oxygenated synthetic and semi-synthetic fluids (192) include organic compounds containing one or more double or triple carbon-carbon bonds which can produce super-oxygenated synthetic compounds using the present invention. Exemplary compounds may be derived from alkenes and olefins. These include, for example, 1-decene or 1-octadecene, and other unsaturated alkenes and olefins. These may be used as base stocks, in pure mixtures or in combinations of same. In addition, optional additives may be used to enhance oxygenated machining fluid properties such as extreme pressure capability, anti-corrosiveness, viscosity, cooling capacity, and hydroxyl content; and which generally do not interfere with ozonation reactions of the present invention. In situations where a particular additive would hinder oxygenation reactions of the present invention, it may be added after ozonation reactions. Exemplary optional additives for oxygenated synthetic fluids are described in Table 3.

(55) TABLE-US-00003 TABLE 3 Exemplary (Optional) Additives for Oxygenated Synthetic Fluids Property Exemplary Additives Extreme Pressure and Molybdenum Disulfide (MoS.sub.2), Dimethyl Anti-Wear Sulfoxide (DMSO), Dimethyl Sulfone (DMSO2), and Polyfluoroalkyl polyether (PFPE) Corrosion Prevention Zinc Dithiophosphate Viscosity Modifiers and Volatile methyl siloxanes Diluents Cooling Capacity Dissolved gases: CO.sub.2, N.sub.2, Air Hydroxyl Content 1,2 tetradecanediol

(56) An exemplary synthetic fluid composition for use with the present invention is described in Table 4.

(57) TABLE-US-00004 TABLE 4 Exemplary Oxygenated Synthetic Fluid Composition Component Percent by Volume Oleyl Alcohol 50% 1-octadecene 47% 1,2 tetradecanediol 3%

(58) During ozonation reactions using apparatus and processes described in of the present invention, the exemplary composition of Table 4 produces an oxygen-rich mixture of oleyl alcohol, 1-decene, 1,2 tetradecanediol, oleyl ozonide, decanealdehyde, dissolved ozone and oxygen gases. Residual ozone gas and oxygen gas (free unbound oxygen content) may be discharged from the mixture though the introduction (sparging and pressurization) of pure carbon dioxide or nitrogen gas. This also terminates residual ozonation reactions. For example a mixing and reaction test was performed. The ingredients listed in Table 4 are mixed and are fully miscible with mechanical agitation. An oxygen saturated machining fluid is obtained by ozonating using the apparatus and method of the present invention for 16 hours at 250 mg/hour ozone dose rate. There is a strong odor of ozone that is greatly diminished to almost imperceptible by sparging the solution with air for several minutes. The mixture is thicker than the non-ozonated alcohol which is indicative of ozonide formation and cross-linking.

(59) In certain machining applications, the presence of water to provide enhanced cooling and hydroxyl chemistry may be beneficial. In such cases, semi-aqueous oxygenated fluids or oxygenated microemulsions are desirable. Oxygenated microemulsions (194) include water (deionized water preferred) in combination with various amounts of organic compounds containing one or more double or triple carbon-carbon bonds which can produce super-oxygenated synthetic compounds using the present invention. Exemplary compounds may be derived from bio-based, alkenes and olefins. These include, for example, oleyl alcohol, 1-decene or 1-octadecene, and other unsaturated bio-based oils and alcohols and unsaturated synthetic alkenes and olefins. These may be used as ozonated working solutions or water-diluted concentrates containing ozonides. In addition, optional additives may be used to enhance oxygenated machining fluid properties such as extreme pressure capability, anti-corrosiveness, viscosity, surface tension, electrical conductivity (for use in processes requiring electrical conductivity of machining fluids such as electrolytic in-process dressing (ELID) used in dicing operations) and hydroxyl chemistry content; and which generally do not interfere with ozonation reactions of the present invention. In situations where a particular additive would hinder oxygenation reactions of the present invention, it may be added after ozonation reactions. Exemplary optional additives for oxygenated microemulsions are described in Table 5.

(60) TABLE-US-00005 TABLE 5 Exemplary (Optional) Additives for Oxygenated Microemulsions Property Exemplary Additives Extreme Pressure and Molybdenum Disulfide (MoS.sub.2), Dimethyl Anti-Wear Sulfoxide (DMSO), Dimethyl Sulfone (DMSO2), and Polyfluoroalkyl polyether (PFPE) Corrosion Prevention Zinc Dithiophosphate Surface Tension and Oleyl Alcohol, Triton X-100 (non-ionic Emulsifier surfactant) Cooling Capacity Dissolved gases: CO.sub.2, N.sub.2, Air Electrical Conductivity Organic and Inorganic Salts

(61) An exemplary oxygenated microemulsion composition for use with the present invention is described in Table 6.

