WO2009076151A1

WO2009076151A1 - Formulation of a metalworking fluid

Info

Publication number: WO2009076151A1
Application number: PCT/US2008/085483
Authority: WO
Inventors: Lloyd E. Hundley; Ji Cui
Original assignee: Chemetall Corp
Current assignee: Chemetall Corp
Priority date: 2007-12-10
Filing date: 2008-12-04
Publication date: 2009-06-18
Anticipated expiration: 2010-06-10
Also published as: MX2010006315A; EP2075319A1; KR20160120787A; CA2708595A1; JP2011506683A; CN106635320A; US20090149359A1; JP5704921B2; MX360113B; BRPI0822063A2; KR20100135218A; CA2708595C; CN101970621A

Abstract

Non-oil containing metalworking fluids, also known as synthetic metalworking fluids having an engineered particle size of greater than 120 nanometers upon dilution. The expansive particle size results in a substantial increase in lubricity, suitable for the heavy-duty operations previously attainable only with oil-containing products. Additionally, this non-oil containing metalworking lubricant optionally incorporates positive attributes of oil-containing products, including excellent corrosion inhibition and heavy-duty operation capable lubricity.

Description

FORMULATION OF A METALWORKING FLUID

RELATED APPLICATIONS

[0001] [Not Applicable]

FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [0002] [Not Applicable]

[MICROFICHE/COPYRIGHT REFERENCE]

[0003] [Not Applicable]

BACKGROUND OF THE INVENTION

[0004] This invention relates to non-oil containing metalworking fluids, also known as synthetic metalworking fluids. [0005] Metalworking is defined as shaping metallic work-pieces to conform to a desired set of geometric specifications. Metalworking comprises two basic categories, cutting and forming. Cutting operations include grinding, turning, milling, tapping, broaching and hobbing. Forming operations include hot and cold rolling, drawing, forging, stamping and blanking. [0006] Metalworking fluids are essential in both cutting and forming operations. They must provide for lubrication between the work-piece and tool and also provide cooling by removing the heat generated during the metalworking operations.

[0007] Lubrication is defined as the reduction of friction between two moving surfaces. The two main types of lubrication in metalworking operations are hydrodynamic and boundary or extreme pressure (EP). Hydrodynamic lubrication involves separating the moving surfaces by a film of fluid lubricant. Boundary or EP lubrication minimizes the wear experienced when surfaces rub together. Polymeric lubricity agents can provide both types of lubrication. [0008] Metalworking fluids are classified into two main segments, oil containing and non-oil containing. The oil-containing segment comprises straight oils, soluble oils, and semi-synthetics, all of which utilize mineral oil as the primary lubricant. The non-oil segment is known as synthetics, which include compositions of lubricity-producing additives in an aqueous transport system or diluent. The soluble oil and semi-synthetic products enjoy an 80% share of the market, the non-water reducible straight oils segment have a 10% share, while the synthetics comprise 10% of the market.

[0009] Existing types of metalworking fluids have advantages and drawbacks. The oil containing products have the advantages of excellent lubricity, a wide range of applications, and barrier protection of sumps from corrosion. The drawbacks of oil-containing metalworking fluids are that water hardness often impacts the fluid stability, foaming is a frequent problem due to their inclusion of higher detergency emulsifiers, they entrain a greater dirt load, they cost more to dispose of and to clean out of a tank, and they have greater microbial problems.

[0010] The use of synthetics is encouraged for a variety of factors from environmental issues to the microbial advantages. However, most customers continue to use oil containing products because of their good lubricity at a low comparative cost, and because of the increased maintenance corrosion issues associated with synthetics. Synthetic sumps, lacking the protective barrier film provided by oil, can corrode and "freeze" machining system bolts, making maintenance difficult. Additionally, high lubricity performance synthetic products are expensive when compared with similar lubricity performance oil containing products. Their reduced physical lubricity on a cost basis with semi-synthetics restrains their use in heavy-duty operations.

BRIEF SUMMARY OF THE INVENTION

[0011] An aspect of the invention relates to an entirely new class of metalworking fluid products. This new chemistry incorporates a synergistic blend of carboxylic acid salts, boundary lube fatty acids, and EO/PO polymers, which react to form a moiety which, in certain embodiments, may optionally have enhanced particle size, exceptional lubricity or both. In addition, for certain embodiments use dilutions are opaque and mimic the appearance of oil-based solutions.

