Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/10—Alloys containing non-metals
  • C22C1/1078—Alloys containing non-metals by internal oxidation of material in solid state

Definitions

• This invention relates to dispersion strengthened metals and more particularly to a metal modified dispersion strengthened copper.
• Dispersion strengthened copper has high strength and electrical conductivity at room temperature. It also has excellent structural stability up to temperatures approaching the melting point of the matrix (1083°C. ; 1981°F.). This stability is responsible for its excellent strength retention characteristics at and after exposure to elevated temperatures. These properties are derived from the relatively small amounts (e.g., 0.05% to 5.0% as the metal) of dispersoid which is generally a stable metal oxide, especially a refractory metal oxide, such as alnmina, silica, magnesia, thoria, beryllia, zirconia or the like. Alumina, Al 2 O 3 , generated internally from aluminum metal by internal oxidation is commonly used. Reference may be had to U. S. Patent No.
• dispersion strengthened copper there are many applications in the field where one or more of the basic characteristics of dispersion strengthened copper are important, but one or more additional requirements render dispersion strengthened copper unsuitable.
• a case in point is eyeglass frame wire. This application, for example, requires that the material have strength retention ability when exposed to brazing temperatures, generally in the 1200°F. to 1600°F. (649°C. to 871°°.) range. In addition, it must have spring properties superior to what dispersion strengthened copper has.
• dispersion strengthened copper can be significantly improved by alloying the copper with other metals (in addition to the solute metal for internal oxidation), particularly tin.
• Copper alloy metallurgy teaches that copper - tin alloys (bronzes) do indeed have superior spring properties.
• a dispersion strengthened copper - tin bronze has the desired combination of elevated temperature strength retention and high elastic limit. The presence of aluminum and alu ⁇ rinum oxide (for dispersion strengthening) surprisingly does not detract from the ability of the tin to impart elasticity to the final product.
• Other dispersion strengthened copper/metal alloys are also useful, e.g. , DSC/silicon; DSC/aluminum/silicon; DSC/nickel/tin; DSC/zinc/tin; DSC/tin/phosphorus; DSC/nickel/phosphorus.
• a dispersion strengthened copper powder is first produced by any process, but preferably that disclosed in Nadkarni 3,779,714.
• the dispersion strengthened copper powder is then thoroughly blended with a modifier metal powder, e.g. , tin or zinc or mixed tin/zinc.
• the resulting blend is heat treated in a metal can, e.g. , copper, to alloy the constituents and consolidated by hot or cold working, e.g. , by extrusion, swaging or rolling or combinations thereof, to at least 90% of theoretical density and preferably 100% of theoretical density.
• the resultant dispersion strengthened copper alloy e.g.
• bronze or brass containing from .1% to 40% by weight of metal modifier has the desired properties of the DSC as well as the modification in properties induced by the alloy metal, e.g. , springiness in the cold rolled condition and higher ductility in the annealed condition.
• Exemplary alloys of dispersion strengthened copper may be made in a similar manner, e.g., 90 copper, 10 tin; 98 copper, 2 silicon; 90 copper, 9 aluminum, 1 silicon; copper with up to 20% nickel and 10% tin; copper with 1% nickel and 0.3% phosphorus.
• Figure 1 is a process flow sheet illustrative of the process of the present invention.
• Figure 2 is a graph showing comparative data for tensile strength (solid line) and yield strength (dotted line) with respect to the amount of cold working for dispersion strengthened copper, phosphor bronze and dispersion strengthened bronze produced in accordance with the process hereof.
• Figure 3 is a graph comparing tensile (solid line) and yield strengths (dotted line) with annealing temperature for the three materials used in developing Figure 2.
• Figure 4 is a load extension curve for a dispersion strengthened bronze specimen having a gage width of 0.250" and a thickness 0.027" and a gage length of 1 inch.
• the invention is concerned with alloys of dispersion strengthened copper and a process of making such alloys.
• the process contemplates starting with a dispersion strengthened copper and alloying it in the powder state with an alloying metal or metals, preferably of high purity, consolidation as by extrusion, swaging and rolling or hot forging to yield a fully dense bar or rod, followed by solution annealing and cold working.
• Dispersion strengthening of the copper can be achieved by any of the known methods, such as internal oxidation of a solute metal, mechanical mixing of a refractory oxide, co-precipitation, mechanical alloying, etc. These procedures are well known in the art.
• the above mentioned patent to Nadkarni 3,779,714 is exemplary as are the patents to Alexander et al 3,085,876, and Her 3,143,789.
