WO2005108530A1 - Composition lubrifiante de formation de metal contenant du nitrure de bore - Google Patents

Composition lubrifiante de formation de metal contenant du nitrure de bore Download PDF

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Publication number
WO2005108530A1
WO2005108530A1 PCT/US2005/015128 US2005015128W WO2005108530A1 WO 2005108530 A1 WO2005108530 A1 WO 2005108530A1 US 2005015128 W US2005015128 W US 2005015128W WO 2005108530 A1 WO2005108530 A1 WO 2005108530A1
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WO
WIPO (PCT)
Prior art keywords
lubricant
boron nitride
process according
oil
film
Prior art date
Application number
PCT/US2005/015128
Other languages
English (en)
Inventor
Frank K. Botz
Margaret A. Handley
Original Assignee
The Lubrizol Corporation
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 The Lubrizol Corporation filed Critical The Lubrizol Corporation
Publication of WO2005108530A1 publication Critical patent/WO2005108530A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0239—Lubricating
    • B21B45/0242—Lubricants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
    • B21J3/00—Lubricating during forging or pressing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C10M2201/082—Inorganic acids or salts thereof containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C10M2205/0265—Butene used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal

Definitions

  • TITLE METAL FORMING LUBRICANT COMPOSITION CONTAINING BORON NITRIDE
  • the field of invention is lubricants for metal forming operations such as bending, stamping, and extrusion.
  • the lubricant includes boron nitride in layer lattice or hexagonal form.
  • the lubricant also includes an appropriate liquid carrier in which the boron nitride particles are dispersed.
  • boron nitride (BN) in the layer-lattice or hexagonal form has properties similar to graphite, and consequently should act as a good lubricant.
  • BN has potential as lubricating oil additive.
  • literature distributed by GE Advanced Ceramics Corporation who markets BN hexagonal powders BN generated the lowest Coefficient of Friction (cof) in Falex 4-Ball tests compared to other well known solid lubricant powders that included molybdenum disulfide, Teflon (PTFE), antimony oxide, and graphite when compared at 5% levels in an oil.
  • PTFE Teflon
  • U.S. patent 5,783,308 entitled "Ceramic Reinforced Fluoropolymer” a combination of BN and particulate fluoropolymer (PTFE) is patented for providing exceptional lubricity properties. This technology is sold by Acheson Colloids Corporation under the trade name Cerflon.
  • chlorinated paraffin is known to provide good EP lubrication of over a wide range of operating conditions and temperatures.
  • chlorinated and other EP chemistries are perceived by some as an environmental concern, and substitutes are being sought.
  • a process for metal forming such as stamping, bending, or extrusion is described wherein the improvement comprises the use of a lubricant that comprises boron nitride particles of the hexagonal or layer lattice type dispersed in a liquid lubricant.
  • a lubricant that comprises boron nitride particles of the hexagonal or layer lattice type dispersed in a liquid lubricant.
  • a small percentage by weight of said boron nitride dramatically increases the film strength of the lubricant composition during the extreme pressure portions of a metal forming operation. In areas of the metal forming operation not subjected to extreme pressure or heat the liquid lubricant portion of the lubricant composition provides adequate lubrication.
  • the environmentally acceptable lubricant composition replaces current technology which uses chlorinated paraffins and/or a variety of other extreme pressure additives that are not perceived to be as environmentally benign as liquid lubricants and said boron nitride.
  • a preferred liquid lubricant includes polyol esters such as natural vegetable oils. It is also desirable to control the polarity and viscosity of the liquid lubricant such that said boron nitride remains dispersed in the hydrodynamic lubricating film between the metal being deformed and the equipment applying stress to deform and shape the metal during metal forming.
  • Figures 1-7 show the performance (coefficient of friction) of various lubricants in twist compression tests (TCT) under various pressures and conditions.
  • Figure 1 shows a comparison of two different oils with 1% boron nitride.
  • Figure 2 show the effect of pressure with boron nitride.
  • Figure 3 shows the effect of pressure on molybdenum disulfide.
  • Figure 4 shows a comparison of a chlorine containing lubricant to a boron nitride containing lubricant.