[0012] In certain embodiments, the metalworking fluid compositions can have a volume average particle size of 125 nm or greater when diluted between

0.1 and 50 percent by volume. The compositions comprise:

(a) one or more polymeric lubricity agents;

(b) one or more carboxylic acid salts;

(c) one or more emulsifying or dispersing agents; and (d) a transport component.

[0013] Certain embodiments can be synthetic metalworking fluids that demonstrate an engineered increase in lubricity while still providing corrosion protection and microbial control.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS [0014] [Not Applicable]

DETAILED DESCRIPTION OF THE INVENTION

[0015] In an embodiment, the present metalworking lubricants can have a volume average particle size of 125 nm or greater when diluted between 0.1 and 50 percent by volume. In one embodiment, the compositions can comprise: (a) one or more polymeric lubricity agents;

(b) one or more carboxylic acid salts;

(c) one or more emulsifying or dispersing agents; and

(d) a transport component.

[0016] More particularly, the compositions can comprise: (a) 1 to 80 percent by volume of one or more block copolymers as the polymeric lubricity agent;

(b) 1 to 40 percent by volume of one or more carboxylic acid salts; -A-

(c) 1 to 20 percent by volume of one or more emulsifying or dispersing agents; and

(d) 1 to 97 percent by volume of a transport component. [0017] In another embodiment, the compositions can comprise: (a) 5 to 40 percent by volume of one or more block copolymers as polymeric lubricity agents;

(b) 3 to 30 percent by volume of one or more carboxylic acid salts;

(c) 2 to 12 percent by volume of one or more emulsifying agents; and

(d) 18 to 90 percent by volume of a transport component. [0018] In yet another embodiment, the compositions can comprise:

(a) 15 to 25 percent by volume one or more block copolymers as polymeric lubricity agents;

(b) 5 to 15 percent by volume of one or more carboxylic acid salts;

(c) 3 to 8 percent by volume one or more emulsifying or dispersing agents; and

(d) 52 to 77 percent by volume of a transport component. [0019] Each component and examples of it is further described below.

POLYMERIC LUBRICITY AGENTS

[0020] The polymeric lubricity agents can be, for example, EO/PO copolymers. The EO/PO polymers can comprise, for example one or more of the following. The EO/PO copolymers can be block copolymers having a central polyoxypropylene block with a polyoxyethylene chain at either end. The EO/PO copolymers can be block copolymers comprising a central polyoxyethylene block with a polyoxypropylene chain at either end. The EO/PO copolymers can be tetrablock copolymers derived from the sequential addition of ethylene oxide and propylene oxide to ethylenediamine. The EO/PO copolymers can be ethylene oxide / propylene oxide copolymers having at least one terminal hydroxyl group. The EO/PO copolymers can be water-soluble lubricant base stocks of random copolymers of ethylene oxide and propylene oxide. The EO/PO copolymers can be a water-soluble polyoxyethylene or polyoxypropylene alcohol or a water- soluble carboxylic acid ester of such alcohol. The EO/PO copolymers can be alcohol-started base stocks of all polyoxypropylene groups with one terminal hydroxyl group. The EO/PO copolymers can be monobasic or dibasic acid esters, polyol esters, polyalkylene glycol esters, polyalkylene glycols grafted with organic acids, phosphate esters, polyisobutylenes, polyacrylonitriles, polyacrylamides, polyvinylpyrrolidones, polyvinyl alcohols, or copolymers of acrylic acid or methacrylic acid and an acrylic ester. [0021] Specifically contemplated polymers include a polypropylene glycol block copolymer, a polyethylene glycol block copolymer, or a polyethylene glycol/ polypropylene glycol block copolymer.

CARBOXYLIC ACID SALTS

[0022] Partially neutralized carboxylic acid salts are contemplated to provide a lipophilic moiety for the polymeric lubricity agents to network with and provide for the engineering of a larger particle size. The salts can be made, for example, by partial neutralization of free carboxylic acids, fats, or oils using any of the alkaline agents described in this specification. Specifically contemplated cations of the salts include alkali metal or alkanolamine salts, such as a sodium salt (made for example by treating an acid with sodium hydroxide). The pH of the partial neutralization is dependent upon the alkaline agent used. Many of these carboxylic acid salts additionally provide their own boundary lubrication as well.

