CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional

Patent Application No. 62/570,617 filed October 10, 2017, which application is incorporated herein by reference in its entirety.

FIELD OF TH E INVENTION

[0002] The present invention relates generally to compositions for fabricating materials where heat is generated (e.g., the cutting of metal or stone), concentrates thereof, and methods of making and using the compositions.

BACKGROUN D

[0003] During the process of fabricating (e.g., cutting) solid materials such as stone or metal (e.g., drilling a hole in metal or cutting a piece of metal into smaller pieces), fluids are typically utilized to lubricate the cutting or shaping device in order to lessen wear and tear on the device involved in fabrication. The fluid, e.g., metal cutting fluid, is applied at the location where the material, e.g., metal, is being cut by the cutting device, e.g., a blade. The fluid provides various functions, including helping to dissipate the heat that is generated during the fabricating process, e.g., the cutting action. Absent dissipation, the heat can cause warpage and/or other damage to one or both of the cutting device and the material, e.g., metal, that is being cut. Other advantage of fabrication fluids include enhancing tool life, improving surface finish, and flushing away chips from the cutting zone. Practically all cutting fluids presently in use fall into one of four categories: 1) straight oils, 2) soluble oils, 3) semisynthetic fluids, and 4) synthetic fluids.

[0004] Straight oils are non-emulsifiable and are used in machining operations in an undiluted form. They are composed of a base mineral or petroleum oil and often contains polar lubricants such as fats, vegetable oils and esters as well as extreme pressure additives such as chlorine, sulphur and phosphorus. Straight oils provide the best lubrication and the poorest cooling characteristics among cutting fluids.

[0005] Soluble oil fluids form an emulsion when mixed with water. The concentrate consists of a base mineral oil and emulsifiers to help produce a stable emulsion. They are used in a diluted form (usual concentration = 3 to 10%) and provide good lubrication and heat transfer performance. They are widely used in industry and are the least expensive among all cutting fluids.

[0006] Semi-synthetic fluids are essentially combination of synthetic and soluble oil fluids and have characteristics common to both types. The cost and heat transfer performance of semi-synthetic fluids lie between those of synthetic and soluble oil fluids.

[0007] Synthetic fluids contain no petroleum or mineral oil base and instead are formulated from alkaline inorganic and organic compounds along with additives for corrosion inhibition. They are generally used in a diluted form (usual concentration is 3 to 10%). Synthetic fluids often provide the best cooling performance among all cutting fluids and the poorest lubricating characteristics among cutting fluids.

[0008] There is a need for improved fabrication fluids, e.g., improved metal cutting fluids. The present disclosure is directed to fulfilling this need.

SU MMARY

[0009] Briefly stated, the present disclosure provides fabricating fluid concentrates, e.g., metal cutting, fabricating fluid compositions, e.g., metal cutting fluids, which are diluted forms of the concentrates, methods of making the concentrates and the

compositions, and methods of using the concentrates and the compositions in material fabrication processes, e.g., in order to cut metal, stone, plastic, etc.

[0010] In one embodiment, the present disclosure provides a composition comprising water and non-volatile components (also referred to herein as solids, even though some of the non-volatile components may be, in a pure state, liquids). The solids include one or more surfactants, where exemplary surfactants are anionic surfactants and amphoteric surfactants. For example, the solids may include a first surfactant selected from amphoteric surfactants, a second surfactant selected from anionic surfactants, and a third surfactant selected from an amphoteric and an anionic surfactant, the third surfactant being different from the first and second surfactants. The solids also include one or more agents selected from anti-rust and anti-corrosion agents, which will be referred to herein collectively as anti-rust agents.

[0011] Optional non-volatile components present in the composition include one or more of a thickener, also referred to as a thickening agent, which is suitable for increasing the viscosity or body of the composition; an inorganic salt which is water soluble at the concentration utilized in the composition; an organic solvent which is miscible with water at the concentration utilized in the composition; a de-foaming agent, which term includes anti- foaming agents, which is used in an amount effective to mitigate foaming of the

composition during use; and a coloring agent, also referred to herein as a colorant, that imparts coloration to the composition.

[0012] As mentioned previously, the compositions of the present disclosure include water in addition to the non-aqueous ingredients which are non-volatile. In one

embodiment, the composition contains relatively little water, so that the composition has a high concentration of non-volatile components. Such a composition may be referred to herein as a concentrate (or concentrated) composition, or a metal cutting concentrate. The concentrate may be provided to facilities that cut metal or otherwise fabricate materials, where the operators in those facilities may dilute the concentrate with an amount of water that provides a fluid having suitable properties for the particular fabrication situation, e.g., cutting metal or other material. For example, cutting bronze may benefit from a different dilution of the concentrate than is utilized for cutting a different metal, such as stainless steel. In one embodiment, the concentrate is 5-50% by weight of water. In another embodiment, the concentrated composition is 40-50% by weight water, and 50-60% by weight of non-aqueous components, including a surfactant, an anti-rust agent, and at least one of a thickening agent suitable for an aqueous composition, and an inorganic salt. In another embodiment, the present disclosure provides metal cutting fluids that are ready-to- use in a metal cutting operation. In such ready-to-use compositions, the water content will typically be in the range of 75-99% by weight, or 75.0-99.9% by weight, or 90-99% by weight water, or 90.0-99.9% by weight water, or 97.0-99.9 wt% water, or 98.0-99.9 wt% water, or 99.0-99.9 wt% water.

[0013] In one embodiment, the composition comprises water, a first surfactant selected from amphoteric surfactants, a second surfactant selected from anionic surfactants, a third surfactant selected from an amphoteric and an anionic surfactant, the third surfactant being different from the first and second surfactants, an inorganic salt, an organic solvent, a thickening agent, an anti-rust agent, and a de-foaming agent.

[0014] The following numbered embodiments are additional exemplary

embodiments of the compositions of the present disclosure: ) A fabricating fluid composition comprising water, a first surfactant, a thickening agent, and an anti-rust agent.

) A fabricating fluid composition comprising water, a first surfactant, an inorganic salt, and an anti-rust agent.

) A composition of embodiments 1 or 2 wherein the first surfactant is an anionic surfactant.

) A composition of embodiment 3 wherein the first surfactant is an anionic surfactant comprising a sulfonate group or comprising a sulfate group.

) A composition embodiment 3 wherein the first surfactant is sodium dodecylbenzene sulfonate.

) A composition of embodiment 3 wherein the first surfactant is sodium laureth sulfate.

) A composition of embodiments 1 or 2 wherein the first surfactant is an amphoteric surfactant.

) A composition of embodiment 7 wherein the amphoteric surfactant comprises a betaine group.

) A composition embodiment 7 wherein the first surfactant is cocamidopropyl betaine.0) A composition of embodiments 1 or 2 comprising two surfactants, each of the two surfactants being an anionic surfactant.

1) A composition of embodiment 10 wherein the two surfactants are a sulfate- containing surfactant and a sulfonate-containing surfactant.

2) A composition of embodiment 10 wherein the two surfactants are sodium laureth sulfate and sodium dodecylbenzene sulfonate.

3) A composition of embodiments 1 or 2 comprising two surfactants, one being an anionic surfactant and the other being an amphoteric surfactant.

4) A composition of embodiment 13 wherein the two surfactants are a sulfate- containing anionic surfactant and a betaine-containing amphoteric surfactant.

5) A composition of embodiment 14 wherein the sulfate-containing anionic surfactant is sodium laureth sulfate and the betaine-containing amphoteric surfactant is cocamidopropyl betaine.

6) A composition of embodiment 13 wherein the two surfactants are a sulfonate- containing anionic surfactant and a betaine-containing amphoteric surfactant. ) A composition of embodiment 16 wherein the sulfonate-containing anionic surfactant is sodium dodecylbenzene sulfonate and the betaine-containing amphoteric surfactant is cocamidopropyl betaine.

) A composition of embodiments 1 or 2 comprising three surfactants, two of the three surfactants being non-identical anionic surfactants and one of the three surfactants being an amphoteric surfactant.

) A composition of embodiment 18 wherein the three surfactants are a sulfate- containing surfactant, a sulfonate-containing surfactant, and a betaine-containing surfactant.

) A composition of embodiment 19 wherein the three surfactants are sodium dodecylbenzene sulfonate, sodium laureth sulfate, and cocamidopropyl betaine.) A composition of embodiments 1 or 2 wherein the anti-rust agent is sodium nitrite.) A composition of embodiment 20 wherein the anti-rust agent is sodium nitrite.) A composition of embodiments 1 or 2 comprising a thickening agent which is a cellulosic thickening agent.

) A composition of embodiment 23 wherein the cellulosic thickening agent is hydroxyl ethyl cellulose.

) A composition of embodiment 20 comprising a thickening agent which is a cellulosic thickening agent.

) A composition of embodiment 25 wherein the cellulosic thickening agent is hydroxyl ethyl cellulose.

) A composition of embodiments 1 or 2 comprising an inorganic salt which is calcium chloride.

) A composition of embodiment 20 comprising an inorganic salt.

) A composition of embodiment 28 wherein the inorganic salt is calcium chloride) A composition of embodiments 1 or 2 comprising a defoaming agent.

) A composition of embodiment 30 wherein the defoaming agent is a silicone polymer.) A composition of embodiment 20 comprising a defoaming agent.

) A composition of embodiment 32 wherein the defoaming agent is a silicone polymer.) A composition of embodiment 20 comprising one or more of a cellulosic thickening agent, an inorganic salt, and a defoaming agent. 35) A composition of embodiment 20 comprising a cellulosic thickening agent, an inorganic salt, and a defoaming agent.

36) A composition of embodiment 1 comprising water, sodium dodecylbenzene

sulfonate, sodium laureth sulfate, cocamidopropyl betaine, a thickening agent such as a cellulosic thickening agent, and an anti-rust agent.

37) A composition of embodiment 2 comprising water, sodium dodecylbenzene

sulfonate, sodium laureth sulfate, cocamidopropyl betaine, an inorganic salt such as calcium chloride, and an anti-rust agent.

The composition may be used for metal fabrication, and may be referred to alternatively as a metal fabrication composition, or a metal working composition, or a metal cooling composition, or a metal cutting composition. The composition may also be used for fabricating parts made from stone, plastic or glass, or other solid material that may be fabricated by tooling in a heat-generating process.

[0015] In one embodiment, the present disclosure provides a method of making a concentrated composition, e.g., a metal cutting fluid concentrate, by combining the ingredients as discussed herein. Optionally, the ingredients may be combined in a batch method. In this embodiment, a composition, e.g., a metal cutting fluid concentrated composition is prepared by a method comprising adding to a container, hot water, one or more surfactants such as an anionic surfactant, an amphoteric surfactant, and optionally a third surfactant selected from an anionic surfactant and an amphoteric surfactant, where the third surfactant is different from the already added anionic and amphoteric surfactants. Additional optional ingredients include an inorganic salt, an organic solvent, a thickening agent, an anti-rust or anti-corrosion agent, a coloring agent, and a de-foaming agent;

wherein after an addition of a component to the container, a resulting mixture is stirred until it reaches a completely or nearly homogeneous state, for example, for about 30 minutes with minimal foam generation before addition of a next component. In one embodiment, an inorganic salt, an organic solvent, a thickening agent, an anti-rust or anti- corrosion agent, and a de-foaming agent are added to the container.

[0016] For example, the present invention provides a process for making a fabricating fluid composition, such as a composition suitable for metal cutting, comprising:

a) heating water to about 70-80°C to provide hot water;

b) adding an anionic surfactant to the hot water; c) adding an amphoteric surfactant to the mixture of step b);

d) adding hot water to the mixture of step c);

e) optionally adding a third surfactant to the mixture of step d), the third

surfactant selected from an anionic surfactant and an amphoteric surfactant, the third surfactant being different from the anionic surfactant and the amphoteric surfactant already present in the mixture;

f) adding inorganic salt to the mixture of step e);

g) cooling the mixture of step f) to ambient temperature; and

h) adding thickening agent to the mixture of step f);

wherein after an addition of a component, a resulting mixture is stirred for a time effective to achieve a homogeneous or nearly homogeneous mixture, typically about 30 minutes, with minimal foam generation before addition of a next component. Exemplary optional ingredients that may be used in the process include an inorganic salt, an organic solvent, a thickening agent, an anti-rust or anti-corrosion agent, a coloring agent, and a de-foaming agent. In one embodiment, an inorganic salt, an organic solvent, a thickening agent, an anti- rust or anti-corrosion agent, and a de-foaming agent are added to the mixture.

[0017] In one embodiment, the present disclosure provides a method of making a composition, e.g., a metal cutting fluid concentrate, by a continuous method. In this embodiment, a composition, e.g., a metal cutting fluid concentrate is prepared by providing a continuous reactor, charging water to the continuous reactor, adding to the water in the continuous reactor a) an anionic surfactant, b) an amphoteric surfactant, and optionally c) a third surfactant selected from an anionic surfactant and a cationic surfactant, the third surfactant being different from the anionic and amphoteric surfactant already charged to the reactor; and mixing components a), b) and optionally c) to provide a homogeneous mixture. Optionally, the water in the continuous reactor is maintained at a temperature in excess of 50°C. Optionally, additional ingredients are added to the formulation, such as organic solvent, inorganic salt, a thickening agent, an anti-rust or anti-corrosion agent, a coloring agent, and a de-foaming agent. In one embodiment, each of an organic solvent, inorganic salt, a thickening agent, an anti-rust or anti-corrosion agent, and a de-foaming agent are added to the mixture. Optionally, a mixer selected from an inline mixer and a static mixer is present in the continuous reactor.

[0018] In one embodiment, the present disclosure provides a method for forming a fabrication fluid from a precursor concentrate, e.g., a metal cutting fluid composition from the metal cutting fluid concentrate. According to this embodiment, water and concentrate are combined in a suitable watenconcentrate ratio, and the two components are mixed together to form the metal cutting fluid composition. In various optional embodiments, the concentrate is diluted by a factor of 5x, or lOx, or 15x. To be clear, a dilution of 5x refers to combining 100 parts of concentrate with 500 parts of water, where parts may be in either liquid or solid measurement forms, e.g., grams, kilograms, liters.

[0019] In one embodiment, the present disclosure provides a method for cutting metal, where the method comprises applying an effective amount of the metal cutting fluid composition of the present disclosure onto metal being cut. The metal cutting fluids of the present disclosure may be applied to metal during the process in which the metal is being cut. One exemplary process for applying the compositions of the present disclosure is flood application, wherein a flood of cutting fluid is applied onto the workpiece being cut.

Another exemplary process for applying the compositions of the present disclosure is jet application, wherein a jet of cutting fluid is applied onto the workpiece directed at the cutting zone. Another exemplary process for applying the composition of the present disclosure is mist application, wherein cutting fluid is atomized by a jet of air and the mist is directed at the cutting zone of the workpiece.

[0020] The following numbered embodiments are additional exemplary

embodiments of the methods of machining meal of the present disclosure, with reference to the foregoing composition embodiments:

38) A method of machining a material selected from metal, stone, glass and plastic, comprising applying a composition comprising a composition of any of embodiment 1-37 to a piece of material being machined, in an amount and time that are effective to dissipate heat from the material being machined.

39) The method of embodiment 38 wherein the material being machined is metal

selected from aluminum alloy, brass, casting iron, bronze, low-carbon steel, stainless steel, alloy steel, and titanium alloy.

40) The method of embodiment 38 whrein the material being machined is stone.

41) The method of embodiment 38 wherein the material being machined is glass.

42) The method of embodiment 38 wherein the material being machined is plastic. 43) The method of embodiment 38 wherein the piece of material being machined is being subjected to a process selected from broaching, tapping, hobbing, cutting, drilling, milling, turning, sawing, honing, and grinding.

[0021] The details of one or more embodiments are set forth in the description below. The features illustrated or described in connection with one exemplary embodiment may be combined with the features of other embodiments. Other features, objects and advantages will be apparent from the description and the claims. In addition, the disclosures of all patents and patent applications referenced herein are incorporated by reference in their entirety.

