CA2561903A1 - Machinable copper-based alloy and production method - Google Patents
Machinable copper-based alloy and production method Download PDFInfo
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- CA2561903A1 CA2561903A1 CA002561903A CA2561903A CA2561903A1 CA 2561903 A1 CA2561903 A1 CA 2561903A1 CA 002561903 A CA002561903 A CA 002561903A CA 2561903 A CA2561903 A CA 2561903A CA 2561903 A1 CA2561903 A1 CA 2561903A1
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 75
- 239000000956 alloy Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000010949 copper Substances 0.000 title abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052802 copper Inorganic materials 0.000 title abstract description 8
- 238000005266 casting Methods 0.000 claims abstract description 16
- 230000003068 static effect Effects 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 238000009718 spray deposition Methods 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 238000009749 continuous casting Methods 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 3
- 238000001816 cooling Methods 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000005491 wire drawing Methods 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 20
- 239000011133 lead Substances 0.000 abstract description 18
- 239000011135 tin Substances 0.000 abstract description 11
- 229910052718 tin Inorganic materials 0.000 abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 229910001369 Brass Inorganic materials 0.000 abstract description 4
- 239000010951 brass Substances 0.000 abstract description 4
- 229910052745 lead Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 17
- 238000005496 tempering Methods 0.000 description 9
- 241000252233 Cyprinus carpio Species 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007921 spray Substances 0.000 description 5
- 229910018100 Ni-Sn Inorganic materials 0.000 description 4
- 229910018532 Ni—Sn Inorganic materials 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000005204 segregation Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000001330 spinodal decomposition reaction Methods 0.000 description 3
- 241000237858 Gastropoda Species 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 238000012345 traction test Methods 0.000 description 2
- 229910000549 Am alloy Inorganic materials 0.000 description 1
- 241000331231 Amorphocerini gen. n. 1 DAD-2008 Species 0.000 description 1
- XUKUURHRXDUEBC-KAYWLYCHSA-N Atorvastatin Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CC[C@@H](O)C[C@@H](O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-KAYWLYCHSA-N 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- 229910017532 Cu-Be Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 101100247628 Mus musculus Rcl1 gene Proteins 0.000 description 1
- 241000566150 Pandion haliaetus Species 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- VRUVRQYVUDCDMT-UHFFFAOYSA-N [Sn].[Ni].[Cu] Chemical compound [Sn].[Ni].[Cu] VRUVRQYVUDCDMT-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 201000002266 mite infestation Diseases 0.000 description 1
- -1 nicl<ol Chemical compound 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
Abstract
The invention relates to alloys based on copper, nickel, tin and lead, which are obtained by means of continuous or semi-continuous casting, static casting into billets, or spray casting into billets and which can undergo spinodal hardening. The machinability index of the inventive alloys is greater than 80 %, in relation to standard ASTM C36000 brass, and can go up to 90 %. According to the invention, the alloy contains between 1 wt.- % and 20 wt.- % Ni, between 1 wt.- % and 20 wt.- % Sn and between 0.1 wt.- % and 4 wt.- % Pb, the remainder comprising essentially Cu and, optionally, up to 10 % of one or more of the following elements, namely Fe, Zn, Mn, and/or up to 5 % of one or more of the following elements, namely Zr, Nb, Cr, Al, Mg.
Description
Mathittable copperJbased alloy and production method Technical field The present invention concerns are alloy based on copper, nickel, 'tin, lead anc9 its production method. !n partic~.llar, tho~.lgh not exclusively, S the preserot iroverttion concerns am alloy based on copper, nicl<ol, tin, lend easily m~lchiroed by ttlrroirlg, slicing or milling.
State of the art Alloys based on copper, nickel end tin <3re Known arld widely used. -they offer excellerlt mechanical properties and exhifJit a strolig t~Zrderair~g during strain-hardening. Their mechanical properties arc' fl.lrther improved by the known feat-acing treatment such as spinodal decormposition. For ~n alloy containing, by weigklt, 15% of nickel arld F3%
of tire (standard alloy ASTM C7?.9(~p), the mechar~ic~ll resistance earl reach 1 S00 MPa.