[0023] The carboxylic acids used as feedstocks can be linear or branched, saturated or unsaturated free carboxylic acids. The acids can be saturated or unsaturated, and sites of unsaturation can be cis or trans configured. The acids can be dicarboxylic acids, tricarboxylic acids, or ester, amine, amide, or ethoxylated derivatives of carboxylic acids. Alternatively, fats or oils of animal or vegetable origin can be neutralized directly to provide the carboxylic acid salts.

[0024] The following are some of the examples of contemplated carboxylic acids or sources of same: caproic (also known as hexanoic) acid, enanthic (also known as heptanoic) acid, caprylic (also known as octanoic) acid, pelargonic (also known as nonanoic) acid, isononanoic acid, capric (also known as decanoic) acid, neodecanoic acid, lauric (also known as dodecanoic) acid, stearic (also known as octadecanoic) acid, arachidic (also known as eicosanoic) acid, palmitic (also known as hexadecanoic) acid, erucic acid, oleic acid, arachidonic acid, linoleic acid, linolenic acid, myristic (also known as tetradecanoic) acid, behenic (also known as docosanoic acid, alpha-linolenic acid, docosahexanoic acid, ricinoleic acid, butyric acid, lard oil, tallow oil, butter, coconut oil, palm oil, cottonseed oil, wheat germ oil, soya oil, olive oil, corn oil, sunflower oil and rapeseed or canola oil.

EMULSIFYING OR DISPERSING AGENTS

[0025] Diluting the metalworking fluid composition with water forms an opaque emulsion. At a concentration above 10%, the emulsion may require stabilization. Emulsifying or dispersing agents are contemplated to provide stabilization of the engineered large particle emulsion. [0026] The emulsifying or dispersing agents may be one or more of the following: alkanolamides, alkylaryl sulfonates, alkylaryl sulfonic acids, amine oxides, amide 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 esters and oils, ethoxylated phenols, fatty amines and esters, glycerol esters, glycol esters, imidazolines and imidazoline derivatives, lignin and lignin derivatives, maleic or succinic anhydrides, methyl esters, monoglycerides and derivatives, naphthenic acids, olefin sulfonates, phosphate esters, polyalkylene glycols, polyethylene glycols, polyols, polymeric (polysaccharides, acrylic acid, acrylamide), propoxylated & ethoxylated fatty acids, alcohols or 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 of alcohols, ethoxylated alcohols, or fatty esters, sulfonates of dodecyl and tridecylbenzenes, naphthalene, an alkyl naphthalene, or petroleum, sulfosuccinamates, sulfosuccinates and derivatives, or tridecyl and dodecyl benzene sulfonic acids.

CORROSION INHIBITING COMPONENT

[0027] Oil-containing products rely heavily on the oil itself to form a barrier coating of corrosion protection. Non-oil-containing products optionally can attain this corrosion protection by chemical means. A corrosion inhibitor is a chemical compound that, when added in a small concentration, stops or slows down the corrosion of metals and alloys.

[0028] Some of the mechanisms for the corrosion inhibitors are the formation of a passivation layer (a thin film on the surface of the material that stops access of the corrosive substance to the metal), inhibiting either the oxidation or reduction part of the redox corrosion system (anodic and cathodic inhibitors), or scavenging the dissolved oxygen.

[0029] There are many different materials that fall into this group. Some examples are alkali and alkanolamine salts of carboxylic acids, undecandioic or dodecanedioic acid or their salts, C₄-₂₂ carboxylic acids or their salts, boric acid and its salts, tolytriazole and its salts, benzotriazoles and their salts, imidazolines and their salts, alkanolamines and amides, sulfonates, alkali and alkanolamine salts of naphthenic acids, phosphate ester amine salts, alkali nitrites, alkali carbonates, carboxylic acid derivatives, alkylsulfonamide carboxylic acids, arylsulfonamide carboxylic acids, fatty sarkosides, phenoxy derivatives and sodium molybdate.