DETAILED DESCRIPTION OF THE INVENTION

[0022] In one aspect, the present disclosure provides a materials fabrication composition, such as a metal cutting fluid composition, in both concentrated and diluted (ready to use) form. In another aspect, the present disclosure provides a method of forming a fabrication fluid in a concentrated form and then diluting that concentrated composition to a dilute form. In another aspect, the present disclosure provides a method of using the compositions in a method wherein a material is fabricated, such as a metal cutting operation. Thus, in another aspect, the present disclosure provides a method of forming fabricating fluid compositions, e.g., a metal cutting fluid composition, in a concentrated form and then diluting that concentrated composition to a dilute form. In another aspect, the present disclosure provides a method of using the compositions in a material cutting or shaping process, e.g., a metal cutting operation. When the present disclosure refers to a metal cutting fluid or a metal cooling fluid, it should be understood that these fluid composition may be used generally in material fabrication, e.g., glass fabrication, stone fabrication, and plastic fabrication, and are not limited in use to metal fabrication. Thus, the metal cutting or metal cooling compositions may be used for metal cutting or fabrication, but may also be used for the fabrication of other materials such as stone or plastic or glass where fabrication generates heat that is desirably dissipated during the fabrication process.

[0023] In one embodiment, the present disclosure provides a composition comprising water and non-volatile components (also referred to herein as solids, even though some of the non-volatile components may be, in a pure state, liquids). The solids include one or more surfactants, where exemplary surfactants are anionic surfactants and amphoteric surfactants. For example, the solids may include a first surfactant selected from amphoteric surfactants, a second surfactant selected from anionic surfactants, and a third surfactant selected from an amphoteric and an anionic surfactant, the third surfactant being different from the first and second surfactants. The solids also include one or more agents selected from anti-rust and anti-corrosion agents, which will be referred to herein collectively as anti-rust agents.

[0024] Optional non-volatile components present in the composition include one or more of a thickener, also referred to as a thickening agent, which is suitable for increasing the viscosity or body of the composition; an inorganic salt which is water soluble at the concentration utilized in the composition; an organic solvent which is miscible with water at the concentration utilized in the composition and has a boiling point above the boiling point of water, e.g., a boiling point of at least 125°C, or at least 150°C, or at least 170°C; a de- foaming agent, which term includes anti-foaming agents, which is used in an amount effective to mitigate foaming of the composition during use; and a coloring agent, also referred to herein as a colorant, that imparts coloration to the composition.

[0025] In one aspect, the fluid composition contains no carbon-halogen bonds, and thus is more environmentally friendly than alternative fluid compositions that contain one or more components having such bonds.

[0026] The fluid of the present disclosure provides the following effects during materials fabrication, and particularly during metal machining. Primary effects include lubricating the cutting process primarily at low cutting speeds, cooling the workpiece primarily at high cutting speeds, and flushing chips away from the cutting zone. Secondary effects include corrosion protection of the machined surface, and enabling part handling by cooling the hot surface. Process effects of using cutting fluids of the present disclosure in machining include: longer tool life, reduced thermal deformation of workpiece, better surface finish, and ease of chip and swarf handling.

[0027] The compositions of the present disclosure provide good heat transfer performance, good lubrication performance, good chip flushing performance, good generation of fluid mist, good fluid carry off in chips, and good corrosion inhibition. The compositions in emulsion form exhibit good fluid stability.

[0028] It is noted that, as used in this specification and the intended claims, the singular form "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an amphoteric surfactant" includes a single amphoteric surfactant as well as one or more of the same or different amphoteric surfactants.

Components

[0029] The compositions of the present disclosure include at least one surfactant. In one embodiment, the compositions contain an amphoteric surfactant. In another embodiment, the compositions contain an anionic surfactant. In one embodiment the compositions contain two different amphoteric surfactants, optionally in combination with an anionic surfactant. In one embodiment the compositions contain two different anionic surfactants, optionally in combination with an amphoteric surfactant.

Amphoteric Surfactant

[0030] In one embodiment, the compositions of the present disclosure include at least one, and optionally include more than one, amphoteric surfactant. As used herein, an amphoteric surfactant is a molecule that contains both a positively charged atom and a negatively charged atom. Surfactant molecules may include polymeric components, and may also include a counterion(s) such as sodium and ammonium, however the counterion is not considered to be one of the positively or negatively charged atoms that qualifies the molecule as being an amphoteric surfactant.

[0031] The positively charged atom may be, for example, a nitrogen atom which provides, e.g., an ammonium group, or may be a sulfur atom which provides, e.g., a sulfonium group. The presence of a positive charge on a particular atom may be a function of the pH to which the molecule is exposed. In other words, the amphoteric surfactant of the present disclosure need not have a positively charged atom and a negatively charged atom at every pH of the surrounding solution, but may have these charged atoms only within a pH range. For example, when the molecule has a nitrogen atom that bears a positive charge, that charge may only be present when the pH of the surrounding solution (an aqueous solution) is sufficiently low that the nitrogen atom becomes protonated. This occurs, for example, when the nitrogen atom is part of a primary, secondary or tertiary amine. Alternatively, the nitrogen atom may be part of a quaternary ammonium ion which maintains its positive charge regardless of the pH of the surrounding solution.

[0032] The negatively charged atom may be, for example, an oxygen atom which may be part of a recognized functional group such as a carboxylate, sulfate, sulfonate, or phosphate group. As with the positive charge, the presence of a negative charge on a particular atom may be a function of the pH to which the molecule is exposed. In other words, the amphoteric surfactant of the present disclosure need not have a negatively charged atom and a positively charged atom at every pH of the surrounding solution, but may have these charged atoms only within a pH range. For example, when the molecule has an oxygen atom that bears a negative charge, that charge may only be present when the pH of the surrounding solution (an aqueous solution) is sufficiently high that the oxygen atom becomes deprotonated. This may occur, for example, when the oxygen atom is part of, e.g., a carboxylic acid group, where only the carboxylate form of the carboxylic acid group has a negatively charged oxygen atom while the corresponding carboxylic acid form has a neutral oxygen atom.

[0033] In summary, the amphoteric surfactant need not have both a positively charged atom and a negatively charged atom throughout the entire possible pH range of the surrounding solution, but will have these two charged atoms at some pH range, which is sometimes referred to in the art as the isoelectric pH range. When the amphoteric surfactant has both a positively and negatively charged atom, the surfactant may be said to be in its zwitterionic form. When a chemical structure of an amphoteric surfactant is provided herein, the term X may be used to refer to the counterion which may be associated with the positively or negatively charged atom within the isoelectric pH range. Exemplary cationic counterions are sodium and ammonium. Exemplary anionic counterions are chloride and phosphate. Noteworthy is that either the positive or negative charge may be delocalized over a plurality of atoms. For example, when the negative charge is on an oxygen atom, and that oxygen atom is part of a carboxylate group, the negative charge is delocalized over both of the oxygen atoms of the carboxylate group.

[0034] In addition, and as with all surfactants, the amphoteric surfactant will have both a lipophilic (a.k.a., hydrophobic) region and lipophobic (a.k.a., hydrophilic) region. The lipophilic region may be referred to as the fatty region. The fatty region may be composed of the hydrocarbon portion which is present in a naturally occurring fatty acid, fatty alcohol, fatty amine or the like, however it may alternatively be formed synthetically, i.e., it may be a synthetically produced fragment such as polyethylene, polypropylene, poly(propylene oxide), etc. As used herein, and when describing a class of amphoteric surfactant, the term "R" will be used to refer to a fatty region of the molecule. In various embodiments, R designates a medium or long chain fatty group, such as: a C6-C24 fragment, i.e., a molecular fragment having at least 6 and up to 24 carbon atoms, and optionally any other atoms, e.g., hydrogen, halogen (e.g., F, CI, Br), nitrogen, and oxygen; C6-C24 hydrocarbon, i.e., a molecular fragment having 6-24 carbon atoms and sufficient hydrogen atoms to complete the valencies of the carbon atoms; C8-C22 fragment; C8-C22 hydrocarbon; C10-C20 fragment; C10-C20 hydrocarbon; C12-C18 fragment; and C12-C18 hydrocarbon. In various embodiments, R has at least 6, or at least 8, or at least 10, or at least 12, or at least 14, or at least 16 carbon atoms. In various embodiments, R has no more than 30, or no more than 26, or no more than 24, or not more than 22, or no more than 20, or no more than 18 carbon atoms. The term R may represent an alkyl group, where the term alkyl refers to linear, branched or cyclic saturated hydrocarbon groups, generally having any of the number of carbon atom ranges specified above (e.g., C6-C24 refers to an alkyl group having 6 to 24 carbon atoms). Examples of alkyl groups include 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, caprylic, capric, lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, and behenic.

[0035] The following several paragraphs provide exemplary specific surfactant categories and examples of specific amphoteric surfactants that may be incorporated into the fluid compositions of the present disclosure. It should be noted that the categories are not mutually exclusive in that a specific amphoteric surfactant may fall into more than one category, i.e., two categories may overlap in terms of the surfactants that are encompassed within a category. There is a diverse nomenclature used in the surfactant art to categorize and recognize classes of amphoteric surfactants specifically, and surfactants in general, where that nomenclature often does not provide for mutually exclusive categories of surfactants. Nevertheless, the following provides for amphoteric surfactants useful in the present disclosure. For convenience, the surfactant may be identified by reference only to its charged portion. For instance, the amphoteric surfactant may be referred to as a betaine, or a betaine surfactant in order to indicate that the amphoteric surfactant contains a betaine group. As another example, when the amphoteric surfactant comprises a hydroxysultaine group, such a surfactant may be referred to either as a hydroxysultaine surfactant, or when the context permits, even more simply as a hydroxysultaine.

Alternatively, it may be said that the amphoteric surfactant comprises a specifically identified charged group such as a betaine or betaine group, a hydroxysultaine group, an amine oxide group, etc.

[0036] In some of the following chemical structures the term "L" is used to refer to a linking group. A linking group is a short chain of atoms that links together two noted functional groups present in the amphoteric surfactant. In one embodiment, L is methylene, i.e., -CH2-. In one embodiment, L is ethylene, i.e., -CH2CH2-. In one

embodiment, L is propylene, i.e., -CH2CH2CH2-. The linking group may include a substituent on an alkylene chain, where the substituent may be, e.g., halogen, hydroxyl or short-chain (about C1-C4) alkyl. In one embodiment, L is hydroxyl substituted propylene,

e.g., -CH2CH(OH)CH2-. In another embodiment, L is methyl substituted methylene, e.g., - CH(CH3)-. In one embodiment, L is methylene, ethylene or propylene, each optionally substituted with hydroxyl. In one embodiment, L is dimethylether, i.e., -CH2-O-CH2-. In one embodiment, L is a chain of 1-5 atoms selected from carbon and oxygen, where the chain is optionally substituted with hydroxyl or halide.

[0037] Any of the following terms may be used to specifically recite an "amphoteric surfactant" to thereby provide a selection of amphoteric surfactants that are useful in an embodiment of the present disclosure: alkyl amidopropyl betaine, alkyl amine oxide, alkyl amphoacetates, alkyl betaine, alkyl carboxyglycinate, alkyl glycinate, alkyl sulphobetaine, sultaine, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl

hydroxysultaines, acyl taurate and acyl glutamate. Each of these terms is known in the art, and many of these terms are described below.

[0038] In one embodiment, the amphoteric surfactant is a betaine surfactant, which means that the surfactant includes a betaine group. The betaine surfactant may be an alkyl amido propyl betaine which may be represented by the chemical structure CH3-(CH2)n- CON H-CH2CH ₂ CH2-N(CH3)2-CH2-COOX when the alkyl group is a linear alkyl group. More generally, an amido propyl betaine may be represented by the chemical structure R-CON H- CH2CH2CH2-N(CH3)2-CH2-COOX. These are both examples of alkyl amido betaines.

[0039] In one embodiment, the amphoteric surfactant is an alkyl amido sulfobetaine which may be represented by the chemical structure R-CON H-L-N(CH3)2-(CH ₂ )m-S0 ₂ OX wherein L is propylene. A subset of this class is the alkylbenzene dimethyl ammonium propanesulfonates obtained by quaternization of the alkylbenzene dimethyl amine with propanesulfone. Again, the propylene linking group L may be substituted, e.g., with a hydroxyl group (which provides for 2-hydroxy-l-propanesulfonate derivatives) to provide another amphoteric surfactant suitable for use in the present compositions.

[0040] In one embodiment, the amphoteric surfactant is an alkyl amino acid amphoteric surfactant which may be represented by the chemical structure R-NH-L-COOX, where R and L are defined above. For example, R may be derived from coconut oil, L may be ethylene and X may be sodium ion.

[0041] In one embodiment, the amphoteric surfactant is an alkyl betaine amphoteric surfactant which may be represented by the chemical structure R-N(CH3)2-L-COOX where R is an alkyl group and L is a linking group. As with other amphoteric surfactants disclosed herein, the R group may be a fatty group rather than being limited to an alkyl group, however in one embodiment the R represents an alkyl group. As mentioned previously, the linking group may be, and in one embodiment is a methylene group. However alkyl betaines also include the -(N,N,N-trialkyl ammonium) alkanoates, having the structure R ¹ - N(R ² )(R ³ )-C(R ⁴ )H-COOX where L is an alkyl substituted methylene group. Various alternative and sometimes more specific names are used to name alkyl betaines, for example, N-alkyl- Ν,Ν-dimethylglycine; N-alkyl-N,N-dimethyl-N-carboxymethyl ammonium betaine; alkyl- dimethyl ammonium acetate or alkyl-dimethyl ammonium ethanoate. The Cosmetic, Toiletry and Fragrance Association, Inc. (CTFA) uses the name alkyl-betaine for these products.

[0042] In one embodiment, the amphoteric surfactant is an alkyl imidazoline derived amphoteric surfactant which may be represented by the chemical structure R-CONH-L- N(CH2CH20H)CH2COONa. In another embodiment, the alkyl imidazoline derived amphoteric surfactant is a diacid which may be represented by the chemical structure R- CON(CH ₂ CH ₂ OH)-L-N(CH2COONa)2. In either of these embodiments, the linker L is optionally ethylene.

[0043] In one embodiment, the amphoteric surfactant is an alkyl imino diacid amphoteric surfactant which may be represented by the chemical structure R- N(CH2CH2COONa)2. In alternative embodiments, the alkyl imino diacid amphoteric surfactant is represented by the chemical structure R-N(CH2CH2CH2COONa)2 or R- N(CH ₂ COONa) ₂ .

[0044] In one embodiment, the amphoteric surfactant is an alkyl sulfobetaine amphoteric surfactant. The chemical structure of an alkyl sulfobetaine may be represented as R-N(CH3)2-L-S0 ₂ 0X (also sometimes represented as -L-SO3X) where R is alkyl and L is methylene. The following are exemplary of specific alkylsulfobetaines that may be used in the practice of the present invention: caprylyl sulfobetaine, hexadecyl sulfobetaine, lauryl sulfobetaine, myristyl sulfobetaine, n-octyl sulfobetaine, palmityl sulfobetaine, tetradecyl sulfobetaine,

[0045] In one embodiment, the amphoteric surfactant is an alkyl sultaine, which is a term favored by CTFA. Alkyl sultaine are sulfobetaine amphoteric surfactants that include the propanesulfonate group, i.e., L-SO3X wherein L is propylene. An alkyl sultaines has the chemical structure R-N(CH3)2-CH2CH ₂ CH2-S0 ₂ OX.

[0046] In one embodiment, the amphoteric surfactants is an amido propyl betaine which may be represented by the chemical structure R(C=0)-NH-(CH2)3-N(CH ₃ )2-CH ₂ COOX. This class of amidopropyl betaine may also be referred to as an alkyl amido propyl betaine since R may be alkyl group. An alkylamidopropyl betaine surfactant is typically synthesized by reaction of a fatty acid, for example the fatty acid from natural oils such as coconut oil, and 3,3-dimethylaminopropylamine to provide an amidopropyl dimethylamine

intermediate, which in turn is reacted with sodium monochloroacetic acid to provide the corresponding betaine. A betaine surfactant is commonly named after the source of the fatty acid used in its preparation, e.g., coconut oil provides for cocamidopropyl betaine, and isostearic acid provides for isostearmidopropylbetaine. Many alkylamidopropyl betaine surfactants suitable for use in the present invention are commercially available in solid and solution form, and may be purchased from various suppliers.

