US3894957A - Copper-lead alloys for lubricants and bearings - Google Patents

Copper-lead alloys for lubricants and bearings Download PDF

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US3894957A
US3894957A US321030A US32103073A US3894957A US 3894957 A US3894957 A US 3894957A US 321030 A US321030 A US 321030A US 32103073 A US32103073 A US 32103073A US 3894957 A US3894957 A US 3894957A
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lead
copper
alloy
promoter
homogeneity
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Charles E Lundin
Robert Turkisher
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    • 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
    • C10M103/04Metals; Alloys
    • 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
    • C10M125/04Metals; Alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16CSHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/02Parts of sliding-contact bearings
    • F16C33/04Brasses; Bushes; Linings
    • F16C33/06Sliding surface mainly made of metal
    • F16C33/12Structural composition; Use of special materials or surface treatments, e.g. for rust-proofing
    • F16C33/121Use of special materials
    • 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
    • C10M2201/04Elements
    • C10M2201/05Metals; Alloys
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Semi-solids; greasy

Definitions

  • ABSTRACT This disclosure is directed to copper-lead alloys for lubricants and bearings.
  • the copper-lead alloys have a fine and even dispersion of the lead particles in a copper matrix.
  • the alloy is made by adding an effective amount of a homogeneity promoter to a mixture of molten lead and copper.
  • the promoter comprises elemental carbon and an alkali and/or alkaline earth metal compound capable of reacting to form a gas, or a rare earth metal compound in the form of an oxide or carbonate.
  • the lubricants comprise the copper-lead alloy in powdered form, as a dry lubricant, in a carrier, or in a base of a grease or oil.
  • the bearings comprise the copper-lead alloy as a load-bearing surface.
  • This invention relates to lubricants and bearings of homogeneous copper-lead alloys.
  • homogeneous is used herein to refer to an improved alloy having a fine and even dispersion of the phases.
  • the foregoing and other objects are accomplished by the use of copper-lead alloys which are made by adding effective amounts of a homogeneity promoter to the molten metal.
  • the promoter may comprise elemental carbon and an alkali or alkaline earth metal compound which reacts under the molten conditions present during the alloying and casting of the copper and lead to form a gas. Details regarding the preparation of the alloy appear in our above-noted U.S. Pat. No. 3,556,779 and U.S. Pat. application Ser. No. 53,953.
  • the mechanism provided by the promoter is one of innoculation of a fine dispersion of the lead particles in a copper matrix. Examples of such compounds are sodium carbonate and calcium carbonate.
  • Promoters containing rare earth metals may also be used in this invention. Details regarding this promoter to make copper-lead alloys are set forth in copending Pat. application Ser. No. 62,338 filed Aug. 10, 1970 now U.S. Pat. No. 3,720,507.
  • Copper-lead alloys for use in the present invention are produced in varying proportions of copper and lead.
  • the proportions may be varied as desired and as the specific application dictates. It has been found that alloys of substantial utility are those which contain 5 to 55% lead and to 45% copper. The problem of separation and segregation of the lead and copper is greatest with a high lead content.
  • the promoter of this invention therefore provides its greatest utility at lead contents of from 20 to 45%. If the lubricating qualities of the alloy are to be increased, the proportion of lead should be in the higher range. If it is desirable to increase the strength of the material, a lesser proportion of lead should be utilized.
  • Additional elements may be added for their well-known enhancement of particular properties such as zinc, tin, nickel, etc., in amounts up to about 10% by weight of the alloy.
  • the copper-lead alloy used in this invention may contain significant amounts of aluminum to harden the alloy, for example, up to about 10%. The details regarding the preparation of such alloys are set forth in patent application Ser. No. 112,421 filed Feb. 3, 1971.
  • the elemental carbon component is preferably finely powdered graphite. Although coarser carbon may be used, the larger particles tend to decrease the efficiency of the process, presumably due to reduced surface area to volume ratio.
  • Other forms of carbon include bone-black, carbonblack, charcoal and the like.
  • the alkali metal compound may be lithium, potassium or sodium (or other metals of Group In of the Periodic Table), preferably combined as a carbonate.
  • Thealkaline earth compound may be calcium, strontium or barium (or other metals of Group 2a of the Periodic Table), preferably combined as a carbonate. Combinations of alkali and alkaline earth compounds may be used, for example, a mixture of sodium and calcium carbonate.
  • the terms rare earths and rare earth carbonates as used throughout this application are intended to include scandium, yttrium, lanthanum and the lanthanides, the latter term encompassing those metals having atomic numbers from 58 to 71.
  • the preferred rare earths are cerium and yttrium and mixtures thereof with lanthanum, praseodymium, samarium and europium.
  • the preferred rare earth compounds are the halocarbonates, particularly the fluorocarbonates of the above metals.
  • the carbonates and oxides of the rare earths are also suitable.
  • the rare earth compounds may be used with or in place of the alkali and/or alkaline earth compounds.
  • the amount of homogeneity promoter used must be at least that amount which ensures formation of a uniformly dispersed mixture of lead and copper which does not segregate on solidification;
  • a preferred effective range of the proportions has been found to be about 1-5 grams of carbon or graphite powder and about 3-15 grams of metal compound for each pound of alloy. Below this proportion improvements in homogeneity are obtained, but. the effect is less pronounced when a very minor amount of promoter is used.
  • Higher amounts of the homogeneity promoter may be used, for example, up to 10 grams of graphite and 30 grams of 'the metal compound-for each pound of alloy. Although these and even greater amounts provide an improved alloy in accordance with the present invention, the use of greater amounts from an economic standpoint is less attractive.
  • the maximum proportion of the promoter is determined by characteristic requirements of the alloy and economic considerations.
  • the promoter is partially decomposed to form gases which provide a stirring and nucleation effect and that the undecomposed portion of the promoter also provides nucleation sites.
  • the carbonate melts well below the reaction temperature range and decomposes at the higher temperatures into carbon monoxide gas and the metal oxide.
  • the oxide in turn is reduced by the carbon to form additional carbon monoxide and metal.
