Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
  • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
  • B22D23/003—Moulding by spraying metal on a surface
• • 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
  • C22C1/04—Making non-ferrous alloys by powder metallurgy
  • C22C1/0425—Copper-based alloys
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C9/00—Alloys based on copper
  • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
  • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
  • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
  • C23C4/123—Spraying molten metal

Definitions

• the invention relates to the field of copper, nickel and tin alloys with spinodal decomposition and their manufacturing process.
• American patent n ° 4052204 describes compositions of Cu Ni Sn alloys which may contain Fe, Zn, Mn, Zr, Nb, Cr, Al, Mg. Furthermore, a selective composition of Sn and Ni makes it possible, according to American patent n ° 4090890, to obtain a band resistant to folding.
• US Patent No. 4,260,432 describes a composition of Cu Ni Sn alloy with Mo, Nb, Ta, V, Fe comprising hot or cold shaping, intermediate annealing followed by quenching, shaping cold and final income.
• European patent n ° 079755 describes a process for manufacturing a Cu Ni Sn alloy, which may contain other elements in small quantities, such as Fe, Mg, Mn, Mo, Nb, Ta, V, Al, Cr, Si, Zn, Zr and using a powder metallurgy technique previously obtained by atomization and which comprises a step of compacting the powders to form a strip, a step of sintering, cooling, cold rolling with intermediate annealing followed by quenching, a final annealing followed by quenching and a tempering step.
• a powder metallurgy technique previously obtained by atomization and which comprises a step of compacting the powders to form a strip, a step of sintering, cooling, cold rolling with intermediate annealing followed by quenching, a final annealing followed by quenching and a tempering step.
• the subject of the invention is the economical industrial manufacture of finished or semi-finished products based on Cu Ni Sn alloys with spinodal decomposition, which may contain other minor addition elements, not presenting any tin segregation ; it also relates to a process for manufacturing all of the products demanded by the market for this type of alloy regardless of their shape or size, by combining in a single step the rapid solidification of the liquid metal and obtaining blank (semi-finished product) suitable for hot and cold processing.
• the object of the invention is to improve the machinability to the point of allowing the industrial manufacture of parts which hitherto could not have been with this type of alloy.
• the weight composition of Ni is between 8 and 16% and that of Sn between 4 and 10%.
• niobium-titanium coming from superconductive cables nickel-titanium vaning alloy with shape memory
• an alloy is prepared in the liquid state, based on Cu, Ni, Sn with Ti and possibly Pb, by melting in an induction furnace provided with a crucible made of silicon carbide , of a mixture in the proportions of the nominal composition of the alloy, of electrolytic copper at 99.99% of copper by weight, of electrolytic nickel at 99.92% of nickel by weight and of electrolytic tin at 99, 9% tin by weight and containing very little carbon (C ⁇ 0.002%), as well as titanium, preferably in the form of recycling metal for economic reasons.
• the fusion is done under cover of good quality charcoal, previously ignited, up to 1280 or 1300 ° C to be sure that all the nickel is melted.
• the electrolytic grade tin is then introduced using a graphite bell, in the proportion corresponding to the nominal composition of the alloy which it is desired to manufacture. If necessary, lead is added in the same way and wait 20 minutes for the temperature to reach 1100-1200 ° C.
• the free titanium is measured in the bath; in fact, titanium intervenes in the process itself on the one hand as a decarburization agent for nickel so that, if the nickel supplied was of lower quality, therefore of greater carbon content, a greater quantity of Ti would be transformed into insoluble titanium carbide; titanium also acts as a deoxidizing agent in the bath, the titanium oxide also being insoluble in the bath.
• the determination of the free Ti makes it possible to precisely adjust the composition of the Ti bath by introducing Ti in the form of a Cu-Ti master alloy to obtain the nominal Ti content. We wait another 10 min and we clean the alloy before pouring. The liquid alloy (after possible filtration) is ready to be transformed into a semi-finished product by spray-deposition.
• spray-deposition is meant a process in which the molten metal is divided in the form of fine liquid droplets which are then directed and agglomerated on a substrate so as to form a massive and coherent deposit containing a low closed porosity.
• This deposit can be in the form of billets, trays, plates, tubes whose geometry is controlled, or of blanks of various shapes ready for example to be forged, which we will denote by the general term of "semi-finished product".
