WO2000043470A1 - Composition a base d'eau pour usinage des metaux - Google Patents

Composition a base d'eau pour usinage des metaux Download PDF

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Publication number
WO2000043470A1
WO2000043470A1 PCT/US2000/001533 US0001533W WO0043470A1 WO 2000043470 A1 WO2000043470 A1 WO 2000043470A1 US 0001533 W US0001533 W US 0001533W WO 0043470 A1 WO0043470 A1 WO 0043470A1
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WO
WIPO (PCT)
Prior art keywords
metal
composition
agents
composition according
soap
Prior art date
Application number
PCT/US2000/001533
Other languages
English (en)
Inventor
Denis R. Castaing
David L. Elliott
Original Assignee
Nalco Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nalco Chemical Company filed Critical Nalco Chemical Company
Priority to AU26235/00A priority Critical patent/AU2623500A/en
Publication of WO2000043470A1 publication Critical patent/WO2000043470A1/fr

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    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
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    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
    • C10M125/30—Clay
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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    • C10M129/60—Tall oil acids
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • the present invention relates to a metal working fluid or metal forming composition. More particularly this invention relates to water based metal lubricant compositions.
  • the composition of the present invention is useful in metal forming processes and applications such as drawing, rough and fine blanking, stamping, and other metal moving operations.
  • a suitable metal forming lubricant In addition to being lubricious under extreme operating conditions, a suitable metal forming lubricant must also possess other characteristics in order that it may be successfully used in a commercial setting. For example, the lubricant must not build up on the die, otherwise "break through” or striations may be formed. In some cases, the lubricant has formed a residue of sufficient size such that the fully formed workpiece contains hollows corresponding to the built up residue, and thus produces a part that is not the mirror image of the die.
  • Lubricants usually liquid lubricants, are used in metal working operations to reduce friction between the surface of metal being worked and a surface of the apparatus carrying out the operation.
  • a liquid lubricant reduces friction by separating the two surfaces with a thin fluid film having little resistance to shear.
  • the pressure between a surface of the metal being worked and a surface of the apparatus is so great that the fluid film of a liquid lubricant may be squeezed out so allowing actual metal-to-metal contact with the result that excessive damage to the surfaces may occur.
  • Solid film lubricants have been developed to provide much greater load bearing properties and thus greater performance, avoiding some of these problems. However, solid lubricants have their own disadvantages. Solid lubricants are harder to manufacture, are more difficult to apply to the metal surfaces, and are more difficult to remove after the metal has been worked, than liquid lubricants.
  • a lubricant may be expected to fulfill certain other requirements if it is to be useful industrially. For instance, it should be easy to apply and easy to remove it should afford some protection to the metal surface during handling and storage, it should present no health hazard to persons coming into contact with it and, obviously, should be inert to the surfaces with which it comes into contact. Many lubricants produce severe stains on the surface of the metal during annealing thereof. It is, therefore, highly desirable to avoid such staining by using a lubricant having the properties demanded by the particular conditions under which the lubricated metal is to be worked and which is also non-staining.
  • a lubricant that has the high performance characteristics of solid lubricants but yet has the handling advantages of a liquid lubricant, particularly an aqueous lubricant. It would be further desirable to provide a low viscosity water based lubricant with the performance characteristics of solid lubricants that is environmentally friendly.
  • the composition of the present invention comprises 1) a soap, 2) a nonvolatile ester, and 3) a particulate component. These main components of the composition according to the present invention are in an aqueous base.
  • the metal working process according to the present invention comprises a) applying the composition above to a metal surface of a workpiece, thereby forming a coated metal surface, b) contacting said coated metal surface with a metal working tool, and c) working said workpiece.
  • the inventors have unexpectedly discovered a metal forming composition that has high performance characteristics and is easily handled in metal forming processes.
  • This composition can be a low viscosity water based lubricant that is environmentally friendly and has high performance characteristics, even under great pressures.
  • the product is in the form of a thick but flowing liquid emulsion.
  • Its unique technical attribute or advantage is a novel combination of lubricity additives (soap) and barrier additives (non-volatile ester and particulate), giving the composition superior performance without the use of traditional extreme pressure additives that contain undesirable components such as sulfur compounds, halogenated organics (i.e. chlorinated compounds), or phosphates. These can be added to give even greater performance if desired if there are no environmental concerns.
  • This invention is designed for cold-working or cold-forming processes of metals. Examples of metals are ferrous types such as steel, stainless steel, leaded steel, galvanized iron or steel, and other ferrous alloys; and non-ferrous types such as aluminum, brass, zinc, lead, copper, titanium, silver, and the like.
  • metal forming is meant any process that is designed to alter the shape of metal without producing chips (metal fragments). These processes include but are not limited to forging; extrusion; rod, wire or tube drawing; rolling; and sheet forming.
