KR20100135218A - Formulation of a metalworking fluid - Google Patents

Abstract

The present invention relates to non-oil metalworking fluids, also known as synthetic metalworking fluids having a processed particle size of greater than 120 nanometers when diluted. The expanded particle size substantially increases lubricity and is suitable for heavy-duty processes previously only achieved by oil-containing products. In addition, this non-oil containing metalworking fluid optionally includes the positive properties of oil-containing products, including good corrosion inhibition and lubricity for use in heavy-duty processes.

Description

FORMULATION OF A METALWORKING FLUID

The present invention relates to a non-oil metalworking fluid, also known as synthetic metalworking fluid.

Metal working is defined as molding a metallic work-piece to a desired set of geometric specifications. Metal processing includes two basic categories: cutting and forming. Cutting processes include grinding, turning, milling, tapping, broaching and hobbing. The forming process includes cold rolling, drawing, forging, stamping and blanking.

Metalworking fluids are essential for both cutting and forming processes. Lubrication must be provided between the work-piece and the tool and cooling must also be provided by removing heat generated during the metalworking process.

Lubrication is defined as the reduction of friction between two moving surfaces. Two major types of lubrication in the metalworking process are hydrodynamic and boundary or extreme pressure (EP) lubrication. Hydrodynamic lubrication involves separating surfaces that are moved by a membrane of liquid lubricant. Boundary or EP lubrication minimizes the wear experienced when surfaces rub against each other. Polymeric lubricants can provide all of these types of lubrication.

The metal working fluid is largely divided into two parts, oily and non-oil. The oily portion includes straight oils, soluble oils, and semi-synthetic oils, all using mineral oils as basic lubricants. Non-oily moieties are known as composites, which comprise a composition of lubricity-providing additives in an aqueous transport system or diluent. Soluble oils and semi-synthetic products have an 80% share of the market, a non-water reducible straight oil portion has a 10% share, and the composite has a 10% market.

The forms of metalworking fluid present have advantages and disadvantages. Oil-containing products have the advantages of good lubricity, a wide range of applications, and barrier protection of sumps from corrosion. Disadvantages of oil-containing metalworking fluids are that water hardness often affects fluid stability, foaming due to the inclusion of higher detergency emulsifiers is often a problem, is accompanied by larger dirt loads, and placement of tanks And more costly to clean the tank, with greater microbial problems.

The use of compounds is encouraged for a number of factors, from environmental issues to microbial benefits. However, the continued use of oil-containing products by most customers is due to their excellent lubricity and increased maintenance corrosion problems associated with composites at low relative costs. Synthetic sumps that lose the protective barrier film supplied by the oil can corrode and "freeze" the processing system bolts, making maintenance difficult. In addition, high lubrication performance synthetic products are expensive compared to similar lubrication performance oil containing products. Their reduced physical lubricity at a price based on semi-composites limits their use in heavy-duty processes.

Summary of the Invention

Aspects of the present invention relate to an entirely new class of metalworking fluid products. This novel compound includes a reciprocal blend of carboxylates, boundary lubricating oil fatty acids, and EO / PO polymers, which may react and, in certain embodiments, may optionally have increased particle size, excellent lubricity, or both. To form a moiety. In addition, the dilution used in certain embodiments is opaque and looks like the appearance of an oil-based solution.

In certain embodiments, the metalworking fluid composition may have a volume average particle size (volume average particle size) of 125 nm or greater, when diluted to 0.1-50% by volume. The composition,

(a) one or more polymeric lubricity agents;

(b) one or more carboxylates;

(c) one or more emulsifiers or dispersants; And

(d) includes a transport component.

Certain embodiments may be synthetic metalworking fluids engineered to show increased lubricity while providing corrosion protection and microbial control.

Detailed description of the invention

In one embodiment, the metallurgical lubricant of the present invention may have a volume average particle size of 125 nm or greater when diluted to 0.1 to 50 volume percent. In one embodiment, the composition of the present invention,

(a) at least one polymeric lubricant;

(b) one or more carboxylates;

(c) one or more emulsifiers or dispersants; And

(d) may contain transport components.

More specifically, the composition of the present invention,

(a) 1 to 80 volume percent of one or more block copolymers as polymer lubricants;

(b) 1 to 40 volume percent of one or more carboxylates;

(c) 1 to 20 volume percent of one or more emulsifiers or dispersants; And

(d) from 1 to 97 volume percent of transport components.