[0047] The following are specific exemplary amidopropyl betaines that may be used in the practice of the present invention: almondamidopropyl betaine, apricotamidopropyl betaine, avocadamidopropyl betaine, babassuamidopropyl betaine, behenamidopropyl betaine, canolamidopropyl betaine, capryl/capramidopropyl betaine (formed from a mixture of caprylic acid and capric acid), coco/oleamidopropyl betaine,

coco/sunfloweramidopropyl betaine (formed from a blend of coconut and sunflower seed oils), cupuassuamidopropyl betaine (formed from the pulp of the cupuassu tree), isostearamidopropyl betaine, lauramidopropyl betaine, meadowfoamamidopropyl betaine (formed from meadowfoam seed oil), milkamidopropyl betaine, minkamidopropyl betaine (formed from mink oil), myristamidopropyl betaine, oatamidopropyl betaine (formed from Avena Sativa (oal) kernel oil), oleamidopropyl betaine, olivamidopropyl betaine, palmamidopropyl betaine (formed from palm oil), palmitamidopropyl betaine, palm kernelamidopropyl betaine (formed from palm kernel oil), ricinoleamidopropyl betaine, sesamidopropyl betaine, shea butteramidopropyl betaine (formed from Butyrospermum Parkii (shea butter)), soyamidopropyl betaine, stearamidopropyl betaine, tallowamidopropyl betaine, undecylenamidopropyl betaine, and wheat germamidopropyl betaine (formed from the oil in wheat germ).

[0048] In one embodiment, the amphoteric surfactant is an amine oxide amphoteric surfactant which may be represented by the chemical structure R-N(CH3)2-0- where R is a lipophilic group. An exemplary R group is a lipophilic alkyl group, where amine oxide surfactants having an alkyl group for R are commonly known as alkyl amino oxides.

Exemplary alkyl groups are caprylic, capric, lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, and behenic. Exemplary amine oxide amphoteric surfactants include

cocamidopropylamine oxide and lauryldimethylamine oxide (also known as

dodecyldimethylamine oxide, Ν,Ν-Dimethyldodecylamine N-oxide, and DDAO),

soyamidopropylamine oxide and myristamine oxide. The nitrogen atom of the amine group may be bonded to two methyl groups as shown above, however as an alternative, the nitrogen atom may be bonded to two hydroxyethyl group to provide the structure R- N(CH ₂ CH ₂ OH) ₂ -0-.

[0049] In one embodiment, the amphoteric surfactant is an amino acid amphoteric surfactant. This type of amphoteric surfactant displays a zwitterionic structure within a certain pH range, which depends on the structure of the surfactant. A common example of this type of amphoteric surfactant is the amino acids of the structure R-NH-CH2CH2-COOH where R is a fatty group. These are sometimes referred to as fatty amino acids, or more precisely as fatty aminopropionates when in the corresponding carboxylate form. A variation on this structure has two carboxylic acid groups, i.e., has the structure R- N(CH2CH2COOH)2, which are named as fatty iminodipropionates when in the corresponding carboxylate form. Any of these classes of amphoteric surfactants may be used in the compositions of the present disclosure.

[0050] In one embodiment, the amphoteric surfactant is an amphoacetate amphoteric surfactant which includes the chemical structure -CH2-CO2X in addition to a fatty group and a chemical group that will become positive charged under suitable pH. These surfactants are sometimes referred to as amphoglycinates. In one embodiment, the amphoacetate amphoteric surfactant may be represented by the chemical structure R(CO)NH-CH ₂ CH2-N(CH2CH ₂ OH)(CH2C02X) wherein R may be an alkyl group or R(CO) may be a fatty acyl group derived from a fatty acid such as found in coconut oil to provide, e.g., cocoamphoacetate. Such amphoacetate surfactants may be prepared by reacting a compound of formula R(CO)NH-CH2CH2-N HCH2CH20H with formaldehyde and a cyanide as disclosed in US Patent 6232496. Under appropriate conditions, this amphoacetate may interconvert to the corresponding amphoacetate amphoteric surfactant comprising an imidazolium group which provides a positively charged chemical group, such as

lauroamphoacetate (sodium salt).

[0051] The amphoacetate amphoteric surfactant may comprise two, rather than one, acetate group, to provide an amphoteric surfactant having the chemical structure R(CO)N H-CH ₂ CH2-N(CH2CH20CH2C02X)(CH2C0 ₂ X). Exemplary amphoacetate amphoteric surfactants include disodium cocoamphodiacetate, sodium cocoamphoacetate, disodium lauroamphoacetate, and sodium lauroamphoacetate.

[0052] In one embodiment, the amphoteric surfactant is an amphopropionate amphoteric surfactant which includes the chemical structure -CH2CH2-CO2X in addition to a fatty group and a chemical group that will become positive charged under suitable pH. Such amphoteric surfactants may be prepared from acrylic acid as described in US Patent 6030938. Exemplary amphopropionate amphoteric surfactants are the sodium salts of capryloamphopropionate, lauriminodipropionate, isostearyl amphopropionate and cocoamphopropionate. The amphopropionate amphoteric surfactant may comprise two, rather than one, propionate group, to provide an amphoteric surfactant having the chemical structure R(CO)NH-CH ₂ CH2-N(CH2CH20CH2CH2C0 ₂ X) (CH ₂ CH ₂ C0 ₂ X). This subclass of amphopropionate amphoteric surfactants is known as amphodipropionate amphoteric surfactants, where exemplary amphodipropionate amphoteric surfactants are the disodium salt of cocoamphodipropionate (also known as N-(2-coconut oil amidoethyl)-N-(2-(2- carboxyethyl)oxyethyl)-beta-aminopropionic acid, disodium salt) and

capryloamphodipropionate.

[0053] In one embodiment, the amphoteric surfactant is a betaine surfactant.

Betaine refers to surfactant molecules incorporating both a positively charged (cationic) functional group such as a phosphonium or quaternary ammonium group which bears no hydrogen atom, and a negatively charged (anionic) functional group such as a carboxylate group or an oxyanion. In a betaine, the cationic and anionic groups are not adjacent to one another. The betaine surfactants as referred to herein will meet the foregoing definition, and will in addition have a lipophilic moiety. In one embodiment, the cation is a quaternary amine. In one embodiment, the anion is carboxylate. In another embodiment the anion is oxyanion. In another embodiment the anion is sulfate. In another embodiment, the anion is sulfonate. In another embodiment, the anion is phosphate. Many commercially available betaines have a dialkyl substituted dimethylammonium group. Despite the prevalence of this group in commercial amphoteric surfactants, the amphoteric surfactants useful in the present disclosure do not necessarily (although they may) have a dimethylammonium group. More generally, they have a dialkylammonium group, so as to provide, e.g., a trialkylammonium alkanoate of the chemical structure R ¹ -N(R ² )(R ³ )-CH2COOX. In other words, R ² and R ³ are not necessarily methyl. Some exemplary betaines are alkyl dimethylbetaines of the chemical structure R-N(CH3)2-CH2-COOH, and alkyl

amidopropyldimethylbetaines of the structure R-CON H-CH ₂ CH ₂ CH2-N(CH3)2-CH2-COOH.

[0054] In one embodiment, the amphoteric surfactant is a hydroxysultaine having the chemical structure R-N(CH3)2-CH2CH(OH)-S03X where R is a fatty group, e.g., a long chain alkyl group. A hydroxysultaine is often named after the source of the R group, so that, for example, a hydroxysultaine derived from coconut oil may be named cocamidopropyl hydroxysultaine (however it is also known as coco hydroxysulfaine, and CAHS). Other exemplary hydroxysultaine amphoteric surfactants include lauramidopropyl

hydroxysultaine, oleamidopropyl hydroxysultaine, tallowamidopropyl hydroxysultaine, erucamidopropyl hydroxysultaine, and lauryl hydroxysultaine.

[0055] In one embodiment, the amphoteric surfactant is an imidazoline derivative amphoteric surfactant, sometimes referred to as an imidazolinium derivative. Representing the chemical structure of an imidazoline derivative amphoteric surfactant is complicated by the fact that imidazolines characteristically hydrolyze when exposed to water. Fatty imidazolines hydrolyze slowly on exposure to moist air, giving an alkyl amidoamine.

Accordingly, the alkyl amidoamine amphoteric surfactants already described elsewhere herein, are examples of imidazolinium derivative amphoteric surfactants. In general, imidazolinium derivative amphoteric surfactants, sometimes referred to as imidazoline amphoterics, are well known in the art as a class of surfactant. In one embodiment, the amphoteric surfactant is an imidazoline derivative, optionally a fatty alkyl imidazoline. This type of amphoteric surfactant form cations in acidic solutions, anions in alkaline solutions, and 'zwitterions' in mid-pH range solutions. The mid-pH range, also referred to as the isoelectric range, within which the imidazoline surfactant has a neutral charge, is compound specific and depends on the precise structure of the compound, which will affect the alkalinity of the nitrogen atom and the acidity of the carboxylic group. Exemplary suitable imidazoline type amphoteric surfactants include, without limitation, 2-cocoyl-2- imidazolinium hydroxide-l-carboxyethyloxy disodium.

[0056] The imidazolinium derivative amphoteric surfactant may be prepared by reaction of sodium chloroacetate and the corresponding 2-alkyl-l-(2-hydroxyethyol-)-2- imidazoline. This reaction product is commonly assigned to have the following chemical structure:

wherein R is a hydrophobic group. The reactions that produce these cyclic imidazolinium derivatives can be readily extended to provide the corresponding open chain molecules having the following structures: RCO-NH-CH ₂ CH2-N(CH2CH ₂ OH)CH2COO- (with one equivalent of sodium chloroacetate) and RCO-NH-CH ₂ CH2-N(CH2CH ₂ OH)(CH2COO-)2 (with two equivalents of sodium chloroacetate). Such open chain structures are often called imidazoline derivatives, or alkyi (when R is an alkyi group) amido amino acids (when a single equivalent of sodium chloroacetate has been employed in its preparation).

[0057] Commercially available amphoteric imidazolinium may be one or more of the foregoing structures, which are suitable for use in the present disclosure. A little care should be taken in selecting the imidazolinium derivative because the same term is somewhat confusingly used to refer to cationic (as opposed to amphoteric) surfactants that incorporate or are prepared from imidazolines, e.g., the cationic surfactants having the following structure:

Accordingly, those skilled in the art will sometimes refer specifically to amphoteric imidazolinium surfactants to distinguish from so-called imidazolinium surfactants that are cationic.

[0058] Examples of suitable amphoteric imidazolinium derivatives having R groups selected from C6-C22 alkyl, e.g., caprylic, capric, lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, and behenic.

[0059] In one embodiment, the amphoteric surfactant is a phosphinatebetaine amphoteric surfactant. Phosphinatebetaines are similar to alkybetaines and sulfobetaines where the carboxy or sulfonic group has been replaced by a phosphine group. A phosphinatebetaine may be represented by the chemical structure R-N(CH3)2-L-P(=0)(R)OX. L may be, for example, propylene.

[0060] In one embodiment, the amphoteric surfactant is a phosphonatebetaine amphoteric surfactant. Phosphonatebetaines are similar to alkybetaines and sulfobetaines where the carboxy or sulfonic group has been replaced by a phosphonate group. A phosphonatebeaine may be represented by the chemical structure R-N(CH3)2-L- P(=0)(OR)OX. L may be, for example, propylene.

[0061] In one embodiment, the amphoteric surfactant is a pyridinium alkanoate

amphoteric surfactant, which may be represented by the chemical structure

where R is a fatty group, e.g., a medium or long chain alkyl. The pyridinium alkanoate illustrated in the carboxylic acid form, however at suitable pH the carboxylic acid (-COOH) group will convert to the carboxylate (COOX) group.

[0062] In one embodiment, the amphoteric surfactant is a sulfate ion-containing amphoteric surfactant. The sulfate ion group may be readily added to fatty unsaturated amines, such as oleylamine (l-amino-9,10-octadecene) to provide the corresponding sulfate ion-containing amphoteric surfactant with the name 9-(10)-hydroxyoctadecylamine.

[0063] In one embodiment, the amphoteric surfactant is a sulfatobetaine, also known as an alkyldimethylammonium alkyl sulfate, which may be represented by the chemical structure R-N(CH3)2-L-OS03X. Sulfatobetaines are examples of sulfate ion- containing amphoteric surfactants that also contain the betaine group.

[0064] In one embodiment, the amphoteric surfactant is a sulfobetaine amphoteric surfactant. The chemical structure of the basic compound may be represented as R- (CH3)2-L-S0 ₂ 0X (also sometimes represented as -L-SO3X). As commercially available, many sulfobetaines have L as propylene, and such amphoteric surfactants may be used in an embodiment of the present disclosure. Sulfobetaines are an example of sulfonic acid- containing amphoteric surfactants which also include a betaine group. This class of betaine amphoteric surfactant includes ammonium alkane sulfonates and 2-(N-alkyl-N,N- dimethylammonium) ethane sulfonates. Sulfobetaines also include trialkyl ammonium compounds similar to alkylbetaines but having the carboxyl group replaced by an alkylsulfonate group. When R is a lipophilic alkyl group, this class of sulfobetaine may be referred to as an alkylsulfobetaine. The alkylsulfobetaine surfactants are commonly named after the long chain alkyl group present in their structure. For example, when R has 12 carbons atoms in a straight chain, i.e., is lauryl, the corresponding sulfobetaine is known as lauryl sulfobetaine.

[0065] There are a great many sulfobetaine surfactants which are a variation on the classic structure shown above. For example, the propylene ((0-12)3) group designated by "L" may be substituted with various functional groups, e.g., halogen, hydroxyl, and methoxy. The R group need not be a straight chain alkyl group, but may be a branched or even alicyclic or aromatic hydrocarbon. Indeed, the R group need not even be a hydrocarbon. Primarily, the R group needs to be lipophilic, and a great many chemical structures provide that property. Examples of sulfobetaine surfactants suitable for use in the present invention but which do not fall within the scope of the classic structure shown above are N-(3- cocoamidopropyl)-N,N-dimethyl-N-(2-hydroxy-3-sulfopropyl)amm onium betaine, and 3-[(3- chloroamidopropyl) dimethylammonium]-l-propanesulfonate.

[0066] In one embodiment, the amphoteric surfactant is a sulfonic acid-containing amphoteric surfactant. For example, the amphoteric surfactant may be an N-alkyl taurine of the chemical formula RNH-CH2CH2-SO3H where R is an alkyl group. In a related

embodiment, R is a fatty group. Another sulfonic acid-containing amphoteric surfactant may be prepared by sulfonation of the linear amidoamine precursor to 1-hydroxyethyl 2- alkyl imidazoline, so as to provide R-CON H-CH2CH2-N(CH ₂ CH ₂ 0H)CH2CH ₂ S03H where R may be a fatty group, e.g., an alkyl group.

[0067] Specific examples of amphoteric surfactants and classes thereof that may be used in the present compositions include, without limitation, cocoamidopropylamine oxide, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, cocodimethyl sulphopropyl betaine, disodium cocoamphodipropionate, lauryl amine oxide, lauryl amido propyl betaine; lauryl betaine, lauryl hydroxyl sulfobetaine, myristamine oxide, sodium cocoamphoacetate, and stearyl betaine. As mentioned previously, these terms do not necessarily define mutually exclusive groups of surfactants, i.e., a specific amphoteric surfactant may fall within the scope of two or more sets of amphoteric surfactants each defined one of the selected terms.

Anionic Surfactant

[0068] In one embodiment, the fluid compositions of the present disclosure include at least one, and optionally include more than one, anionic surfactant. Suitable exemplary anionic surfactants include, without limitation, alkyi sulfates, alkylether sulfates, alkylsulfonates, alkylaryl sulfonates, alkyi succinates, alkyi sulfosuccinates, N- alkoylsarcosinates, acyl taurates, acyl isethionates, alkyi phosphates, alkyi ether phosphates, alkyi ether carboxylates, . alpha. -olefinsulfonates, and the alkali metal and alkaline earth metal salts and ammonium and triethanolamine salts thereof. Such alkyi ether sulfates, alkyi ether phosphates and alkyi ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, and in some embodiments, 1 to 3 ethylene oxide units, per molecule. For convenience, an anionic surfactant may be referred to by reference to the anionic group that forms the charged portion of the surfactant. For example, an anionic surfactant that comprises a sulfonate group may be referred to as a sulfonate surfactant, or even more simply when the context permits, as a sulfonate. As a further example, an anionic surfactant that comprises a sulfate group may be referred to as a sulfate surfactant, or when the context permits, even more simply as a sulfate.

