The dilemma of promoting green products: what we know and don't know about biobased metalworking fluids.[ILLUSTRATION OMITTED]
For many decades, concerns have been growing about negative environmental, health, and safety impacts of chemicals and products that are derived from petroleum-based feedstocks. As a result, the search for environmentally friendly Environmentally friendly, also referred to as nature friendly, is a term used to refer to goods and services considered to inflict minimal harm on the environment. products, commonly referred to as "green products," has received worldwide attention in recent years. The U.S. and countries in Europe have continued to provide financial support toward research and development of "green products." In the U.S., many firms design and manufacture a myriad of biobased products and sell them as "green products" or "sustainable products."
Advocates of biobased products argue that these products are "green" because they are safer, more ecologically friendly, and healthier than their counterparts that are derived from petroleum feedstock feed·stock
Raw material required for an industrial process.
Noun 1. feedstock - the raw material that is required for some industrial process
raw material, staple - material suitable for manufacture or use or finishing (Honary, 2001). Little research, however, has focused on what actually constitutes "green products."
No universally agreed-upon criteria exist to define a "green product." It is generally construed as a product that will not damage environmental compartments such as air, water, or soils to a degree that will be socially, ecologically, and economically acceptable by society. In addition, "green products" will not affect consumers' or workers' health and safety. A study conducted recently used criteria such as global warming global warming, the gradual increase of the temperature of the earth's lower atmosphere as a result of the increase in greenhouse gases since the Industrial Revolution. and ozone depletion potential The ozone depletion potential (ODP) of a chemical compound is the relative amount of degradation to the ozone layer it can cause, with trichlorofluoromethane (R-11) being fixed at an ODP of 1.0. Chlorodifluoromethane (R-22), for example, has an ODP of 0.05. , pH, flammability flam·ma·ble
Easily ignited and capable of burning rapidly; inflammable.
[From Latin flamm , and volatile organic compounds to evaluate biobased floor strippers Notable strippers of the past
Biobased lubricants lubricants
preparations for the lubrication of passages to reduce frictional injury, e.g. oily preparations, including petroleum jelly, lanolin or water-soluble preparations such as methyl cellulose. are a class of the so-called "green products" on the market today. They include metalworking fluids (MWFs), greases, hydraulic oils, and turbine oils. Manufacturers, formulators, and suppliers contend that biobased MWFs will soon replace the conventional petroleum-based MWFs as "green products." By the very nature of the functions of an MWF MWF Monday Wednesday Friday
MWF Married White Female
MWF Metalworking Fluid
MWF Mauritian Wildlife Foundation (Mauritius)
MWF Map Window File
MWF Mark Wilkinson Furniture
MWF Manitoba Wildlife Federation , however, biobased MWFs products must be formulated to meet the technical performance and other expectations of consumers in terms of efficiency and cost. As a result, petroleum-based MWF formulations use a series of additives to withstand robust work environments involving cooling of metal parts running against one another, usually in machine shops.
Recognizing that both conventional and biobased MWFs will require various additives to function well under various conditions, the goal of our study was to identify categories of these two MWFs and compare and contrast their health and safety aspects on the basis of their composition. In other words Adv. 1. in other words - otherwise stated; "in other words, we are broke"
put differently , our study was designed to investigate if the additives used in one type of MWF formulation varied significantly from the other and what this means in terms of their health and safety impacts.
Materials and Methods
Our study was designed to investigate various categories of petroleum-based MWFs on the market and compare with biobased MWFs in terms of the composition or additives used in their formulations. To accomplish this objective, surveys and informal telephone interviews were administered to various formulators of biobased MWFs in the U.S. Relevant journals, books, trade magazines, and materials, particularly material safety data sheets (MSDS MSDS Material Safety Data Sheets, see there ), were used as additional sources of information.
Surveys and Telephone Interviews
A questionnaire was designed and sent as a mail survey followed by formal and informal telephone interviews with the manufacturers and formulators of biobased MWFs in the U.S. Eleven manufacturers and one university research laboratory were contacted for this survey. This segment of stakeholders Stakeholders
All parties that have an interest, financial or otherwise, in a firm-stockholders, creditors, bondholders, employees, customers, management, the community, and the government. was considered a good source of primary information in our study. Only one perceived limitation of this method existed: a lack of cooperation due to the desire to protect market niche and trade secrecy, including pending patents.
The survey questionnaire focused on requesting generic information related to the MWFs and the additives that were being used to formulate biobased MWFs in particular. The main question asked was about the broad categories of additives used to make biobased MWFs, and the follow-up questions requested the specific types and amount of additives used in the biobased MWFs.