In another embodiment, the composition of the present invention,

(a) 5 to 40 volume percent of one or more block copolymers as polymer lubricants;

(b) 3 to 30 volume percent of one or more carboxylates;

(c) 2 to 12 volume percent of one or more emulsifiers; And

(d) 18 to 97 volume percent of transport components.

In another embodiment, the composition of the present invention,

(a) 15 to 25 volume percent of one or more block copolymers as polymer lubricants;

(b) 5 to 15 volume percent of one or more carboxylates;

(c) 3 to 8 volume percent of one or more emulsifiers or dispersants; And

(d) 52 to 77 volume percent of the transport component.

Each of these components and examples are further described below.

Polymer grease

For example, the polymeric lubricant can be an EO / PO copolymer. EO / PO polymers may include, for example, one or more of the following. The EO / PO copolymer can be a block copolymer having polyoxyethylene chains at both ends and polyoxypropylene blocks at the center. The EO / PO copolymer can be a block copolymer having polyoxypropylene chains at both ends and comprising polyoxyethylene blocks at the center. The EO / PO copolymer can be a tetrablock copolymer derived from the sequential addition of ethylene oxide and propylene oxide to ethylenediamine. The EO / PO copolymer can be an ethylene oxide / propylene oxide copolymer having one or more terminal hydroxyl groups. The EO / PO copolymer can be a water soluble lubricant base stocks of random copolymers of ethylene oxide and propylene oxide. The EO / PO copolymer can be a water soluble polyoxyethylene or polyoxypropylene alcohol or a water soluble carboxylic acid ester of such alcohol. The EO / PO copolymer can be an alcohol-based base stock of all polyoxypropylene groups with one terminal hydroxyl group. EO / PO copolymers are monobasic or dibasic acid esters, polyol esters, polyalkylene glycol esters, polyalkylene glycols grafted with organic acids, phosphate esters, polyisobutylene, polyacrylonitrile, polyacrylamides, poly Vinylpyrrolidone, polyvinyl alcohol, or copolymers of acrylic acid or methacrylic acid and acrylic acid esters.

Particularly contemplated polymers include polypropylene glycol block copolymers, polyethylene glycol block copolymers, or polyethylene glycol / polypropylene glycol block copolymers.

Carboxylate

Partially neutralized carboxylates are contemplated to provide hydrophobic moieties for polymer lubricants in the network and to provide engineering of larger particle sizes. Salts can be prepared, for example, by partial neutralization of free carboxylic acids, fats, or oils using any of the alkaline agents described herein. Particularly contemplated salts include cation salts of alkali metals or alkanolamines, such as sodium salts (eg, prepared by treating acid with sodium hydroxide). The pH of the partial neutralization depends on the alkaline agent used. Many of these carboxylate salts additionally provide their own boundary lubrication.

The carboxylic acid used as feedstock may be a linear or branched, saturated or unsaturated free carboxylic acid. The acid may be saturated or unsaturated and the unsaturated position may be in cis or trans configuration. The acid can be a dicarboxylic acid, tricarboxylic acid, or ester, amine, amide, or ethoxylated derivative of carboxylic acid. Alternatively, animal or vegetable fats or oils can be directly neutralized to provide carboxylates.

The following are some examples of carboxylic acids or their sources to be considered: capric acid (also known as hexanoic acid), enantiic acid (also known as heptanoic acid), caprylic acid (also known as octanoic acid), and pelagonic acid (furnace) Also known as nanic acid), isononanoic acid, capric acid (also known as decanoic acid), neodecanoic acid, lauric acid (also known as dodecanoic acid), stearic acid (also known as octadecanoic acid), arachidic acid ( Also known as eicosanoic acid), palmitic acid (also known as hexadecanoic acid), erucic acid, oleic acid, arachidonic acid, linoleic acid, linolenic acid, myristic acid (also known as tetradecanoic acid), behenic acid (as docosanic acid) Also known), alpha-linolenic acid, docosahexanoic acid, ricinonoic acid, butyric acid, lard oil, tallow oil, butter, coconut oil, palm oil, cottonseed oil, wit oil, soya oil, olive oil, corn oil, sunflower oil And rapeseed or canola oil.