[0069] In one embodiment, the anionic surfactant is a carboxylic acid or carboxylate, having the anionic group -C(0)-0- in addition to a fatty group. The fatty group, designated R herein, may be an alkyi group, in which case the carboxylate may be referred to as an alkyi carboxylate. Exemplary alkyi carboxylates are the sodium or potassium or ammonium salts of fatty acids such as stearic acid and oleic acid. Potassium oleate is an exemplary alkyi carboxylate. The fatty group may alternatively be a polyalkylene oxide group which is not water soluble. Some carboxylate anionic surfactants are prepared from an alkyi alcohol, such as octanol, which is then reacted with ethylene oxide to provide the polyoxyethyelene extended octanol known as polyoxyethylene (8) octyl ether carboxylic acid, when the average number of ethylene oxide units per molecule is 8.

[0070] In one embodiment, the anionic surfactant is a diphenyl oxide. A

diphenyloxide may also be viewed as a subclass of sulfonate anionic surfactants, since the aromatic rings of the diphenyl precursor is sulfonated in order to provide the diphenyl oxide anionic surfactant. The diphenol precursor is typically a diphenylether, i.e., Ar-O-Ar, where one or both of the aromatic rings (Ar) may be substituted with an alkyl group. The diphenyl oxide anionic surfactant may be represented by the chemical formula XS03-Ar(R)-0-Ar(R)- SO3X where R is hydrogen or alkyl at each position of the aromatic ring that is not sulfonated or bonded to the ether oxygen. Exemplary diphenyl oxide anionic surfactants include disulfonated diphenyl oxide with alkyl substitution such as disulfonated diphenyl oxide with linear decyl substitution, disulfonated diphenyl oxide with linear dodecyl substitution, disulfonated diphenyl oxide with branched decyl substitution, any of which may be neutralized with sodium, potassium or ammonium.

[0071] In one embodiment, the anionic surfactant is a phosphate ester, which may be a monophosphate ester of the chemical structure R-0-P(0)(OH)2, i.e., or a phosphate diester of the chemical structure R-0-P(0)(OH)-0-R where the two Rs in the diester may be the same or different. The R group is a fatty group, i.e., a non water soluble group. The R group may be an alkyl group, and phosphate esters having R=a I kyl are typically made from the corresponding alkyl alcohol. In one embodiment, the R group is a polyalkylene oxide group so as to provide a polyether phosphate ester of the formula R-(OCH ₂ CH ₂ )n-0- P(0)(OH) ₂ . A common naming convention for polyether phosphate esters provides the number of polyoxyethylene groups in the surfactant, e.g., polyoxyethylene (10). The R group in the polyether phosphate may be an alkyl group (when the polyether phosphate is derived from an alkyl alcohol), an aryl group (when the polyether phosphate is derived from an aromatic alcohol, e.g., phenol), or an alkyl aryl group, e.g., alkyl-substituted phenol such as nonyl-phenol. Exemplary phosphate esters include polyoxyethylene ( 10) nonylphenol phosphate, polyoxyethylene (4) phenol phosphate, and CsHi7 phosphate. Commercial preparations of phosphate esters often provide a mixture of phosphate monoester and phosphate diester, which may be used in the compositions of the present disclosure.

[0072] In one embodiment, the anionic surfactant is a sarcosinate, i.e., a compound having the chemical structure R-C(0)-N(CH3)-CH2-C02X where R is a fatty group. The sarcosinate surfactants include an N-acyl group, where the fatty acid from which the acyl is derived is typically used to name the sarcosinate. Exemplary sarcosinates include sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, and the ammonium ion equivalents. [0073] In one embodiment, the anionic surfactant is a sulfate, i.e., a compound having the anionic -O-SO3X group in addition to a fatty group. The fatty group may be a long chain alkyl group, where an alkyl group in a surfactant may be branched or straight chain. The fatty group need not be an alkyl group, however alkyl groups are commonly available from many plant and animal oils, and so are a ready source of fatty groups for surfactants. Exemplary sulfate anionic surfactants include sodium laureth sulfate, sodium dodecyl sulfate, sodium decyl sulfate, sodium octyl sulfate, ammonium lauryl sulfate, sodium lauryl sulfate, sodium rrideceth sulfate, Ci2-i4-ierf-alkyl-ethoxylated sodium sulfate, and poly(oxy- 1,2-ethanediyl), -sulfo- -(nonylphenoxy) ammonium salt.

[0074] In one embodiment, the anionic surfactant is a sulfoacetate, i.e., a compound having the anionic -CH2-SO3X group in addition to a fatty group. A common fatty group has the structure R-O-C(O)-, where R is an alkyl group, e.g., Cs-Cis straight chain alkyl.

Exemplary sulfoacetate anionic surfactants are sodium lauryl sulfoacetate and the ammonium salt of cetyl sulfoacetate. Sulfoacetates may be prepared as described in, e.g., US Pat. No. 5616782.

[0075] In one embodiment, the anionic surfactant is a sulfonate, i.e., a compound having the anionic -SO3X group in addition to a fatty group. The fatty group may be, for example, a long chain alkyl group. The sulfonate may be regarded as having the chemical structure R-SO3X. In one embodiment, the R group is derived from a fatty acid, and is a straight long chain alky group such as stearyl and oleyl. Long chain olefins are often used as precursors to sulfonates, since the double bond may be treated to convert it to a sulfonate group. Such sulfontes are often named by the precursor which is used to form the sulfonate, such as C14-C16 olefin sulfonate, where C14-C16 denotes that a mixture of olefins having 14 and 16 carbons was sulfonates to provide the anionic surfactant. In one embodiment, the R group is an alkylbenzene group, for example, a dodecylbenzene group. The alkyl group, e.g., the dodecyl group, may be a linear alkyl group or a branched alkyl group. Exemplary sulfonate anionic surfactants are linear dodecylbenzene sulonate and branched dodecylbenzene sulfonate. As always, the anionic group may be neutralized with any suitable cation, e.g., sodium, potassium, ammonium, etc.

[0076] In one embodiment, the anionic surfactant is a sulfosuccinate, i.e., a compound having the chemical structure based on sulfonated succinic acid, i.e., Fatty Group-0-C(0)-CH2-CH(sulfate)-C(0)-0-R (which may be a fatty group or hydrogen). Sulfosuccinates are generally sodium salts of alkyl esters of sulfosuccinic acid that are a result of condensation of maleic anhydride with a fatty alcohol, followed by sulfonation with sodium bisulfite (NaHSC ). As shown by the foregoing chemical structure, a sulfosuccinate will have at least one fatty group, and may have two fatty groups. However, when the sulfosuccinate has one fatty group, it may also have an anionic carboxylate group rather than a second fatty group. Exemplary sulfosuccinate anionic surfactants include sodium dioctyl sulfosuccinate (having two fatty groups) and disodium laureth sulfosuccinate (which has one fatty group, one sulfate group and one carboxylate group, and is also known as DLS).

[0077] Additional specific examples of anionic surfactants include, without limitation, ammonium lauryl sulfosuccinate, sodium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, triethanolamine dodecylbenzenesulfonate, sodium lauryl sarcosinate, ammonium lauryl sulfate, sodium oleyl succinate, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.

[0078] In one embodiment, the fluid concentrations and compositions of the present disclosure contain a third surfactant selected from amphoteric and anionic surfactants. The third surfactant is non-identical to, i.e., is not the same as, either of the first (the amphoteric) or the second (the anionic) surfactants. Any of the amphoteric and anionic surfactants disclosed previously are optionally used as the third surfactant in the present formulations, so long as it (the third surfactant) is not the same as the first or second surfactant. In one embodiment, the third surfactant is of a different class from the first or second surfactant, i.e., the third surfactant has a different functional group from the functional groups that provide the charged functionality present in the first and second amphoteric or anionic surfactant. For example, if the second surfactant is a sulfate anionic surfactant, then the third surfactant is not a sulfate, but is instead, e.g., a sulfonate anionic surfactant.

[0079] Amphoteric and/or anionic surfactants suitable for use in the present invention may be obtained from one or more of the following exemplary manufacturers and/or suppliers: Aceto Corp. (Allendale, NJ); Air Products (Allentown, PA); Akzo Nobel Chemicals Co. (Chicago, IL); AIzo International (Sayreville, NJ); BASF Corp. (Florham Park, NJ); Clariant Corp. (Frankfurt, Germany); Croda, Inc. (Edison, NJ); Dow Chemical (Midland M l); E. I. du Pont de Nemours & Co., Inc. (Wilmington, DE); Harcros Chemicals, Inc. (Kansas City, KS); Huntsman Corp. (St. Lake City, UT); Kaiser Industries Ltd. (Bahadurgarh, Haryana, India), Kao Chemicals. (Tokyo, Japan); Lonza, Inc. (Basel, Switzerland); NOF Corporation (Tokyo, Japan); Pilot Chemicals (Cincinnati, OH); Procter & Gamble (Cincinnati, OH); Solvay-Rhodia (Courbevoie, France); Stepan Co. (Northfield, IL); and Unilever PLC (London, England).

Optional Components

[0080] The following ingredients are optionally present in the compositions of the present disclosure, however the present disclosure also provides that each of the following ingredients may be specifically excluded from being present in the composition of the present disclosure.

[0081] The compositions of the present disclosure may include an anti-rust agent, which may also be referred to herein as an anti-corrosion agent. An exemplary anti-rust agent is sodium nitrite. Other exemplary anti-rust agents are sodium benzoate, organic boron compounds, amines, aminophosphate compounds, zinc dialkyldithiophosphate, and tall oil fatty acids. The anti-rust agent may be present in the composition at an amount of less than 10 w% of the composition directly used as a material fabrication fluid, e.g., as a metal cutting fluid. In optional embodiments, that amount is less than 9 wt%, or less than 8 wt%, or less than 7 wt%, or less than 6 wt%, or less than 5 wt %, or less than 4 wt%, or less than 3 wt%, or less than 2 wt%, or less than 1 wt%, or less than 0.5 wt%, or less than 0.1 wt%. The amount may also be expressed in terms of a minimum amount, such as at least 500 ppm, or at least 1000 ppm, or at least 1500 ppm, or at least 2000 ppm, or at least 2500 ppm, 0.5 wt%, or at least 1 wt%, or at least 1.5 wt%, or at least 2 wt%, or at least 2.5 wt%, or at least 3 wt%, or at least 3.5 wt%, or at least 4 wt%, or at least 4.5 wt%, or at least 5 wt%. Anti-rust agents are well known commercial materials.

[0082] The compositions of the present disclosure may include a colorant, such as a dye or pigment. The coloring agent should be used in a small amount, just enough to impart color visible to the eye, when the composition is being applied to material, e.g., metal, to be cut or otherwise shaped. Colorants are well known commercial materials.

[0083] The compositions of the present disclosure may include a de-foaming agent which may also be referred to as an anti-form agent. A suitable de-foaming agent is a silicone polymer. Silicone defoaming agents are well known commercial materials. Dow Corning (Michigan, USA) sells such de-foaming agents. Another suitable de-foaming agent is tributylphosphate.

[0084] The compositions of the present disclosure may include a thickening agent.

As used herein, upon addition to, or inclusion in, an aqueous fluid composition or concentrate thereof, the thickening agent increases the viscosity of the composition. The inclusion of a thickening agent provides for, among other things, an improved adhesion of the composition to a surface. This is particularly advantageous when the surface is not horizontal and so the material fabrication composition will tend to fall down the surface under the force of gravity absent the present of a thickening agent. The thickening agent may be water soluble. Thickening agents for aqueous compositions are well known in the art, may be referred to as an aqueous thickening agent, and any of such thickening agents may be used in the present compositions.

[0085] The amount of thickening agent to be included in the composition will depend on the precise identity of the thickening agent and the desired viscosity of a concentrated form of the material fabrication fluid composition. For a thickening agent selected from a cellulosic or polyamide thickening agent, and to achieve a viscosity similar to that of whole milk or orange juice, the thickening agent will typically be present in the composition at weight percent of 0.1 weight percent, based on the total weight of the composition, when the composition is a concentrate having about 5-25% total solids. The viscosity of the concentrate may be varied, primarily by the incorporation of more or less thickener. If a more viscous concentrate is desired, the addition of more thickening agent will provide for a more viscous composition. Alternatively, a more effective thickening agent may be utilized, i.e., a thickening agent that achieves the same increase in viscosity but at a lower concentration.

[0086] In one aspect, the thickening agent may be a polyhydroxy polymer, e.g., a polysaccharide such as a cellulosic or a functionalized cellulosic. When the thickening agent is a polysaccharide, the polysaccharide may have at least 50, or at least 100, or at least 150, or at least 200 saccharide units per polymer chain. The number average molecular weight of the polysaccharide may be at least 13,000 or at least 17,000 or at least 21,000 or at least 25,000.

[0087] In one aspect, the thickening agent is a polyhydroxy small molecule, such as glycerol. A polyhydroxy small molecule has a molecular weight of less than 500 g/mol and has at least three hydroxyl groups. [0088] In one aspect, the thickening agent is a cellulosic, which includes derivatives of cellulosic resins. A suitable cellulosic is hydroxyethylcellulose (HEC). HEC is a derivative of cellulose wherein the -CH2OH groups are converted to -CH2OCH2CH2OCH2CH2OH groups, and -OH groups are converted to— OCH2CH2OH groups. HEC is commercially available in many grades, which vary as to molecular weight and degree of derivatization, which in turn lead to different solution viscosities (typically measured at 2% solids in water). Suitable H EC is Cellosize™ from Dow Chemical (Midland, Ml) and Aqualon™ from Ashland Chemical (Covington, KY).

[0089] Other suitable cellulosic thickening agents include methyl cellulose, ethyl cellulose, methyl hydroxyethylcellulose, methyl hydroxypropylcellu lose,

hydroxypropylcellulose, and anionic (salt) forms such as sodium carboxymethylcellulose, dihydroxypropyl ethers of cellulose (see, e.g., U.S. Pat. No. 4,096,326),

[0090] Suitable polyhydroxy polymers other than cellulosics include corn starch or modified corn starch, potato starch or modified potato starch, and pectin or modified pectin.

[0091] The thickening agent may be a polyacrylamide. Suitable polyacrylamide thickening agents may be selected from copolymers of acrylamide and ammonium acrylate; copolymers of acrylamide or methacrylamide and methacryloyloxyethyltrimethylammonium halide, for example chloride; and copolymers of acrylamide and 2-acrylamido-2- methylpropanesulphonic acid. These copolymers may be prepared in the presence of a crosslinking agent, where exemplary crosslinking agents include divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers or allylic ethers of alcohols of the sugar series, such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol and glucose. See, e.g., U.S. Pat. Nos. 2,798,053 and 2,923,692. The polyacrylamide may be ionic and neutralized with a neutralizing agent such as sodium hydroxide, potassium hydroxide, aqueous ammonia or an amine such as triethanolamine or monoethanolamine. Ionic polyacrylamides may be prepared by copolymerizing acrylamide and sodium 2-acrylamido-2-methylpropanesulphonate via a radical route using initiators of the azobisisobutyronitrile type and by precipitation from an alcohol such as tert-butanol. A crosslinked copolymer of acrylamide and methacryloyloxyethyltrimethyl-ammonium chloride may be obtained by copolymerization of acrylamide and dimethylaminoethyl methacrylate quaternized with methyl chloride, followed by crosslinking with a compound containing olefinic unsatu ration, such as methylenebisacrylamide.