To complement the above method, MSDS were obtained from the Internet and used to identify and quantify additives used to formulate biobased MWFs. Ideally, section 2 of any MSDS is generally supposed to be a public source of this category of information by providing the identity, amount, and possibly the toxic properties of chemicals. A Hazard Communication Standard (HCS HCS - Heterogeneous Computer System
A distributed system project. ) requires manufacturers and suppliers of chemicals to provide or make available to the public through MSDS any toxicity information for each chemical product stored, manufactured, or transported (Hazard
Communication, 2011). Employers and employees can rely upon this information to make informed decisions on the type of engineering controls or personal protective equipment or other preventive measures to use when they are handling a chemical or product containing toxic agents in the workplace and in the community setting. The strength of the MSDS in this regard is to provide information useful for evaluating health and safety aspects of various products. By using a chemical abstract service number, composition can be reported and subsequently determine a product's health and safety from other related toxicity databases.
Literature review of peer-reviewed journals and other open-access publications was used to document various classes of petroleum-based MWFs and the properties of additives used in different classes of biobased MWFs. The Journal of Cleaner Production, Journal of Industrial Ecology industrial ecology
Discipline that traces the flow of energy and materials from their natural resources through manufacture, the use of products, and their final recycling or disposal. Research in industrial ecology began in the early 1990s. , Industrial Lubrication lubrication, introduction of a substance between the contact surfaces of moving parts to reduce friction and to dissipate heat. A lubricant may be oil, grease, graphite, or any substance—gas, liquid, semisolid, or solid—that permits free action of and Tribology tribology
Study of the interactions of sliding surfaces. It includes three subjects: friction, wear, and lubrication. Many manifestations of tribology are beneficial and make modern life possible. , Tribology International, and industry trade magazines such as Lubes 'n' Greases and the Agricultural-Based Industrial Lubricant Lubricant
A gas, liquid, or solid used to prevent contact of parts in relative motion, and thereby reduce friction and wear. In many machines, cooling by the lubricant is equally important. magazine of the University of Northern Iowa The University of Northern Iowa, in Cedar Falls, Iowa, was founded in 1876, as the Iowa State Normal School. It has colleges of Business Administration, Education, Humanities and Fine Arts, Natural Sciences, and Social and Behavioral Sciences, and a graduate school. were particularly useful for this purpose. In addition, proceedings from national and international conferences on tribology and product design were used. Electronic journal databases from various libraries were used to search for the availability of journals by using key words such as additives, biolubricants, life cycle assessment of biolubricants, and industrial ecology of the industrial lubricants.
Results and Discussion
Our study can report four classes of conventional petroleum-based MWFs as documented by the National Institute for Occupational Safety and Health (NIOSH NIOSH National Institute for Occupational Safety & Health, see there
NIOSH Recommendations for Safety & Health Standards
Agent NIOSH REL*/OSHA PEL† Health effects , 1998). These MWFs are categorized as straight oils, soluble oils, synthetic, and semisynthetic semisynthetic /semi·syn·thet·ic/ (-sin-thet´ik) produced by chemical manipulation of naturally occurring substances.
1. . The four classes of petroleum-based MWFs reported by NIOSH are dependent upon the amount of the base oil or feedstock and the quantity of water used in each formulation (Gauthier, 2003; Whittaker, 1997). NIOSH has described the health and safety aspects of these petroleum based MWFs in detail (Whittaker, 1997).
Straight-oil MWFs, also referred to as "neat oil," are comprised of nearly 100% of base oils; this means that they are made up of severely refined mineral or petroleum products (Gauthier, 2003; Whittaker, 1997). In other scenarios, straight-oil MWFs have base oils derived from animals, marine life, or vegetables in combination with mineral oils (Gauthier, 2003; Whittaker, 1997). As expected, straight-oil-based MWFs are designed to improve the metalwork as a coolant coolant (kōō´lnt),
n but at the same time to prevent rusting of metal parts during operations, particularly in moderate- to heavy-duty machining work environments. It is reported that since the amount of petroleum feedstock used to formulate this category of MWFs is close to 100%, very few additives, and only in small quantities, are usually added to this category of MWFs (Childers, 1994).
Soluble-oil MWFs are defined as emulsion emulsion: see colloid.
Mixture of two or more liquids in which one is dispersed in the other as microscopic or ultramicroscopic droplets (see colloid). Emulsions are stabilized by agents (emulsifiers) that (e.g. fluids containing much less severely refined petroleum or vegetable oils <onlyinclude> This list of vegetable oils includes all vegetable oils that are extracted from plants by placing the relevant part of the plant under pressure to extract the oil. than straight oil. The composition of severely refined petroleum or vegetable oils lies between 30% and 85% of petroleum-based feedstocks. The remaining components required to formulate these products are emulsifiers, pH stabilizers, rust preservatives preservatives,
n.pl food additives that hinder spoilage by reducing the growth of microorganisms. Include nitrates and nitrites, benzoates and sulfites, and many others. , antifoaming agents, corrosion inhibitors, lubricity lu·bric·i·ty
The quality or condition of being lubricious.