Emulsifier or Dispersant

Dilution of the metalworking fluid composition with water forms an opaque emulsion. At concentrations above 10%, the emulsion may require stabilization. Emulsifiers or dispersants are contemplated to provide stabilization of the planned large particle emulsion.

Emulsifiers or dispersants may be one or more of the following: alkanolamides, alkylaryl sulfonates, alkylaryl sulfonic acids, amine oxides, amides and amine soaps, block copolymers, carboxylated alcohols, carboxylic acids or fatty acids, ethoxylated Alcohols, ethoxylated alkylphenols, ethoxylated amines or amides, ethoxylated fatty acids, ethoxylated fatty acid esters and oils, ethoxylated phenols, fatty amines and esters, glycerol esters, glycol esters, imidazolines and already Dazoline derivatives, lignin and lignin derivatives, maleic or succinic anhydrides, methyl esters, monoglycerides and derivatives, naphthenic acid, olefin sulfonates, phosphate esters, polyalkylene glycols, polyethylene glycols, polyols, polymers (polysaccharides, acrylic acid , Acrylamide), propoxylated and ethoxylated fatty acids, alcohols Are alkyl phenols, quaternary surfactants, sarcosine derivatives, soaps, sorbitan derivatives, sucrose and glucose esters and derivatives, sulfates and sulfonates of oils and fatty acids, sulfates and sulfonates of ethoxylated alkylphenols, Sulfates, ethoxylated alcohols, or fatty acid esters of alcohol, dodecyl and tridecylbenzene, naphthalene, alkyl naphthalene, or sulfonates, sulfosuccinamate, sulfosuccinates and derivatives of petroleum, or tridecyl and dodecyl benzene Sulfonic acid.

Corrosion inhibitor

Oil-containing products rely heavily on the oil itself to form a boundary coating of corrosion protection. Non-oil containing products can optionally achieve this corrosion protection by chemical means. Corrosion inhibitors are chemical compounds that, when added in small concentrations, stop or slow the corrosion of metals and alloys.

Some mechanisms for corrosion inhibitors include a passivation layer that inhibits the oxidation or reduction portion of the redox corrosion system (anode and cathode inhibitors) or scavenges dissolved oxygen; Formation of a thin film on the surface).

There are many other substances included in this group. Some examples include alkali and alkanolamine salts of carboxylic acids, undecanoic acid or dodecanoic acid or salts thereof, C _{4 -22} carboxylic acids or salts thereof, boric acid and salts thereof, tolytriazole and salts thereof, benzotriazole And salts thereof, imidazolines and salts thereof, alkanolamines and amides, sulfonates, alkali and alkanolamine salts of naphthenic acid, phosphate ester amine salts, alkali nitrites, alkali carbonates, carboxylic acid derivatives, alkylsulfonamides Carboxylic acids, arylsulfonamide carboxylic acids, fatty sarkosides, phenoxy derivatives and sodium molybdate.

Alkali

In some instances to maintain alkaline and pH buffering, the alkaline agent provides the desired pH for the product. Examples of alkali agents are alkanolamines-primary, secondary and tertiary, aminomethylpropanol (AMP-95), diglycolamine (DGA), monoethanolamine (MEA), monoisopropanolamine (MIPA), butylethanolamine (NBEA), dicyclohexylamine (DCHA), diethanolamine (DEA), butyl diethanolamine (NBDEA), triethanolamine (TEA), metal alkali hydroxides, potassium hydroxide, sodium hydroxide, magnesium Hydroxides, lithium hydroxides, metal carbonates and bicarbonates, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, but are not limited to these. Preferred alkali agents for certain embodiments are metal alkali hydroxides.

The pH contemplated for the composition is optionally 3 or more, optionally 3 to 10, optionally 4 to 9, optionally 4 to 8.

Other ingredients

The composition may also include anti-foaming agents and / or biocides or bactericides as well as any other common or novel additives.

Transportation components

Preferred transport components, which may also be referred to as dispersion medium or vehicle, are mainly, optionally entirely, water. Optionally, however, the composition may contain one or more oils, preferably less than 10 volume percent. These can be any common lubricants. Given the mixed oil and water transport components, emulsifiers can be used to make a stable emulsion of water and oil.

The positive properties of current useful non-oil products are optionally maintained in this composition as well as optionally including one, one or more, or all of the following: environmental compliance, good cooling, good chip removal or setting properties, long Sump life and good biological resistance.