  • the metal may also be above its boiling point and released in gaseous form.
  • the combined action of the gases cause the vigorous stirring action. Agitation continues through the cooling step and it is in this stage when the agitation is believed to be most effective.
  • the agitation prevents gross separation of the lead and the copper phases and further provides many more nucleation sites for the solid, copper-rich dendrites to form from the liquid.
  • the additional nucleation sites cause the final solidified structure to be fine-grained and further allows more efficient and homogeneous entrapment and entrainment of the lead phase in the copper matrix.
  • innoculation occurs by unreacted (or partially reacted) carbonate and graphite during stirring of the melt. The innoculation by these particles which are not fully decomposed to gases provides sites for the nucleation and growth of fine lead particles.
  • the combined action promotes a random, fine-grained dispersion of lead in copper which is mandatory for the optimum characteristics and requirements of a bearing alloy and lubricant.
  • the novel copper-lead alloys used in this invention have a finer and more uniform dispersion of the lead in the copper.
  • the composition of the alloy is from 5 to 55% lead, preferably 20 to 45% lead, 95 to 45% copper, preferably 80 to 55% copper, with up to of other metals, preferably zinc and/or tin, with only minor amounts of other metals, and trace amounts of the homogeneity promoter.
  • This copper-lead alloy may also be used in an aluminum matrix, as set forth in the above-noted patent application Ser. No. 112,421.
  • the average particle size of the lead in the copper matrix is between 0.002 to 0.020 mm diameter. Larger particles of lead occur but only a .very minor amount of segregation occurs, which is not detrimental. An average particle size of 0.002 to 0.010 mm for copper-lead alloys having to 45% lead produces an excellent alloy for use in the present invention. The average particle size remains within the above ranges even after the alloy is remelted or recast, although some minor agglomeration does occur.
  • segregation as used in this application is intended to refer to lead particles having a diameter greater than about 1 mm.
  • the alloys of this invention have only a minor amount of segregation. preferably about 0%.
  • the massive segregation which occurs without the homogeneity promoter of this invention is normally exhibited as a layering of the lead. Minor segregation is evidenced by lead particles having a size of about 0.5 mm, but this is not a serious problem if such particles are well dispersed and constitute less than 5% of the lead volume.
  • Another advantage of this process is the remelt capability of the copper-lead alloy without substantial segregation. This effect is desirable particularly if the material is produced as a solid billet which is to be subsequently cast into a desired form.
  • the remelt capability without undesirable segregation may be due to remnants of the homogeneity promoter remaining in the alloy, or may be a function of the fineness of the original dispersion.
  • the homogeneity promoter has a lingering effect in improving the homogeneity of the alloy it may be desirable upon successive remelts, or where the original alloy composition remains molten for an extended period of time, to add the homogeneity promoter in increments. For example, when the alloy remains molten for a period of 10 minutes to an hour, a second addition of the promoter in an amount within the preferred effective range should be made prior to using (i.e., casting) the alloy.
  • Additional additives may be used in combination with the above-described homogeneity promoter.
  • a metal phosphate such as ortho lead phosphate, ortho cupric phosphate or ortho tin phosphate.
  • copper of the desired quantity is placed in a graphite crucible and brought to a temperature of l,250l350C using an induction heater.
  • the lead and the homogeneity promoter are added to the melt preferably with stirring.
  • violent agitation of the liquid mixture ensues with the formation of gas.
  • the temperature of the mixture is maintained for at least 1 minute and preferably 3 minutes for best results.
  • the melt is then allowed to cool through its solidification temperature during which time the agitation continues. After solidification the temperature of the alloy is permitted to drop to ambient levels preferably not too slowly.
  • the resulting solid structure of the ingot is free of porosity.
  • the mixture may be cast at conventional temperatures such as l,000-l,l00C.
  • novel alloys of copper-lead prepared by the foregoing method have the structural characteristics required to produce optimum antifrictional qualities.
  • the purity is high since the alloy has been thoroughly deoxidized.
  • the homogeneity promoter is almost undetectable by emission spectroscopy analysis.
  • the lead phase is finely and randomly dispersed throughout the copper matrix. These factors contribute to a low coeffielectrical resistivity.
  • they may be ,sintered, I fabricated and machined without losing their superior antifriction qualitiesv a
  • the alloy made by the above procedure is particularly useful as a bearing surface. It is suited for'use Y when high or low temperatures and high stressesare present. Most standard methods for making bearings and bearing surfaces may be employed.
  • the bearing can be made by casting techniques, as, set forth in greater detail in patent application S er. No. 53,953. Additionally, powder metallurgical techniques are useful.
  • the alloy in bonding the alloy of the present invention to steel, the alloy can be powdered utilizing an atomization method. The steel is heated untilit-turns blue (approximately 6()() F) and the powder made from the alloy is then sprayed .ontoth e steel surface; The heat from the surface of the steel bonds the copperlead alloy to the steel on contact.
  • the powdered alloy can be preheated to soften or melt the
  • the alloy may also be used as a dry lubricant, or in a minor amount of a carrier such as an oil or grease or a'v'olatile' organic compound, which is sufficient to fatrical contacts.
  • Plastic, rubber or fiber surfaces can also be treatedwith the powdered alloy under conditions of heat-orpressure; or during fabrication techniques such as moldingln this manner the additive can be used on "snowmobile plastic support members which are in surface of the powder which is sprayed upon a base sur face.
  • the base is preferably first grit-blasted to roughen its surface and the powder may be heated for spraying with an oxy-acetylene torch under slightly reducing conditions. This technique is suitable for adding a 1/16 inch layer to thrust bearing pads.
  • the powdered alloy can also be sintered onto a steel backing to providea thicker bearing surface.
  • a very thin intermediate layer of, for example, tin or zinc can
  • the alloys may also be used in ordnance developments such; as for small arms on the inside surface of gun barrels. w
  • the alloy is combinedrinpo'wdered form with other lubricants such as greas'es:and oils in quantities ranging preferably from a trace to'ifour ounces per pound of the grease or oil.