ALKALINITY AGENTS

[0030] Alkalinity agents provide for the desired pH of the product and, in some cases for reserve alkalinity and pH buffering. Examples of the alkalinity agents include but are not limited to alkanolamines - primary, secondary and tertiary, aminomethylpropanol (AMP-95), diglycolamine (DGA), monoethanolamine (MEA), monoisopropanolamine (MIPA), butylethanolamine (NBEA), dicylclohexylamine (DCHA), diethanolamine (DEA), butyldiethanolamine (NBDEA), triethanolamine (TEA), metal alkali hydroxides, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, metal carbonates and bicarbonates, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate. A preferred alkalinity agent for certain embodiments is a metal alkali hydroxide. [0031] The pH contemplated for the composition optionally is 3 or greater, optionally from 3 to 10, optionally from 4 to 9, optionally from 4 to 8.

OTHER INGREDIENTS

[0032] The composition can also contain an anti-foaming agent and/or a biocide or a fungicide, as well as any other conventional or novel additives.

TRANSPORT COMPONENT

[0033] The preferred transport component, which can also be referred to as the dispersion medium or vehicle, is largely, optionally entirely, water. Optionally, however, the composition may contain one or more oils, preferably at less than 10 percent by volume. These may be any conventional lubricating oils. An emulsifier can be used to make a stable emulsion of the oil with water, if a composite oil and water transport component is contemplated.

[0034] The positive attributes of currently available non-oil products optionally are maintained in this composition as well as optionally including one, more than one, or all of the following: environmental compliance, good cooling, good chip removal or settling characteristics, long sump life and good biological resistance.

[0035] In the claimed invention, the working metal fluid composition, when diluted between 0.1 and 50 percent by volume can have a lubricity, measured by tapping torque instruments, of less than 8000 Newton-cm^"1. [0036] The compositions may optionally have one or more of the following favorable properties in a low-oil (i.e. no more than 10% by volume oil) or an essentially or entirely oil-free formulation:

• the lubricity of oil containing products,

• a lubricity/cost performance point approaching that of oil containing products, • reduced worker irritation (irritation is associated with higher pH products),

• the rust or other corrosion protection of oil containing products, or

• an alkanolamine free chemistry. PARTICLE SIZE

[0037] The present compositions as formulated contain particles, as will be seen in the Examples below. Larger particles are contemplated to provide greater lubricity, though the invention is not limited according to the accuracy of this theory. The contemplated particles of any embodiment optionally have a volume average diameter of from 120 to 100,000 nanometers (nm), alternatively from 120 to 100,000 nm, alternatively from 1 20 to 10,000 nm, alternatively from 120 to 5000 nm, alternatively from 125 to 10,000 nm, alternatively from 125 to 5000 nm,, alternatively from 125 to 2000 nm, alternatively from 140 to 10,000 nm, alternatively from 140 to 5000 nm, alternatively from 140 to 2000 nm, alternatively from 200 to 10,000 nm, alternatively from 200 to 5,000 nm, alternatively from 200 to 2000 nm, alternatively from 220 to 10,000 nm, alternatively from 220 to 5,000 nm, alternatively from 220 to 2000 nm, alternatively from 350 to 10,000 nm, alternatively from 350 to 5,000 nm, alternatively from 350 to 2,000 nm.

EXAMPLES

[0038] The foregoing may be better understood by reference to the following examples, which are intended to illustrate methods for carrying out the invention and are not intended to limit the scope of the invention.

EXAMPLE 1

[0039] The materials A through E of Table 1 were employed in a tapping torque operation involving the tapping of 6061 aluminum. The concentrates were first diluted to a 7.5% by volume solution before testing. The tapping torque test is a quantitative measure of the lubricity performance of metalworking fluids. It has an ASTM standard method designation of D5619. Tapping torque reflects the industrial machining process in a better way than other tests, which commonly are carried out by rubbing two metal surfaces together. It is an excellent method of discriminating metalworking fluid (MWF) product machining performance in the laboratory. Tapping Torque results have been proven to correlate well with field machining performance.

[0040] The tapping torque instrument is designed to measure the lubricity of MWFs while actual cutting is performed. During the tapping operation, the

Tapping Torque instrument measures the instantaneous torque 250 times as the tap advances throughout the depth of the cut. Specialized software then facilitatθs data analysis. Tapping torque is expressed in units of N-m (Newton- meters) or N-cm (Newton-centimeters). Products with high lubricity will generate lower torque values. Conversely, low lubricity products will generate high torque values. In this way the instrument quantifies the differences in lubrication performance between products.