[0092] The thickening agent may be a polyacrylic acid. Suitable polyacrylic acid thickening agents are commercially available. For example, Lubrizol (Wickliffe, Ohio) sells their Carbopol™ synthetic thickeners that are made from polyacrylic acid. The polyacrylic acid may be neutralized in order to adjust its thickening behavior. For example, polyacrylic acid may be neturalized with ammonium ions using, e.g., ammonium hydroxide. Ashland Chemical markets their Carbomer™ line of crosslinked polyacrylic acids. Again, these polymers need to be neutralized in order to provide effective thickening behavior.

[0093] The thickening agent may be a gum or a derivative thereof. Examples include locust bean gum and derivatives, guar gum and derivatives, and xanthan gum and derivatives. Exemplary gum derivatives include sulfonated gum, e.g., sulfonated guar, hydroxypropyl derivatized gum, e.g., hydroxypropyl guar, cationic derivatives, e.g., cationic guar,

[0094] The thickening agent may be a hydrophobically modified thickening agent. In one aspect, the thickening agent comprises a hydrophobic group such as a hydrophobic alkyl chain, where suitable examples of such thickening agents include hydrophobically modified ethylene oxide urethane (HEUR) polymer, hydrophobically modified alkali soluble emulsion (HASE) polymer, hydrophobically modified hydroxyethyl cellulose (HMHEC), and

hydrophobically modified polyacrylamide (HM PA). HEUR polymers are linear reaction products of diisocyanates with polyethylene oxide end-capped with hydrophobic hydrocarbon groups. HASE polymers are homopolymers of (meth)acrylic acid, or copolymers of (meth)acrylic acid, (meth)acrylate esters, or maleic acid modified with hydrophobic vinyl monomers. HMHEC refers to hydroxyethyl cellulose modified with hydrophobic alkyl chains. HM PA refers to copolymers of acrylamide with acrylamide modified with hydrophobic alkyl chains (N-alkyl acrylamide).

[0095] In one aspect, the fluid composition of the present disclosure includes an inorganic salt of an organic or inorganic acid. Suitable inorganic salts of organic acids include ammonium citrate, calcium acetate, copper acetate, copper citrate, magnesium citrate, melamine phosphate salt, nickel acetate, potassium acetate, potassium citrate, sodium acetate, sodium bitartrate, strontium acetate, urea phosphate, and zinc acetate.

[0096] The amount of inorganic component present in the composition may be varied over a wide range. Based on the total weight of the solids present in the composition, the inorganic component may constitute from 1% to about 15% of that weight. In various embodiments, the inorganic component is at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 6%, or at least 7%, or at least 8%, or at least 9%, or at least 10%, or at least 11%, or at least 12%, or at least 13%, or at least 14%, or at least 15% of the total weight of the solid components of the composition. In various embodiments, the inorganic component contributes not more than 30%, or 25% or 20% or 15% or not more than 10% of the total weight of the solids present in the composition. As mentioned previously, in one embodiment the inorganic component is an inorganic salt.

[0097] In one aspect, the fluid composition of the present disclosure includes a nonvolatile organic solvent that is miscible with water. As used herein, a non-volatile material or solvent that is a liquid has a boiling point of greater than water, i.e., greater than 100°C. An exemplary organic solvent is ethylene glycol monobutyl ether, also known as BUTYL CELLOSOLVE™.

[0098] As mentioned previously, the present disclosure provides a concentrate composition comprising water and solids, the solids comprising a first surfactant selected from amphoteric surfactants, a second surfactant selected from anionic surfactants, and a third surfactant selected from an amphoteric and an anionic surfactant, the third surfactant being different from the first and second surfactants. Optionally, the third surfactant, but neither of the first or second surfactants, is a fluorosurfactant. The third surfactant may be a fluorinated or perfluorinated anionic fluorosurfactant while the second (anionic) surfactant of the concentrate is non-fluorinated. Alternatively, the third surfactant may be a fluorinated or perfluorinated amphoteric surfactant while the first (amphoteric) surfactant of the concentrate is non-fluorinated. A fluorinated surfactant will contain some C-F bonds and may contain only C-F bonds (in which case it is perfluoronated) and may contain some C-H bonds (in which case it is a hydrofluorocarbon-containing molecule).

[0099] In addition to fluorinated versions of the amphoteric and anionic surfactants identified herein, other exemplary fluorosurfactants that may be included in a concentrate or composition of the present disclosure include the Captstone™ fluorosurfactants and the Forafac™ fluorosurfactants, both from DuPont (Wilmington, DE). Other exemplary fluorosurfactants are those disclosed in any of US Patent Publication No. US 20130112908; US 20120255651; US20110232924; US 20110091408; US 20100168318; and US. Patent No. US 8,287,752; US 8,039,677; US 7,977,426; and US 7,989,568. [00100] However, in another embodiment, the third surfactant is not a

fluorosurfactant. Fluorine-containing compounds should be used with caution since they may have an undesirable bio-persistence profile, and/or they may break down to hazardous materials. In one embodiment, the present concentrates and compositions do not contain any fluorocarbons, while in another embodiment the present concentrates and

compositions do not contain any halocarbons.

Formulations

[00101] The present disclosure provides material fabrication fluids, e.g., metal cutting fluids, in concentrated form as well as in diluted (ready-to-use) forms. The concentrated form may be described in terms of the amounts of the various components, where these amounts are relative to the total amount of surfactant present in the concentrate.

[00102] For example, for each weight part of surfactant (e.g., for each lg, or each 1kg, etc. of surfactant) the concentrate may contain 1-10 weight parts of anti-rust agent. Thus, if the concentrate contains 10 grams of surfactant, the concentrate may also contain from 10- 100 grams of anti-rust agent. Optionally, the concentrate contains at least 1, or at least 2, or at least 3, or at least 4, or at least 5 weight parts of anti-rust agent (relative to 1 weight part of surfactant), and may contain less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5 weight parts of anti-rust agent. In exemplary embodiments, the concentrate contains 1-10, or 2-8, or 3-7, or 4-6 weight parts of anti-rust agent such as sodium nitrite, for each 1 gram of total surfactant present in the concentrate.

[00103] For each weight part of surfactant, the concentrate may contain 0.1-0.5 weight parts of thickener. Thus, if the concentrate contains 10 grams of surfactant, the concentrate may also contain 1-5 grams of thickener. Optionally, the concentrate contains at least 0.1 or at least 0.2, or at least 0.3, or at least 0.4 weight parts of thickener (relative to 1 weight part of surfactant(s)), and may contain less than 0.5, or less than 0.4, or less than 0.3 weight parts of thickener. In exemplary embodiments, the concentrate contains 0.1-0.5, or 0.2-0.4 weight parts of thickener such as hydroxyethylcellulose, for each 1 gram of total surfactant present in the concentrate.

[00104] For each weight part of surfactant, the concentrate may contain 0.05-0.25 weight parts of inorganic salt. Thus, if the concentrate contains 10 total grams of surfactant, the concentrate may also contain 0.5-2.5 grams of inorganic salt. Optionally, the concentrate contains at least 0.05, or at least 0.1, or at least 0.15, or at least 0.2 weight parts of inorganic salt (relative to 1 weight part of surfactant(s) present in the concentrate), and may contain less than 0.25, or less than 0.2, or less than 0.15, or less than 0.1 weight parts of inorganic salt. In exemplary embodiments, the concentrate contains 0.05-0.25, or 0.1-0.2 weight parts of inorganic salt such as calcium chloride.

[00105] For each weight part of surfactant, the concentrate may contain 0.01-0.1 weight parts of non-volatile, water-soluble organic solvent. Thus, if the concentrate contains 10 total grams of organic solvent, the concentrate may also contain 0.1-1 grams of organic solvent. Optionally, the concentrate contains at least 0.01, or at least 0.02, or at least 0.03, or at least 0.04, or at least 0.05, or at least 0.06, or at least 0.07 weight parts of organic solvent (relative to 1 weight part of surfactant(s) present in the concentrate), and may contain less than 0.1, or less than 0.09, or less than 0.08, or less than 0.07, or less than 0.06, or less than 0.05 weight parts of organic solvent. In exemplary embodiments, the concentrate contains 0.01-0.1, or 0.02-0.9, or 0.03-0.8 weight parts of organic solvent such as ethylene glycol butyl ether.

[00106] For each weight part of surfactant, the concentrate may contain 0.2-1.0 weight parts of defoamer. Thus, if the concentrate contains 10 total grams of surfactant, the concentrate may also contain 2-10 grams of defoamer. Optionally, the concentrate contains at least 0.2, or at least 0.3, or at least 0.4, or at least 0.5 weight parts of defoamer (relative to 1 weight part of surfactant(s) present in the concentrate), and may contain less than 1.0, or less than 0.9, or less than 0.8, or less than 0.7, or less than 0.6 weight parts of defoamer. In exemplary embodiments, the concentrate contains 0.2-1.0, or 0.3-0.8, or 0.4- 0.6 weight parts of defoamer such as a silicone defoamer.

[00107] The concentrate will also contain water. The amount of water may vary, but is typically in the range of 5-50% of the weight of the concentrate. In other words, 100 grams of concentrate will include between 5 and 50 grams of water. In optional embodiments, the concentrate is at least 5%, or at least 10%, or at least 15%, or at least 20%, or at least 25% by weight water, while in other optional embodiments, the concentrate is less than 50%, or less than 45%, or less than 40%, or less than 35%, or less than 30% by weight water.

[00108] The present disclosure also provides for diluted forms of the concentrate, which are ready to use in a material fabrication process, such as a metal cutting operation. In optional embodiments, the diluted forms of the concentrate have been diluted sufficiently that their water content is from 75-99%. Dilute forms of the concentrate may be diluted by combining the concentrate with an equal volume of water (a lx dilution), or be prepared by 2x, or 3x, or 4x, or 5x, or 6x, or 7x, or 8x, or 9x, or lOx, or llx, or 12x, or 13x, or 14x, or 15x, or 16x, or 17x, or 18x, or 19x, or 20x dilution, as well as ranges providing by selecting any two of these values. For example, the diluted form may be prepared by a dilution of from 5x-15x, i.e., adding 5-15 volumes of water to each volume of concentrate, or by adding 5-15 weights of water to each weight of concentrate.

[00109] In one embodiment, the present disclosure provides a composition comprising water and solids, the solids comprising at least one surfactant, such as an amphoteric first surfactant, an anionic second surfactant, and a third surfactant selected from an amphoteric and an anionic surfactant, the third surfactant being different from the first and second surfactants. In optional embodiments: the water comprises 75 to 95 wt% of the composition; e.g., the water comprises 75 to 80 wt% of the composition or the water comprises 80 to 85 wt% of the composition or the water comprises 85 to 90 wt% of the composition or the water comprises 95 to 95 wt% of the composition. In optional embodiments: the amphoteric surfactant(s) comprises 10 to 30 wt% of the solids or 15 to 25 wt% of the solids; e.g., the amphoteric surfactant(s) comprises 10 to 15 wt% of the solids or the amphoteric surfactant(s) comprises 15 to 20 wt% of the solids or the amphoteric surfactant(s) comprises 20 to 25 wt% of the solids or the amphoteric surfactant(s) comprises 25 to 30 wt% of the solids. In an optional embodiment, the amphoteric surfactant(s) comprise 1 to 5 wt% of the composition. In optional embodiments, the anionic surfactant(s) comprise 45 to 85 wt% of the solids; e.g., the anionic surfactant(s) comprise 45-55 wt% of the solids or the anionic surfactant(s) comprise 55-65 wt% of the solids or the anionic surfactant(s) comprise 65-75 wt% of the solids or the anionic surfactant(s) comprise 75-85 wt% of the solids. In an optional embodiment, the anionic surfactant(s) comprise 5 to 25 wt% of the composition.

[00110] In additional optional embodiments, the amphoteric surfactant is one or more betaines selected from cocodimethyl sulphopropyl betaine, lauryl betaine and cocamidopropyl betaine; the anionic surfactant is one or more surfactants selected from ammonium lauryl sulfosuccinatem, sodium lauryl sulfate, sodium laureth sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, triethanolamine dodecylbenzenesulfonate, sodium lauryl sarcosinate, ammonium lauryl sulfate, sodium oleyl succinate, sodium dodecyl sulfate, sodium decyl sulfate, sodium octyl sulfate, and sodium dodecylbenzene sulfonate; the composition further comprises an inorganic salt, where optionally the inorganic salt comprises 2 to 20 wt% of the solids; the composition further comprises a thickening agent, where optionally the thickening agent comprises 0.1 to 5 wt% of the solids.

[00111] As mentioned previously, the compositions of the present disclosure may include both of an amphoteric surfactant (and optionally more than one amphoteric surfactant) and an anionic surfactant (and optionally more than one anionic surfactant). In one aspect, the one or more amphoteric surfactant(s) contribute about an equal weight to the composition as do the one or more anionic surfactant(s). In other aspects, and again as measured on a weight basis, the amphoteric surfactant(s) contribute a lesser weight to the total weight of the composition than do the anionic surfactant(s), where in various embodiments the amphoteric surfactant(s) contribute from 1 to 50%, or from 5 to 40%, or from 10 to 30% or from 15 to 25% of the total weight of the anionic and amphoteric surfactants.

[00112] When the composition contains two of an amphoteric surfactant, or two of an anionic surfactant, the two surfactants are not necessarily present in equal weight amounts. In various embodiments, the composition comprises a first and a second anionic surfactant, where the first surfactant provides 1 to 50% of the total weight of the first and second surfactant. In additional embodiments, the first surfactant provides 1-40%, or 1- 30%, or 1-20%, or 1 to 10%, or 1 to 5% of the total weight of the first and second anionic surfactants. Likewise, in various embodiments, the composition comprises a first and a second amphoteric surfactant, where the first amphoteric surfactant provides 1 to 50% of the total weight of the first and second surfactant, and in additional embodiments, the first amphoteric surfactant provides 1-40%, or 1-30%, or 1-20%, or 1 to 10%, or 1 to 5% of the total weight of the first and second amphoteric surfactants.

[00113] In one embodiment, a mixture of two amphoteric surfactants are included in a material fabrication fluid, e.g., a metal cutting fluid composition, of the present disclosure. For instance, mixtures of any of the previously mentioned amphoteric surfactants may be used. When two amphoteric surfactants are present in a composition, those two surfactants will be present in relative amounts, based on the weight of each the surfactants in the composition. For example, if the composition contains equal weights of the two amphoteric surfactants, then those two surfactants are present in a weight ratio of 1:1. If the composition contains twice as much of a first surfactant than of a second surfactant, then those two surfactants are present in a weight ratio of 1:2. If the second surfactant is present within a range of permissible weights, relative to the weight of the first surfactant, and that range is between "equal to the weight of the first surfactant" and "twice as much as the weight of the first surfactant" such that those two surfactants are present in a weight ratio of l:(l-2).

[00114] As mentioned above, in one embodiment the present disclosure provides for the presence of two amphoteric surfactants in a composition. In various embodiments, those two amphoteric surfactants may be present at any of the following relative amounts: 1:1; l:(l-5); 1:(1-10); 1:(1-15); l:(l-20); l:(l-25); l:(l-30); 1:(5-10); 1:(5-15); l:(5-20); 1:(5- 25); l:(5-30); 1:(10-15); l:(10-20); l:(10-25); l:(10-30); l:(15-20); l:(15-25); l:(15-30); 1:(20- 25); and l:(25-30).

[00115] In one embodiment, a mixture of two anionic surfactants are included in a material fabrication fluid, e.g., a metal cutting fluid composition, of the present disclosure. For instance, mixtures of any of the previously mentioned anionic surfactants may be used. When two anionic surfactants are present in a composition, those two surfactants will be present in relative amounts, based on the weight of each the surfactants in the composition. For example, if the composition contains equal weights of the two anionic surfactants, then those two surfactants are present in a weight ratio of 1:1. If the composition contains twice as much of a first surfactant than of a second surfactant, then those two surfactants are present in a weight ratio of 1:2. If the second surfactant is present within a range of permissible weights, relative to the weight of the first surfactant, and that range is between "equal to the weight of the first surfactant" and "twice as much as the weight of the first surfactant" such that those two surfactants are present in a weight ratio of l:(l-2).