1!p Another favorable property o'f the Cul-Ni-5 alloys is that they offer good trik~ofogical properties, comEoarable to those o-f bronzes, while' exhibiting st~pc~rior mechanical properties.
Another advantage of these materials is Choir oxcellernt fiorrllability, combirled with 'favorable elastic properties. Moreover, these.
~~I~Uys Uffer cl goOd rE.'sl5'~clrlCC'. dgdirl5'l COrrO5lorl and arl C'XCC'lIC'nt rC'Slst~'3r'1CC' to the constraints' heat relaxa'tior~. f=or this reason, the ~r.r-Ni-Sn springs do not lose their compression force with age, even rlrlder vibrations and strong boat strossos.
Theac~ favorable properties, col~nbir~ed with good heat and ~5 electricity Cor~ldllctlvlty, moan that these materials tare widely rlsed 'for making highly reliablo connectors for telecomrnunicatiorls and 'the car indrlstry. These alloys are also ~.lsed in several switches or~d electrical or s Nl r-. r nl.. > m: ~-Z
electromechanical devices or as supports of electronic components or for making bearing friction surfaces srabjected to high charges.
The Cr.u-Be alloys can be machined fairly weft and can contend with and were outperform the mechanical properties of Cr.l-Ni-Sn alloys.
The' machinability index of the Cu-Be alloys car-~ reach 50-~0% relatively to standard ASTM C3G000 brass. Their cost is however' high and their productiorn, rrse and recycling are particularly constraining because of the ber'yllirrm's higl7 toxicity. The resistance to the constraints' heat relaxation of 'these materials is lower ~cl-~an tf~oat o~t~'the Cu-Ni-Sri for ternperat~.rres 1(7 above 150-1'75°~:.
One' inconvenience of the Cru-Ni-Sn alloys is however that they are poorly sr.lited to processes si-rch as milling, tr_~rr~iry or sliciroc~ ar is ar~y other known process. A further ir~cor~veroiertce of these n3loys is Cheir strong segiegwlior~ during cosUirog.
15 It is thus an aim of the present invention to propose ar-~ alloy associating the favorable mechanical characteiistics of alloys based on copper, nickel and tin with a good workability.
It is ~rnother aim of the present inver~liol~ to propose a method for prodecir~g a rnachinable product on the basis of Crn~Ni~sl~ free from the' 20 incorwer~icnccs of the prior art.
ft is another airt~ of 'the present irmeotion to propose a machiuable alloy combir~ir~g high elasticity arid rnechar~icnl resistance characteristics brlt free 'from berylli~rrn or 'toxic eiernervts.
A IVrr~ther airn of the present irvver~tior~ is to propose a r~nc~tl~ocf for 25 producir~d a rnachirnable product on the basis of Crl-Ni-Sn allowing the problems relative to se c3regation to be solved.
~l-hese aims are ~~chieved by the product and thc~ method that arc' the object of the independent claims of corresponding category and 5Mf-_-1-AI_-2_r'C:1 notably by a machinable product composed of an alloy camprisir~g between 1 % arid 20% by weigl'~t of Ni, between 1 % ancf 7_0% by weight of Sn, betweero 0.1 % arid 4% of Pb, the remainder being constituted essentially of Cu, having ur'~dergorve a heat homogenizing treatment comprising a step o'f~ heatirng said alloy followed by a step of cooling at a speed sufficiently slaw to prevent 'fissuring.
pet~_i_Ied..descripvtior~ ofythe inveroior~
the present irwention concerns alloys oro the basis of copper, nickel, tin and lead Obtc~rneC:l by c~ cOntrnL.roUS Or S2lTll-CUrltlr'tUUUS
C~35'tIr7C) method, a static billet casting or casting by spr~yforming. -fhe copper-nickel-tin alloys have a long solidification interval leading to a considerable segregation durirog c~s'ting. Uf the 'fo~.~r aforementioned processes, casting by sprzyformir~g, also known by the name "Osprey" method, ar-id described far exarnple ire patent FPO?_?_573? makes it a possible 20 ob'lain an almost W homoger~or~s microstructrare presc~ntinc~ 7 f1'tlnlr'1'lr'71 degree of segrecla'tlon.