  • forging are such operations as open-die forging, cogging, closed die forging, coining, nosing, upsetting, heading, piercing, hobbing, roll forging, orbital forging, ring rolling, rotary swaging of bars and tubes, and radial forging.
  • rolling are flat rolling or shape rolling.
  • sheet forming examples are blanking, piercing, press bending, deep drawing, stamping, stretch forming, spinning, hydroforming, rubber-pad forming, shallow recessing, explosive forming, dimpling, roll forming, or flanging.
  • the composition form can be either a solid, a paste, or a liquid. Preferred is a liquid of pourable viscosity.
  • the soap component can be present at concentrations between 3 and 25%, with 10-20% preferred, and 12-18% most preferred.
  • the ester can be present at concentrations between 2 and 20%, with
  • the particulate component can be present at concentrations from 5 to 40%, with 10-30% preferred and 15-30% most preferred.
  • the preferred particulate material is a ground kaolin having particle size from 0.1 to 10 microns, with 0.5 to 5 more preferred and 1 to 2 most preferred.
  • Other particulate materials which are useful in this invention are bentonite clays and calcium carbonate.
  • the pH of the composition can be from 6.5 to 11.5, with 8 to 10.5 preferred and 8.5 to 10 most preferred.
  • the significance of pH is that the preferred compositions need to have pH greater than about 8.5 to have suitable corrosion resistance for commercial applications, but pH lower than about 10 to avoid causing skin irritation or other health or environmental problems.
  • the composition should contain customary additives such as corrosion inhibitors, yellow-metal protection additives, biocides, and dyes.
  • the composition may further contain other additives such as viscosity modifiers, buffering agents, alkalinity control agents, fragrances, odor masking agents, extreme pressure additives such as active sulfur containing agents, phosphate esters, or organic chlorine-containing agents, supplemental lubricity agents, surfactants, wetting agents, dispersants, emulsifiers, coupling agents, and solvents or oils.
  • the metal lubricant composition according to the present invention is an aqueous system and preferably contains low to no organic solvents and therefore would be a composition that did not have volatile organics (VOCs) and would be a low VOCs composition.
  • VOCs volatile organics
  • the extreme pressure additives if employed in the water-base lubricant composition of the present invention can be at a level of 0.01 to about 35%, preferably about 0.01 to about 22%, and highly preferred at about 1 to about
  • the extreme pressure additives enhance the metal forming process under extremely high pressure conditions.
  • the extreme pressure additives are selected from the group consisting of phosphate esters, sulfurized fatty acids, phosphosulfurized vegetable oils, and mixtures thereof.
  • the biocides employed in the water-base lubricant composition of the present invention are at a level from 0 to about 5%, preferably about 0.01 to about 2%, and highly preferred at about 0.05 to about 1 % by weight.
  • the biocide or preservative agents of the present invention are preferably selected from the group consisting of polyamino derivatives, triazine derivatives, benzisothiazolinone derivatives, and mixtures thereof.
  • a specific preferred example includes 1 ,2-benzisothiazolin-3-one.
  • Aqueous lubricating compositions of the present invention are usually supplied in a concentrated form.
  • the lubricant composition may be employed in concentrated form for difficult metal forming operations.
  • the concentrate lubricant can be diluted with water to fit the particular metal working needs.
  • the amount of dilution can be determined by actual operation of the metal working machinery on a particular workpiece. Satisfactory metal working applications have used dilution ratios of
  • the preferred method of application of the lubricant composition of the present invention is by spraying the composition on the surface of the dies or directly upon the workpiece, however, swabbing, dipping, or the like may also be employed.
  • the soap component according to the present invention is preferably metal, or amine salt of a 10 to 30 carbon fatty acid.
  • Preferred metals of the metal salt are alkali metal and alkaline earth metals, with alkali metals being more preferred. Examples of more preferred soaps include the salts of the following:
  • Linoleic Acid (18 carbons, with 9,12-unsaturation) isostearic Acid (18 carbons, fully saturated, branched)
  • Tall Oil Fatty Acid (mixture of oleic, linoleic, and rosin acids, significant unsaturation)
  • Non-Volatile Ester Component The non-volatile ester component of the composition of the present invention is designed to provide lubricity and can be either polymeric or non- polymeric. This non-volatile ester component is preferably water dispersible.
  • this non-volatile ester component is not completely soluble an aqueous media, however, it is somewhat hydrophilic and can be at least partially hydrated in an aqueous medium.
  • This non-volatile ester component more preferably can be solubilized with an emulsifier.
  • This non-volatile ester component also provides for tackiness of the composition as well as a chemical barrier and provides separation from the tool and the workpiece.
  • Preferred examples of this non-volatile ester component include:
  • Doverlube B-902 (Dover Chemicals) Non-polymeric ester, low iodine value.
  • Methyl Tallate (Rhodia) Non-polymeric ester, high iodine value
  • Syn-Ester GY-25 (Gateway Additives Co.) Polymeric ester, low iodine value
  • the particulate component of the present invention is preferably a swelling clay, a non-swelling clay, or organically modified clay; more preferably a non- swelling clay.
  • This particulate component provides a barrier layer between the tool and the workpiece.
  • the swelling clay or swellable clay component of the structuring system can be a clay mineral of the smectite type.
  • the clay can be naturally occurring or synthetic and of the dioctahedral or trioctahedral type. Examples of the natural clays that may be used in this invention are montmorillonites, hectorites, nontronites, beidillites, saponites, and sauconites.
  • smectite type clay should preferably be in an alkali or alkaline earth metal exchange form.