[00116] As mentioned above, in one embodiment the present disclosure provides for the presence of two anionic surfactants in a composition. In various embodiments, those two anionic surfactants may be present at any of the following relative amounts: 1:1; 1:(1- 5); 1:(1-10); 1:(1-15); l:(l-20); l:(l-25); l:(l-30); 1:(5-10); 1:(5-15); l:(5-20); l:(5-25); 1:(5- 30); 1:(10-15); l:(10-20); l:(10-25); l:(10-30); l:(15-20); l:(15-25); l:(15-30); l:(20-25); and l:(25-30). [00117] In one embodiment the present disclosure provides a material fabrication fluid, e.g., a metal cutting fluid concentrate composition, that contains 10-25 wt% of a first anionic surfactant, optionally a sulfonate surfactant such as sodium dodecylbenzene sulfonate, optionally 12-23 wt% or optionally 15-20 wt% of the first anionic surfactant; 5-15 wt% of an amphoteric surfactant, optionally a betaine surfactant such as cocamidopropyl betaine, optionally 7-13 wt% or optionally 7-11 wt% of the betaine surfactant; 1-10 wt% of a second anionic surfactant, optionally a sulfate surfactant such as sodium laureth sulfate or sodium dodecyl sulfate, optionally 2-8 wt% or 3-7 wt% of the second anionic surfactant; up to about 5 wt% of an organic solvent, optionally a glycol ether such as ethylene glycol butyl ether, optionally 1-4 wt% or 2-3 wt% of glycol ether; 2-15 wt% of a thickener such as a cellulosic thickener, e.g., hydroxyethyl cellulose, optionally 4-12 wt% or 6-10 wt% of the thickener; up to about 10 wt% of calcium chloride, optionally 2-7 wt% or 3-6 wt% of calcium chloride. Optionally the concentrate may contain a third anionic surfactant, such as sodium octyl sulfate, in an amount of up to about 5 wt%. Water will also be present in the concentrate. The total non-aqueous content of the concentrate is about 25-75 wt%, or about 30-70 wt%, or about 35-55 wt%, or about 40-50 wt% (in the last case the water content is 50-40 wt%).

[00118] In one embodiment, the present disclosure provides a composition including a first anionic surfactant at a concentration of 0.1-0.3 wt% (i.e., 0.1-0.3 g of first anionic surfactant in 100 g of the composition, i.e., 1000-3000 ppm of first anionic surfactant), a second anionic surfactant different from the first anionic surfactant at a concentration of 0.01-0.10 wt% (i.e., 100-1000 ppm of second anionic surfactant), an amphoteric surfactant at a concentration of 0.05-0.15, (i.e., 500-1500 ppm of amphoteric surfactant), and anti-rust agent at a concentration of 0.1-0.3 wt% (i.e., 1000-3000 ppm of anti-rust agent). The composition optionally also contains thickening agent at a concentration of 0.05-0.15 wt% (500-1500 ppm of thickening agent), and/or inorganic salt at a concentration of 0.01-0.1 wt% (100-1000 ppm of inorganic salt), and/or non-volatile organic solvent at a

concentration of 0.01-0.1 wt% (100-1000 ppm of non-volatile organic solvent), and/or defoaming agent at a concentration of 0.05-0.2 wt% (i.e., 500-2000 ppm of defoaming agent). In one embodiment, the composition contains each of these components, i.e., each of first anionic surfactant, second anionic surfactant, amphoteric surfactant, anti-rust agent, thickening agent, inorganic salt, non-volatiles organic solvent and defoaming agent. In one embodiment, the composition contains each of these components, i.e., each of first anionic surfactant which is a sulfonate-containing surfactant, second anionic surfactant which is a sulfate-containing surfactant, amphoteric surfactant which is a betaine-containing surfactant, anti-rust agent, thickening agent which is a cellulosic thickening agent, inorganic salt, non-volatiles organic solvent and defoaming agent. In one embodiment, the composition contains each of these components, i.e., each of first anionic surfactant which is a sulfonate-containing surfactant, second anionic surfactant which is a sulfate-containing surfactant, amphoteric surfactant which is a betaine-containing surfactant, anti-rust agent which is sodium nitrite, thickening agent which is a hydroxyethyl cellulose, inorganic salt which is calcium chloride, non-volatiles organic solvent which is ethylene glycol butyl ether, and defoaming agent which is a silicone defoaming agent.

[00119] In one embodiment, the present disclosure provides a composition including a first anionic surfactant at a concentration of about 0.2 wt% (i.e., about 0.2 g of first anionic surfactant in 100 g of the composition, i.e., about 2000 ppm of first anionic surfactant), a second anionic surfactant different from the first anionic surfactant at a concentration of about 0.05 wt% (i.e., about 500 ppm of second anionic surfactant), an amphoteric surfactant at a concentration of about 0.09 wt% (i.e., about 900 ppm of amphoteric surfactant), and anti-rust agent at a concentration of about 0.2 wt% (i.e., about 2000 ppm of anti-rust agent). The composition optionally also contains thickening agent at a

concentration of 0.05-0.15 wt% (500-1500 ppm of thickening agent) or about 800 ppm thickening agent, and/or inorganic salt at a concentration of 0.01-0.1 wt% (100-1000 ppm of inorganic salt) or about 400 ppm inorganic salt, and/or non-volatile organic solvent at a concentration of 0.01-0.1 wt% (100-1000 ppm of non-volatile organic solvent) or about 200 ppm of non-volatile organic solvent, and/or defoaming agent at a concentration of 0.05-0.2 wt% (i.e., 500-2000 ppm of defoaming agent) or about 1000 ppm of defoaming agent. In one embodiment, the composition contains each of these components, i.e., each of first anionic surfactant, second anionic surfactant, amphoteric surfactant, anti-rust agent, thickening agent, inorganic salt, non-volatiles organic solvent and defoaming agent. In one embodiment, the composition contains each of these components, i.e., each of first anionic surfactant which is a sulfonate-containing surfactant, second anionic surfactant which is a sulfate-containing surfactant, amphoteric surfactant which is a betaine-containing surfactant, anti-rust agent, thickening agent which is a cellulosic thickening agent, inorganic salt, non-volatiles organic solvent and defoaming agent. In one embodiment, the composition contains each of these components, i.e., each of first anionic surfactant which is a sulfonate-containing surfactant, second anionic surfactant which is a sulfate-containing surfactant, amphoteric surfactant which is a betaine-containing surfactant, anti-rust agent which is sodium nitrite, thickening agent which is a hydroxyethyl cellulose, inorganic salt which is calcium chloride, non-volatiles organic solvent which is ethylene glycol butyl ether, and defoaming agent which is a silicone defoaming agent.

[00120] The following are some additional exemplary embodiments of the compositions of the present disclosure, where metal cutting composition and metal cooling composition are used interchangeably:

1) A metal cutting composition comprising water, a first surfactant, a thickening agent such as a cellulosic thickening agent, and an anti-rust agent.

2) A metal cutting composition comprising water, a first surfactant, an inorganic salt such as calcium chloride, and an anti-rust agent.

3) A metal cooling composition of any of embodiments 1-2 wherein the first surfactant is an anionic surfactant.

4) The composition of any of embodiments 1-3 wherein the first surfactant is an anionic surfactant comprising a sulfonate group.

5) The composition of any of embodiments 1-4 wherein the first surfactant is sodium dodecylbenzene sulfonate.

6) The composition of any of embodiments 1-5 comprising a second surfactant,

wherein the second surfactant is an amphoteric surfactant.

7) The composition of any of embodiments 1-6 comprising a second surfactant,

wherein the second surfactant is an amphoteric surfactant comprising a betaine group.

8) The composition of any of embodiments 1-7 comprising a second surfactant,

wherein the second surfactant is cocamidopropyl betaine.

9) The composition of any of embodiments 1-8 comprising a third surfactant, wherein the third surfactant is an anionic surfactant.

10) The composition of any of embodiments 1-9 comprising a third surfactant, wherein the third surfactant is an anionic surfactant comprising a sulfate group. 11) The composition of any of embodiments 1-10 comprising a third surfactant, wherein the third surfactant is sodium laureth sulfate.

12) The composition of any of embodiments 1-11 wherein the anti-rust agent is sodium nitrite.

13) The composition of any of embodiments 1-12 comprising a thickening agent which is a cellulosic thickening agent, wherein the cellulosic thickening agent is hydroxyl ethyl cellulose.

14) The composition of any of embodiments 1-13 comprising a defoaming agent.

15) The composition of any of embodiments 1-14 comprising a defoaming agent,

wherein the defoaming agent is a silicone polymer.

16) The composition of any of embodiments 1-15 comprising a first surfactant that

comprises a sulfonate group and a second surfactant that comprises a sulfate group.

As discussed below, the present disclosure also provides a method of machining metal, comprising applying a composition comprising a composition of any of embodiments 1-16 to a piece of metal being machined, in an amount and time that are effective to dissipate heat from the metal being machined. The machining process may achieve cutting of the metal, and thus be referred to as a cutting process. The machining process may be any of broaching, tapping, hobbing, cutting, drilling, milling, turning, sawing, honing or grinding, which are examples of the machining processes that may be used in the method of the present disclosure.

[00121] The following are some additional exemplary embodiments of the compositions of the present disclosure. A composition comprising water, a first surfactant, a thickening agent, and an anti-rust agent. The first surfactant may be an anionic surfactant, such as a sulfonate- or sulfate-containing surfactant. Optionally, the first surfactant is sodium dodecylbenzene sulfonate. Optionally, the first surfactant is sodium laureth sulfate. Rather than being an anionic surfactant, the first surfactant may be an amphoteric surfactant, such as a betaine-containing surfactant, e.g., cocamidopropyl betaine.

Optionally, the composition may include two surfactants, where each is an anionic surfactant, e.g., wherein the two surfactants are a sulfate-containing surfactant and a sulfonate-containing surfactant such as sodium laureth sulfate and sodium dodecylbenzene sulfonate. Optionally, the composition may include two surfactants, where one is an anionic surfactant and the other is an amphoteric surfactant, such as a sulfate-containing anionic surfactant and a betaine-containing amphoteric surfactant where the sulfate-containing anionic surfactant may be sodium laureth sulfate and the betaine-containing amphoteric surfactant may be cocamidopropyl betaine. Optionally, the composition may include two surfactants, where one is an anionic surfactant and the other is an amphoteric surfactant, such as a sulfonate-containing anionic surfactant and a betaine-containing amphoteric surfactant, where the sulfonate-containing anionic surfactant may be sodium

dodecylbenzene sulfonate and the betaine-containing amphoteric surfactant may be cocamidopropyl betaine. Optionally, the composition may include three surfactants, two of the three surfactants being non-identical anionic surfactants and one of the three surfactants being an amphoteric surfactant, where these three surfactants may optionally be a sulfate-containing surfactant, a sulfonate-containing surfactant, and a betaine- containing surfactant, e.g., sodium dodecylbenzene sulfonate, sodium laureth sulfate, and cocamidopropyl betaine. When present, the sulfonate-containing surfactant may be present at a concentration of about 1800 ppm, e.g., 1000-3000 ppm. When present, the sulfate-containing surfactant may be present at a concentration of about 500 ppm, e.g., 100-1000 ppm. When present, the amphoteric surfactant may be present at a

concentration of about 900 ppm, e.g., 500-1500 ppm. The composition will contain an effective amount of an anti-rust agent as described herein, where the anti-rust agent may be, e.g., sodium nitrite. The concentration of the anti-rust agent may be about 100-5000 ppm, or about 1000-3000 ppm, or about 2000 ppm. The thickening agent is described herein, and may be, e.g., a cellulosic thickening agent such as hydroxyl ethyl cellulose. The concentration of the thickening agent in the composition may be about 100-2000 ppm, or about 500-1500 ppm, or about 800 ppm. The composition may optionally contain, and in one embodiment does contain, a defoaming agent as described herein. An exemplary defoaming agent is a silicone polymer. When present, the defoaming agent may be present at a concentration of about 100-5000 ppm, or about 500-2000 ppm, or about 1000 ppm.

[00122] The following are some additional exemplary embodiments of the compositions of the present disclosure. A composition comprising water, a first surfactant, an inorganic salt, and an anti-rust agent. The first surfactant may be an anionic surfactant, such as a sulfonate- or sulfate-containing surfactant. Optionally, the first surfactant is sodium dodecylbenzene sulfonate. Optionally, the first surfactant is sodium laureth sulfate. Rather than being an anionic surfactant, the first surfactant may be an amphoteric surfactant, such as a betaine-containing surfactant, e.g., cocamidopropyl betaine.

Optionally, the composition may include two surfactants, where each is an anionic surfactant, e.g., wherein the two surfactants are a sulfate-containing surfactant and a sulfonate-containing surfactant such as sodium laureth sulfate and sodium dodecylbenzene sulfonate. Optionally, the composition may include two surfactants, where one is an anionic surfactant and the other is an amphoteric surfactant, such as a sulfate-containing anionic surfactant and a betaine-containing amphoteric surfactant where the sulfate-containing anionic surfactant may be sodium laureth sulfate and the betaine-containing amphoteric surfactant may be cocamidopropyl betaine. Optionally, the composition may include two surfactants, where one is an anionic surfactant and the other is an amphoteric surfactant, such as a sulfonate-containing anionic surfactant and a betaine-containing amphoteric surfactant, where the sulfonate-containing anionic surfactant may be sodium

dodecylbenzene sulfonate and the betaine-containing amphoteric surfactant may be cocamidopropyl betaine. Optionally, the composition may include three surfactants, two of the three surfactants being non-identical anionic surfactants and one of the three surfactants being an amphoteric surfactant, where these three surfactants may optionally be a sulfate-containing surfactant, a sulfonate-containing surfactant, and a betaine- containing surfactant, e.g., sodium dodecylbenzene sulfonate, sodium laureth sulfate, and cocamidopropyl betaine. When present, the sulfonate-containing surfactant may be present at a concentration of about 1800 ppm, e.g., 1000-3000 ppm. When present, the sulfate-containing surfactant may be present at a concentration of about 500 ppm, e.g., 100-1000 ppm. When present, the amphoteric surfactant may be present at a

concentration of about 900 ppm, e.g., 500-1500 ppm. The composition will contain an effective amount of an anti-rust agent as described herein, where the anti-rust agent may be, e.g., sodium nitrite. The concentration of the anti-rust agent may be about 100-5000 ppm, or about 1000-3000 ppm, or about 2000 ppm. The inorganic salt is described herein, and may be, for example, calcium chloride. The concentration of the inorganic salt in the composition may be about 50-2000 ppm, or about 100-1000 ppm, or about 400 ppm. The composition may optionally contain, and in one embodiment does contain, a defoaming agent as described herein. An exemplary defoaming agent is a silicone polymer. When present, the defoaming agent may be present at a concentration of about 100-5000 ppm, or about 500-2000 ppm, or about 1000 ppm. Methods of Manufacture

[00123] In one aspect, the present disclosure provides methods of preparing the material fabrication fluid, e.g., the metal cutting fluid concentrate compositions and the corresponding metal cutting fluid compositions as identified herein. In general, the concentrates are prepared by combining water with one or more surfactants selected from anionic and amphoteric surfactants, along with optional ingredients. The compositions are prepared by diluting the concentrate with water or aqueous solution.

[00124] In one embodiment, a concentrate is prepared by combining a first surfactant which is an amphoteric surfactant, a second surfactant which is an anionic surfactant, and a third surfactant selected from an amphoteric and an anionic surfactants, where the third surfactant is other than the first or second surfactants. The concentrate may optionally contain additional surfactant(s), i.e., a fourth, fifth, etc. surfactant. In addition, or alternatively, the concentrate may contain active ingredient(s) other than surfactant, e.g., inorganic components, organic solvents and thickening agents. The compositions are water based, in other words, they are aqueous compositions in that the carrier is primarily water. The compositions may be prepared by any of the following methods.

[00125] In one embodiment, a container of water is provided. This container holds between about 5 and 20 Kg of water. This method may be scaled up or down so as to provide the desired amount of fluid concentrate. The initial amount of water is about 5- 40%, or about 10-30% of the total amount of water in the concentrate. The water may be at ambient temperature or it may be at an elevated temperature. Elevated temperatures of below the boiling point of water, i.e., below 100°C, or below 90°C, or below 80°C, or below 70°C may be used. Elevated temperatures in excess of the ambient temperature, e.g., above 25°C, or above 30°C, or above 40°C, or above 50°C, or above 60°C, or above 70°C may be used.