In 'this process, a metal billet is obtained by contirmrarrs depositing of artdmized droplets. "I'E~Ze segredatioo carp take place only on the scale' of the ator~iz~d droplets. The clif'fusior~ distarvces reqceired 'for dir~~inishing the segregation are th~.ls shortened. Irn the Case wl' corotine.roces or semi-7_0 cor-~tinuot-rs casting, the segregation is stronger than with 'the sprayforming process, br-et it remair-~s sr-efficiently reduced to void an excessive fragility of tEte alloy. ~~fhe static billet casting leads to a strong segrc~c~ation that can be elimir~a~ted only by a prolorycd heat processing.
Lead being essen'tiolly insol~rble in 'the other metals of the alloy, 75 the prodLlct obt~in~d will comprise lead particles dispersed in a Cry-Ni--sn matrix. Drjring the machining operations, floe lead has a It.rbricating effect and facilitates the fragrz~er~tation of the slivers.
The quantity of fend introd~.rced in the alloy depernds ora 'the degree of rnachrnabllity that one streves to achieve. Geroerally, a qr.ranti'ty of 3o lead up to several percents by weight can be introduced Wlt~lUUt the alloy's mechanical properties at normal tc~mpc~ratr-ere being modified. lwlowever, an~r: one.-z-her above 'the lead melting point (327 °C), the liquid lead strongly weakens the alloy. Alloys containing lead are thus difficult to make, on the one hand because they have a very strongly pronounced tendency towards fissuring and, Ur'1 the other hand, because they can exhibit a two-phased crystallographic strrscture containing are undesirable weakening phase.
°fhe method of the present invention makes it possible to produce a rr~achirzabfe Cu-Ni-Sr~~Pb prodr.lct contairrir2g up to several percents by weigh~l of lead, without it fissuring during fabrication, and having excellent mechanical properties, The ratio of lead cc~n vary between 0.1 % and 4% by weight, preferably between 0,7.% and .3% by weigf7~t, even more preferably between 0.5% and 1.5% by weight.
After smelting in the foundry, the production methods can be decomposed In slrCCe55ive Sll-lgs: far the first slug, two cases must be considered according to whether the product is manufactured by contir,uor.~s casting at small dianoeter or by static billet casting, sprayforming, semi~continirous or contirmoras casting at large dir~me-cer.
'T'he pr-odt.rcts of the invention are characterized by their excc~llc~nt rnachinability, wf'~ich is c3reater than that of Cr.r-Be .~Iloys. The machirrability index of the inventive alloys exceeds X30% relatively to standard AS~rM
?0 C36000 brass and can even reach ~~0%.
First-sl~.y-g:
Alloys obtained by contim.rous sm~3lf-diameter thread casting, c.g.
of 25mm or less, urodergo a heat homogenizing irea~er7ren~l or a step of cold deformration by harnrneriry followed by a horr,oger~izir~g t~r,d 75 recrystailization treatment. 'fire temperatr.rre of the heat tremurnere mast be within the range where the alloy is arse-phased. Cooling after ll7e heat treatment must occur at a speed sirfficier~tly slow to prevent fissnriry of tire alloy drre to internal cor~s~trair~~ts generated by the temperature differences d~.iring cooling, and st~f-licier~~lly fast -to limit the: formation of r~ two-phased 30 strncturc~. If the speed is too slow, a considerable yrantity of secorod phase s nn r_ rm--z-ro:: r a carp appear. ~hhis second phase is very fragile and greatly reduces the alloy's deformability. The critical cooling speed reqraired to avoid the formation of too large a quantity of second phase will depend on the alloy's chemistry and is grea'ter'for a higher quantity of nic!<c~l and tin.
Moreover, during cooling, transitory internal constraints r'~re generated within the alloy. They are linked to t~mperat~.ire differences between the surface and the center of the product. If these constraints exceed the alloy's resistance, the la'c'ier will 'fiss~~re arid is roo longer ~.rsable.
Ir7terrval constraints dr.re to cooling are all 'the higher the more the prodract's diameter is large. The critical cooling speeds to avoid fissuring thus depend on 'the product's diameter. This problem is even more acute wi't~5 Cu-Ni-5n-Pb alloys since above its ~rreltiog temperature of 327°C, lead strongly w~al<ens the alloy.