  • the resulting combination is a lubricant which fully coats moving parts thereby increasing the life of these parts. Maintenance requirements are also reduced.
  • the alloy is of value when the lubricant combination is used in sealed units where frequent changes of lubricant are uneconomical. In this application the'improved "'results are obtained over a longer period of timewhen'higher per-' centages of lead are used in the alloy.
  • powdered copper-lead alloys are preferaf bly used in amounts from about '15 to"'25%',although higher or lower amounts can be used.
  • Emmet 3 and 4. resulted in alloys of suitable .-'qi1ality for. bearing materials.
  • a powdered mixture was prepared from 2.2 pounds of graphite and 4.8 pounds of sodium carbonate. The mixture was added to a molten alloy comprising approximately 20% lead, 4% Zinc, 75% copper and minor amountsof antimony,'nickel and other constituents.
  • the bath contained about 400 pounds of metal at about 2,300-2,'400F.
  • the molten metal was then centrifu- 'gallycast by conventional procedures to form a motor 5 pressure. Upong-cooling the bearing was broken in a press andathe internal structure visually examined. It
  • EXAMPLE 8 Nine pounds of copper were placed in an induction heater and brought to 1,300C. Six pounds of lead and a mixture of 68.l grams of sodium carbonate and 34.1
  • grams powdered graphite were added to the molten tion of minor amounts is a suitable'technique, such as 2 ounces every 10-15 thousand miles in the crankcase of an automobile.
  • a lineal analysis was made of the particle size and spacing of the product.
  • the specimens were measured on a microscope with a Filar eyepiece that was calibrated in millimeters. Random traverses were conducted in a linear fashion across the surface of the metallographically prepared surface. Three traverses were run with about 200 measurements per traverse. Then the specimen was prepared with a surface perpendicular to the original surface and two more traverses were conducted at 200 measurements per traverse.
  • molten mass was atomized in an inert atmosphere (nitrogen and argon are suitable) to form a powder.
  • the powder which passed through a 325 mesh screen was collected; this powder had an average particle size of about 6 to 10 microns and was used in the following example.
  • EXAMPLE 14 The powdered alloy of Example 13 was used as a lubricant in automobile engines in amounts of from onethird to two-thirds of an ounce per quart of motor oil. Two ounces of the powder were mixed with one half quart of W Valvoline motor oil and added to the crankcase of a Volkswagen (which already contained about 2 /2 quarts of oil) with the engine running. Prior to the use of the copper-lead additive, the car had been Traverses Perpendicular to Axis of lngot Average Average Distance Particle Standard Between Standard Size Deviation Particles Deviation Traverse No. 1 0.0043 mm 0.0020 mm 0.0086 mm 0.0096 mm Traverse No.
  • EXAMPLES 10-12 Three castings were made, each weighing 15 pounds. The additive used was 136 grams sodium carbonate and 34 grams graphite in each example. The ratios of copper to lead were 60:40, 70:30 and 80:20, respectively. Each finished casting was then separately melted and poured into a high velocity stream of nitrogen to obtain a fine powder. The powders were sintered and compacted into bearing rings according to conventional techniques. The bearings were examined by the photomicrographic technique and showed a fine dispersion of the constituents. This evidences the excellent remelt capability of the alloys of the present invention and the capability of forming powders for a wide variety of industrial uses. The powder need not be made from a melt of the casting but may be formed directly from a mix of the molten metal and promoter.
  • EXAMPLE 1 3 The amount of the homogeneity promoter was 1 per- :cent by weight of the molten metal. After 1 miriutethe the four cylinders was 100 pounds. After driving the car with the additive for 65 miles the engine compression was determined and found to have increased about 5% (compression 105 pounds), and after 700 miles the compression increased an additional 10% (compression 1 15 pounds). The examination of parts in contact with the copper-lead-oil lubricant showed that the alloy was burnished onto the bearing surface (a copper color in areas of wear was very noticeable).
  • a lubricating material comprising an oil or grease which has distributed therein a powdered homogeneous alloy, said alloy containing copper and lead and trace remnants of the products from a homogeneity promoter in molten copper and lead, said homogeneity promoter comprising elemental carbon and a metal compound selected from the group consisting of compounds of an alkali metal and an alkaline earth metal.
  • said alloy comprises about 5 to 55% lead, and about to 45% copper wherein the lead is in the form of a fine dispersion in a copper matrix, and the average diameter 9 of said lead particles is between about 0.002 mm to 0.02 mm.
  • the lubricating material of claim 1 wherein said alloy comprises about 20 to 45% lead, wherein the lead is in the form of a fine dispersion in a copper matrix, and the average diameter of said lead particles is between about 0.002 to 0.01 mm.
  • the lubricating material of claim 1 wherein said alloy has an average particle size of about 6 to 10 microns.
  • a composition comprising a powdered homogeneous alloy consisting essentially of copper and lead, and a homogeneity promoter which is the reaction product of elemental carbon with an alkali metal compound selected from the group consisting of sodium carbonate and potassium carbonate in molten copper and lead, and a petroleum or vegetable based lubricant.
  • composition of claim 8 wherein the alloy comprises from a trace to 4 ounces per pound of said lubricant.
  • composition of claim 8 wherein said alloy comprises about 20-45% lead.
  • a composition comprising a powdered homogeneous alloy comprising a mixture of copper and lead, wherein said mixture comprises from 555% lead and from 9545% copper, and wherein the total of said lead and copper in said mixture is at least and trace remnants of the products from a homogeneity promoter in molten copper and lead, said homogeneity promoter comprising elemental carbon and a rare earth metal compound selected from the group consisting of oxides, carbonates and halocarbonates, and a petroleum or vegetable based lubricant.
  • composition of claim 11 wherein the alloy comprises from a trace to 4 ounces per pound of said lubricant.
  • composition of claim 11 wherein said alloy comprises about 20 45% lead.
  • a composition comprising a powdered homogeneous alloy comprising copper and lead, and trace remnants from a homogeneity promoter comprising elemental carbon and an alkali or alkaline earth metal compound capable of reacting to form a gas in molten copper and lead, and a petroleum or vegetable based lubricant.
  • composition of claim 14 wherein the alloy comprises from a trace to 4 ounces per pound of said lubricant.
  • composition of claim 14 wherein said alloy comprises about 20 45% lead.

