WO1996040847A2 - Lubrification amelioree faisant appel a de l'acide borique comme additif - Google Patents

Lubrification amelioree faisant appel a de l'acide borique comme additif Download PDF

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Publication number
WO1996040847A2
WO1996040847A2 PCT/US1996/009586 US9609586W WO9640847A2 WO 1996040847 A2 WO1996040847 A2 WO 1996040847A2 US 9609586 W US9609586 W US 9609586W WO 9640847 A2 WO9640847 A2 WO 9640847A2
Authority
WO
WIPO (PCT)
Prior art keywords
boric acid
composition
resin composition
lubricating
additive
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1996/009586
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English (en)
Other versions
WO1996040847A3 (fr
Inventor
Ali Erdemir
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arch Development Corp
Original Assignee
Arch Development Corp
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 Arch Development Corp filed Critical Arch Development Corp
Priority to CA002223330A priority Critical patent/CA2223330C/fr
Priority to EP96923237A priority patent/EP0865478A4/fr
Priority to JP9501873A priority patent/JPH11507676A/ja
Publication of WO1996040847A2 publication Critical patent/WO1996040847A2/fr
Anticipated expiration legal-status Critical
Publication of WO1996040847A3 publication Critical patent/WO1996040847A3/fr
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26Compounds containing silicon or boron, e.g. silica, sand
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/06Metal compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087Boron oxides, acids or salts