  • Peptizing agents such as hexametaphosphate, pyrophosphate, or other polyelectrolytes known to the art can be used.
  • organically modified swellable clays such as CLAYTONE from Southern Clay Products Inc. can be used. Examples of non-swelling clays include attapulgite (Attagel) and kaolin (Astra-Glaze).
  • the clay may be present at about 0.1 to 30%, preferably about 1 to 25%, and most preferably about 5 to 20% by weight of the final products.
  • the use of excessive amounts of clay within the formulas that contain high levels of other solids can lead to viscosities considerably above the preferred range.
  • particulate component of the present invention examples include molybdenum disulfide, graphite, boron nitride, talc, calcium carbonate, mica, and magnesium oxide.
  • Examples of more preferred particulate additives according to the present invention include the following clay or particulate additives:
  • Claytone 2000 (Southern Clay Products, Inc.) Organically-modified clay.
  • Kaolin is the most preferred inorganic particulate component used in composition of the present invention, due in part to its cost, the resulting viscosity of the composition, and good performance in metal working.
  • Kaolin is a clay, consisting substantially of kaolin minerals, that is naturally white or nearly white, or can be beneficiated to white or nearly white.
  • Kaolin clay pigments are obtained from kaolin.
  • Kaolin is a type of rock formed through weathering or hydrothermal alteration of feldspar or mica minerals to kaolin minerals, or a sedimentary rock containing a high concentration of kaolinite particles or grains. Sedimentary kaolin rocks contain mostly clay or silt sized particles of kaolin minerals and fine and coarse particle size impurities. Some of the impurities (e.g. fine ferruginous or titaniferous impurities) impart undesirable color to the clay. Other impurities have an undesirable effect on the rheology of the kaolin, and still other impurities are coarse particles called "grit" that are generally above 45 microns which may cause scratching and/or abrasion if used in most applications.
  • impurities e.g. fine ferruginous or titaniferous impurities
  • Kaolinite is the primary mineral in the kaolin clay widely used in the paper industry as fillers and/or coating pigments. Kaolin is also called china clay or hydrous kaolin. Its particles occur over a range of sizes and aspect ratios. Aspect ratio can be defined as the diameter of a kaolin particle divided by its thickness.
  • a kaolin crude will not contain particles of a single size, such as, for example, particles all of which are 2 microns.
  • a degritted (where 45 micron particles are removed) kaolin crude will contain particles ranging in size from submicron or colloidal to particles 20 micrometers or larger.
  • Kaolins from different deposits, or even from different parts of the same deposit can vary widely in the content of impurities, particle size distribution, as well as shape of the kaolin particles.
  • kaolin particles finer than about 1 micrometer are composed of individual platelets, and particles larger than about 1 micrometer are composed of stacks or booklets of several platelets mixed with discrete platelets.
  • Particle sizes of kaolins are conventionally determined by sedimentation using Stokes Law to convert settling rates to particle size distribution, and assume a spherical particle shape for the kaolin particles, hence, the use of the conventional term "equivalent spherical diameter (e.s.d.)" to designate particle size.
  • the composition should contain customary additives such as corrosion inhibitors, yellow-metal protection additives, biocides, and dyes.
  • the composition may further contain other additives such as viscosity modifiers, buffering agents, alkalinity control agents, fragrances, odor masking agents, extreme pressure additives such as active sulfur containing agents, phosphate esters, or organic chlorine-containing agents, supplemental lubricity agents, surfactants, wetting agents, dispersants, emulsifiers, coupling agents, and solvents or oils.
  • customary additives such as corrosion inhibitors, yellow-metal protection additives, biocides, and dyes.
  • the composition may further contain other additives such as viscosity modifiers, buffering agents, alkalinity control agents, fragrances, odor masking agents, extreme pressure additives such as active sulfur containing agents, phosphate esters, or organic chlorine-containing agents, supplemental lubricity agents, surfactants, wetting agents, dispersants, emulsifiers, coupling agents,
  • Lubricity Addco DF-1 Alkanolamide, Gateway Additives Co.
  • Emulsifier
  • Composition 1 was tested for lubricity using a Draw Bead Simulator. This instrument tests the lubricating characteristics of various metal forming compositions and their relative value in drawing and stamping operations. The test entails coating the dies and a standardized test strip (2 x 18 x 0.03") with the candidate composition, clamping the strip in the dies (with a specific drawing load), and pulling the strip through the dies for a distance of approximately 5 inches. The loads experienced while pulling the strip through the dies are recorded. The SLT number relates the candidate composition performance to a 1200 second viscosity oil standard. The SLT number will thus be lower as the drawing (metal forming) efficiency of the composition improves.
  • Composition 1 was compared via Draw Bead Simulation to a standard composition (Composition 2) consisting of 20% chlorinated paraffin in a 100- second oil.
  • Composition 2 a standard composition
  • This type of composition would have excellent drawing/stamping performance in the metal forming industry, as the chlorinated paraffin is a common extreme pressure additive used in many commercial or industrial operations.
  • the results of draw bead testing are as follows:
  • the soap component is a tall oil fatty acid.
  • the ester component is Syn- Ester GY-25 (Gateway Additives).
  • the particulate is Astra-Glaze (ECC) kaolin.
  • Customary additives included caustic soda, alkanolamide emulsifier, Surfonic
  • composition according to the present invention containing all three components (#1) has superior drawing performance over non-inventive compositions.
  • Example 1 The formula in Example 1 was modified with the substitution of the following particulate components:

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Lubricants (AREA)

Abstract

La présente invention concerne une composition pour l'usinage des métaux. Cette composition contient 1) un savon, 2) un ester non volatil, et 3) un composant particulaire. Les principaux composants de la composition de la présente invention sont réunis dans une base aqueuse. La composition lubrifie le métal et permet d'usiner le métal à froid, sans formation de paillettes et sans fatigue du métal.
PCT/US2000/001533 1999-01-22 2000-01-21 Composition a base d'eau pour usinage des metaux WO2000043470A1 (fr)

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US60/116,964 1999-01-22

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010040859A2 (fr) * 2008-10-10 2010-04-15 Magna Steyr Fahrzeugtechnik Ag & Co Kg Produit anticorrosion
WO2010040860A3 (fr) * 2008-10-10 2010-06-17 Magna Steyr Fahrzeugtechnik Ag & Co Kg Procédé de fabrication et première mise en service d'une boîte avec un lubrifiant à base aqueuse et lubrifiant de ce type
CN104480459A (zh) * 2014-11-25 2015-04-01 三达奥克化学股份有限公司 拉拔磷化常温皂化剂及制备方法
CN105296060A (zh) * 2014-07-03 2016-02-03 G·S·拉维 一种新型水基金属加工液组分
CN107614666A (zh) * 2015-05-29 2018-01-19 日本帕卡濑精株式会社 含水润滑膜剂、表面处理金属材料、以及金属材料的含水润滑膜形成方法
CN110452764A (zh) * 2019-08-20 2019-11-15 嘉兴市国龙石油化工股份有限公司 一种低粘度水性高压锅深冲压拉伸油及其制备方法
CN114517118A (zh) * 2020-11-20 2022-05-20 中国石油化工股份有限公司 一种石墨炔润滑油组合物及其制备方法