Abstract

This disclosure is directed to copper-lead alloys for lubricants and bearings. The copper-lead alloys have a fine and even dispersion of the lead particles in a copper matrix. The alloy is made by adding an effective amount of a homogeneity promoter to a mixture of molten lead and copper. The promoter comprises elemental carbon and an alkali and/or alkaline earth metal compound capable of reacting to form a gas, or a rare earth metal compound in the form of an oxide or carbonate. The lubricants comprise the copper-lead alloy in powdered form, as a dry lubricant, in a carrier, or in a base of a grease or oil. The bearings comprise the copper-lead alloy as a load-bearing surface.

Description

United States Patent Lundin et a1.
1 1 COPPER-LEAD ALLOYS FOR LUBRICANTS AND BEARINGS [76] Inventors: Charles E. Lundin, PO. Box 624,
Evergreen, Colo. 80439; Robert Turkisher, 218 Crystal Hills Blvd., Manitou Springs, Colo. 80829 [22] Filed: Jan. 4, 1973 21 Appl. No.: 321,030
Related US. Application Data [63] Continuation-in-part of Ser. No. 53,953, July 10, 1970, Pat. No. 3,719,477, I which is a continuation-in-part of Ser. No. 706,640. Feb. 19, 1968, Pat. No. 3,556,779.
[52 U.S. C1. 252/26; 252/56 R [51] Int. Cl..... Cl0m 1/54; C10m 3/48 ;C10m 5/28 [58] Field of Search 252/26, 56 R [56] References Cited UNITED STATES PATENTS 1,642,347 9/1927 Williams et 31.... 252/12 2,321,203 6/1943 Henry et a1. 252/26 2,543,741 2/1951 Sweifel l 252/26 3,063,941 11/1962 Wilson.... 252/26 3,232.872 2/1966 Kohn 252/26 [4 July 15, 1975 3,549,531 12/1970 Santt 252/26 FOREIGN PATENTS OR APPLICATIONS 874,264 8/1961 United Kingdom 252/26 Primary ExaminerDelbert E. Gantz Assistant Examiner-l. Vaughn [5 7] ABSTRACT This disclosure is directed to copper-lead alloys for lubricants and bearings. The copper-lead alloys have a fine and even dispersion of the lead particles in a copper matrix. The alloy is made by adding an effective amount of a homogeneity promoter to a mixture of molten lead and copper. The promoter comprises elemental carbon and an alkali and/or alkaline earth metal compound capable of reacting to form a gas, or a rare earth metal compound in the form of an oxide or carbonate.
The lubricants comprise the copper-lead alloy in powdered form, as a dry lubricant, in a carrier, or in a base of a grease or oil.
The bearings comprise the copper-lead alloy as a load-bearing surface.
16 Claims, N0 Drawings COPPER-LEAD ALLOYS FOR LUBRICANTS AND BEARINGS CROSS-REFERENCES This application is a continuation-in-part of our copending application Ser. No. 53,953 filed July 10, 1970 now U.S. Pat. No. 3,719,477, which in turn is a continuation-in-part of our patent application Ser. No. 706,640 filed Feb. 19, 1968, now U.S. Pat. No. 3,556,779. This application is also directed to subject matter divided out of said applications.
DISCLOSURE OF THE INVENTION This invention relates to lubricants and bearings of homogeneous copper-lead alloys. The term homogeneous is used herein to refer to an improved alloy having a fine and even dispersion of the phases.
Attempts to produce homogeneously dispersed copper-lead alloys have been made in order to provide such alloys which have high thermal conductivity, low electrical resistivity and a low coefficient of friction. These properties are highly desirable for metals used to make bearings or as a bearing material and as a dry lubricant or as an additive to liquid or viscous lubricants made of petroleum or vegetable bases. However, many problems have not been solved by the prior art in attempting to make homogeneously dispersed copperlead alloys. The basic problem with these alloys is the prevention of massive separation and segregation of the copper and lead. This tendency to separate and segregate increases as the lead content rises in the copperlead alloy. Another problem associated with the use of prior alloys is that even if there is initial homogeneity, under high stress and temperature conditions, the lead has a tendency to separate and segregate from the copper. A further problem associated with copper-lead alloys in the prior art is that the lead tends to segregate from the copper when it is being remelted and recast into other shapes and forms.
It is therefore an object of the present invention to provide bearings, bearing materials, dry lubricants, and petroleum and vegetable based lubricants comprising a homogeneous cop'peelead alloy.
Other objects will be apparent from a reading of the specification and claims of this application.
Briefly, in accordance with the present invention, the foregoing and other objects are accomplished by the use of copper-lead alloys which are made by adding effective amounts of a homogeneity promoter to the molten metal. The promoter may comprise elemental carbon and an alkali or alkaline earth metal compound which reacts under the molten conditions present during the alloying and casting of the copper and lead to form a gas. Details regarding the preparation of the alloy appear in our above-noted U.S. Pat. No. 3,556,779 and U.S. Pat. application Ser. No. 53,953. The mechanism provided by the promoter is one of innoculation of a fine dispersion of the lead particles in a copper matrix. Examples of such compounds are sodium carbonate and calcium carbonate. Promoters containing rare earth metals may also be used in this invention. Details regarding this promoter to make copper-lead alloys are set forth in copending Pat. application Ser. No. 62,338 filed Aug. 10, 1970 now U.S. Pat. No. 3,720,507.
Many procedures are available in the art for making and using alloys, for example, see U.S. Pat. No. 3,544,314. However, the use of the homogeneity promoters described in the present and related applications leads to copper-lead alloys having a finer and more uniform dispersion of lead in copper and such alloys are particularly suited for use in bearings and lubricants.
Copper-lead alloys for use in the present invention are produced in varying proportions of copper and lead. The proportions may be varied as desired and as the specific application dictates. It has been found that alloys of substantial utility are those which contain 5 to 55% lead and to 45% copper. The problem of separation and segregation of the lead and copper is greatest with a high lead content. The promoter of this invention therefore provides its greatest utility at lead contents of from 20 to 45%. If the lubricating qualities of the alloy are to be increased, the proportion of lead should be in the higher range. If it is desirable to increase the strength of the material, a lesser proportion of lead should be utilized. Additional elements may be added for their well-known enhancement of particular properties such as zinc, tin, nickel, etc., in amounts up to about 10% by weight of the alloy. The copper-lead alloy used in this invention may contain significant amounts of aluminum to harden the alloy, for example, up to about 10%. The details regarding the preparation of such alloys are set forth in patent application Ser. No. 112,421 filed Feb. 3, 1971.