In the method of the present irvverotior~, cooling after heat treatment occc.rrs at a predetermined speed -taking into acco~~r~'t the alloy's chemistry and the transversal dimerosior-~, or diameter, of the produc't. -1-he cooling speed must be at the same tirrre sr.rfficiently slow to prevent fiss~~ring and sufficiently great to prevent too large a qr.rantity of fragilizir~g phase to form.
Unrir~g rnanufacturc~ of a large-diameter prodt.ict, 'the in'ter'nal corostrariro'ts due to 'floe temperature differences are greater Chars irv a small-dimensioro product, or~d the cooling speed mast conseqr.rently be limited. At the same tune, strong propor'tior~s of Ni arid Sn promote the formation of a fragilizing phase and require a fv3ster cooling.
z5 Alloys ohtained by sprayforrnirog, static billet casting or sc~mi~~
corotimaor-rs casting undergo a hot extrusio~o 'lreatmerot. ~f-his is also the caso for con'tir~e-roras casting if the product is of I~~rge diameter. Cooling during extrusion rz~ust be svafficiently slow to prevent fissurirog and srnf'Ficier~tly fast to limit the formation of a fragilizing secorrci phase. Alterroalively, if cooling during extrr.rsion is too slow, heat homogenizing arnd recrys'tallizatior~
snn r-rm--z-r~~_ r treatments as explained l7ere above for the case of small-diameter continuous-casting products mt.~st follow extrusion.
Once the 'first sfe~g has been made, 'the final rnachinable product must be either ob'tair~ed directly by one or several cold deformation operations, e.g. by rolling, wire-drawing, stretch-forming or- any other cold deformation process, or obeairoed by one or several successive slt.rgs.
5ycc.~SSiveslugs:
from the first slug, the followiry slugs are obtained by oroe or several cold deformation operations followed by a heat recrystaliiz~tion 30 treatmervt. '1"he temperature of the recrystallization treatment must be within the range where 'the alloy is one-phased. Coolirng after the heat treatment mtast have a speed st~'f'ficier~tly slow to prevent fissuring but always sufficierotly fast. to limit 'the 'forrna'lior~ of a two-phased s'lrurtt_tre.
'l~~hrot.rgh successive slr.rgs, thC'_ slZe Of the product is redrmed. From the las~c slug, the fiir~ol product is obtained by one or several cold deforr~~atior~
opc~ratior~s.
The mech<3nical properties of the alloy oi.~tain~c~ corn be snbseqetewtly increased by a spinad~~l decomposition heat treatr'aoerot. -1-iois trezornewt cao 'take place before the final machining or after the latter.
70 f-ierewfter, examples of rz~ethods ~~nd of rn7chinable prodt.rcts according to the preserot ir~ver7~tior~ will be presented. Ira the following examples, the cooling ternperotures refer to thc~ enter of the prodt.rct.
F. x ~-rz~_p 1-c---1-The chemical corrrposition of tt~e alloy in this c~xamp(e is given by table 1:
snnrr nl -z-hc:-r c~~~e 1 CompUrlerlt ~rbpOrtibrv. (by WeLC~ht~
Cll ren'lalnder Ni 7.5%
5n 5%
Pb 1 Mn 0.1%-1%
other <_0.5%
Manganese is introduced in the composition as deoxidizer, It is however possible to use ir~ste~d other eiemerr'ts or deVICes preventing the alloy from oxidizing.
This ailoy carp be cast according to the different methods merotior~ed furtk7er above. Irr this example, this alloy is obtained by contirvitous billet cas'tirng with a diameter of lFiUmm.