(62) TABLE-US-00006 TABLE 6 Exemplary Oxygenated Microemulsion Composition Percent by Volume Component (Ranges) Water, Deionized (18 megaohms) 50%-95% Oleic Acid 0.5%-45% Triton X-100 0.1%-5%

(63) During ozonation reactions using apparatus and processes described in of the present invention, the exemplary composition of Table 6 produces an oxygen-rich mixture of water, oleic acid, ozonides, and dissolved ozone and oxygen gases. Residual ozone gas and oxygen gas (i.e., dissolved unbound oxygen content) may be discharged from the mixture though the introduction (sparging and pressurization) of pure carbon dioxide or nitrogen gas. This also terminates residual ozonation reactions. It is also noteworthy that the compounds produced vis--vis ozonolysis of oleic acid in the presence of water produces hydrolyzed by-products of oleic acid-derived ozonides such as carboxylic acids and aldehydes. In a first experimental test, the ingredients listed in Table 6 are mixed using olive oil, water and surfactant, which initially separate into two distinct phases. A milky-white and stable microemulsion is produced in less than 10 minutes of ozonation with the ozone sparging action providing adequate mechanical agitation. Another experiment was performed. Oxygenated oil was obtained by ozonolysis of a soybean oil mixture for 16 hour at 250 mg/hour ozone dose rate. Following this, a few drops of Triton X-100 was mixed into 20 grams of ozonated soybean oil, and 250 ml of water was added to the mixture and agitated for 30 minutes to form an opaque, stable microemulsion. It is noteworthy that a microemulsion produced with oxygen-saturated oil is much more viscous than the microemulsion produced by first combining ingredients of Table 6, followed by ozonolysis.

(64) The present invention can be used in numerous machining and metalworking applications. The addition of expandable gases into solution, and particularly carbon dioxide, can be used to produce bubbly flow which enhances heat dissipation in the cut zone and separation of microscopic particles from solution. The selection of machining fluids for use in the present invention such as 1-decene that can dissolve large volumes of, and are highly soluble in, carbon dioxide increases both the heat capacity of the machining fluid (volume of CO.sub.2 dissolved in machining fluid) and efficiency of post-cleaning operations and recovery of the machining oils (volume of machining fluid dissolved in CO.sub.2) for reuse. Thus a novel closed-loop method and process for machining and cleaning a substrate combines the present invention with exemplary and patented CO.sub.2 composite spray and liquid CO.sub.2 immersion cleaning processes and apparatuses developed by the present inventor. This is the subject of a separate and co-pending provisional patent application by the present inventor.