As to the homogeneity promoter used for alloys in this invention, it has been found that the elemental carbon component is preferably finely powdered graphite. Although coarser carbon may be used, the larger particles tend to decrease the efficiency of the process, presumably due to reduced surface area to volume ratio. Other forms of carbon include bone-black, carbonblack, charcoal and the like.
The alkali metal compound may be lithium, potassium or sodium (or other metals of Group In of the Periodic Table), preferably combined as a carbonate. Thealkaline earth compound may be calcium, strontium or barium (or other metals of Group 2a of the Periodic Table), preferably combined as a carbonate. Combinations of alkali and alkaline earth compounds may be used, for example, a mixture of sodium and calcium carbonate. The terms rare earths and rare earth carbonates as used throughout this application are intended to include scandium, yttrium, lanthanum and the lanthanides, the latter term encompassing those metals having atomic numbers from 58 to 71. The preferred rare earths are cerium and yttrium and mixtures thereof with lanthanum, praseodymium, samarium and europium. The preferred rare earth compounds are the halocarbonates, particularly the fluorocarbonates of the above metals. The carbonates and oxides of the rare earths are also suitable. The rare earth compounds may be used with or in place of the alkali and/or alkaline earth compounds.
The amount of homogeneity promoter used must be at least that amount which ensures formation of a uniformly dispersed mixture of lead and copper which does not segregate on solidification; A preferred effective range of the proportions has been found to be about 1-5 grams of carbon or graphite powder and about 3-15 grams of metal compound for each pound of alloy. Below this proportion improvements in homogeneity are obtained, but. the effect is less pronounced when a very minor amount of promoter is used. Higher amounts of the homogeneity promoter may be used, for example, up to 10 grams of graphite and 30 grams of 'the metal compound-for each pound of alloy. Although these and even greater amounts provide an improved alloy in accordance with the present invention, the use of greater amounts from an economic standpoint is less attractive. The maximum proportion of the promoter is determined by characteristic requirements of the alloy and economic considerations.
Although the exact mechanism is not completely understood, and patentability is not dependent thereupon, it is believed that the promoter is partially decomposed to form gases which provide a stirring and nucleation effect and that the undecomposed portion of the promoter also provides nucleation sites. The carbonate melts well below the reaction temperature range and decomposes at the higher temperatures into carbon monoxide gas and the metal oxide. The oxide in turn is reduced by the carbon to form additional carbon monoxide and metal. The metal may also be above its boiling point and released in gaseous form. The combined action of the gases cause the vigorous stirring action. Agitation continues through the cooling step and it is in this stage when the agitation is believed to be most effective. The agitation prevents gross separation of the lead and the copper phases and further provides many more nucleation sites for the solid, copper-rich dendrites to form from the liquid. The additional nucleation sites cause the final solidified structure to be fine-grained and further allows more efficient and homogeneous entrapment and entrainment of the lead phase in the copper matrix. Also, innoculation occurs by unreacted (or partially reacted) carbonate and graphite during stirring of the melt. The innoculation by these particles which are not fully decomposed to gases provides sites for the nucleation and growth of fine lead particles. The combined action promotes a random, fine-grained dispersion of lead in copper which is mandatory for the optimum characteristics and requirements of a bearing alloy and lubricant. An additional benefit of the emission of carbon monoxide, or gaseous metal, is to produce a reducing atmosphere over the alloy during the liquification and solidification which almost completely prevents oxidation of the alloy from the air. Thus, it is not necessary to employ artificial protective atmospheres to reduce severe metal loss due to oxidation. However, if desired inert atmospheres may be used in addition to blanket the system. v
The novel copper-lead alloys used in this invention have a finer and more uniform dispersion of the lead in the copper. The composition of the alloy is from 5 to 55% lead, preferably 20 to 45% lead, 95 to 45% copper, preferably 80 to 55% copper, with up to of other metals, preferably zinc and/or tin, with only minor amounts of other metals, and trace amounts of the homogeneity promoter. This copper-lead alloy may also be used in an aluminum matrix, as set forth in the above-noted patent application Ser. No. 112,421.
The average particle size of the lead in the copper matrix is between 0.002 to 0.020 mm diameter. Larger particles of lead occur but only a .very minor amount of segregation occurs, which is not detrimental. An average particle size of 0.002 to 0.010 mm for copper-lead alloys having to 45% lead produces an excellent alloy for use in the present invention. The average particle size remains within the above ranges even after the alloy is remelted or recast, although some minor agglomeration does occur.
The term segregation as used in this application is intended to refer to lead particles having a diameter greater than about 1 mm. The alloys of this invention have only a minor amount of segregation. preferably about 0%. The massive segregation which occurs without the homogeneity promoter of this invention is normally exhibited as a layering of the lead. Minor segregation is evidenced by lead particles having a size of about 0.5 mm, but this is not a serious problem if such particles are well dispersed and constitute less than 5% of the lead volume.
Another advantage of this process is the remelt capability of the copper-lead alloy without substantial segregation. This effect is desirable particularly if the material is produced as a solid billet which is to be subsequently cast into a desired form. The remelt capability without undesirable segregation may be due to remnants of the homogeneity promoter remaining in the alloy, or may be a function of the fineness of the original dispersion.
Although the homogeneity promoter has a lingering effect in improving the homogeneity of the alloy it may be desirable upon successive remelts, or where the original alloy composition remains molten for an extended period of time, to add the homogeneity promoter in increments. For example, when the alloy remains molten for a period of 10 minutes to an hour, a second addition of the promoter in an amount within the preferred effective range should be made prior to using (i.e., casting) the alloy.
Additional additives may be used in combination with the above-described homogeneity promoter. For example, from 1 to 10 grams of a metal phosphate may be used, such as ortho lead phosphate, ortho cupric phosphate or ortho tin phosphate.