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US4419254A (en) * 1980-05-09 1983-12-06 Toshiba Silicones Limited Method of protecting silver contacts
EP0412788A1 (fr) * 1989-08-09 1991-02-13 Nihon Parkerizing Co., Ltd. Méthode de lubrification pour traitement de matériaux mÀ©talliques lors du travail plastique à froid
US5156756A (en) * 1990-04-23 1992-10-20 Kabushiki Kaisha Tokai Rika Denki Seisakusho Lubricant for an electrical sliding contactor
US5780400A (en) * 1996-10-07 1998-07-14 Dover Chemical Corp. Chlorine-free extreme pressure fluid additive
US5804536A (en) * 1996-04-01 1998-09-08 Ntn Corporation Solid lubricant for bearings comprising a mixture containing a lubricating grease and polyethylene powder

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Publication number Priority date Publication date Assignee Title
US4419254A (en) * 1980-05-09 1983-12-06 Toshiba Silicones Limited Method of protecting silver contacts
EP0412788A1 (fr) * 1989-08-09 1991-02-13 Nihon Parkerizing Co., Ltd. Méthode de lubrification pour traitement de matériaux mÀ©talliques lors du travail plastique à froid
US5156756A (en) * 1990-04-23 1992-10-20 Kabushiki Kaisha Tokai Rika Denki Seisakusho Lubricant for an electrical sliding contactor
US5804536A (en) * 1996-04-01 1998-09-08 Ntn Corporation Solid lubricant for bearings comprising a mixture containing a lubricating grease and polyethylene powder
US5780400A (en) * 1996-10-07 1998-07-14 Dover Chemical Corp. Chlorine-free extreme pressure fluid additive

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010040859A2 (fr) * 2008-10-10 2010-04-15 Magna Steyr Fahrzeugtechnik Ag & Co Kg Produit anticorrosion
WO2010040860A3 (fr) * 2008-10-10 2010-06-17 Magna Steyr Fahrzeugtechnik Ag & Co Kg Procédé de fabrication et première mise en service d'une boîte avec un lubrifiant à base aqueuse et lubrifiant de ce type
WO2010040859A3 (fr) * 2008-10-10 2010-07-15 Magna Steyr Fahrzeugtechnik Ag & Co Kg Produit anticorrosion
US8782894B2 (en) 2008-10-10 2014-07-22 Magna Steyr Fahrzeugtechnik Ag & Co. Kg Method for producing and commissioning a transmission with a water-based lubricant, and such a lubricant
CN105296060A (zh) * 2014-07-03 2016-02-03 G·S·拉维 一种新型水基金属加工液组分
CN104480459A (zh) * 2014-11-25 2015-04-01 三达奥克化学股份有限公司 拉拔磷化常温皂化剂及制备方法
CN107614666A (zh) * 2015-05-29 2018-01-19 日本帕卡濑精株式会社 含水润滑膜剂、表面处理金属材料、以及金属材料的含水润滑膜形成方法
CN107614666B (zh) * 2015-05-29 2020-12-11 日本帕卡濑精株式会社 含水润滑膜剂、表面处理金属材料、以及金属材料的含水润滑膜形成方法
CN110452764A (zh) * 2019-08-20 2019-11-15 嘉兴市国龙石油化工股份有限公司 一种低粘度水性高压锅深冲压拉伸油及其制备方法
CN114517118A (zh) * 2020-11-20 2022-05-20 中国石油化工股份有限公司 一种石墨炔润滑油组合物及其制备方法
CN114517118B (zh) * 2020-11-20 2022-12-13 中国石油化工股份有限公司 一种石墨炔润滑油组合物及其制备方法

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