F_i_rst__sly,lg: the' billets are extri.aded for example to o diameter of l 8mrz~. At the exit of the extrctsior~ die, the' alloy is cooled by ~
strea~'n o'f compressed air allowing a cooling speed of 50°C/rnir~ to 300°Clmin to be achieved, as rneasr.rred a't the cer~'ler of 'the alloy. This speed is sufficic~ntfy slow to avoid fissuring and sufficiently fast to limi't'the 'formation of a fragilizing S(?COrld pklc7se, cooling by water spray ccm also be r.rsed, possibly allowing cooling sp~c~ds of .300°Clmin to 1000°Clmin to be achieved without fissuring of the material. Other means for reaching a suitable cooling speed car? also be l.~sed. If cooling at the exit of the extrrrsior~ die' is not sr~fficiet~tly fast, a too great a proportion of second pi~ase care form, tf~e alloy will have 'to ttrldergo o horr~oc~er~ization treatrnerl'l with 'the sarme characteristics for the cooling speed at a tempera'tr_rre wi'tl'~in the rar~de where the alloy is 2U one-phased, i.e. betweero 690°C anc3 92()'C for tk7e cornpositiorn of table 1.
S_c~co»c~ slug: the material of the first slag of a diameter ofi 1 t3mm is rolle;~d to a diamc~t~r of 13mm thin ar~n~aled ire a through-'type fe.rrnace or removable cover f~.irnacc. For the alloy with the chemical cornpositioro ofi exar7iple 1, the annealing temper~~trirc~ must be comprised betweero 59U~C
7.5 and 9?0°C. A cooling spc~c~d on the order of 10°Clmin is sufficient to limit the formation of second phase' for this compasitior~ and this diameter of s ran:w n n-z-sm-l3mm, Furthermore, water spray cooling at speed of 300°Clmin tQ
3000°C/mir~ allows fissuring to be prevented and the formation of a fragilizing secorod phase to be limited.
Fi-r~is_h_ir~~: the rrraterial of tile second slag is wire-drawr-~ or stretch-formed to a diameter of 8mm to obtain a machir~able product. A
spinodal decomposition ~CreaOrner~~l is finally perforrmed on the machinable produce or orr the rnachiroed pieces to obtairo optimal mechanical propertres.
F_x,~ m_EOl ~..
The chemical composition of the alloy ire this example is given by table Z:
Table z Component Proportion (by weight) Cu rernairrder In this exacmple, this Ni 9% alloy is obtained by continuous 5n 0% 15 thread castirog with a di~rz~eter of Pb 1 Mrl 0,1 %-1 % 18mrZ~.
Imp~iri~ties <0.5%
I-irs 5~~ag: the thread ~.mdergoes a homogenization treatrnent in a tf~rough-type fv_irn~ce at a temperotrire between 700°C and 970°C, corresponding to the one~phase ,~0 mange of thc~ chemical composition of exarT~ple 7. A cooling speed between 100°Clrnin and 1000°Clr~~rir~ allows fissuring to be prevented arod the proportion of fragilizir~g second phase to be limited. Such cooling speeds can for- exarrrple be achieved by usiry compressed air, water spray or a gaslwater excharngirog cooler.
25 Ser_o~yc~ slug: the rnateriol of the first slug of a diarr~e~ter of lF3mm is rolled, wire-drawn or stretch-'formed co a diameter of l3r~nm then oranealed in za through-type furnace at a temperature conoprised between 700°C and 920°C. WiOir a diameter o~F l3mrn and the chemical composition snntrm...o.io.:r c3 of table ~, a cooling speed betweero 100°Clrnin to 3000°Clrnin allows the formation of a second phase to be limited while avoiding fissuring.
Third-s!_rrg: the material of 'the second slug at a diameter of l3rnm is rolled, wire-drawn or stretch-formed to a diameter of 10mm then a annealed in a throragh-type 'furnace or tempering furnace at a temperature comprised betweero 700°C anc9 920°C. With a diameter of 10mm and the chemical composiliora ov table 2, a cooling sped betweew100°Clmin to 15000°Umin allows the formation of a second phase to be limited withor.rt any fissurirog being created.