In the claimed invention, the processed metal fluid composition, when diluted to 0.1 to 50 volume percent, may have a lubricity of less than 8000 Newton-cm ^{- 1 as} measured by tapping torque instruments.

 The composition may optionally have one or more of the following desirable properties in a low-oil (ie up to 10 vol% oil) or substantially or completely oil-free formulation:

● lubricity of oil-containing products,

Lubricity / cost-to-performance ratio points close to that of oil-containing products,

Reduced worker irritation (irritation is associated with higher pH products),

Rust or other corrosion protection of oil-containing products; or

• Chemistry without alkanolamines.

Particle size

As can be seen in the examples below, the formulated compositions of the present invention contain particles. Although the present invention is not limited by the accuracy of this theory, larger particles are considered to provide greater lubricity. The contemplated particles of any embodiment are optionally 120 to 100,000 nanometers (nm), alternatively 120 to 100,000 nm, alternatively 120 to 10,000 nm, alternatively 120 to 5000 nm, alternatively 125 to 10,000 nm Alternatively 125 to 5000 nm, alternatively 125 to 2000 nm, alternatively 140 to 10,000 nm, alternatively 140 to 5000 nm, alternatively 140 to 2000 nm, alternatively 200 to 10,000 nm, Alternatively 200 to 5,000 nm, alternatively 200 to 2000 nm, alternatively 220 to 10,000 nm, alternatively 220 to 5,000 nm, alternatively 220 to 2000 nm, alternatively 350 to 10,000 nm, alternatively With a volume average diameter of 350 to 5,000 nm, alternatively 350 to 2,000 nm.

Example

The foregoing may be better understood with reference to the following examples, which are intended to illustrate the method for carrying out the invention, but are not intended to limit the scope of the invention.

Example 1:

From materials A in Table 1, E was used in a tapping torque process involving tapping of 6061 aluminum. Prior to testing, the concentrate was first diluted to 7.5% by volume solution. The tapping torque test is a quantitative measure of the lubricity performance of a metal working fluid. It has an ASTM standard method designation of D5619. Tapping torques reflect industrial machining processes in a better way than other tests, which are usually done by rubbing two metal surfaces together. This is an excellent way to distinguish the performance of metalworking fluid (MWF) products in the laboratory. Tapping torque results have been found to correlate well with the field of machining operations.

The tapping torque device is designed to measure the lubricity of the MWF during the actual cutting. During the tapping process, the tapping torque device measures 250 times the torque instantaneously than the tap advance over the depth of the cut. Specialized software then facilitates data analysis. The tapping torque is expressed in units of N-m (Newton-meters) or N-cm (Newton-cm). Highly lubricating products will produce lower torque values. On the other hand, low lubricity products will produce high torque values. In this method, the device quantifies the difference in lubricity performance between products.

A disadvantage of the tapping torque device is that the measured absolute torque value depends on and is varied by the diameter of the tap used. Therefore, in order to eliminate these geometric effects, it is effective to express lubricity as torque per area and describe the energy it takes for the tap to rotate one turn. Formula for this is,

E / A = (2'r) / r2

Where t = torque value, r = radius of tap, E / A = energy per area and unit is Nm ⁻¹ (Newtons per meter) or N-cm ⁻¹ (Newtons per centimeter).

Lubricity data identified as E / A is shown in Table 1. The lower the E / A value, the better the lubricity and processing performance. All samples were diluted to 7.5% by volume with water prior to testing.

Example 2:

The materials in Table 1 were used in particle size processes involving the measurement of volume average particle size in nanometers. Prior to testing, the concentrate was first diluted with 7.5 volume% solution using water. The particle sizing device uses high efficiency dynamic light scattering to quantify particle sizes of 20 to 100,000 nanometers.

All samples were diluted to 7.5% by volume prior to testing. The resulting particle size is shown in Table 1.

Example 3:

Material C from Table 1 was measured at two different concentrations for particle size, and appearance and emulsion stability were evaluated at each concentration. The results are shown in Table 2, which shows large average particle size, opaque appearance, and good stability at each concentration. Larger particle sizes are a feature of better lubricants. Typical synthetic MWFs, when diluted, form a clear solution with a particle size of less than 100 nanometers. Dilutions of Sample C have a particle size of 3.5 to 20 times larger than the maximum particles shown by a typical synthetic MWF.