• This deposit can be separated from the substrate which serves as a support and in this case, the semi-finished product consists only of alloy based on Cu Ni Sn; it can also be kept integral with the substrate so as to obtain, after transformation, a multilayer composite with an alloy part based on Cu Ni Sn and a part made of material constituting said support.
• the material of said support is preferably based on copper, aluminum, stainless steel.
• spray-deposition a technique of this type is referred to as "spray-deposition" by the Anglo-Saxons; it is described in the following patent applications: GB-B-1379261, GB-B-1472939, GB-B-1548616, GB-B-1599392, GB-A-2172827, EP-A-225080, EP-A- 225732, WOA-87-03012.
• the transformation of the semi-finished products uses, alone or in combination, the known means of deformation of the metal, such as, according to the geometric characteristics of the semi-finished product, hot rolling, cold rolling, hot spinning, drawing, forging, wire drawing.
• Another processing method is hot forging when massive parts are needed.
• the semi-finished product is generally passed over a lathe to bring its outer surface in the form of a cylinder of revolution with precise dimensions.
• the implementation annealing is a so-called “flash” annealing, that is to say comprising a very rapid rise in temperature; this temperature is between 450 ° C. and a temperature slightly lower than that of the liquidus, for example that of the liquidus reduced by 30 ° C. This temperature is preferably between 650 and 850 ° C.
• very rapid rise we mean an ascent rate which can range from 50 ° C per minute for semi-finished products of larger cross section to 500 ° C per second for semi-finished products of smaller cross section, such as wires of small cross section.
• the practical means for carrying out the flash annealing of the invention are either known in themselves, or adaptable from known means.
• flash annealing is preferably obtained with a continuous process as opposed to the process discontinuous by "batch", the semi-finished product itself being either continuous (strip) or discontinuous (tray, plate).
• a second important parameter is the actual heating technique: calories can be provided by an external source to the semi-finished product, by radiation, convection or conduction; this family of techniques is called “indirect heating” and is represented by electric resistance ovens, gas ovens with radiation or direct action of the flame on the product to be treated, ovens with salt bath or with fluidized bed .
• calories are generated within the semi-finished product during processing, according to techniques known as "direct heating” such as heating by Joule effect or by induction.
• Annealing is always followed by rapid quenching, carried out according to known means; in fact, if the cooling rate were too low, it could start to harden by spinodal decomposition, undesirable at this stage.
• the product obtained is subjected to a heat treatment of tempering, at an average temperature between 200 and 400 ° C, which ensures hardening by spinodal decomposition.
• the spinodal decomposition is influenced by the local tin content so that it is essential to obtain finished products of hardness and more generally of homogeneous mechanical characteristics, to maintain, until the final tempering phase, a homogeneous tin distribution.
• the means used in the invention make it possible to keep both the tin and the lead in the finely dispersed state.
• the invention makes it possible to obtain, on an industrial scale and economically, machinable products based on Cu Ni Sn of hardness high and homogeneous.
• the process developed by the applicant can also be applied to other copper alloys. It is of great interest to obtain copper alloys free of segregation, in particular in the case of alloys having a wide solidification interval, such as bronzes and particularly those based on Cu and Sn.
• composition of this billet was:
• the bar is thus qualified for the manufacture of connectors.
• This plate was then cold rolled to 1 mm thick.
• the product obtained is therefore a composite of 0.5 mm of copper intimately bound to 0.5 mm of Cu15Ni8Sn.
• the product was used to manufacture connectors, in which the electric current is conducted by copper while the elasticity and resistance to stress relaxation is ensured by the Cu15Ni8Sn alloy. .

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Plasma & Fusion (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Conductive Materials (AREA)

Applications Claiming Priority (2)

Publications (1)

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Citations (4)

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• 1990
  • 1990-05-11 FR FR9006489A patent/FR2661922B1/fr not_active Expired - Fee Related
• 1991
  • 1991-05-06 US US07/696,127 patent/US5196074A/en not_active Expired - Fee Related
  • 1991-05-06 EP EP91420149A patent/EP0456591A1/de not_active Withdrawn

Patent Citations (4)

Non-Patent Citations (1)

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