  • Figure 5 shows a comparison of a lubricant without boron nitride to one including boron nitride.
  • Figure 6 shows a castor oil based lubricant with different amounts of boron nitride.
  • Figure 7 shows the need to keep the boron nitride dispersed in a lubricating film.
  • BN containing lubricants have also responded to pressure in a similar manner to typical EP chemistry.
  • Laboratory test results indicate that BN as solid additive to liquid forming lubricants has the possibility for use as a substitute for typical EP chemistry in difficult metal forming applications, and consequently may be used to eliminate the perceived problems related to environmental, health, disposal issues of chlorinated paraffin and other EP chemistries.
  • BN powders also are preferable to other typical layer lattice additives, such as graphite and molybdenum disulfide in being cleaner and safer to use.
  • Component (a) is an oil of lubricating viscosity. This may be from about 2 to about 2000 cSt at 100 C.
  • oils may be chosen from any of the American Petroleum Institute base oil categories I-V.
  • Mineral oils and other petroleum distillates function with boron nitride particles of hexagonal form less effectively than oils from polyol esters, thus polyol esters are preferred.
  • the performance of petroleum distillates with boron nitride particles of hexagonal form can be improved somewhat by increasing the viscosity of the oil with viscosity modifiers. The viscosity increase is anticipated to result in better more stable dispersion of the boron nitride through the lubricating film and thereby increases film strength and lubrication performance.
  • Polyol esters of the saturated and unsaturated type are believed to be effective in this application. Saturated polyol esters are believed to have higher thermal stability.
  • Unsaturated polyol esters such as vegetable and animal triglycerides have been found to be particularly effective with boron nitride particles. These may be partially or fully hydrogenated to improve thermal stability and to modify their viscosity. These may be modified with additives known to the art of lubrication. Specific examples of this type of component include oils from canola, castor, soybean or soya, rapeseed, corn, and any other commonly available vegetable oil. Animal triglyceride oils include whale oil, lard, tallow, fish oil, etc.
  • the amounts of component (a) in the compositions of the present invention are generally about 1 to 95 or 99.9 % by weight of the lubricious film, more desirably from about 40 to about 80 or 99.9%, and preferably from about 49.5 to about 95 or 99.9 % by weight of the lubricious film.
  • Component (b) is particulate boron nitride powder in layer lattice or hexagonal form. Specific examples of this type of component include AC-6003, HCV, and GPC grades available from General Electric Advanced Ceramics.
  • the amounts of component (b) in the compositions of the present invention are generally
  • the boron nitride of hexagonal form can have almost any particle size that can be readily dispersed without undue settling in the oil of lubricating viscosity.
  • Preferred particle sizes for easy dispersion and lack of settling include from about 0.1 to about 100 or 200 microns, more preferably from about 0.1 to about 100 microns in diameter, and most preferably from about 0.1 to about 50 microns in diameter.
  • Optional component (c) is a polymeric viscosity modifier such as is well known to the lubricant art.
  • polymeric viscosity modifiers include polyisobutylene, polymethacrylate, olefin copolymer, esters of styrene- maleic anhydride copolymers, hydrogenated styrene-diene copolymers, hydrogenated radial polyisoprene.
  • polyisobutylene viscosity modifiers having a viscosity of about 2000 cSt at 100 C such as Amoco Indopol HI 500.
  • component (c) in the compositions of the present invention are generally about 2 to about 90% by weight, desirably about 2 or 10 to about 60% by weight, and preferably from about 2 or 10 to about 49.5% by weight based on the weight of the lubricious films.
  • Optional component (d) is a second, third, or more additional oils of lubricating viscosity. These can include petroleum based oils such as mineral oil, and the various higher grade oils of the API base oils. Specific examples of this type of component are typical petroleum base oils, both naphthenic and paraffinic, with viscosities that range from 70 SUS to that of 150 or higher bright stock.
  • the amounts of component (d) in the compositions of the present invention are generally about 1 to about 95% by weight, desirably from about 10 or 20 to about 80% by weight, and preferably from about 10 or 20 to about 60% to about weight based on the weight of the lubricious film.