1() Fo~.irth-sl-a.yg: the material of the tl7ird slug a~t a diameter of l0mm is rolled, wire-drawn or stretch-formed 'to a dizo~neter of 7mm then annealed ire a through-'type 'furnace or tempering furr~.-~ce at a temperatrare comprised betweerv '700"C arod 920"C. With a diameter of 7mm and the Chemic7l Cor'npositiorl of table 2, a cooling speed between 100°C/min to 15 20000"Clmin allows the forrz~atior~ of a fragiiizing SecUrld phase to be limited withor.rt any fissr.rrir~g being created.
f:yivftf~ slug: the material of the fourth slug at a diarzieter of 7a~m is rollecJ, wire-drawn or stretch-formed to a diameter of 5mrz~ then ar~r~ealed irr a tfirorrgh~type f«rnac~ or t~mpcrirlg furnace at a ternperatnre 20 comprised b.ntwc~c~n 700"C armJ 9z0"C. lNitl~ a diameter of 5rnrn arnd ~lhe chervical composition of table z, a coalir~d speed between 100°Clmirr to 30000"C/r~~ir~ allows the for matioro of a fragilizing second phase to be limited withornt ar~y fi5surir~g being created. A cooling speed on the order of 15000°Clrniro can be acP~ieved by tempering in appropriate fluids.
25 Sixtp_sliig: the material of the fifth sl~.rg at a diarz~eter of 5mm is rolled, wire-drawn or stretch-formed to a diameter of 3mm, ar~r~ealed in a through-type furnace or tempering fr.rrnace at a temperat~.rre comprised betweern 700"C arid 92_0°C, then cooled at a cooling speed comprised belweer~ 100°Clrnin to 40000"C/rr~in.
sMr_nnc_-z-ro: r SeverytPy.sl_r.i.~: the material of the sixth slag aU a diameter of 3mm is rolled, wire-drawn or stretch-formed to a diameter o~f zmm, annealed ire a through-type furnace or tempering furnace at a ternperatr.rre comprised between 700°C and 920°C, then cooled at a cooling sped comprised 5 between 100°Clmin to 40000"Clmin.
Eigtyth slug: Ohe material of the seventh slug at ~3 diameter of 7mm is rolled, wire-drawn or stretch-formed to a diameter of 1,60mm, annealed in a through-type ~furr~ace or tempering furnace at a temperature com~~rised between 700°C and 920°C, and then cooled at a cooling speed 1U cornprised between 100°C/min to 500UU°Clr~nin.
f~irpishing: 'the material of the eighth slug is rolled, wire-drawn or strotch~formed to a diameter of lrnm to obtain a m~ichinable product. A
spinodal decomposition treatrnewt is finally performed on the m7chiroable product or on the machined pieces to obtain optimal rrrec.hanic~~l properties.
1 he "AS I M 'lest method for rnachin<~bility" test proposes a method for determiroirag ~cF~e rnachinability index relatively to standard Cu7r~39f~b3, or c:3f~000 brass. "fhe machinability index of the alloy according tc~ this aspect of the invention is better by F30%.
LxampLe 3 The chemical CUrllpOSltlOrl Of thc~ alloy ire this example is the sar~c~
as that of the secorvd example given by table 2_. In this example, the alloy is obtained by COiltlr~lllOUS C~~Stll'1C~ at a diameter of ?..5mm.
Fi_rst___sf_r,ag: the thread cast at a diameter of ?5mrrr is hammered to z5 a diameter of 1Umm. The hammering allows the material to deform with a considerabie redaction rate without prior heat homogenizing treatment.
Wi~lh tlois method, a high remainder ratio of fragilizing second phase can be Oolerated at this stage. The second phase carp reach a volume ratio orr the orc9er of 50%_ snnc rnr, z-nc:r After hammering, the thread at a diameter of l6mm undergoes homogenizing and recrystallization treatment in a thrm.rgh~~typc~ furnace.
The terr~perature of the heat treatment must be comprised between 7p0°C
and 9~0°C. The following cooling will take place at a speed comprised beUween 100°C/min and 300o°C/r7~ir~. These cooling speeds make it possible to prevent ~fissrtrir7g ar7d to limit the ratio of second phase for a product of this diameter arid of this corn position. 5tich speeds carp be obtained by using compressed air, w~rler spray or gaslwater exchangers.
F-in_ist~ing: the materizol of the first slug is wire-drawn or stretch-formed to a diameter of 1Ornm to ok~tain a machinabfe product. A spinodal deCOmpositiorl treatment is finally performed on the machinzble product or oro the machined pieces to obtairo optimal mechanical properties.