(65) FIG. 18 gives an exemplary apparatus and method that employs a thermoelectric heat pump, high pressure liquid pump, and a long PEEK capillary reactor to accelerate the reaction of dissolved ozone gas with unsaturated lubricant to form an oxygenated lubricant, and to meter same into a coaxial MQL spray applicator, which then combines oxygenated lubricant droplets with a vortex-tube cooled propellant gas to form a cool oxygenated MQL spray. Referring to FIG. 18, an unsaturated liquid lubricant (200), located in a non-pressurized and vented container (202), is cooled to temperature below ambient temperature using a thermoelectric cooler (204) incorporating a fan (206) to remove excess heat contained in said lubricant to the atmosphere. The temperature is lowered within the range of between 20 degrees C. to 30 degrees C. to form a subcooled unsaturated liquid lubricant therein. Following temperature lowering, an ozonated airstream is sparged through the subcooled lubricant for a time to dissolve ozone gas into solution as well as begin the process of oxygenating said subcooled liquid lubricant. This is accomplished as follows. Air is drawn into and through a filter-dryer (208), for example a filter-dryer such as available from Parker Filters, Model DD10-02, using an air pump (210) to produce a stream (212) of clean-dry air containing 20% oxygen gas. Clean-dry air (212) is pumped into and through an ozonator (214) to produce an ozonated air having a concentration of between 0.2 mg/hour and 15000 mg/hour, check valve (216), and through a gas sparger (218) located within said container (202) and submerged at the lower level of subcooled liquid lubricant (200) contained therein. A simple electronic controlled timer (220) may be used to preform said ozonation process for a pre-determined time to produce a desired level of initial oxygenation, which besides time, is dependent upon the degree of unsaturation within the lubricant chemistry, volume of same, and concentration of ozone gas sparged through the solution. The stoichiometry of ozone reaction with unsaturated bonds is roughly 1 mole of ozone per mole of unsaturated carbon-carbon bonds. Subcooled and ozone gas-saturated liquid lubricant is drawn through a bottom port and pipe (222) and into an air-driven high pressure liquid pump (224), for example a Model M21 HP Pump, available from Haskel International, Burbank, Calif. The high pressure pump (224) fluid compression pressure is proportional to its air drive pressure. Air drive pressure is derived from a supply of compressed air (226), which is regulated between 40 psi and 150 psi using a high-flow pressure regulator (228), and flowed through a flow control valve (230) to the high pressure pump (224). Subcooled and ozone gas-saturated liquid lubricant is pressurized into and through a PEEK capillary reactor tube assembly (232) at a pressure of between 1 atm and 150 atm. Higher reaction pressures produce faster ozone reactions with unsaturated bonds, depleting residual ozone gas contained within solution. The PEEK capillary tube reactor assembly (232) comprises PEEK tubing having an internal diameter ranging from 0.020 inches to 0.080 inches and a length of between 1 feet and 20 feet. A micrometering valve (234) is used to control back-pressure and flow of the ozone-reacted lubricant within the capillary reactor assembly (232) and flow through a PEEK capillary delivery tube (236). The PEEK capillary delivery tube (236) has an internal diameter ranging from 0.020 inches to 0.080 inches and a length of between 1 feet and 20 feet. Said PEEK capillary delivery tube (236) traverses coaxially and internally within a second propellant gas tube (238), containing a cooled and flowing propellant gas, and is mixed within (240) and projected from a coaxial or Coanda mixing nozzle (242). The subcooled and ozone-saturated lubricant flows at a flowrate of between 20 mls/hour and 250 mls/hour. Cool propellant gas is derived from a supply of compressed air (226), which is regulated between 40 psi and 150 psi using a high-flow pressure regulator (244), and flowed through a flow control valve (246) and into and through the inlet of a Vortex gas cooling tube (248), such as available from AirTx (http://www.airtx.com), to produce a cold propellant gas stream and waste hot gas stream. The cold propellant gas stream (250) to flowed through a pipe (252) and into and through the coaxial delivery assembly comprising the propellant gas tube (238) containing PEEK capillary delivery tube, and mixing nozzle (242). Waste hot gas (254) is discharged from the system.

(66) Finally, and again referring to FIG. 18, a inert purge gas may be used to eliminate residual ozone gas from subcooled lubricant (200) to cease ozonation reactions in preparation for use or prior to draining residual reacted lubricant. A source of inert purge gas (256) such as air, nitrogen or carbon dioxide is optionally ported through a control valve (258), controlled by a timer (260), and connected to gas sparger (218), depicted as connecting segment (A). Following ozone purging operations, residual lubricant (200) may be drained from the container (202) through a drain pipe (262) and drain valve (264), and collected from a drain port (266).

(67) It should be noted that the present invention is not limited to the example compositions, spray applicators, and applications described herein. For example, the present invention may be used to form oxygenated fluids for flooded application, and applied in through-tool and through-spindle machine tool configurations, and is beneficial for dicing, drilling, tapping, threading, milling, broaching, turning, swaging, stamping, rolling, splitting, among many other machining and metalworking applications, as well as general machine lubrication applications.

(68) As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure. Further, the terms and phrases used herein are not intended to be limiting; but rather, to provide an understandable description of the invention.

(69) The terms a or an, as used herein, are defined as one or more than one. The term plurality, as used herein, is defined as two or more than two. The term another, as used herein, is defined as at least a second or more. The terms including and/or having, as used herein, are defined as comprising (i.e., open language). The term coupled, as used herein, is defined as connected, although not necessarily directly, and not necessarily mechanically.

(70) Any element in a claim that does not explicitly state means for performing a specific function, or step for performing a specific function, is not be interpreted as a means or step clause as specified in 35 U.S.C. Sec. 112, Paragraph 6. In particular, the use of step of in the claims herein is not intended to invoke the provisions of 35 U.S.C. Sec. 112, Paragraph 6. Any headings or labels within the text of the specification are for the convenience of the reader and are not intended to be limiting.