In one method of making the alloy used in the present invention, copper of the desired quantity is placed in a graphite crucible and brought to a temperature of l,250l350C using an induction heater. When the copper is melted and has attained the appropriate temperature, as for example about 1,275C, the lead and the homogeneity promoter are added to the melt preferably with stirring. Thereupon violent agitation of the liquid mixture ensues with the formation of gas. The temperature of the mixture is maintained for at least 1 minute and preferably 3 minutes for best results. The melt is then allowed to cool through its solidification temperature during which time the agitation continues. After solidification the temperature of the alloy is permitted to drop to ambient levels preferably not too slowly. Surprisingly, in spite of the gas evolved during the solidification of the melt, the resulting solid structure of the ingot is free of porosity. After the mixture has been formed it may be cast at conventional temperatures such as l,000-l,l00C.
The novel alloys of copper-lead prepared by the foregoing method have the structural characteristics required to produce optimum antifrictional qualities. The purity is high since the alloy has been thoroughly deoxidized. Also, the homogeneity promoter is almost undetectable by emission spectroscopy analysis. The lead phase is finely and randomly dispersed throughout the copper matrix. These factors contribute to a low coeffielectrical resistivity. In addition, they may be ,sintered, I fabricated and machined without losing their superior antifriction qualitiesv a The alloy made by the above procedure is particularly useful as a bearing surface. It is suited for'use Y when high or low temperatures and high stressesare present. Most standard methods for making bearings and bearing surfaces may be employed. The bearing can be made by casting techniques, as, set forth in greater detail in patent application S er. No. 53,953. Additionally, powder metallurgical techniques are useful. As an example, in bonding the alloy of the present invention to steel, the alloy can be powdered utilizing an atomization method. The steel is heated untilit-turns blue (approximately 6()() F) and the powder made from the alloy is then sprayed .ontoth e steel surface; The heat from the surface of the steel bonds the copperlead alloy to the steel on contact. Alternatively the powdered alloy can be preheated to soften or melt the The alloy may also be used as a dry lubricant, or in a minor amount of a carrier such as an oil or grease or a'v'olatile' organic compound, which is sufficient to fatrical contacts. Plastic, rubber or fiber surfaces can also be treatedwith the powdered alloy under conditions of heat-orpressure; or during fabrication techniques such as moldingln this manner the additive can be used on "snowmobile plastic support members which are in surface of the powder which is sprayed upon a base sur face. The base is preferably first grit-blasted to roughen its surface and the powder may be heated for spraying with an oxy-acetylene torch under slightly reducing conditions. This technique is suitable for adding a 1/16 inch layer to thrust bearing pads. The powdered alloy can also be sintered onto a steel backing to providea thicker bearing surface. In another technique a very thin intermediate layer of, for example, tin or zinc, can
be electroplated or flame sprayed onto the steel surface followed by the application of a coating of the coppersurface. The bond.- is strong enough to: 'resisthigh stresses that result frorn bearing forces whileprovid-ing excellent bearing properties. The alloys may also be used in ordnance developments such; as for small arms on the inside surface of gun barrels. w
Another manner in which the alloy can beused is as an additive to lubricants; The alloy is combinedrinpo'wdered form with other lubricants such as greas'es:and oils in quantities ranging preferably from a trace to'ifour ounces per pound of the grease or oil. The resulting combination is a lubricant which fully coats moving parts thereby increasing the life of these parts. Maintenance requirements are also reduced. The alloy is of value when the lubricant combination is used in sealed units where frequent changes of lubricant are uneconomical. In this application the'improved "'results are obtained over a longer period of timewhen'higher per-' centages of lead are used in the alloy.
In greases, powdered copper-lead alloys are preferaf bly used in amounts from about '15 to"'25%',although higher or lower amounts can be used. For ex'ample,
substantial amounts of the additive can' be lused greases for heavy duty gears. In oils, particularly'con ventional motor oils. lesser amounts are used, for example from about M; to 5%-of'the alloy based'on the?" weight of the oil, and depending upon thetolerances and wear of the bearing surfaces. The repeated addiammunition, rotating bands forlarger caliber shells or contact with the underside of the rotating drive belts. This invention will be illustrated in greater detail by EXAMPLES 1-6 In these examples the alloys contained copper to lead in weight'proportion of 60 to the total weight of each ingot was one#four'th of a pound. The copper was heatedto about 1,275 in a crucible in an induction oven. .At this temperature the balance of the lead was added to the copper together with the components shown in the table below. The proportion of components added are listed in grams for each pound of the "total of copper and lead. Results are tabulated as percent segregationin the alloy metals.
Table Graphite Percent Example Na CQ'; Powder Segregation 1 (Control) 100 2 22.5 5- l O 3 22.5 6.8 4 O 4 4.5 4.5 0 5 l 2.5 25 6. 2.3" 4.5
Emmet 3 and 4. resulted in alloys of suitable .-'qi1ality for. bearing materials.
g g EXAMPLE 7 A i A powdered mixture was prepared from 2.2 pounds of graphite and 4.8 pounds of sodium carbonate. The mixture was added to a molten alloy comprising approximately 20% lead, 4% Zinc, 75% copper and minor amountsof antimony,'nickel and other constituents.
The bath contained about 400 pounds of metal at about 2,300-2,'400F. The molten metal was then centrifu- 'gallycast by conventional procedures to form a motor 5 pressure. Upong-cooling the bearing was broken in a press andathe internal structure visually examined. It
was observedthat excellent-dispersion of the constitucuts. of the alloy was obtained. I
EXAMPLE 8 Nine pounds of copper were placed in an induction heater and brought to 1,300C. Six pounds of lead and a mixture of 68.l grams of sodium carbonate and 34.1
grams powdered graphite were added to the molten tion of minor amounts is a suitable'technique, such as 2 ounces every 10-15 thousand miles in the crankcase of an automobile.
'copper. The melt was held at 1,294C for 2 minutes outsidei surface. Itwas split and a. physical examination t P showed n6 lead segregation. A photomicrographic examination of the structure showed a fine dispersion of the constituents. Photomicrographs of the product appear as FIGS. 1 and 2 in Ser. No. 53,953.