Definitions

  • This invention is directed to an improved lubricant prepared from a mixture of boric acid and oil or grease or other such base medium lubricant.
  • This invention also relates to an improved self-lubricating composite lubricant prepared from a mixture of boric acid and/or boric acid-forming boron oxide and various engineering polymers. More particularly, the invention relates to a mixture containing boric acid particles in a mixture and/or suspension with a particular range of particle sizes and amounts.
  • Lubricants serve an important function in preserving machine components and extending machine operating lifetimes. Optimization of lubricant properties has remained a primary objective as machines are operated under more demanding and difficult conditions associated with increased efficiency and performance. Numerous additives have been developed, but much remains to be done to accommodate the increased demands now being made of lubricants. Objects of the Invention.
  • FIGURE 1 is a graphic illustration comparing the coefficients of friction of a polyimide resin composite and a polyimide resin having incorporated therein a boric acid additive, in accordance with the present invention, as explained in Table III below and the accompanying text.
  • the upper plot shows the coefficient determined for the base polyimide system and the lower plot corresponds to a polyirnide/boric acid/oxide composite of the present invention. Consistent with the referenced ASTM procedure, the comparison was conducted at 10 N, 6 rpm, 24-80% R.H. and RTemp. Siimmarv of the Invention.
  • the present invention is a lubricating composition including a solid crystalline boric acid and a non-aqueous base lubricant.
  • the non-aqueous base lubricant includes but is not limited to petroleum oils, mineral oils, synthetic oils, silicon oils, mixtures of these oils, non-aqueous solvents, mineral greases, synthetic-based greases and mixtures thereof.
  • the friction and wear-reducing boric acid is about 0.05-50 weight percent of the composition.
  • the boric acid is about 0.1-1.0 weight percent of the composition.
  • the boric acid has a crystal dimension of about 0.1-40 microns.
  • increasing advantage is gains through use of boric acid having a smaller particulate/ciystalline size. Any particulate/ciystalline dimension is limited only by the technology available to provide the boric acid of this invention.
  • the weight percent of the boric acid component is limited only by available formulation techniques and those quantities of boric acid which are required to improve lubricity. The same and similar features of this invention apply with equal effect to resin compositions, including those described below.
  • Embodiments of such lubricating compositions can further include additives such as antioxidants, metal passivators, rust inhibitors, viscosity index improvers, poor-point depressants, dispersants, detergents, extreme pressure additives, anti-wear additives, and mixtures thereof.
  • additives such as antioxidants, metal passivators, rust inhibitors, viscosity index improvers, poor-point depressants, dispersants, detergents, extreme pressure additives, anti-wear additives, and mixtures thereof.
  • an additional additive is a dispersant
  • the dispersant is present in an amount sufficient to maintain the boric acid dispersed homogeneously throughout the base lubricant.
  • a highly-preferred embodiment is one where the base lubricant is a grease.
  • a highly-preferred embodiment is an oil composition having added thereto a lubricating composition such as that described above.
  • the base lubricant can be or include a non-aqueous solvent having a higher concentration or weight percent of boric acid, such that upon addition to an oil composition the boric acid is present therein in an amount sufficient to provide the desired lubricating properties.
  • the lubricating compositions of the present invention can be used as a concentrate for subsequent addition to oils, greases and the like.
  • the present invention is a solid resin composition including a particulate boric acid additive and a synthetic polymer, whereby the boric acid additive is disbursed within the polymer in an amount sufficient to lubricate the composition during formation from its components and subsequent processing.
  • the additive is the hydration product of boric acid and water under resin formation and/or processing conditions. Regardless of additive identity, the boric acid additive is about 0.05-50 weight percent of the composition. In highly-preferred embodiments, the boric acid additive is about 0.1-1.0 weight percent.
  • the boric acid additive has a particulate dimension of about 0.1-500 microns.
  • particulate dimension it will be understood by those skilled in the art made aware of this invention, that dimension can be a function of resin application, as well as processing and formulation parameters. In addition to the considerations previously mentioned, any particulate dimension technologically achievable can be used with the present invention, realizing that crystal fracture may decrease the observed lubricity from the level desired.
  • polymers useful in conjunction with the present resin composition include but are not limited to polyimides, polyamides, epoxies, polyolifims, including ®Teflon materials and structurally-related fluorinated polymers, and polyurethanes.
  • a polymer can be a thermoset plastic material.
  • Various embodiments of this invention can be used in conjunction with other lubricants and/or fillers, including but not limited to graphite, molybdenum disulf ⁇ de, and fluorinated polyethylenes.
  • such resin compositions can include carbon fibers.
  • the present invention is a self-lubricating resin composition including a boric acid additive and a thermoset polymer, whereby the boric acid additive is dispersed within the composition in an amount sufficient to reduce the coefficient of friction of the composition.
  • the additive is boric oxide, such that boric acid is formed upon reaction with water under resin formulation and/or prpcessing conditions.
  • the additive is a friction or wear-reducing boric oxide
  • such an additive is preferably about 0.05-50 weight percent of the composition.