[Late Latin lbricit aids, viscosity modifiers, biocides, and extreme pressure additives such as chlorine, sulfur, and phosphorus-based additives.
Soluble oil-based MWFs are often diluted with water in the range of 5%-25%, creating the need to use biocides and emulsifiers as a way to limit environmental conditions conducive for bacteria or fungal fungal /fun·gal/ (fun´g'l) fungous; pertaining to fungi.
fun·gal or fun·gous
1. Of, relating to, resembling, or characteristic of a fungus.
2. growth (Hewstone, 1994; John, Bhattacharya, & Raynor, 2004).
Soluble oil-based MWFs were developed between 1910 and 1920 to replace strait-oil MWFs because the latter had many risks, including high flammability and poor cooling properties (Wu & Dacre, 1997). Due to the nature of the components used in this category of MWFs, technical performance characteristics of most soluble-oil MWFs are reported to be "extraordinarily good" when used in a high-temperature environment.
Synthetic Oil-Based MWFs
The third category of petroleum-based MWFs falls under the category of the synthetic oil-based MWFs that evolved in the 1950s as the concentrates of synthetic esters esters (esˑ·terz),
n.pl organic compounds synthesized from acids and alcohols, typically possessing fruity aromas. and organic and inorganic salts (Nachtman & Kalpakjian, 1985). Several additives are reported under this category of MWFs: synthesized hydrocarbons, polyglycols and phosphate esters, corrosion inhibitors, and biocides; and emulsifiers, chelating, anti-wear, wetting and coupling agents, rust preservatives, corrosion inhibitors, extreme pressure, antifoaming agents, surfactants, and dyes are often added in the formulation of these products (Fritz, 2006).
The fourth category of petroleum-based MWFs is semisynthetic oil-based MWFs, commonly referred to as "preformed" emulsions (Choi, Ahn, Kwon, & Chun, 1997). These MWFs contain water in the range of 30%-40% and severely refined petroleum oils almost in the same percentage range (Ratoi, Anghel, Bovington, & Spikes, 2000). Additives reported for these products are emulsifiers, coupling agents, extreme pressure and antiwear agents, antifoaming and defoaming compounds, rust preservatives, and corrosion inhibitors.
Analyzing the additives presented above for petroleum-based MWFs categories echoes the sentiments that they seem to be a huge "library of cookbooks" or "a black box of chemical blends (Wu & Dacre, 1997)." This observation is also supported by the NIOSH findings of the additives used in the petroleum-based MWFs as evident in Table 1 (Bartz, 1998).
From the literature review, we recognized that a large and complex nature of additives is available for use with MWFs and other lubricant formulations on the market (Figure 1). The U.S. market for these additives for this purpose alone is about 33% of the total world demand or approximately 1.1 million tons (Modern Applications News, 2001). The market value of additives to support these traditional MWF formulations and other industrial lubricants worldwide is about $7.5 million (Lin & So, 2004).
Results of survey and telephone conversations with stakeholders in the industry inquiring about biobased MWFs indicate that three main classes of biobased MWFs are identified (Table 2) as opposed to the four classes of conventional MWF products that are identified and reported in literature through NIOSH documents. It can be reported that Table 2 shows a high resemblance to Table 1 for various types of additives commonly found in the conventional or petroleum-based MWFs as reported in NIOSH studies.
Out of 10 manufacturers or formulators who were contacted for this study, four (40%) responded to the question about the identity of the additives that were used in their biobased MWFs formulations. For example, one manufacturer noted that "we don't use sulfur, chlorine, or phosphate-based additives, but other manufacturers in the biobased industry do." Another biobased MWFs formulator expressed similar concerns over the products they formulated. He noted that biobased feedstocks form a large percentage of the company's biobased MWFs, however, they include other additives in the formulations in the form of "oilness additives" in order to control wetting, emulsification, and other properties that include colloidal colloidal
of the nature of a colloid.
a bath containing gelatin, bran, starch or similar substances, to relieve skin irritation and pruritus. stability of the final biobased MWFs. These two statements point out the possible use of additives that are also commonly or similarly used in the conventional petroleum-based MWFs.
As expected, none of the manufacturers or formulators of biobased MWFs disclosed information related to the identity or amount of the specific additives used to formulate their biobased MWFs. This outcome can only be perceived as an attempt to control market niche by protecting trade secrets and other related technical information.
MSDS and Information on Additives Found in the Biobased MWFs
Eleven MSDS were downloaded from the Internet and analyzed. As expected, most MSDS did not provide valuable information about the specific types and amounts of additives used to formulate biobased MWFs. Three out of 11 MSDS revealed the three categories of biobased MWFs as straight-oil, water-soluble, or semisynthetic-based MWFs.