[0041] One drawback of the tapping torque instrument is in that the absolute torque values measured are dependent upon and will vary with the diameter of the tap used. Therefore, in order to cancel out these geometric effects it is efficacious to express the lubricity as the torque per area to describe the energy it takes for a tap to make one revolution. The equation for this is

E/A = (2 Y) / r2 where t= torque value, r = the radius of the tap, E/A = energy per area and the units are N-m^"1 (Newtons per meter) or N-cm^"1 (Newtons per centimeter).

[0042] The lubricity data is presented in Table 1 , identified as E/A. The lower the E/A value, the better the lubricity and machining performance. All samples were diluted with water to 7.5% by volume before testing.

Example 2:

[0043] The materials of Table 1 were employed in a particle size operation involving the measurement of the volume average particle size in nanometer units. The concentrates were first diluted with water to a 7.5% by volume solution before testing. The particle-sizing instrument uses high efficiency dynamic light scattering to quantify particle sizes of 20 to 100,000 nanometers.

[0044] All samples were diluted to 7.5% by volume before testing. The resulting particle sizes are shown in Table 1 .

Example 3

[0045] Material C from Table 1 was tested at two different concentrations for particle size, and evaluated at each concentration for appearance and emulsion stability. The results are shown in Table 2, which shows a large average particle size, opaque appearance, and excellent stability at each concentration. A larger particle size is characteristic of a better lubricant. Typical synthetic MWFs, when diluted, form clear solutions with particle size of less than 100 nanometers. Dilutions of sample C have particle sizes 3.5 to 20 times larger than the maximum size seen with typical synthetic MWFs.

Table 2

[0046] From examples 1 -3 it is seen that optimal lubricity and particle size is obtained with sample C which combines 10% carboxylic acid - alkali salts and 20% Pluronic "R" block copolymer. This ratio gives the maximum volume average particle size and maximum lubricity.

[0047] It is also apparent from the examples that to a large degree, the lubricity of a composition is a function of its volume average particle size. Increasing volume average particle size results in increased lubricity. [0048] From example 3 it is seen that an increased concentration of sample C results in significantly larger volume average particle size. This explains the necessity of emulsifiers to stabilize higher concentrations of sample C. Without emulsifiers, it is believed that the particle size of higher concentrations would continue to agglomerate to an unstable state. [0049] 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. It is therefore intended that such changes and modifications be covered by the appended claims.

Claims

1 . A metalworking fluid composition with a volume average particle size of 125 nm or greater when diluted between 0.1 and 50 percent by volume comprising: (a) one or more polymeric lubricity agents;

(b) one or more carboxylic acid salts;

(c) one or more emulsifying or dispersing agents; and

(d) a transport component.

2. The composition of claim 1 including one or more oils at less than 10 percent by volume.

3. The composition of any preceding claim wherein the transport component comprises water.

4. The composition of any preceding claim including a corrosion inhibiting component.

5. The composition of any preceding claim wherein the corrosion inhibiting component comprises one or more of the following: alkali and alkanolamine salts of carboxylic acids, undecanedioic or dodecanedioic acid and their salts, C₄-₂2 carboxylic acids and their salts, boric acids, compounds and their salts, tolytriazole and its salts, benzotriazoles and its salts, imidazolines and its salts, alkanolamines and amides, sulfonates, alkali and alkanolamine salts of naphthenic acids, phosphate ester amine salts, alkali nitrites, alkali carbonates, carboxylic acid derivatives, alkylsulfonamide carboxylic acids, arylsulfonamide carboxylic acids, fatty sarkosides, phenoxy derivatives and sodium molybdate.

6. The composition of any preceding claim wherein the pH is from 3 to 9.

7. The composition of any preceding claim including an alkalinity agent.

8. The composition of claim 7 wherein the alkalinity agent is one or more of the following: alkanolamines - primary, secondary and tertiary, aminomethylpropanol (AMP-95), diglycolamine (DGA), monoethanolamine (MBA), monoisopropanolamine (MIPA), butylethanolamine (NBEA), dicylclohexylamine (DCHA), diethanolamine (DEA), butyldiethanolamine

(NBDEA), triethanolamine (TEA), metal alkali hydroxides, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, metal carbonates and bicarbonates, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.

9. The composition of claim 7 or 8 wherein the alkalinity agent is a metal alkali hydroxide.

10. The composition of any preceding claim including an anti foaming agent.

1 1 . The composition of any preceding claim including a biocide and/or a fungicide.