  • the additive is boric oxide present at about 1.0-20 weight percent of the composition.
  • the additive is preferably a particulate dimension that about 0.1-500 microns.
  • Such self-lubricating resins can include carbon fibers as an additional component.
  • an additive to a base lubricant takes the form of a dispersion of boric acid or boric acid-forming boron oxide.
  • the boric acid additive of this embodiment is available in the form of solid particles with particle sizes in the range of about 0.5 to 100 microns in diameter.
  • the preferred form of this additive is essentially boric acid powders and is available from U.S. Borax Co. of Los Angles, CA.
  • the resulting lubricant with boric acid dispersion therein takes advantage of the low friction properties of boric acid when suspended in lubricants.
  • base lubricants are oils such as petroleum based oils, synthetic oils, mineral oils, hydrocarbon based oils and silicon oils or other suitable lubricants which preferably do not react with boric acid.
  • undesirable reactions can include destruction or substantial disturbance of the layered crystal structure of boric acid.
  • the particles of boric acid under high pressure and frictional traction, interact with load-bearing surfaces to provide excellent resilience and load carrying capacity.
  • the layer structure of crystalline boric acid particles can slide over each other with relative ease and can reduce friction and wear.
  • boric acid is particularly useful for systems running at temperatures up to about 170°C. The boric acid is then dispersed as a component in base lubricants with the result being a substantially improved performance for the mixture.
  • boric acid and boric acid-forming boric oxide can be mixed with polymers and used as a lubricant for temperatures up to about 170°C.
  • the resulting lubricant provides an improved performance for the mixture.
  • Tests show an improvement of the order of 10-1,000% over that for a corresponding conventional lubricant, particularly for lubricating systems where the lubricant is being circulated.
  • the particle size for boric acid is from about 0.2 to 40 microns to facilitate the formation of a stable suspension with the boric acid being present in a amount of at least 0.1 to 0.2% by weight.
  • the amount of solid particles that can be mixed and/or dispersed in the oil will be dependent on the size of the particle. The smaller the size of particle, the greater the amount of particles that can be suspended in oil.
  • the preferred range for oils is about 0.5 to 50% by weight and for greases is about 1-50% by weight with the most prefened range being 1-15% for oils and 1- 20% for greases.
  • the size and amount of boric acid particles to be added to oils and greases will be generally determined by the intended use of the resulting lubricant mixture having the solid particles in suspension. Conventional equipment and techniques can be employed to achieve substantially uniform or stable dispersion or distribution of the additive in the final mixture.
  • Stable dispersion means a mixture in which solid lubricating particles remain as separate, discrete particles in the presence of a stabilizer and a carrier fluid medium. Methods of achieving a uniform dispersion of the particles in the base lubricant are well-known to those in the art. Concentrates comprising higher amounts of boric acid can also be prepared first and then added to conventional oils or greases.
  • the lubricants can, in addition, contain other additives which are added to improve the fundamental properties of lubricants even further.
  • additives may include: antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents, extreme pressure additives of liquid and solid types and anti-wear additives.
  • the base lubricant greases useful in the preparation of the lubricant composition of the invention can be any of the known greases employed as bases for extreme pressure applications.
  • the self-lubricating polymer composites prepared according to this invention afford 50% to 90% reduction in friction while reducing wear to unmeasurable levels. It has been found that boron oxide particles incorporated in conventional polymers enhance their antiwear and antifriction properties and increase their mechanical strength and load carrying capacity.
  • the lubricant additive of present invention provides moving resin/polymer surfaces with very low friction and wear. Therefore, sliding performance and wear life of these polymers increase substantially. While the temperature, noise level and vibration of sliding bodies decrease, efficiency increases markedly.
  • the additive of this invention is boron oxide and available in the form of solid part cles with particle sizes of below about 0.5 to 1,000 microns in diameter.
  • the mixtures of this invention are unique and take advantage of the slippery boric acid films that form spontaneously on the surface of boron oxide mixed with a suitable polymer.
  • the particles of boron oxide, imder high pressure and frictional traction, interact with load-bearing surfaces and form a boric acid film of excellent resilience and load carrying capacity.
  • Boric oxide particles mixed with polymers form boric acid on the exposed surface by reacting with moisture in the surrounding atmosphere.
  • the surface film consisting of the layers of crystalline boric acid and these layers can slide over each other with relative ease and reduce friction and wear.
  • the particle size of boric acid-forming boron oxide be in the range of 0.1 to 500 microns, and in an amount greater than 0.05% by weight, depending on the intended use of polymers.
  • the amount of solid boron oxide particles that can be mixed and/or dispersed in the polymer will be dependent on the size of the particle. The smaller the size of particle, the greater the amount of boron oxide that can be incorporated in polymers.
  • a prefened range is 0.05% to 50% by weight with a most prefened range being 1 to 20%.