Although one could tell from the MSDS that biobased MWFs formulations contained soybean oil Soy´bean oil
n. 1. an oil obtained from the soybean (Glycine max), rich in protein, fats, sterols, and phospholipids, used as a food and in paints and varnishes and in various industrial applications; - as the main feedstock, other additives were not disclosed. A possible explanation for this could be the reluctance to reveal trade secrets and protection of pending patents. Nondisclosure of information can be crucial in evaluating the health and safety aspects of products and a comparative assessment can be relatively difficult to conduct in this situation. It is reasonable to assume that manufacturers are weighing the benefits of selling their biobased MWFs in a competitive market versus the burden of disclosing trade secret information through publicly available MSDS (Norrby, 2003). As expected, an HCS, which mandates disclosure of information on chemicals, has not been successful in this regard.
Regarding information disclosure on MSDS, Section 1910.1200(g)(2)(i)(c)(1) of HCS states the following: " ... the chemical and common name(s) of all ingredients which have been determined to be health hazards, and which comprise 1% or greater of the composition, except that chemicals identified as carcinogens Carcinogens
Substances in the environment that cause cancer, presumably by inducing mutations, with prolonged exposure.
Mentioned in: Colon Cancer, Rectal Cancer under paragraph (d) of this section shall be listed if the concentrations are 0.1% or greater"; and Section 1910.1200(g)(2)(i)(c)(2) of this HCS law adds, "the chemical and common name(s) of all ingredients which have been determined to be health hazards, and which comprise less than 1% (0.1% for carcinogens) of the mixture, if there is evidence that the ingredient(s) could be released from the mixture in concentrations which would exceed an established OSHA permissible exposure limit The Permissible Exposure Limit (PEL or OSHA PEL) is a legal limit in the United States for exposure of an employee to a substance, usually expressed in parts per million (ppm), or sometimes in milligrams per cubic metre (mg/m3). or ACGIH ACGIH American Conference of Governmental Industrial Hygienists, Inc. Threshold Limit Value threshold limit value
n. Abbr. TLV
The maximum concentration of a chemical allowable for repeated exposure without producing adverse health effects. , or could present a health risk to employees (Hazard Communication, 2011)."
Table 3 provides only scanty information about biobased MWFs and the additives. This information may not be useful to make informed decisions about the extent of "greenness" of biobased MWF formulations. The language in the HCS is clear about the content of MSDS. We can only speculate that perhaps the disclosure of trade secrets is the main reason why manufacturers of biobased MWFs, who claim to be promoting these formulations as "green products," would not want to disclose information related to the individual components used to formulate such biobased products.
The only useful information appearing to promote biobased MWFs is presented in Table 2 showing that the feedstock (base oil) used in these products is within 5%-90%. Biobased feedstock, such as high oleic o·le·ic
1. Of, relating to, or derived from oil.
2. Of or relating to oleic acid. rapeseed rapeseed
the seed of Target rape grown specifically for the seed and its oil.
as oil cake or meal after rapeseed oil is removed this is a high-protein feed supplement used in cattle. , is derived from sunflower sunflower, any plant of the genus Helianthus of the family Asteraceae (aster family), annual or perennial herbs native to the New World and common throughout the United States. oils, soybean soybean, soya bean, or soy pea, leguminous plant (Glycine max, G. soja, or Soja max) of the family Leguminosae (pulse family), native to tropical and warm temperate regions of Asia, where it has been , or canolas, or the lard, neatsfoot, and tallow tallow, solid fat extracted from the tissues and fatty deposits of animals, especially from suet (the fat of cattle and sheep). Pure tallow is white, odorless and tasteless; it consists chiefly of triglycerides of stearic, palmitic, and oleic acids. oils (Durak, 2004). While Table 3 illustrates the world production of biobased feedstocks and their corresponding fatty acids, Table 4 is an illustration of comparative performance of different base oils or feedstocks used to formulate MWFs.
Conclusion and Recommendations
Our study confirms that as many additives are used in the biobased MWF formulations as in the traditional or conventional petroleum-based MWF formulations. Some additives, such as biocides, can potentially be toxic, ecologically damaging, and probably unsafe. Our study did not address this issue in detail. With the information available now, it is difficult to conclude if biobased MWFs can be promoted as substitutes to petroleum MWFs in order to protect workers' health and safety or contribute to sustainability, as widely perceived.
Looking at the results of our study, it is relatively difficult to accept biobased MWFs as "green products" without subjecting them to a rigorous process of assessment on the basis of health and safety criteria regardless whether the feedstock used are biobased, which can be biodegradable biodegradable /bio·de·grad·a·ble/ (-de-grad´ah-b'l) susceptible of degradation by biological processes, as by bacterial or other enzymatic action.
adj. . Perhaps biodegradability biodegradability
Capacity of a material to decompose by biological action. The term usually refers to the environmental breakdown of waste by microorganisms. Generally, plant and animal products are biodegradable, whereas mineral substances (e.g. should not be the only deciding factor to categorize cat·e·go·rize
tr.v. cat·e·go·rized, cat·e·go·riz·ing, cat·e·go·riz·es
To put into a category or categories; classify.
cat biobased MWFs as "green products" until a thorough knowledge of the health and safety information of individual additives is presented (Table 5). Until then, precautionary measures should be taken when promoting biobased MWFs as "green products" to avoid health and safety impacts of these products that could be similar to those presented by petroleum-based MWFs.