12. The composition of any preceding claim wherein the polymeric lubricity agent is a block copolymer.

13. The composition of any preceding claim wherein the polymeric lubricity agent is one or more of the following: block copolymers comprising of a central polyoxypropylene block with a polyoxyethylene chain at either end, block copolymers comprising of a central polyoxyethylene block with a polyoxypropylene chain at either end, tetrablock copolymers derived from the sequential addition of ethylene oxide and propylene oxide to ethylenediamine, ethylene oxide/ propylene oxide copolymers having at least one terminal hydroxyl group, water-soluble lubricant base stocks of random copolymers of ethylene oxide and propylene oxide, a water-soluble polyoxyethylene or polyoxypropylene alcohol or a water-soluble carboxylic acid ester of such alcohol, alcohol-started base stocks of all polyoxypropylene groups with one terminal hydroxyl group, monobasic and dibasic acid esters, polyol esters, polyalkylene glycol esters, polyalkylene glycols grafted with organic acids, phosphate esters, polyisobutylenes, polyacrylonitriles, polyacrylamides, polyvinylpyrrolidones, polyvinyl alcohols and copolymers of acrylic acid or methacrylic acid and an acrylic ester.

14. The composition of any preceding claim wherein the polymeric lubricity agent is polypropylene glycol block copolymer.

15. The composition of any preceding claim wherein the polymeric lubricity agent is polyethylene glycol block copolymer.

16. The composition of any preceding claim wherein the polymeric lubricity agent is polyethylene glycol / polypropylene glycol block copolymer.

17. The composition of any preceding claim wherein the carboxylic acid salt comprises an alkali and/or alkanolamine salt of C4-C22 carboxylic or fatty acids and esters.

18. The composition of any preceding claim wherein the carboxylic acid salt is comprising one or more of the following: 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, eicosanoic acid, docosanoic acid, docosahexanoic acid, erucic acid, arachidonic acid, lard oil, tallow oil, butter, coconut oil, palm oil, cottonseed oil, wheat germ oil, soya oil, olive oil, corn oil, sunflower oil and rapeseed or canola oil.

19. The composition of any preceding claim wherein the emulsifying or dispersing agent is one or more of the following: alkanolamides, alkylaryl sulfonates, alkylaryl sulfonic acids, amine oxides, amide 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 esters and oils, ethoxylated phenols, fatty amines and esters, glycerol esters, glycol esters, imidazolines and imidazoline derivatives, lignin and lignin derivatives, maleic or succinic anhydrides, methyl esters, monoglycerides and derivatives, naphthenic acids, olefin sulfonates, phosphate esters, polyethylene glycols, polyols, polymeric (polysaccharides, acrylic acid, acrylamide), propoxylated & ethoxylated fatty acids, alcohols or 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 ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of fatty esters, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalene and alkyl naphthalene, sulfonates of petroleum, sulfosuccinamates, sulfosuccinates and derivatives, tridecyl and dodecyl benzene sulfonic acids.

20. The composition of any preceding claim wherein the metalworking fluid composition, when diluted between 0.1 and 50 percent by volume has a lubricity, as measured by tapping torque instruments, of less than 8000 Newton- cm 1 .

21 . The metalworking fluid composition of any preceding claim comprising:

(a) 1 to 80 percent by volume of one or more block copolymers;

(b) 1 to 40 percent by volume of one or more carboxylic acid salts;

(c) 1 to 20 percent by volume of one or more emulsifying agents; and

(d) a transport component.

22. The metalworking fluid composition of any preceding claim comprising:

(a) 5 to 40 percent by volume of one or more block copolymers;

(b) 3 to 30 percent by volume of one or more carboxylic acid salts;

(c) 2 to 12 percent by volume of one or more emulsifying agents; and (d) a transport component.

23. The metalworking fluid composition of any preceding claim comprising:

(a) 15 to 25 percent by volume one or more block copolymers; (b) 5 to 15 percent by volume one or more carboxylic acid salts;

(c) 3 to 8 percent by volume one or more emulsifying agents;

(d) a transport component.

24. The metalworking fluid composition of any preceding claim, having a volume average diameter of from 120 to 100,000 nanometers (nm), alternatively from 125 to 10,000 nm, 140 to 10,000 nm, alternatively from 220 to

10,000 nm, alternatively from 350 to 5,000 nm, alternatively from 350 to 2,000 nm.