[00126] The one or more surfactants are then added to the water. In one

embodiment an amphoteric surfactant is added to the water, followed by the sequential addition of a first and second anionic surfactant. In an alternative embodiment, an anionic surfactant is added first to the water, followed by an amphoteric surfactant, which in turn is followed by the addition of either a second anionic surfactant or a second amphoteric surfactant. In another embodiment, the first and second anionic surfactants are added sequentially, followed by the addition of an amphoteric surfactant. [00127] After the addition of a surfactant to the water, the resulting mixture is stirred to provide a homogeneous or near homogeneous state. Stirring may be performed leisurely or vigorously, however in either event it is preferred that undue amounts of foam are not created. Foam typically results from the entrapment of air in the mixture, where air tends to become entrapped when there is a significant vortex created during the mixing process and/or when the stirring device repeated enters and exits the mixture. Foam retention also tends to be greater when the viscosity of the mixture is greater. These situations are preferably avoided in order to minimize foam production. In order to assure good mixing, a stirring time of about 15-60 minutes may be employed after the addition of each surfactant.

[00128] Depending on the presence or absence of insulation surrounding the container in which the concentrate is being prepared, the temperature of the mixture may drop during the surfactant addition and stirring steps. Alternatively, the temperature of the mixture may be maintained at or nearly at the original temperature of the water by, for example, maintaining gentle heating directed to the sides and/or the bottom of the container which holds the concentrate. Alternatively, or additionally, heating coils may be positioned within the container to add or withdraw heat from the concentrate as desired.

[00129] As surfactant is added to the water, the viscosity of the mixture will tend to increase. A solution of increased viscosity will tend to entrap air more readily than does a lower viscosity solution, all other factors being equal. In order to reduce the viscosity of a mixture, additional water may be added to the mixture after the addition of any of the first, second or third surfactants. For example, an amount of water which is about 5-40%, or about 10-30% of the total amount of water in the concentrate may be added to the mixture after the first addition of surfactant. In addition, or alternatively, an amount of water which is about 5-40%, or about 10-30% of the total amount of water in the concentrate may be added to the mixture after the second addition of surfactant.

[00130] After all of the surfactants have been added and thoroughly mixed into the water, optional ingredient(s) may be added to the resulting mixture. For example, an inorganic component, e.g., an inorganic salt, may be added to the mixture, followed by stirring to completely dissolve the inorganic component. The optional ingredient(s) may be added to the warm or hot mixture, or to the mixture after it has cooled down to room temperature. Since the concentrate will typically be stored and used at room temperature, any optional ingredients that will significantly impact the viscosity or flow properties of the mixture are typically added to the mixture at room temperature.

[00131] The surfactants and optional ingredients may be added to the water in a neat form, i.e., without being in contact with a solvent, or may be added in a diluted form, i.e., in contact with a solvent so as to provide a solution, paste, dispersion, etc. of the ingredient. In one embodiment, the surfactants are added to water in the order of their solids content in water, with the more concentrated ingredient being added first. In other words, if a surfactant is at 50% solids and another surfactant is at 25% solids, then the surfactant at 50% solids is added to water before the surfactant at 25% solids is added to the mixture.

[00132] The concentrate may be prepared in a batch, continuous or semi-continuous mode. In a batch mode, ingredients are added sequentially to a container of water, until all of the ingredients have been added, in which case a batch of concentrate has been prepared. In a continuous mode, water is propelled through a pipe or other conduit, and various ingredients are added to the water at various points along the conduit. For example, the conduit may be fitted with T-valves, where an ingredient may be fed into the water, or aqueous mixture, through the T-valve. The conduit may also contain mixers within the conduit, either static or inline mixers, to facilitate the creation of a homogenous mixture after an ingredient has been added to the water or aqueous mixture. For example, water and a first surfactant may be fed into a pipe and pass through a mixer. Typically a static mixer is adequate if the surfactant is pre-dissolved in water. Otherwise, an inline mixer is typically preferred. Thereafter, a second surfactant is added to the conduit downstream of the mixer, which again goes through a mixing process. Finally, a third surfactant is added to the aqueous mixture, following by mixing as needed, so as to provide an aqueous mixture comprising three surfactants. Thereafter, additional, optional ingredients may be added to the conduit, through a T-valve for example, following by suitable stirring, to form the final concentrate.

[00133] To facilitate mixing of the various ingredients, and to minimize vortex formation and consequently foam formation, baffles may be installed within the batch or continuous reactor. Suitable mixing equipment, such as agitators, impellers, static mixers, colloid mills, and homogenizers are made and sold by, e.g., Chemineer (Dayton, Ohio) and Sulzer (Winterthur, Switzerland).

[00134] In an alternative embodiment for a continuous process, three T-valves are located at the beginning of the conduit, at a location after water has already been added to the conduit. The first, second and third surfactants are each delivered into the conduit through one of the three T-valves. In this manner, all of the three surfactants are combined essentially at the same time, and then the resulting mixture is passed through an inline or static mixer within the conduit, to provide a homogenous aqueous mixture. Optional ingredients are then added to the homogeneous aqueous mixture as desired, to provide the final concentrate.

[00135] In either a continuous or batch process, the water and/or aqueous mixture may be heated to a temperature in excess of ambient temperature, e.g., a temperature between 50°C and 90°C. Heating may be accomplished by routine methods known in the art. The elevated temperature may be maintained as needed to facilitate prompt mixing of the ingredients to form a homogeneous mixture.

[00136] Accordingly, in one embodiment, the present disclosure provides a continuous process for making a material fabrication fluid, e.g., a metal cutting fluid concentrated composition. The process comprises providing a continuous reactor, charging water to the continuous reactor, adding to the water in the continuous reactor the desired one or more surfactants, e.g., a) a first anionic surfactant, b) a second amphoteric surfactant, and c) a third surfactant selected from an anionic surfactant and a cationic surfactant, the third surfactant being different from the first surfactant and the second surfactant; and mixing components a), b) and c) to provide a homogeneous mixture. Optionally, the continuous reactor is maintained at a temperature in excess of 50°C. Also optionally, a mixer selected from an inline mixer and a static mixer is present in the continuous reactor.

Method of Use

[00137] The present disclosure provides fabrication fluids, e.g., fluids useful in metal cutting, that may be used in the course of materials fabrication, e.g., cutting metal. In one embodiment, the fluid concentrate of the present disclosure is diluted with water to provide a composition that may be applied to tooling involved in material fabrication, e.g., a metal cutting fluid composition that is applied directly to the metal. The concentrate will have a solids level or content, measured as the sum of the weights of the non-aqueous

components in the concentrate, divided by the total weight of the concentrate. When water is combined with concentrate so as to form a metal cutting fluid composition, the metal cutting fluid composition will likewise have a solids level or content, which will be less than the solids level or content of the concentrate. In various embodiment, the

composition is formed by combining sufficient water with the concentrate so as to provide a metal cutting fluid composition having a weight percent solids, based on the total weight of composition, of 0.1%, or 0.5%, or 1%, or 1.5%, or 2%, or 2.5%, or 3%, or 3.5%, or 4%, or 4.5%, or 5%, or 5.5%, or 6%, or 6,5%, or 7%, or 7.5%, or 8%, or 8.5%, or 9%, or 9.5%, or 10%, or 10.5%, or 11%, or 11.5%, or 12%, or 12.5%, or 13%, or 13.5%, or 14%, or 14.5%, or 15%, or 15.5%, or 16%, or 16.5%, or 17%, or 17.5%, or 18%, or 18.5%, or 19%, or 20%, or a concentration within a range provided any of the two aforesaid solids percent values, e.g., 0.5% to 4%.

[00138] In one aspect, the prepared person will have a supply of metal cutting fluid concentrate in storage, readily available when needed to cut metal, and with access to a method of combining the concentrate with water so as to form a metal cutting fluid composition. Optionally, the metal cutting fluid concentrations as disclosed herein may be diluted with water to create a metal cutting fluid composition.

[00139] Cutting fluid maintenance involves checking the concentration of soluble oil emulsions (using refractometers), pH (using a pH meter), the quantity of tramp oil (hydraulic oil leaking into the cutting fluid system) and the quantity of particulates in the fluid. Action taken to maintain the fluid includes adding make-up concentrate or water, skimming of tramp oil, adding biocides to prevent bacterial growth and filtering the particulates by centrifuging.

[00140] The cutting fluid within a coolant system degrades with time due to bacterial growth and contamination with tramp oil and fine metal swarf from the machining operation. When it becomes uneconomical to maintain the fluid by regular make-up operations it is dumped. Prior to letting the fluid flow into a sewer system, it should be treated to bring the fluid composition to safe disposal levels.

[00141] Some metals are more difficult to machine than others. Stainless steel, exotic alloys and very hard metals demand a very high level of performance from the cutting fluid. Other metals, like brass and aluminum, are easy to machine with general-purpose oils. Where tough, low-machinability metals are involved, it is advantageous to use highly additized cutting oil with excellent extreme-pressure (EP) and anti-weld capability. Most often, these oils contain active sulfur and chlorine to protect the tooling and ensure good parts finish. In one embodiment, the cutting fluid of the present invention include active sulfur and/or chlorine.

[00142] For brass, aluminum, many carbon steels and low-alloy steels, a cutting oil with lubricity additives, friction modifiers and mild EP/anti-weld performance is sufficient. These oils are generally formulated with sulfurized fat (inactive) and/or chlorinated paraffin. Active cutting oils (containing active sulfur) should not be used for brass and aluminum, as they will stain or tarnish the finished parts. Oils formulated for brass and aluminum are often called "non-staining" oils. In one embodiment, the cutting fluid of the present invention includes one or more of lubricity additives, friction modifiers, sulfurized fat (inactive) and chlorinated paraffin.

[00143] Easy machining operations (turning, forming, drilling, milling, etc.) can be performed at higher speeds and require high levels of cooling with only modest EP capability. The milder operations can be performed with lower viscosity, lightly additized fluids. Difficult machining operations must be run at lower speeds and require a great deal of anti-weld protection. Oils designed specifically for the most difficult operations, like thread-cutting or broaching, are generally higher in viscosity and loaded with EP additives like active sulfur and chlorine.

[00144] The type of machinery will also dictate some of the cutting oil characteristics. For example, screw machines experience heavy cross-contamination between the lube oil and cutting oil. For this reason, these machines frequently run on dual-purpose or tri- purpose oils that can be used in the lube boxes, hydraulics and cutting oil sumps.

[00145] Grinders, gun drills and deep-hole drilling machines require lighter viscosity oils for high rates of cooling, good chip and swarf flushing, through-the-tool delivery and high-pressure application without foaming. CNC OEMs may place restrictions on the cutting oil due to potential incompatibility between the cutting fluid and machine components, such as seals. Centerless grinders may require a tougher fluid than surface grinders.

[00146] In general, the compositions of the present disclosure, in a ready-to-use form, may be applied during a material fabrication process. As used herein, material fabrication, which may also be referred to as machining, is a process whereby a tool makes contact with, and is used to modify the shape or surface of, a material by any suitable method, and heat is generated at the contact point between the material and the tooling. Examples include cutting into the material with a blade, drilling a hole in the material with a drill bit, and removing a surface layer of the material with a lathe. Another example of material fabrication is stamping. The composition may be applied to the material being fabricated and/or the tooling that comes into contact with the material being fabricated. Examples of the application process include flooding, spraying, dripping, misting, and brushing the composition onto the part being fabricated and/or the associated tooling that contacts the part being fabricated. The material being fabricated may be, for example, metal, stone or plastic. The composition, after application, will maintain the

tooling/material interface at a relatively cool temperature so that harm, e.g., warpage, is avoided for each of the material being fabricated and the tooling doing the fabricating. The composition may also provide lubricating properties.

[00147] For example, when the fabrication fluid is a metal cutting fluid, the fluid provides coolant and lubricant properties as need for metal working processes, such as machinery and stamping. Metal cutting generates heat due to friction, which can deform the material. Coolants work to remove the heat from the machinery and materials so it can speed the cutting process, making the machines more productive. Besides cooling, cutting fluids also aid the cutting process by lubricating the interface between the tool's cutting edge and the chip. By preventing friction at this interface, some of the heat generation is prevented. This lubrication also helps prevent the chips from being welded onto the tool, which would interfere with subsequent cutting. Most metal working and machining processes can benefit from the use of cutting fluids, depending on the workpiece material.

[00148] The compositions of the present disclosure provide one or more of the following benefits in materials fabrication: keeping the workpiece at a stable temperature (which is critical when working to close tolerances); maximizing the lifetime of the cutting tip by lubricating the working edge and reducing the top welding; ensuring safety for the people handling it (toxicity, bacteria, and fungi) and for the environment upon disposal; and preventing rust on machine parts and cutters.

[00149] A portion of the fabricating equipment will come into contact with the workpiece being fabricated. For example, the fabricating equipment may have a blade that cuts the material during fabrication. The blade may be metal, e.g., stainless steel, or it may be diamond encrusted. Alternatively, the fabricating equipment may be a turning tool such as a latche or a drill, or a polishing or sanding device.

[00150] Thus, the present disclosure provides methods of delivering a fabrication fluid, e.g., a metal cooling composition, as described herein. In one embodiment, the present disclosure provides a method comprising providing a fabrication composition of the present disclosure, applying that composition to one or both of the material being fabricated and the tooling that is being used to fabricate the material, and fabricating the material with the tooling in the presence of the composition of the present disclosure. The method affords cooling and temperature control at the interface where the tooling contact the fabricated material, and/or provides lubrication at that interface.

[00151] For example, the present disclosure provides a method for fabricating a solid material such as metal, stone, plastic, the method comprising providing a composition of the present disclosure, such as a composition comprising water, a first surfactant, a thickening agent, and an anti-rust agent; applying that composition to the material being fabricated, e.g., by brushing, spraying, or pouring the composition onto the material and/or onto the tooling that does the fabricating, where the composition will transfer to the interface of the tooling/ material during the fabrication process; and fabricating that material with tooling in the presence of the composition.

[00152] As another example, the present disclosure provides a method for fabricating a solid material such as metal, stone, plastic, the method comprising providing a

composition of the present disclosure, such as a composition comprising water, a first surfactant, an inorganic salt, and an anti-rust agent; applying that composition to the material being fabricated, e.g., by brushing, spraying, or pouring the composition onto the material and/or onto the tooling that does the fabricating, where the composition will transfer to the interface of the tooling/ material during the fabrication process; and fabricating that material with tooling in the presence of the composition.

[00153] The stone may be, for example, any of granite, limestone, marble, sandstone, slate, basalt, tavertine or quartzite. Other stones may also be fabricated using the compositions of the present disclosure.

[00154] The plastic may be, for example, a pure polymer such as polypropylene and polyethylene, or a plastic composite, such as a composite of polymer and stone, e.g., CORIAN™. The plastic may be a silicon chip or other silicon product such as a silicon wafer or other silicon material used in the semiconductor industry.

[00155] The composition and methods of use thereof according to the present disclosure achieve one or both of a) a reduction in the heat being generated on the cutting surface to improve the quality of the product (e.g., fewer burrs, smoother cut, less deformation (in the case of plastic); and b) increasing the longevity of the fabricating device. In one embodiment, the compositions of the present disclosure contain little or no oil, and accordingly their use eliminates the problem of disposing of toxic oil-based waste that is associated with alternative fabricating fluids.

[00156] The following examples are provided to illustrate embodiments of the present disclosure and are not to be construed as limiting thereon.

Examples

[00157] In the following examples, the indicated commercial products may not have the solids content or the neutralization indicated as being used in the example. In such a case, the commercial product may be diluted with water to the indicted solids content and/or neutralized with acid or base as needed to provide the indicated neutralized form. The thickening agent is added to provide a final viscosity approximately that of whole milk or orange juice.