Research efforts should focus on identifying the specific types and amount of individual additives that manufacturers use to formulate various biobased MWFs. Regardless of the source, base oils should also be considered as a source of serious health concerns because of the potential of these feedstocks to aerosolize. To avoid this scenario, good housekeeping Good Housekeeping is a women's magazine owned by the Hearst Corporation, featuring articles about women's interests, product testing by The Good Housekeeping Institute, recipes, diet, health as well as literary articles. measures recommended for handling petroleum-based MWFs should also be planned and adopted to control worker and public exposures from aerosols related to working with biobased MWFs.
Another conclusion of our study is that it is difficult to depend on the information from manufacturers of biobased products, MSDS, and other literature sources about the specific types, the amount, and quantity of individual additives used to formulate biobased MWF products. This was anticipated because of the existing trade secret and potential pending patent information. MSDS that were used in our study did not reveal sufficient information to identify and quantify each additive used to formulate the biobased MWF products. It is true to state that information disclosure laws in the U.S. are flawed and they should be reviewed to support sustainable development Sustainable development is a socio-ecological process characterized by the fulfilment of human needs while maintaining the quality of the natural environment indefinitely. The linkage between environment and development was globally recognized in 1980, when the International Union of the biobased industry. One way is to hold manufacturers liable who cannot provide consumers with the information to make informed decisions about the "greenness" of biobased MWFs. Concurrently, a more transparent approval process for approving additives manufactured or used to formulate biobased MWFs and other related biobased products is needed. A process by the Food and Drug Administration designed to approve additives for the food industry can be adopted for the biobased industry.
Acknowledgements: The authors wish to acknowledge the assistance of Lowell Center for Sustainable Production and the Toxics
Reduction Institute, both at the University of Massachusetts Lowell UMass Lowell was named the University of Lowell from 1975 to 1991, and was created from the merger of the Lowell Technological Institute and Lowell State College in 1975. These colleges in turn were originally named the Lowell Textile School, founded in 1895 to train technicians and , for supporting this research. Any views presented in this report are solely those of the authors and do not reflect the official position of these two institutions.
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Kinetics (classical mechanics)
That part of classical mechanics which deals with the relation between the motions of material bodies and the forces acting upon them. and mechanisms of ZDDP adsorption adsorption, adhesion of the molecules of liquids, gases, and dissolved substances to the surfaces of solids, as opposed to absorption, in which the molecules actually enter the absorbing medium (see adhesion and cohesion). on steel surfaces. Journal of Tribology International, 30(6), 445-453.
Yavrouian, A.H., Repar, J., Moran, C.M. Lawton, E.A., & Anderson, M.S. (1994). Additives for high temperature liquid lubricants: Final report. Pasadena, CA: Jet Propulsion Laboratory “JPL” redirects here. For other uses, see JPL (disambiguation).
Jet Propulsion Laboratory (JPL) is a NASA research center located in the cities of Pasadena and La Cañada Flintridge, near Los Angeles, California, USA. , California Institute of Technology California Institute of Technology, at Pasadena, Calif.; originally for men, became coeducational in 1970; founded 1891 as Throop Polytechnic Institute; called Throop College of Technology, 1913–20. . Retrieved from http://www.osti.gov/bridge/ servlets/purl/661602-tMoTH9/webviewable/661602.pdf
Zhang, W., Tanaka, A., Wazumi, K., & Vercamment, K. (2002). Structural, mechanical, and tribological properties of diamond-like carbon films prepared under different substrate bias voltage See bias. . Journal of Diamond and Related Materials, 11, 1837-1844.