Examples 1-3 show that the optimum lubricity and particle size are obtained from Sample C with 10% carboxylic acid-alkali salt and 20% flonic “R” block copolymer combined. This ratio gives the maximum volume average particle size and maximum lubricity.

It is also clear from the examples that most of the time, the lubricity of the composition is correlated with its volume average particle size. Increased volume average particle size results in increased lubricity.

Example 3 shows that increased concentrations of Sample C exhibit a significantly larger volume average particle size. This explains the need for an emulsifier to stabilize higher concentrations of sample C. In the absence of an emulsifier, higher concentrations of particle size are expected to continue to agglomerate and become unstable.

It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the invention and without diminishing its intended advantages. Accordingly, such changes and modifications are intended to fall within the scope of the appended claims.

Claims (24)

(a) at least one polymeric lubricant;
(b) one or more carboxylates;
(c) one or more emulsifiers or dispersants; And
(d) includes transportation components,
A metalworking fluid composition having a volume average particle size of 125 nm or greater when diluted to 0.1 to 50 volume percent. The metalworking fluid composition of claim 1, comprising one or more oils in less than 10 volume percent. 3. The metalworking fluid composition of claim 1 or 2, wherein the transport component comprises water. 4. The metalworking fluid composition of any one of claims 1 to 3 comprising a corrosion inhibiting component. The corrosion inhibiting component according to any one of claims 1 to 4, wherein the corrosion inhibiting component is an alkali and alkanolamine salt of carboxylic acid, undecanoic acid or dodecanediic acid and salts thereof, C _{4 -22} carboxylic acid and salts thereof, boric acid , Compounds and salts thereof, tolytriazole and salts thereof, benzotriazole and salts thereof, imidazolines and salts thereof, alkanolamines and amides, sulfonates, alkali and alkanolamine salts of naphthenic acid, phosphate esters A metal working fluid composition comprising one or more of amine salts, alkali nitrites, alkali carbonates, carboxylic acid derivatives, alkylsulfonamide carboxylic acids, arylsulfonamide carboxylic acids, fatty sarkosides, phenoxy derivatives, and sodium molybdate. The metalworking fluid composition of claim 1, wherein the pH is 3-9. 7. 7. The metalworking fluid composition of any one of claims 1 to 6, comprising an alkaline agent. The method of claim 7, wherein the alkali agent is alkanolamine-primary, secondary and tertiary, aminomethylpropanol (AMP-95), diglycolamine (DGA), monoethanolamine (MEA), monoisopropanolamine (MIPA). ), Butylethanolamine (NBEA), dicyclohexylamine (DCHA), diethanolamine (DEA), butyl diethanolamine (NBDEA), triethanolamine (TEA), metal alkali hydroxide, potassium hydroxide, sodium A metal working fluid composition comprising at least one of hydroxide, magnesium hydroxide, lithium hydroxide, metal carbonates and bicarbonates, sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate. The metal working fluid composition according to claim 7 or 8, wherein the alkali agent is a metal alkali hydroxide. 10. The metalworking fluid composition of any one of claims 1 to 9, comprising an anti foaming agent. 11. The metalworking fluid composition of any one of claims 1 to 10, comprising a biocide and / or a bactericide. 12. The metalworking fluid composition of any one of claims 1 to 11, wherein the polymer lubricant is a block copolymer. 13. The block copolymer according to any one of claims 1 to 12, wherein the polymer lubricant has a polyoxyethylene chain at both ends and comprises a polyoxypropylene block at the center, and has a polyoxypropylene chain at both ends and at the center. Block copolymers comprising polyoxyethylene blocks, tetrablock copolymers derived from sequential addition of ethylene oxide and propylene oxide to ethylenediamine, ethylene oxide / propylene oxide copolymers having one or more terminal hydroxyl groups, ethylene oxide and propylene Water-soluble lubricating oil base stocks of random copolymers of oxides, water-soluble polyoxyethylene or polyoxypropylene alcohols or water-soluble carboxylic acid esters of such alcohols, alcohol-starting of all polyoxypropylene groups having one terminal hydroxyl group ( alcohol-started ) Base stock, mono and dibasic acid esters, polyol esters, polyalkylene glycol esters, polyalkylene glycols grafted with organic acids, phosphate esters, polyisobutylene, polyacrylonitrile, polyacrylamides, polyvinylpi A metalworking fluid composition which is at least one of lollidon, polyvinyl alcohol and copolymers of acrylic or methacrylic acid and acrylic acid esters. 