• the preferred method of forming the dispersion strengthened copper powder is that disclosed by Nadkarni in 3,779,714 or 4,274,873, or 4,315,770.
• the powdered copper/aluminum alloy from atomization is sieved to separate particles greater in size than about 180 microns from the smaller particles. These are milled as in a ball mill or rolling mill to reduce the size or thickness of the particles.
• the particles from each fraction are then internally oxidized with an oxidant such as Cu 2 O at 925°C. for about 60 minutes.
• the internally oxidized copper fractions are then blended for use herein.
• Patent 4,315,770 is directed to a process for producing dispersion strengthened copper powder starting with atomized copper/aluminum alloy particles which are free of surface oxide film.
• dispersion strengthened copper is present in an amount greater than 50%, generally from 55% to 98% by weight, balance alloying metal or metals, and most usefully about 90% by weight.
• the extent of refractory oxide in the DSC is calculated as the metal equivalent broadly and ranges from 0.05% to 5%.
• aluminum oxide as the metal
• a series of commercially available products of this type are marketed under the trademark "Glidcop", a registered trademark of SCM Corporation. These materials have particle sizes in the range of .1 to 180 microns.
• Suitable alloying metals in powder form include tin, zinc, silicon, magnesium, zirconium, beryllium, silver, chromium, iron, nickel, phosphorus, titanium, and mixtures of two or more such alloying metals. These metals are blended with the DSC as the powder by any suitable means, which may include ball milling with or without a liquid medium.
• the particle size of the alloying metal is in the range of from 0.1 to 180 microns. For most purposes a -325 mesh (Tyler) material is satisfactory.
• a convenient process for forming the modified DSC compositions hereof involves forming the powder mix by blending the DSC and powdered alloying metal and placing in a cylindrical copper can.
• the unsealed can containing the powder mixture is then heat treated in a furnace above about 1200°F. (649°C.) under a protective atmosphere for 30 minutes or more.
• the unsealed can is allowed to cool to room temperature while still in a protective atmosphere.
• the fill tube of the can is then sealed and the can reheated to 1450°F. (788°C.) or higher in a nitrogen atmosphere for 45 minutes or more, and hot extruded to a substantially fully dense mass.
• the extruded shape can be further cold worked by processes such as drawing, rolling, swaging, forging. Homogenization treatments are often necessary to obtain uniform alloying and these can be carried out between cold working passes as desired.
• a particular advantage of the present invention is in its ability to produce dispersion strengthened bronze compositions as exemplified above.
• These compositions comprise from .1% to 40% by weight of modifier alloying element or elements selected from aluminum, tin, silicon or mixtures thereof.
• the bronzes hereof are preferably formed from a pre-made internally oxidized dispersion strengthened copper powder and a modifier metal powder.
• the dispersion strengthening agent is a refractory metal oxide such as alumina, silica, thoria, beryllia, zirconia formed in situ, alumina being highly preferred.
• the principal ingredient of the bronzes hereof is, of course, copper with no more than incidental impurities. Because of the manner of making these materials, the composition is substantially uniform throughout.
• Dispersion strengthened bronze made by alloying a 0.20% aluminum dispersion strengthened copper (“Glidcop” AL-20) with tin has mechanical properties that are superior to both "Glidcop” AL-20 and phosphor bronze.
• DSB combines the modes of hardening found in dispersion strengthened copper and phosphor bronze.
• DSC exhibits high strength levels and retains these levels very well after exposure to high temperature.
• Phosphor bronze is a solid solution strengthened alloy that has the ability to develop higher strength levels upon cold working. Phosphor bronze also possesses a straight-line relationship between stress and strain in the elastic region and a sharp yield point. These properties of phosphor bronze make it an ideal material for spring type applications. However, phosphor bronze softens drastically when it is annealed.
• DSB on tine other hand, is found to possess the most desirable qualities in each of these commercial alloys.
• DSB retains its strength very well after exposure to high temperatures (brazing temperatures) . It work hardens rapidly as phosphor bronze does, exhibiting higher yield strength and tensile strength than phosphor bronze for any given amount of cold working.
• DSB also exhibits a straight-line relationship in the elastic portion of the stress-strain curve terminating with a sharp yield point. Like DSC, it resists softening when exposed to high temperatures. Hence, DSB possesses all the qualities required for a good spring material.
• the alloying element may melt but eventually diffuses into the copper matrix via solid state diffusion.