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TABLE 1 Common Additives in Different Classes of Petroleum-Based Metalworking Fluids Classification Component Function Straight Oils Water As a coolant, solvent, Dissolved 10-500 ppm (a) diluents Mineral oils Carries lubricants 60%-100% Emulsifier Emulsifiers n/a Chelating agents Ties up ions in n/a solutions Coupling agents Stabilizes n/a VI modifiers Maintains viscosity Different amounts Detergents Prevents deposit Different amounts formation Plasticizers Reduces tackiness n/a Antimist agents Reduces misting Different amounts Antiweld agents Prevents welding 0%-20% Oiliness agents Increases film Different amounts strength Surfactant wetting Reduces surface 0%-10% agent tension Dispersant Prevents deposit Different amounts formation Passivator Prevents staining Different amounts Antifoaming Prevents foaming 0-500 ppm agents Alkaline reserve Acts as buffer control n/a Dyes Leak detection n/a Odorant Masks odor Different amounts Corrosion Prevents rust and film 0%-10% inhibitors, barrier antirusts Biocides Prevents bacteria/ n/a fungal growth Extreme pressure Reaction lubrication 0%-40% additives Classification Component Soluble Oils Semisynthetic Water 5-40 parts/1 part 10-40 parts/1 part Mineral oils 30%-85% 5%-30% Emulsifier 5%-20% 5%-10% Chelating agents 0%-1% 0%-1% Coupling agents 1%-3% 1%-3% VI modifiers n/a n/a Detergents Different amounts Different amounts Plasticizers Different amounts Different amounts Antimist agents Different amounts n/a Antiweld agents 0%-20% 0%-10% Oiliness agents n/a n/a Surfactant wetting 5%-20% 10%-20% agent Dispersant n/a n/a Passivator n/a n/a Antifoaming 0-500 ppm 0-500 ppm agents Alkaline reserve 2%-5% 2%-5% Dyes 0-500 ppm 0-500 ppm Odorant Different amounts Different amounts Corrosion 3%-10% 10%-20% inhibitors, antirusts Biocides 0%-2% 0%-2% Extreme pressure 0%-20% 0%-10% additives Classification Component Synthetic Water 10-40 parts/1 part Mineral oils n/a Emulsifier 5%-10% Chelating agents 0%-1% Coupling agents 1%-3% VI modifiers n/a Detergents Different amounts Plasticizers Different amounts Antimist agents n/a Antiweld agents 0%-10% Oiliness agents n/a Surfactant wetting 10%-20% agent Dispersant n/a Passivator n/a Antifoaming 0-500 ppm agents Alkaline reserve 2%-5% Dyes 0-500 ppm Odorant Different amounts Corrosion 10%-20% inhibitors, antirusts Biocides 0%-2% Extreme pressure 0%-10% additives Source: Bartz, 1998. (a) ppm = parts per million. TABLE 2 Additives in Three Classes of Biobased MWF Products Investigated Component Function Classification Straight Oils Water As a coolant, -- solvent, diluents Vegetable oils Base oil 70%-100% Emulsifier Emulsifiers n/a (ester of vegetable oil) Chelating agents Tie up ions in n/a solutions Coupling agents Corrosion/emulsion n/a TEA/MEA/DEA Viscosity index Maintain viscosity Present in different modifiers (blown amounts vegetable oil) Detergents Prevents deposit n/a (alcohol ethoxy formation sulphate) Antimist agents Reduce misting Present in different amounts Extreme pressure Prevent wear 0%-20% and antiwear (ZDDP)--phosphate esters Surfactant wetting Reduces surface 0%-10% agent tension (polyisobutylene succinic anhydride amino ester) Passivator Prevents staining Present in different amounts Antifoaming agents Prevent foaming 0%-1% (polydimethylsiloxne) Alkaline reserve Buffer control n/a agents Dyes Color n/a (optional) Odorant (optional) Masks odor Present in different amounts Corrosion Prevent rust 0%-10% inhibitors, antirusts Biocides/ Fungal/bacteria n/a preservative growth Antioxidants Prevent oxidation 0-1000 ppm (a) Component Classification Water-Soluble Oils Semisynthetic Water 5-40 parts/1 part 10-40 parts/1 part Vegetable oils 30%-85% 5%-30% Emulsifier 5%-20% 5%-20% (ester of vegetable oil) Chelating agents 0%-1% 0%-1% Coupling agents 1%-3% 1%-3% TEA/MEA/DEA Viscosity index n/a n/a modifiers (blown vegetable oil) Detergents Present in different Present in