14. The metalworking fluid composition of any one of claims 1 to 13, wherein the polymer lubricant is a polypropylene glycol block copolymer. The metalworking fluid composition of claim 1, wherein the polymer lubricant is a polyethylene glycol block copolymer. 16. The metalworking fluid composition of any one of claims 1 to 15, wherein the polymer lubricant is a polyethylene glycol / polypropylene glycol block copolymer. The metalworking fluid composition of claim 1, wherein the carboxylic acid salt is an alkali and / or alkanolamine salt of a C ₄ -C ₂₂ carboxylic acid or a fatty acid and an ester. 18. The carboxylate according to any one of claims 1 to 17, wherein the carboxylate is butanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, isononanoic acid, decanoic acid, neodecanoic acid, dodecanoic acid, tetradecanoic acid, Hexadecanoic acid, octadecanoic acid, oleic acid, linoleic acid, linolenic acid, alpha-linolenic acid, ricinoleic acid, eicosane acid, docosanic acid, docosahexaic acid, erucic acid, arachidonic acid, lard oil, tallow oil, butter, coconut A metalworking fluid composition comprising at least one of oil, palm oil, cottonseed oil, wheat germ oil, soya oil, olive oil, corn oil, sunflower oil and rapeseed or canola oil. The method of claim 1, wherein the emulsifier or dispersant is an alkanolamide, alkylaryl sulfonate, alkylaryl sulfonic acid, amine oxide, amide and amine soap, block copolymer, carboxylated alcohol, carboxylic acid. Or fatty acids, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated amines or amides, ethoxylated fatty acids, ethoxylated fatty acid esters and oils, ethoxylated phenols, fatty amines and esters, glycerol esters, glycol esters, Imidazoline and imidazoline derivatives, lignin and lignin derivatives, maleic acid or succinic anhydride, methyl esters, monoglycerides and derivatives, naphthenic acid, olefin sulfonates, phosphate esters, polyethylene glycols, polyols, polymers (polysaccharides, acrylic acid , Acrylamide), propoxylated and ethoxylated fatty acids, alcohols or eggs Phenols, quaternary surfactants, sarcosine derivatives, soaps, sorbitan derivatives, sucrose and glucose esters and derivatives, sulfates and sulfonates of oils and fatty acids, sulfates and sulfonates of ethoxylated alkylphenols, alcohols Sulfates, sulfates of ethoxylated alcohols, sulfates of fatty acid esters, sulfonates of dodecyl and tridecylbenzene, sulfonates of naphthalene and alkyl naphthalenes, sulfonates of petroleum, sulfosuccinamate, sulfosuccinates and derivatives, or A metal working fluid composition comprising at least one of tridecyl and dodecyl benzene sulfonic acid. Of less than ^one-of claims 1 to 19 when the method according to any one of claims, wherein the metalworking fluid composition, diluted to 0.1 to 50 volume percent, the tapping torque device (tapping torque instruments) of 8000 Newton-cm as measured by the A metal working fluid composition having lubricity. The method according to any one of claims 1 to 20,
(a) 1 to 80 volume percent of one or more block copolymers;
(b) 1 to 40 volume percent of one or more carboxylates;
(c) 1 to 20 volume percent of one or more emulsifiers; And
(d) a metalworking fluid composition comprising a transport component. The method according to any one of claims 1 to 21,
(a) 5 to 40 volume percent of one or more block copolymers;
(b) 3 to 30 volume percent of one or more carboxylates;
(c) 2 to 12 volume percent of one or more emulsifiers; And
(d) a metalworking fluid composition comprising a transport component. The method according to any one of claims 1 to 22,
(a) 15-25 volume percent of one or more block copolymers;
(b) 5 to 15 volume percent of one or more carboxylates;
(c) 3 to 8 volume percent of one or more emulsifiers; And
(d) a metalworking fluid composition comprising a transport component. 24. The process of any of claims 1 to 23, wherein 120 to 100,000 nanometers (nm), alternatively 125 to 10,000 nm, 140 to 10,000 nm, alternatively 220 to 10,000 nm, alternatively 350 to 5,000 nm, alternatively a metal working fluid composition having a volume average diameter of 350 to 2,000 nm.