A lineal analysis was made of the particle size and spacing of the product. The specimens were measured on a microscope with a Filar eyepiece that was calibrated in millimeters. Random traverses were conducted in a linear fashion across the surface of the metallographically prepared surface. Three traverses were run with about 200 measurements per traverse. Then the specimen was prepared with a surface perpendicular to the original surface and two more traverses were conducted at 200 measurements per traverse.
The resulting data were treated statistically. Standard deviations were calculated and are presented below.
molten mass was atomized in an inert atmosphere (nitrogen and argon are suitable) to form a powder. The powder which passed through a 325 mesh screen was collected; this powder had an average particle size of about 6 to 10 microns and was used in the following example.
EXAMPLE 14 The powdered alloy of Example 13 was used as a lubricant in automobile engines in amounts of from onethird to two-thirds of an ounce per quart of motor oil. Two ounces of the powder were mixed with one half quart of W Valvoline motor oil and added to the crankcase of a Volkswagen (which already contained about 2 /2 quarts of oil) with the engine running. Prior to the use of the copper-lead additive, the car had been Traverses Perpendicular to Axis of lngot Average Average Distance Particle Standard Between Standard Size Deviation Particles Deviation Traverse No. 1 0.0043 mm 0.0020 mm 0.0086 mm 0.0096 mm Traverse No. 2 0.0043 mm 0.0021 mm 0.0083 mm 0.0082 mm Traverse No. 3 0.0043 mm 0.0030 mm 0.0086 mm 0.0080 mm Traverses Parallel to Axis of lngot Traverse No. l 0.0039 mm 0.0018 mm 0.0069 mm 0.0047 mm Traverse No. 2 0.0037 mm 0.0015 mm 0.0069 mm 0.0045 mm EXAMPLE 9 driven 62,000 miles and the average compression on The same procedure set forth in Example 8 was repeated except that the promoter comprised 136 grams of lithium carbonate and 34 grams of powdered graphite. The melt was poured into the graphite mold which was surrounded with sand, which provided for a slower cooling of the casting. The casting provided an acceptable bearing material however it showed a minor amount of segregation.
EXAMPLES 10-12 Three castings were made, each weighing 15 pounds. The additive used was 136 grams sodium carbonate and 34 grams graphite in each example. The ratios of copper to lead were 60:40, 70:30 and 80:20, respectively. Each finished casting was then separately melted and poured into a high velocity stream of nitrogen to obtain a fine powder. The powders were sintered and compacted into bearing rings according to conventional techniques. The bearings were examined by the photomicrographic technique and showed a fine dispersion of the constituents. This evidences the excellent remelt capability of the alloys of the present invention and the capability of forming powders for a wide variety of industrial uses. The powder need not be made from a melt of the casting but may be formed directly from a mix of the molten metal and promoter.
EXAMPLE 1 3 'The amount of the homogeneity promoter was 1 per- :cent by weight of the molten metal. After 1 miriutethe the four cylinders was 100 pounds. After driving the car with the additive for 65 miles the engine compression was determined and found to have increased about 5% (compression 105 pounds), and after 700 miles the compression increased an additional 10% (compression 1 15 pounds). The examination of parts in contact with the copper-lead-oil lubricant showed that the alloy was burnished onto the bearing surface (a copper color in areas of wear was very noticeable).
This invention has been described in terms of specific embodiments set forth in detail. Alternative embodiments will be apparent to those skilled in the art in view of this disclosure, and accordingly such modifications are to be contemplated within the spirit of the invention as disclosed and claimed herein.
We claim:
1. A lubricating material comprising an oil or grease which has distributed therein a powdered homogeneous alloy, said alloy containing copper and lead and trace remnants of the products from a homogeneity promoter in molten copper and lead, said homogeneity promoter comprising elemental carbon and a metal compound selected from the group consisting of compounds of an alkali metal and an alkaline earth metal.
2. The lubricating material of claim 1 wherein said alloy comprises from a trace up to about 4 ounces of alloy per pound of oil or grease.
3. The lubricating material of claim 1 wherein said metal compound is sodium carbonate or potassium carbonate.
4. The lubricating material of claim 1 wherein said alloy comprises about 5 to 55% lead, and about to 45% copper wherein the lead is in the form of a fine dispersion in a copper matrix, and the average diameter 9 of said lead particles is between about 0.002 mm to 0.02 mm.
5. The lubricating material of claim 1 wherein said alloy comprises about 20 to 45% lead, wherein the lead is in the form of a fine dispersion in a copper matrix, and the average diameter of said lead particles is between about 0.002 to 0.01 mm.
6. The lubricating material of claim 1 wherein said alloy has an average particle size of about 6 to 10 microns.
7. The lubricating material of claim 1 wherein said alloy comprises about -45% lead.
8. A composition comprising a powdered homogeneous alloy consisting essentially of copper and lead, and a homogeneity promoter which is the reaction product of elemental carbon with an alkali metal compound selected from the group consisting of sodium carbonate and potassium carbonate in molten copper and lead, and a petroleum or vegetable based lubricant.
9. The composition of claim 8 wherein the alloy comprises from a trace to 4 ounces per pound of said lubricant.
10. The composition of claim 8 wherein said alloy comprises about 20-45% lead.
11. A composition comprising a powdered homogeneous alloy comprising a mixture of copper and lead, wherein said mixture comprises from 555% lead and from 9545% copper, and wherein the total of said lead and copper in said mixture is at least and trace remnants of the products from a homogeneity promoter in molten copper and lead, said homogeneity promoter comprising elemental carbon and a rare earth metal compound selected from the group consisting of oxides, carbonates and halocarbonates, and a petroleum or vegetable based lubricant.
12. The composition of claim 11 wherein the alloy comprises from a trace to 4 ounces per pound of said lubricant.
13. The composition of claim 11 wherein said alloy comprises about 20 45% lead.
14. A composition comprising a powdered homogeneous alloy comprising copper and lead, and trace remnants from a homogeneity promoter comprising elemental carbon and an alkali or alkaline earth metal compound capable of reacting to form a gas in molten copper and lead, and a petroleum or vegetable based lubricant.
15. The composition of claim 14 wherein the alloy comprises from a trace to 4 ounces per pound of said lubricant.
16. The composition of claim 14 wherein said alloy comprises about 20 45% lead.