different (alcohol ethoxy amounts amounts sulphate) Antimist agents Present in different Present in different amounts amounts Extreme pressure 0%-20% 0%-20% and antiwear (ZDDP)--phosphate esters Surfactant wetting 5%-20% 10%-20% agent (polyisobutylene succinic anhydride amino ester) Passivator n/a n/a Antifoaming agents 0%-1% 0%-1% (polydimethylsiloxne) Alkaline reserve 2%-10% 2%-10% agents Dyes 0-500 ppm 0-500 ppm (optional) Odorant (optional) Present in different Present in different amounts amounts Corrosion 3%-10% 10%-20% inhibitors, antirusts Biocides/ 0%-2% 0%-2% preservative Antioxidants n/a n/a (a) ppm = parts per million. TABLE 3 Biobased Feedstock: World Production and Type of Fatty Acid World Production Source (Million Tons/Year) Fatty Acid Type Soybean oil 20 Linoleic oleic Groundnut oil 4 Linoleic oleic Palm oil 16 Palmitic oleic Rapeseed 11.5 Oleic Sunflower 9 Linoleic oleic Beef tallow 7.5 Oleic palmitic stearic Lard 6 Oleic palmitic Coconut oil 3 Lauric Palm kernel oil 2 Lauric Olive oil 2 Oleic Fish oil 1.5 Long chain fatty acids Corn oil 1.8 Linoleic oleic Castor oil 0.5 Ricinoleic Linseed oil 0.6 Linoleic Carbon Chain Length and Source Number of Double Bonds Soybean oil C18:2 or C18:1 Groundnut oil C18:2 or C18:1 Palm oil C16:0 or C18:1 Rapeseed C18:1 Sunflower C18:2 or C18:1 Beef tallow C18:1 or C16:0 or C18:0 Lard C18:1 or C16:0 Coconut oil C12:0 Palm kernel oil C12:0 Olive oil C18:1 Fish oil C20:2 to 6 or C22:2 to 6 Corn oil C18:2 or C18:1 Castor oil C18:1 -OH Linseed oil C18:3 Source: Igartua, 1999. TABLE 4 Relative Comparison and Rating of Different Base oils Characteristic Mineral Polyalpha Oils Olefines Viscosity temperature behavior (VI) 4 (a) 2 Low temperature behavior 5 1 (pour point) Liquid range 4 2 Oxidation stability (aging) 4 2 Thermal stability 4 4 Evaporation loss, volatility 4 2 Fire resistance, flash temperature 5 5 Hydrolytic stability 1 1 Corrosion protection properties 1 1 Seal material compatibility 3 2 Paint and lacquer compatibility 1 1 Miscibility with mineral oil -- 1 Solubility of additives 1 2 Lubricating properties, load 3 3 carrying capacity Toxicity 3 1 Biodegradability 4 3/4 Price relation against mineral oils -- 3-5 Characteristic Polyalkylene Dicarboxylic Glycols Acid Esters Viscosity temperature behavior (VI) 2 2 Low temperature behavior 3 1 (pour point) Liquid range 3 2 Oxidation stability (aging) 3 2/3 Thermal stability 3 3 Evaporation loss, volatility 3 1 Fire resistance, flash temperature 4 4 Hydrolytic stability 3 4 Corrosion protection properties 3 4 Seal material compatibility 3 4 Paint and lacquer compatibility 3 4 Miscibility with mineral oil 5 2 Solubility of additives 4 2 Lubricating properties, load 2 2 carrying capacity Toxicity 3 3 Biodegradability 1/2 1/2 Price relation against mineral oils 6-10 4-10 Characteristic Neopentyl Rapeseed Polyesters Oils Viscosity temperature behavior (VI) 2 2 Low temperature behavior 2 3 (pour point) Liquid range 2 3 Oxidation stability (aging) 2 5 Thermal stability 2 4 Evaporation loss, volatility 1 3 Fire resistance, flash temperature 4 5 Hydrolytic stability 4 5 Corrosion protection properties 4 1 Seal material compatibility 4 4 Paint and lacquer compatibility 4 4 Miscibility with mineral oil 2 1 Solubility of additives 2 3 Lubricating properties, load 2 1 carrying capacity Toxicity 3 1 Biodegradability 1/2 1 Price relation against mineral oils 4-10 2-3 Source: Lin & So, 2004. (a) Evaluation criteria: 1 = excellent; 2 = very good; 3 = good; 4 = moderate; 5 = poor. TABLE 5 Specific Additives in the Biobased Metalworking Fluids Based on Literature Review and Interviews Specific Additive Functions CAS # Zinc dialkyl- Extreme pressure/antiwear 68649-42-3 dithiophosphate (ZDDP) Chlorinated paraffin, Extreme pressure/antiwear n/a sulfur, phosphorous Alkyl hydrogen phosphites Extreme pressure/antiwear n/a S-alkyl O,O dialkyl Extreme pressure/antiwear n/a phosphorodithioate Chlorinated paraffins Extreme