  • the size and amount of boric acid particles to be added to polymers will be determined by the intended use of the resultant composite structure. Conventional equipment and techniques can be employed to achieve an even distribution of the boric oxide additive in the final composition. Such dispersion methods are well-known to those in the art of making dispersions of solids in solid media. These polymers can include plastics, rubbers, elastomers, polyimides, nylons, epoxy resins, and Teflon. The selection of specific polymer for mixing varies with the intended use and can be readily determined by one of ordinary skill in the art.
  • Example 1 Mixture of boric acid and lubricant oil or grease.
  • This example illustrates the extent of performance improvement with the use of a mixture of boric acid and oil or grease.
  • a commercially available mineral and motor oil or grease are mixed with boric acid powder having particle sizes from about 0.2-40 microns in amounts ranging from 1 to 50% by weight.
  • the mixture was put in a glass container and stined vigorously by means of a magnetic stirring device for a period of at least 2 hours.
  • the mixture was then used as a lubricant on a wear test machine whose function and main features may be found in the 1990 Annual Book of ASTM Standards, Volume 3.02, Section 3, pages 391-395.
  • Friction test results from various pin and disk pairs under different loads were evaluated using Friction test results from various pin and disk pairs under different loads. Test conditions: Speed, 1-3 mm/s; Temperature, 22-25 °C; 440C and 52100 steel pins and disks.
  • Example 2 A concentrated (about ten weij »ht perce nt) aqi leous solutic of boric acid was prepared at 70° C, using a magnetic stirrer. Caution was taken to prevent any visible precipitation occurring during mixing/dissolution process.
  • the concentrated boric acid solution was homogeneously combined with a petroleum-based grease product at 70° C, also with magnetic stirring.
  • the combined grease boric acid mixture was placed in a dehydration oven maintained at subatmospheric pressures (between 5 to 27 inches of Hg) and a temperature of about 250° F to induce flash vaporization and provide the resulting grease product.
  • the grease product, prepared as described above, was subjected to raman spectroscopy, a useful technique by which to analyze the crystalline morphology, or lack thereof, of a chemical compound.
  • raman spectroscopy involves the reflection of radiation as a result of a well-defined molecular structure.
  • a crystalline material has a well-defined three dimensional structure which provides a unique raman spectrum
  • an amo ⁇ hous material provides a raman spectrum without any defining characteristics consistent with a material lacking a crystalline structure.
  • the grease product, prepared as described above, was analyzed with raman spectroscopy about 20 hours after preparation, comparing it first to the spectrum of neat grease and then to the spectrum of crystalline boric acid.
  • the boric acid raman spectrum is characterized by a pronounced peak at or about 875 cm'l.
  • the raman spectrum of the aforementioned grease product does not give any response at 875 cm"l, but shows a sha ⁇ peak at 823 cm"l.
  • the spectrum is notable by the absence of the characteristic peak (875 cm-1) of boric acid, demonstrating that the grease mixture product does not include crystalline boric acid.
  • a boric acid/grease mixture prepared according to the present invention, provided a raman spectrum showing a peak at 876 cm _ l» characteristic of crystalline boric acid which is absent in the spectrum of the aforementioned grease product. (The lesser peak intensity and slight positional shift is attributable to a low-concentration mixture versus solid boric acid.)
  • a boric oxide composition was prepared to evaluate the ability of such a composition to form boric acid by absorbing atmospheric moisture. Accordingly, a commercially-available boric oxide powder was placed in a dehydration oven and heated at 350° F under subatmospheric pressures of about 27 inches of Hg for about 20 to 25 minutes to remove any moisture previously absorbed. The anhydrous boric oxide so obtained was combined with a petroleum-based grease by manual and magnetic stirring.
  • the boric oxide/grease mixture so obtained was exposed to atmospheric moisture, at room temperature, for about 20 hours.
  • the raman spectrum of the boric oxide/grease mixture does not show the characteristic peak (875 cm"l) associated with boric acid and attributable to the crystalline structure thereof, demonstrating that boric oxide does not hydrate and form boric acid without exposure to atmospheric moisture and absent specific processing temperatures.
  • Example 3 Mixture of boric acid and boric oxide, which forms boric acid, and polymer.
  • This example illustrates the extent of performance improvement with the use of a mixture of a boric acid additive, when used in conjunction with a number of representative, commercially available polymers.
  • the polymers are mixed with boron oxide powders having particle sizes from about 0.2 to 40 microns in amounts ranging from 1% to 20% by weight.
  • the mixture of polymer and boron oxide powder was put in a glass container and stined vigorously by means of a mechanical mixer for a period of at least two hours. The mixture was first compacted, then hot-pressed and finally cured at an optimum temperature to assume a dense, solid disk shape.
  • Friction test results from various steel pins and selected polymer disks were tested for various steel pins and selected polymer disks. Test conditions: Load, 0.5 to 1 kg; Speed, 1-4 mtn/s; Temperature, 22-25° C; Sliding distance, 180 m; Test pairs, various steel pins and polymer disks with and without boron oxide particles.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions de résines auto-lubrifiantes contenant de l'acide borique comme additif et un polymère synthétique contenant ces produits thermodurcissables.
PCT/US1996/009586 1995-06-07 1996-06-07 Lubrification amelioree faisant appel a de l'acide borique comme additif Ceased WO1996040847A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002223330A CA2223330C (fr) 1995-06-07 1996-06-07 Lubrification amelioree faisant appel a de l'acide borique comme additif
EP96923237A EP0865478A4 (fr) 1995-06-07 1996-06-07 Lubrification amelioree faisant appel a de l'acide borique comme additif
JP9501873A JPH11507676A (ja) 1995-06-07 1996-06-07 ホウ酸添加剤による潤滑作用の改善