Claims (16)

1. A LUBRICATING MATERIAL COMPRISING AN OIL OR GREASE WHICH HAS DISTRIBUTED THEREIN A POWDERED HOMOGENEOUS ALLOY, SAID ALLOY CONTAINING COPPER AND LEAD AND TRACE REMNANTS OF THE PRODUCTS FROM A HOMOGENEITY PREMOTER IN MOLTEN COPPER AND LEAD, SAID HOMOGENEITY PROMOTER COMPRISING ELEMENTAL CARBON AND A METAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF AN ALKALI METAL AND AN ALKALINE EARTH METAL.
2. The lubricating material of claim 1 wherein said alloy comprises from a trace up to about 4 ounces of alloy per pound of oil or grease.
3. The lubricating material of claim 1 wherein said metal compound is sodium carbonate or potassium carbonate.
4. The lubricating material of claim 1 wherein said alloy comprises about 5 to 55% lead, and about 95 to 45% copper wherein the lead is in the form of a fine dispersion in a copper matrix, and the average diameter of said lead particles is between about 0.002 mm to 0.02 mm.
5. The lubricating material of claim 1 wherein said alloy comprises about 20 to 45% lead, wherein the lead is in the form of a fine dispersion in a copper matrix, and the average diameter of said lead particles is between about 0.002 to 0.01 mm.
6. The lubricating material of claim 1 wherein said alloy has an average particle size of about 6 to 10 microns.
7. The lubricating material of claim 1 wherein said alloy comprises about 20-45% lead.
8. A composition comprising a powdered homogeneous alloy consisting essentially of copper and lead, and a homogeneity promoter which is the reaction product of elemental carbon with an alkali metal compound selected from the group consisting of sodium carbonate and potassium carbonate in molten copper and lead, and a petroleum or vegetable based lubricant.
9. The composition of claim 8 wherein the alloy comprises from a trace to 4 ounces per pound of said lubricant.
10. The composition of claim 8 wherein said alloy comprises about 20-45% lead.
11. A composition comprising a powdered homogeneous alloy comprising a mixture of copper and lead, wherein said mixture comprises from 5-55% lead and from 95-45% copper, and wherein the total of said lead and copper in said mixture is at least 90%, and trace remnants of the products from a homogeneity promoter in molten copper and lead, said homogeneity promoter comprising elemental carbon and a rare earth metal compound selected from the group consisting of oxides, carbonates and halocarbonates, and a petroleum or vegetable based lubricant.
12. The composition of claim 11 wherein the alloy comprises from a trace to 4 ounces per pound of said lubricant.
13. The composition of claim 11 wherein said alloy comprises about 20 - 45% lead.
14. A composition comprising a powdered homogeneous alloy comprising copper and lead, and trace remnants from a homogeneity promoter comprising elemental carbon and an alkali or alkaline earth metal compound capable of reacting to form a gas in molten copper and lead, and a petroleum or vegetable based lubricant.
15. The composition of claim 14 wherein the alloy comprises from a trace to 4 ounces per pound of said lubricant.
16. The composition of claim 14 wherein said alloy comprises about 20 - 45% lead.
US321030A 1968-02-19 1973-01-04 Copper-lead alloys for lubricants and bearings Expired - Lifetime US3894957A (en)

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* Cited by examiner, † Cited by third party
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US4076637A (en) * 1976-09-29 1978-02-28 Tyler Corporation Metal dispersions and method for producing same
US4204968A (en) * 1978-08-11 1980-05-27 CLM International Corp. Lubricant additive
US5397485A (en) * 1992-02-14 1995-03-14 Applied Metals Technology, Inc. Power restoring lubricant compositions
CN110331027A (en) * 2019-07-31 2019-10-15 上海金兆节能科技有限公司 The micro lubricating oil of lubricant oil composite and preparation method thereof and combination preparation
CN110373250A (en) * 2019-07-31 2019-10-25 上海金兆节能科技有限公司 Lubricant compositions and preparation method thereof and the combination prepare micro lubricating agent

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US1642347A (en) * 1922-08-17 1927-09-13 Gen Motors Res Corp Bearing
US2321203A (en) * 1941-03-03 1943-06-08 Phillips Petroleum Co Stabilizer for metal dispersions in lubricants
US2543741A (en) * 1948-12-02 1951-02-27 Richfield Oil Corp Lubricating and sealing composition of flake copper, powdered lead, graphite, and petroleum vehicle
US3063941A (en) * 1954-11-05 1962-11-13 Oil Base Non-fluorescing pipe thread composition
US3232872A (en) * 1964-02-05 1966-02-01 Sun Oil Co Greases
US3549531A (en) * 1963-12-18 1970-12-22 Centre Nat Rech Scient Microsphere solid metal lubricant

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1642347A (en) * 1922-08-17 1927-09-13 Gen Motors Res Corp Bearing
US2321203A (en) * 1941-03-03 1943-06-08 Phillips Petroleum Co Stabilizer for metal dispersions in lubricants
US2543741A (en) * 1948-12-02 1951-02-27 Richfield Oil Corp Lubricating and sealing composition of flake copper, powdered lead, graphite, and petroleum vehicle
US3063941A (en) * 1954-11-05 1962-11-13 Oil Base Non-fluorescing pipe thread composition
US3549531A (en) * 1963-12-18 1970-12-22 Centre Nat Rech Scient Microsphere solid metal lubricant
US3232872A (en) * 1964-02-05 1966-02-01 Sun Oil Co Greases

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076637A (en) * 1976-09-29 1978-02-28 Tyler Corporation Metal dispersions and method for producing same
US4204968A (en) * 1978-08-11 1980-05-27 CLM International Corp. Lubricant additive
US5397485A (en) * 1992-02-14 1995-03-14 Applied Metals Technology, Inc. Power restoring lubricant compositions
CN110331027A (en) * 2019-07-31 2019-10-15 上海金兆节能科技有限公司 The micro lubricating oil of lubricant oil composite and preparation method thereof and combination preparation
CN110373250A (en) * 2019-07-31 2019-10-25 上海金兆节能科技有限公司 Lubricant compositions and preparation method thereof and the combination prepare micro lubricating agent

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