pressure/antiwear 108171-26-2 Tricresyl-phosphate (TCP) Antiwear 78-30-8 Dibutyl 3,5-di-t-butyl 4 Antiwear n/a hydroxy benzyl phosphate (DBP) Tri-n-octyl thiophosphate Antiwear n/a (TOTP) Tri-n-octyl Antiwear n/a tetrathiophosphate (TOTTP) Antimony dithiocarbamates Antiwear n/a Molybdenum Antiwear n/a phosphorodithioate T-butyl phthalonitrile Antiwear n/a Zinc Antiwear n/a dialkyldithiocarbamate N-phenyl-1-naphthylamine Antioxidant 90-30-2 Dicarboxylic acid esters Viscosity index modifiers n/a Lubrizol[R]7653 Viscosity index modifiers n/a -butylated phenol n/a (10%-19.9%) -substituted triazole n/a (0.5%-1.5%) -diphenylamine (0.1%-0.9%) 122-39-4 Diamond-like coatings Thermal protection n/a (DLC) Calcium alkaryl Detergent n/a sulphonates Calcium sulfonate Corrosion resistance 61789-86-4 Sodium sulfonate 61789853 Triethanolamine (TEA) pH Stabilizers; surfactants; 102-71-6 corrosion or rust inhibitors Diethanolamine (DEA) 111-42-2 Monoethanolamine (MEA) 141-43-5 Diglycoamine (DGA) or 929-06-6 2-(2-Aminoethoxy)ethanol Diphenylamine Antioxidant n/a Phenol Antioxidant n/a 4,4'-dioctyldiphenylamine Antioxidant -- (DAT) N-phenyl-1-naphthylamine Antioxidant -- (PAN) Triazine Biocides 4719-04-4 1,3,5-Triazine-1,3-5 (2H, 7632-00-0 4H, 6H)-Triethanol (9CT) and S-Triazine-1,3,5 (2H, 4H, 6H)-Triethanol (8CI) Carbamic acid, butyl-, 55406-53-6 3-iodo-2-propynyl ester (IPBC) Hexahydro 1,3,5, tris (2- 4719-04-4 hydroxyethyl)-s-triazine Hexahydro 1,3,5, tris 136356 ethyl-s-triazine Hexahydro 1,3,5 tris (2 n/a hydroxyproyl)-s-triazine Dimethoxane 828-00-2 Methylene-bis-oxazine -- (4,4'- methylenedimorpholine) Polyisobutylylene Antimist n/a Amine borate Alkaline reserves 63231481 1,2,4-Triazole Detergent 288-88-0 Sodium laureth sulfate or Passivator 9004-82-4 sodium lauryl sulfate ethoxylate NaN[O.sub.2] Corrosion inhibitors 7632-00-0 KN[O.sub.2] 7758-09-0 Specific Additive References Zinc dialkyl- Barnes, Bartle, & Thibon, 2001; Nicholls dithiophosphate (ZDDP) et al., 2005; Snyder & Foster, 1983; Wu & Dacre, 1997 Chlorinated paraffin, Childers, 1994; Pawlack, 2003 sulfur, phosphorous Alkyl hydrogen phosphites Bansal, Dohhen, & Sarin, 2002 S-alkyl O,O dialkyl phosphorodithioate Chlorinated paraffins Tricresyl-phosphate (TCP) Choi et al., 1997 Dibutyl 3,5-di-t-butyl 4 Choi et al., 1997 hydroxy benzyl phosphate (DBP) Tri-n-octyl thiophosphate Weimin et al., 2004 (TOTP) Tri-n-octyl tetrathiophosphate (TOTTP) Antimony dithiocarbamates Molybdenum phosphorodithioate T-butyl phthalonitrile Yavrouian, Repar, Moran, Lawton, Zinc & Anderson, 1994 dialkyldithiocarbamate N-phenyl-1-naphthylamine Dicarboxylic acid esters Kenar et al., 2005 Lubrizol[R]7653 Zhang et al., 2002 -butylated phenol (10%-19.9%) -substituted triazole (0.5%-1.5%) -diphenylamine (0.1%-0.9%) Diamond-like coatings Kalin & Vizintin, 2005 (DLC) Calcium alkaryl Bartz, 1998; Boris & Vizintin, 2003; sulphonates Kalin & Vizintin, 2005 Calcium sulfonate Miller, 2009 Sodium sulfonate Triethanolamine (TEA) Diethanolamine (DEA) Monoethanolamine (MEA) Diglycoamine (DGA) or 2-(2-Aminoethoxy)ethanol Diphenylamine Phenol 4,4'-dioctyldiphenylamine Bakunjin, Kuzmina, & Parenago, 2000 (DAT) N-phenyl-1-naphthylamine (PAN) Triazine Miller, 2009; Sollenberg & Stahlbom, 1999 1,3,5-Triazine-1,3-5 (2H, 4H, 6H)-Triethanol (9CT) and S-Triazine-1,3,5 (2H, 4H, 6H)-Triethanol (8CI) Carbamic acid, butyl-, 3-iodo-2-propynyl ester (IPBC) Hexahydro 1,3,5, tris (2- hydroxyethyl)-s-triazine Hexahydro 1,3,5, tris ethyl-s-triazine Hexahydro 1,3,5 tris (2 hydroxyproyl)-s-triazine Dimethoxane Methylene-bis-oxazine (4,4'- methylenedimorpholine) Polyisobutylylene Amine borate 1,2,4-Triazole Sodium laureth sulfate or sodium lauryl sulfate ethoxylate NaN[O.sub.2] KN[O.sub.2] FIGURE 1 Demand for Additives (Tons) in the Industrial Lubricants Industry by Continent Europe 1065; 31% America 1100; 33% Pacific 475; 14% Asia 650; 19% Africa 90; 3% Source: Rajewski, Fokens, & Watson, 2000. Note: Table made from pie chart.