  • the particular relationship between the amounts and types of the above components is that the mix of liquid components, such as vegetable, mineral oil, polyisobutylene, etc., need to be of sufficient viscosity to keep the BN uniformly dispersed for application to the workpiece and create a lubricious layer between the BN particles.
  • the invention is intended for use in metal forming applications such as metal bending, stamping, and extrusion.
  • the invention is also a type of composition that provides enhanced lubricity due to a combination of the quantity, type and properties of hexagonal BN and the lubricating properties provided by the composition of the liquid phase.
  • the BN particles without the liquid phase may not be sufficient at low or high pressures.
  • the liquid phase would have insufficient film strength at higher pressures.
  • the mixed boundary lubrication provided by the liquid phase is as an important component in the reduction of friction as the use of BN powder.
  • the BN powder provides the lubricant film strength that is needed at pressures and temperatures that are similarly provided by EP additives.
  • Lubricant Composition #1 (a) Canola oil (Cargill Agri-Pure 75) 49.5% by weight (b) Polyisobutylene (2000 cSt at 100C) 49.5 (c) Boron nitride (GE AC6003) 1.0 100.0 Lubricant Composition #2: (a) Canola oil (Cargill Agri-Pure 75) 99% by weight (c) Boron nitride (GE AC 6003) 1 100 iricant Composition #3: (d) Rapeseed oil 45% by weight (b) Polyisobutylene (2000 cSt at 100C) 45 (c) Boron nitride (GE HCV) 10 100 Lubricant Composition #4: (a) Castor Oil 99% by weight (c) Boron nitride (GE HCV) _1 100 Lubricant Composition #5: (a) Castor Oil 99.5% by weight (c) Boron nitride (GE HCV) 0.5 100.0 Lubricant Composition #6
  • the boron nitride powders used in these studies were provided by GE Advanced Ceramics Corporation.
  • the canola oil was provided by Cargill, and the castor oil by Alnor Oil Company.
  • the tests of the compositions listed on the previous page were conducted using twist compression to measure effects on friction using pressures that are typical of most metal forming operations.
  • the twist compression test was generally conducted using a workpiece material of AKDQ cold rolled steel, an annular tool composed of D-2 steel rotated at a rate of 9 rpm and under a pressure of 60,000 psi (60 kpsi or 410 MPa) between the tool and the workpiece, wherein the annular tool has an inner diameter of 19.05 mm (0.75 inch), and an outer diameter of 25.4 mm (1 inch)
  • the overall purpose of the twist compression tests was to demonstrate that hexagonal BN enhances lubricity, in particular that it enhances lubricating properties that effect metal forming.
  • a number of experiments were conducted to demonstrate the properties of BN as a lubricant additive.
  • Figure 2 is a set of TCT plots in which composition #1 was tested at various pressures on AKDQ cold rolled steel (CRS) and tested at a rotation rate of 9 rpm. In these plots, the coefficient of friction (cof) decreases as the pressure was increased.
  • BN dispersion achieves a lower cof than the chlorinated fluid indicating its relatively high performance as a lubricant under these test conditions.
  • Experiment 3 indicates that conditions, that were thought to require chlorinated paraffin, would be adequately meet with a BN dispersion. The use of a BN lube would eliminate the perceived environmental, health and safety issues associated with the chlorinated material.
  • Experiment 4 ( Figures 5, 6) The level of BN necessary in a lubricant to improve film strength for a specific set of conditions, in this case as a function of pressure and sliding length, was addressed in experiment 4.
  • a lubricant of the composition #1 containing 1% by BN described performs in TCT equivalent to compositions that containing high levels of chlorinated paraffin or molybdenum disulfide in laboratory twist compression tests.
  • lubricant composition #1 will permit the elimination of EP chemistry for metal forming lubricants typically required in severe applications.
  • the lubricious films of this disclosure need not have other particulate lubricants such as graphite, molybdenum containing solid lubricants etc. to achieve the necessary lubrication under high pressures.
  • a lubricious film that lacks particulate lubricants other than boron nitride of the hexagonal form.
  • the limitations will not generally exclude common oil soluble additives to lubricants such as antioxidants, dispersants, polymeric viscosity modifiers, detergents etc.