• Appreciable melting of the copper matrix or the alloy form by diffusion is undesirable since it would destroy the structure of the base alloy, i.e., copper +Al 2 O 3 dispersion strengthened alloy. Therefore the process for making D.S.B. involves initial melting of tin and subsequent alloying with copper +AI 2 O 3 alloy by solid state diffusion. At the same time, it is required that uniform chemical composition is achieved in the alloy. It is also necessary that formation of any tin oxide is prevented during the process.
• the process of the present invention utilizes several steps to achieve chemical homogeneity in the alloy and to supress the formation of tin oxides. Homogeneity of alloying is achieved most satisfactorily by properly blending the tin powder prior to canning and by solution annealing the extruded fully dense bar. Prevention of tin oxide formation is achieved by heat-treating of the powder mix in protective atmosphere prior to extrusion.
• GlidCop (AL-20) DSC powder frcm a production lot was blended with 1% by weight of a suitable powder metallurgy lubricant, for example 1% zinc-stearate powder, in a double cone blender for 20 minutes. Desired amounts of highest purity tin powder was added to the DSC powder and blending was continued for 30 minutes more. The blended powder was then fed into billet cans.
• a suitable powder metallurgy lubricant for example 1% zinc-stearate powder
• the filled billet can was then placed in a tube furnace maintained at 900°F, tinder hydrogen atmosphere, to permit the lubricant to burn-off which usually took about 20 minutes.
• the furnace temperature was then raised to 1450°F and the billet was heated at this temperature for 30 minutes. Following this the billet was cooled in the cooling zone of the furnace still under hydrogen atmosphere.
• the fill-tube of the billet was then closed and the billet re-heated in a nitrogen atmosphere muffle furnace at 1450°F for 45 minutes.
• the heated billet was extruded into a rectangular bar.
• the cross-section of the extruded bar measured 0.50" x .188" with rounded comers giving an extrusion ratio of 16:1.
• the extrusion die pre-heat temperature was 900°F. + 50°F.
• the extruded bar was de-clad by machining.
• Solution annealing was carried out by heating at 1450°F. for time periods ranging from two to three hours in an atmosphere of nitrogen. This temperature was low enough not to risk substantially melting the matrix and yet high enough for rapid diffusion of tin and copper atoms, to achieve complete alloying.
• the bar was cold worked to the desired temper and then machined into tensile test specimens conforming to ASTM specifications. Some of the strips were annealed at different temperatures ranging from 900°F. to 1250°F. , before testing. Nitrogen atmosphere was used in the furnaces for annealing runs.
• the process steps and mechanical properties of "GlidCop" (AL-20) , Phosphor Bronze, and D.S. Bronze are tabulated in Table 1.
• Tensile strength and yield strength data are plotted as a function of amount of cold work in Figure 2; and as a function of annealing temperature in Figure 3. Since the samples were cold worked by rolling strips, the starting thickness of the extruded bar posed some limitations on the maximum amount of cold work that could be given without making the strip too thin for performing tensile testing.
• the ultimate tensile strength of DSB is considerably higher than that of Phosphor Bronze, having the same chemical composition and same amount of cold work.
• the yield strength of DSB is also considerably greater than that of Phosphor Bronze having the same chemical composition and same amount of cold work.
• Phosphor Bronze exhibits a sharp drop in both ultimate tensile strength and yield strength.
• D.S.B. in contrast to Phosphor Bronze, retains its strength quite well after exposure to these high temperatures. In this respect it is similar to "GlidCop".
• the elastic portion of the stress-strain curve of D.S.B. like that of Phosphor Bronze, is a "straight-line", as shown in Figure 4, "GlidCop” on the other hand has a gradually changing slope in the elastic portion of the stress-strain curve, similar to that of pure copper.
• a straight-line shape of stress-strain curve is highly desirable.
• D.S.B. is more suitable as a spring material than "GlidCop".
• the modulus of elasticity of all three materials is considered to be nearly the same (i.e., 16,000,000 psi).
• DSB is found to be superior to Phosphor Bronze of similar chemistry due to its higher yield strength and tensile strength upon cold working, and due to its ability to retain most of the strength after exposure to temperatures normally anticipated in brazing operations (i.e., 900°F-1200°F). Although one can achieve the strength levels attained in cold worked D.S.B., by taking a Phosphor Bronze of higher tin content, DSB is considered attractive, for two basic reasons: (1) D.S.B.

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• 1984
  • 1984-01-31 DE DE8484901031T patent/DE3479407D1/de not_active Expired
  • 1984-01-31 JP JP59501008A patent/JPS61501097A/ja active Pending
  • 1984-01-31 WO PCT/US1984/000128 patent/WO1985003463A1/fr not_active Ceased
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