Example 1

[00158] To about 10 kg of heated water (about 75°C) is sequentially added the following ingredients, each ingredient addition being followed by stirring for a period of about 30 minutes in a manner that minimizes foam formation: first anionic surfactant solution (about 9 kg at about 60% solids in water of branched chain sodium dodecylbenzene sulfonate, e.g., SULFONIC 100 from Stepan Company, after neutralization with sodium hydroxide), amphoteric surfactant solution (about 4.5 kg at about 35% solids in water of cocamidopropylbetaine, e.g., AMPHOSOL CA from Stepan Company), heated water (about 9 kg), second anionic surfactant solution (about 11 kg at about 3% solids in water of sodium lauryl ether sulfate, e.g., CALFOAM ES-703 from Pilot Chemical Co.), and inorganic salt solution (about 2 kg at about 30% solids in water of calcium chloride, where calcium chloride in both solid and solution forms is available from e.g., OxyChem, Ludington, M l). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) and then thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy methyl cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this mixture is added a desired amount of anti-rust agent, and optionally further added are one or both of defoamer and colorant, to provide the final metal cutting fluid concentrate. Example 2

[00159] To about 10 kg of heated water (about 75°C) is sequentially added the following ingredients, each ingredient addition being followed by stirring for a period of about 30 minutes in a manner that minimizes foam formation: first anionic surfactant solution (about 9 kg at about 53% solids in water of triethanolamine dodecylbenzene sulfonate, CALSOFT T60 (Pilot Chemical), amphoteric surfactant solution (about 4.5 kg at about 35% solids in water of sodium cocoamphoacetate, AMPH ITOL 20Y-B (Kao Chemicals), heated water (about 6.5 kg), second anionic surfactant solution (about 14 kg at about 7% solids in water of ammonium lauryl sulfate, EMAL AD-25R (Kao Chemicals)), and inorganic salt solution (about 2 kg at about 30% solids in water of calcium chloride, where calcium chloride in both solid and solution forms is available from e.g., OxyChem, Ludington, M l). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) and then thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy methyl cellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this mixture is added a desired amount of anti-rust agent, and optionally further added are one or both of defoamer and colorant, to provide the final cutting fluid concentrate.

Example 3

[00160] To about 8 kg of heated water (about 75°C) is sequentially added the following ingredients, each ingredient addition being followed by stirring for a period of about 30 minutes in a manner that minimizes foam formation: first anionic surfactant solution (about 8.5 kg at about 53% solids in water of sodium lauryl sulfoacetate, LATHANOL LAL flake (Stepan Co.), amphoteric surfactant solution (about 6.3 kg at about 30% solids in water of lauryl hydroxysultaine, AMPHITOL 20HD, Kao Chemicals), heated water (about 6.5 kg), second anionic surfactant solution (about 14 kg at about 7% solids in water of sodium octyl phenol ethoxylate sulfate, POE-3, POLY- STEP C-OP3S (Stepan Co.)), and inorganic salt solution (about 2 kg at about 30% solids in water of calcium chloride, where calcium chloride in both solid and solution forms is available from e.g., OxyChem, Ludington, M l). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) and then thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy methyl cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this mixture is added a desired amount of anti-rust agent, and optionally further added are one or both of defoamer and colorant, to provide the final cutting fluid concentrate.

Example 4

[00161] To about 8.5 kg of heated water (about 75°C) is sequentially added the following ingredients, each ingredient addition being followed by stirring for a period of about 30 minutes in a manner that minimizes foam formation: first anionic surfactant solution (about 9 kg at about 53% solids in water of polyoxyethylene (10) nonylphenol phosphate, FOSFODET 9Q/22 (Kao Chemicals)), amphoteric surfactant solution (about 5.3 kg at about 35% solids in water of disodium cocoamphodipropionate, CRODATERIC CADP 38 (Croda)), heated water (about 6 kg), second anionic surfactant solution (about 14 kg at about 7% solids in water of sodium dioctyl sulfosuccinate, STEPWET DOS-70 (Stepan Co.)), and inorganic salt solution (about 3.3 kg at about 30% solids in water of calcium chloride, where calcium chloride in both solid and solution forms is available from e.g., OxyChem, Ludington, Ml). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) and then thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy methyl cellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this mixture is added a desired amount of anti-rust agent, and optionally further added are one or both of defoamer and colorant, to provide the final cutting fluid concentrate.

Example 5

[00162] To about 15 kg of heated water (about 75°C) is sequentially added the following ingredients, each ingredient addition being followed by stirring for a period of about 30 minutes in a manner that minimizes foam formation: first anionic surfactant solution (about 5 kg at about 53% solids in water of polyoxyethylene (8) octyl ether carboxylic acid, AKYPO LF2 (Kao Chemical)), amphoteric surfactant solution (about 8.3 kg at about 30% solids in water of cocamidopropylamine oxide, CALOXAM IN E CPO (Pilot

Chemical)), heated water (about 14 kg), second anionic surfactant solution (about 7.5 kg at about 20% solids in water of sodium lauroyl sarcosinate, MAPROSYL 30-B (Stepan Co.)), and inorganic salt solution (about 3.3 kg at about 30% solids in water of calcium chloride, where calcium chloride in both solid and solution forms is available from e.g., OxyChem, Ludington, M l). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) and then thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy methyl cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this mixture is added a desired amount of anti-rust agent, and optionally further added are one or both of defoamer and colorant, to provide the final cutting fluid concentrate.

Example 6

[00163] To about 14 kg of heated water (about 75°C) is sequentially added the following ingredients, each ingredient addition being followed by stirring for a period of about 30 minutes in a manner that minimizes foam formation: first anionic surfactant solution (about 5.6 kg at about 50% solids in water of potassium oleate, ICTEOL K-50 (Kao Chemicals)), amphoteric surfactant solution (about 8.3 kg at about 30% solids in water of cocamidopropyl betaine, CALTAINE C-35 (Pilot Chemical), heated water (about 15 kg), second anionic surfactant solution (about 6 kg at about 20% solids in water of disulfonated diphenyl oxide with linear decyl substitution, DOWFAX CIOL, (Dow Chemical)), and inorganic salt solution (about 3.3 kg at about 30% solids in water of calcium chloride, where calcium chloride in both solid and solution forms is available from e.g., OxyChem, Ludington, M l). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) and then thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy methyl cellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this mixture is added a desired amount of anti-rust agent, and optionally further added are one or both of defoamer and colorant, to provide the final cutting fluid concentrate.

Example 7

[00164] To about 15 kg of heated water (about 75°C) is sequentially added the following ingredients, each ingredient addition being followed by stirring for a period of about 30 minutes in a manner that minimizes foam formation: first anionic surfactant solution (about 5 kg at about 50% solids in water of isopropylamine dodecylbenzene sulfonate, NINATE 411 (Stepan Co.)), amphoteric surfactant solution (about 10 kg at about 30% solids in water of cocamidopropyl hydroxysultaine, AMPHOSOL CS-50 (Stepan), heated water (about 15 kg), second anionic surfactant solution (about 5 kg at about 30% solids in water of sodium dodecylbenzene sulfonate, M ELIOSOL 50X (Kao Chemical), and inorganic salt solution (about 3.3 kg at about 30% solids in water of calcium chloride, where calcium chloride in both solid and solution forms is available from e.g., OxyChem, Ludington, M l). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) and then thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy methyl cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this mixture is added a desired amount of anti-rust agent, and optionally further added are one or both of defoamer and colorant, to provide the final cutting fluid concentrate.

Example 8

[00165] To about 20 kg of heated water (about 75°C) is sequentially added the following ingredients, each ingredient addition being followed by stirring for a period of about 30 minutes in a manner that minimizes foam formation: first anionic surfactant solution (about 8.4 kg at about 50% solids in water of disulfonated diphenyloxide with alkyl substitution, DOWFAX CIOL (Dow Chemical)), amphoteric surfactant solution (about 6.7 kg at about 30% solids in water of lauramidopropylbetaine, AMPHITOL 20AB (Kao Chemicals), heated water (about 12 kg), second anionic surfactant solution (about 4 kg at about 20% solids in water of sodium C14-C16 olefin sulfonate, ALFANOX 46 (Kao Chemical), and inorganic salt solution (about 1.7 kg at about 30% solids in water of calcium chloride, where calcium chloride in both solid and solution forms is available from e.g., OxyChem, Ludington, M l). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) and then thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy methyl cellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this mixture is added a desired amount of anti-rust agent, and optionally further added are one or both of defoamer and colorant, to provide the final cutting fluid concentrate.

Example 9

[00166] To about 10 kg of heated water (about 75°C) is sequentially added the following ingredients, each ingredient addition being followed by stirring for a period of about 30 minutes in a manner that minimizes foam formation: first anionic surfactant solution (about 9 kg at about 60% solids in water of linear chain sodium dodecylbenzene sulfonate, e.g., CALSOFT F90 (Pilot Chemical)), amphoteric surfactant solution (about 4.5 kg at about 35% solids in water of cocamidopropylbetaine, e.g., AMPHOSOL CA from Stepan Company), heated water (about 9 kg), second anionic surfactant solution (about 11 kg at about 3% solids in water of sodium lauryl ether sulfate, e.g., CALFOAM ES-703 from Pilot Chemical Co.), and inorganic salt solution (about 2 kg at about 30% solids in water of calcium chloride, where calcium chloride in both solid and solution forms is available from e.g., OxyChem, Ludington, Ml). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) and then thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy methyl cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this mixture is added a desired amount of anti-rust agent, and optionally further added are one or both of defoamer and colorant, to provide the final cutting fluid concentrate.

Example 10

[00167] To about 10 kg of heated water (about 75°C) is sequentially added the following ingredients, each ingredient addition being followed by stirring for a period of about 30 minutes in a manner that minimizes foam formation: first anionic surfactant solution (about 9 kg at about 60% solids in water of linear chain sodium dodecylbenzene sulfonate, e.g., CALSOFT F90 (Pilot Chemical)), amphoteric surfactant solution (about 4.5 kg at about 35% solids in water of cocamidopropyl betaine, e.g., AM PHOSOL CA from Stepan Company), heated water with dissolved ethylene glycol butyl ether (about 9 kg water and about 1 kg ether), second anionic surfactant solution (about 11 kg at about 3% solids in water of sodium laureth sulfate, e.g., CALFOAM ES-703 from Pilot Chemical Co.), and inorganic salt solution (about 2 kg at about 30% solids in water of calcium chloride, where calcium chloride in both solid and solution forms is available from e.g., OxyChem, Ludington, M l). The resulting mixture is allowed to cool to ambient temperature (about 8 hours) and then thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy methyl cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this mixture is added a desired amount of anti-rust agent, and optionally further added are one or both of defoamer and colorant, to provide the final cutting fluid concentrate.

Example 11

[00168] The present disclosure provides cutting fluids of high solids content (also referred to as high solids centration), which are called concentrates (or cutting fluid concentrates), and which may be diluted with water prior to being used in a machining or fabricating operation. Table 1 identifies various machining operations characterized by the metal being machined and the process being applied to the metal. The processes are exemplary of the processes used in metal working, such as broaching, tapping, hobbing, cutting, drilling, milling, turning, sawing, honing and grinding. Each of these processes benefits from the application of cutting fluid to the metal during the metal working or machining process, where the desired amount of cutting fluid depends not only on the specific process, but also on the identity of the metal being subjected to the process. In addition to identifying various processes, Table 1 identifies 8 common metals, namely, aluminum (Al) alloy, brass, casting iron (also known as cast iron), bronze, low carbon steel, stainless steel, alloy steel and titanium (Ti) alloy. For each process and metal selected, Table 1 indicates the parts of water that may be added to 1 part of a cutting fluid concentrate of the present disclosure in order to create an effective cutting fluid. For example, bronze may be broached using a cutting fluid prepared from 10 parts of water and 1 part of cutting fluid concentrate of the present disclosure. As another example, titanium alloy may be turned using a cutting fluid prepared by combining anywhere from between 5 to 10 parts of water for each 1 part of cutting fluid concentrate of the present disclosure.

Table 1

[00169] Tablet 1 is based on diluting a concentrate of the present disclosure with water. For example, when the desired operation is broaching with bronze, a dilution of the concentrate of the present disclosure with 10-15 parts water is recommended.

[00170] For example, utilizing a concentrate having 18 wt% sodium dodecyl benzene sulfonate, 9 wt% cocamidopropyl betaine, 8 wt% hydroxyethyl cellulose, 5 wt% sodium laureth sulfate, 4 wt% calcium chloride, 2 wt% ethylene glycol butyl ether and 54 wt% water, this is diluted times 10 with water. Anti-rust agent is added at 1.5 x the concentrate/ 10000 ppm based on 1:150 ratio mix. De-foaming agent is added at 0.15 x the concentrate/ 1000 ppm based on 1:150 ratio mix. Colouring agent is added at 0.0000095 x the concentrate (litres) / 10 ppm of 1:150 ratio mix. The anti-rust agent is based on 1% of fully dilution of the concentrate (1:150 ratio mix). The de-foaming agent is based on 0.01% of fully dilution of the concentrate (1:150 ratio mix). An antibacterial agent may optionally be added.

[00171] The efficacy of the metal cutting fluid concentrations and compositions of the present disclosure may be evaluated by one or more test methods that indicate the effectiveness of the composition during a metal cutting operation.

[00172] For example, a vibration test was performed, comparing a cutting fluid composition as described in Example 11, to a commercial emulsion oil. The cutting occurred during a milling operation at a blade movement of 3,000 rotations per minute, and 250 mm/min. Along the x axle, the vibration was measured to be 0.08179268 for a commercial emulsion oil, vs. 0.056828924 for the metal cutting fluid of Example 11, for a 30.5% decrease in vibration amplitude. Along the y axle, the vibration was measured to be 0.07328386 for the same commercial emulsion oil, vs. 0.044023185 for the metal cutting fluid of Example 11, for a 39.9% decrease in vibration amplitude. Along the z axle, the vibration was measured to be 0.077851914 for the same commercial emulsion oil, vs. 0.059323387 for the metal cutting fluid of Example 11, for a 23.8 decrease in vibration amplitude.

[00173] When a roughness test was performed using a milling operation on medium carbon steel, a commercial emulsion oil provided a roughness of 4.972 as the average R _m ax (μιτι), while the metal cutting fluid of Example 11 provided a roughness of 3.913 R _m ax (μηη). Thus, the metal cutting fluid of the present disclosure provided a 21.3% decrease in the roughness of the cut part compared to a commercial emulsion based oil. Example 12

[00174] As shown in Table 1, a 5 to 15-fold dilution of a material fabrication concentrate of the present disclosure is suitably used for a large variety of metal and other machining operations. In one embodiment, the present disclosure provides compositions resulting from 5 to 15 fold dilution of a concentrate of the present disclosure. In one embodiment, the present disclosure provides compositions resulting from a 5-fold dilution of a concentrate of the present disclosure. In another embodiment, the present disclosure provides compositions resulting from a 15-fold dilution of a concentrate of the present disclosure.

[00175] In one embodiment, the present disclosure provides a composition resulting from a 10-fold dilution of a concentrate of the present disclosure. This composition has 0.2 wt% of sodium dodecylbenzene sulfonte, 0.05 wt% sodium laureth sulfate, 0.09 wt% cocamidopropyl betaine, 0.08 wt% hydroxyethyl cellulose, 0.04 wt% calcium chloride, 0.02 wt% ethylene glycol butyl ether. To this diluted solution is added anti-rust agent to a 0.2 wt% amount and defoaming agent to a 0.1 wt% amount.

[00176] This composition can be used in each of the machinery operations identified in Table 1, i.e., broaching, tapping, hobbing, cutting, drilling, milling, turning, sawing, honing or grinding of any of aluminum (Al) alloy, brass, casting iron (also known as cast iron), bronze, low carbon steel, stainless steel, alloy steel and titanium (Ti) alloy.

[00177] Any of the various embodiments described above can be combined to provide further embodiments. All of the U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification and/or listed in the Application Data Sheet are incorporated herein by reference, in their entirety. Aspects of the embodiments can be modified, if necessary to employ concepts of the various patents, applications and publications to provide yet further embodiments. These and other changes can be made to the embodiments in light of the above-detailed description. In general, in the following claims, the terms used should not be construed to limit the claims to the specific embodiments disclosed in the specification and the claims, but should be construed to include all possible embodiments along with the full scope of equivalents to which such claims are entitled. Accordingly, the claims are not limited by the disclosure.