  • the compositions in some embodiments will be free of conventional extreme pressure additives such as sulfur containing extreme pressure additive, chlorine containing extreme pressure additives, and/or phosphorus containing extreme pressure additives.
  • the lubricious films of this disclosure may contain such extreme pressure additives to provide further lubrications effects unique to the combination.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un lubrifiant pour la formation de métal contenant des particules de nitrure de bore de forme hexagonale dispersées dans un film d'huile compatible à viscosité lubrifiante.
PCT/US2005/015128 2004-04-30 2005-04-29 Composition lubrifiante de formation de metal contenant du nitrure de bore WO2005108530A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US56705104P 2004-04-30 2004-04-30
US60/567,051 2004-04-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015038088A2 (fr) * 2013-09-11 2015-03-19 BORTEK BOR TEKNOLOJlLERI VE MEKATRONIK SANAYI TICARET ANONIM SIRKETI Composition de type additif antisalissures
CN113460980A (zh) * 2021-08-02 2021-10-01 西南交通大学 氟化氮化硼纳米片和高性能工业润滑油脂及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4128486A (en) * 1977-01-27 1978-12-05 Combustion Engineering, Inc. Lubricant for high temperature nuclear service
US4202523A (en) * 1977-07-11 1980-05-13 International Lead Zinc Research Organization, Inc. Boron nitride/elastomeric polymer composition for coating steel casting dies
US5409622A (en) * 1994-02-07 1995-04-25 Orpac, Inc. Surface lubricant for objects contacting forms of water and method of preparation
US5985802A (en) * 1997-06-02 1999-11-16 Watari; Koji High-performance lubricant oil
US6040277A (en) * 1993-09-13 2000-03-21 Dow Corning Corporation Grease compositions employing fluorinated polymer oils and hexagonal lattice boron nitride
US6815400B2 (en) * 2001-06-04 2004-11-09 Halla Climate Control Corp. Method for forming solid film lubricant
US6858569B2 (en) * 1999-10-25 2005-02-22 Nippon Mitsubishi Oil Corporation Cutting or grinding oil composition
US6900163B2 (en) * 2000-09-14 2005-05-31 Aos Thermal Compounds Dry thermal interface material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4128486A (en) * 1977-01-27 1978-12-05 Combustion Engineering, Inc. Lubricant for high temperature nuclear service
US4202523A (en) * 1977-07-11 1980-05-13 International Lead Zinc Research Organization, Inc. Boron nitride/elastomeric polymer composition for coating steel casting dies
US6040277A (en) * 1993-09-13 2000-03-21 Dow Corning Corporation Grease compositions employing fluorinated polymer oils and hexagonal lattice boron nitride
US5409622A (en) * 1994-02-07 1995-04-25 Orpac, Inc. Surface lubricant for objects contacting forms of water and method of preparation
US5985802A (en) * 1997-06-02 1999-11-16 Watari; Koji High-performance lubricant oil
US6858569B2 (en) * 1999-10-25 2005-02-22 Nippon Mitsubishi Oil Corporation Cutting or grinding oil composition
US6900163B2 (en) * 2000-09-14 2005-05-31 Aos Thermal Compounds Dry thermal interface material
US6815400B2 (en) * 2001-06-04 2004-11-09 Halla Climate Control Corp. Method for forming solid film lubricant

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015038088A2 (fr) * 2013-09-11 2015-03-19 BORTEK BOR TEKNOLOJlLERI VE MEKATRONIK SANAYI TICARET ANONIM SIRKETI Composition de type additif antisalissures
WO2015038088A3 (fr) * 2013-09-11 2015-05-07 BORTEK BOR TEKNOLOJlLERI VE MEKATRONIK SANAYI TICARET ANONIM SIRKETI Composition de type additif antisalissures
CN113460980A (zh) * 2021-08-02 2021-10-01 西南交通大学 氟化氮化硼纳米片和高性能工业润滑油脂及其制备方法
CN113460980B (zh) * 2021-08-02 2022-11-08 西南交通大学 氟化氮化硼纳米片和高性能工业润滑油脂及其制备方法

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