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US48165795A 1995-06-07 1995-06-07
US08/481,657 1995-06-07

Publications (2)

Publication Number Publication Date
WO1996040847A2 true WO1996040847A2 (fr) 1996-12-19
WO1996040847A3 WO1996040847A3 (fr) 2001-06-14

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PCT/US1996/009586 Ceased WO1996040847A2 (fr) 1995-06-07 1996-06-07 Lubrification amelioree faisant appel a de l'acide borique comme additif

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EP (1) EP0865478A4 (fr)
JP (1) JPH11507676A (fr)
CA (1) CA2223330C (fr)
WO (1) WO1996040847A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003078555A1 (fr) * 2002-03-18 2003-09-25 Cosmo Oil Lubricants Co., Ltd. Composition d'huile lubrifiante et procede de production associe
CN116715246A (zh) * 2023-07-28 2023-09-08 烟台先进材料与绿色制造山东省实验室 一种掺杂硼具有多级孔结构的二氧化硅微球及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015093443A1 (ja) * 2013-12-16 2017-03-16 旭有機材株式会社 摺動部材用樹脂組成物及び摺動部材

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JPS63291994A (ja) * 1987-05-23 1988-11-29 Kawabata Seisakusho:Kk 潤滑油
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JP2687176B2 (ja) * 1990-04-06 1997-12-08 宇部興産株式会社 熱可塑性樹脂組成物
JP2692474B2 (ja) * 1991-12-25 1997-12-17 住友金属工業株式会社 継目無金属管の熱間圧延用潤滑剤
CA2138275C (fr) * 1992-06-16 1999-12-14 Ali Erdemir Lubrication amelioree a partir d'un melange d'acide borique avec des huiles et des graisses
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JP3124454B2 (ja) * 1994-11-24 2001-01-15 新日本製鐵株式会社 鋼材の熱間圧延用潤滑剤組成物及び鋼材の熱間圧延方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003078555A1 (fr) * 2002-03-18 2003-09-25 Cosmo Oil Lubricants Co., Ltd. Composition d'huile lubrifiante et procede de production associe
CN116715246A (zh) * 2023-07-28 2023-09-08 烟台先进材料与绿色制造山东省实验室 一种掺杂硼具有多级孔结构的二氧化硅微球及其制备方法和应用

Also Published As

Publication number Publication date
CA2223330A1 (fr) 1996-12-19
WO1996040847A3 (fr) 2001-06-14
EP0865478A2 (fr) 1998-09-23
CA2223330C (fr) 2003-03-11
JPH11507676A (ja) 1999-07-06
EP0865478A4 (fr) 2000-04-05

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