Exymple 4 The chemical composition of the alloy in this example is givero by table 3:
Table 3 Component Proportion (by weight) Ct.i remainder Ni 15%
Sri B%
f' k~ 1 ~/
Mn 0.~%..1%
Irllpl.lrItIC'S<0.5%
This alloy can be cast ~ccordir~g to the differewe methods mentioned here above. !r~ this example, this alloy is obtairoeci by sprayforming billets whose diameter is 240mm.
7. Q First_sl_y.g.: the billets arc' extruded for example to a diameter of ZOmm. If the billets' dimensional irregr.il~ritics are too great, a turning step can be necessary before extrr.rsior~. At the exit of the extrusion die, the alloy is cooled by water spray allowing a cooling speed of 300°Clmin to 3000"C/min to be achieved, as measr.rred at the center of the alloy. This snrrr--r-nr.-z-r~~l 1z speed is sufficiently slow to avoid fissuring and sufficiently fast to limit the formation o~f a fragilizing second phase. If cooling at the exit of the extrusion die is clot sufficiently fast, a too great a proportion of second phase carp form. The alloy will then have to undergo a homogenization treatment wiOh the same characteristics for the cooling speed at a temperature within the range where the alloy is one-phased, i.e. beOween 780°C and 920°C for the composition of Uable 3.
Secor~c~,_sly.~g: the material of the first sing at a diameter of 20mrt~
is i~ammc~red to a diameeer o~f 1 1 mm then annealed iro a through-type furnace. For the alloy with the chemical compositioro of example 3, the annealing temperature mast be comprised l~e~tween 780°c~ and 920°C. With a diameter of 1 1 mm end the chemical composition of table 3, a cooling speed comprised bctwe~rr 300°Clmin and 15000°C/min allows the presence of second phase to be lirmited while avoiding fissuring. Use of~ harnmering allows considerable strain-hardening rates to be achieved, e~er~ with a fragile material. With ehis rnPthod, the r-emair~der rate of fragilizing second phase cars be higher ti~an with rolling, wire-drawing or stretch-forrr,irrg methods. Il carp reach values on the order of 50% by volume.
Thi_rd___sI_y_gy the material of the s~cor~d slug at a diameter of 1lmm Z0 is hammered to a diameter of 6,5mm then arvr~ealed iro a ~through,~type furnace or tempering furnace at a temperature comprised between 780°C
and 970"C. With ~3 di<imeter of f,5mm 'the alloy of table 3 allows cooling speeds between 300°Clmin to 70000°Cl~~nirv without any fissr.rring. These speeds oilow the ratio of fragilizind second phase to be limited.
7S Finishing: the material of the third slug is wire-drawn or stretch-~formed to a diameter of 4rnrY~ to obtain a rnachinable product. n spinodal decomposition treatmenO is ~finaily performed on the rnacP~ir~able product or on the machirved pieces 'to obtain optimal mechanical properties.
sMr_ rai_-z-rec-r COO~In(~'_test Samples of the inventive alloy have beero subjected 'to 'test o'f 'fast cooling to determine the occurrence of fisstaring. 'fhe chemical corrtposition of the allay in this test is given by table 2.
The samples were subjected to a heat ~~reatmer~t at a temperature of 800°C and 'then cooled quickly by immersion in a tempering fl~.tid (EXXON XD90) and in water.
I=or each cooling, the cooling sped, in °Clmin, was measured with a -thermocouple at the center of the sample. The presence of fissuring was verified by a traction test.
Tabic 5 i diameOerlmm traction traction test test X~'~O 'l"ate 24000 C7 63000 x U 16000 O 4~35d0 8 12000 O 33000 x 10.8 8300 O -13 6500 Olx 2300 _...._._ -......
(O - st.lccess I
xu failu.lre) The test permits to observe ~thwt'the diame'cers up to about 1Umm can tolerate a coolirvg irt a tempering fluid. Water tsampering, on thc~ other hand, always leads to o fissuring of the sample, ancf this trp to a minimal diarz~eter of 4rorn.
I-or srreall~dimer~sion products of Ctn~Ni~Sn~f'b, cooling speeds c7reoter than 24000°C/min can be used. In this case, water terrrpering can be efficient if the prOdlJCt~S 5170-' IS slIffICICntIy small to limit the transitory internal constraints and thus prevent fissuring from forr,~ing.
The maGhinable prodtacts of the examples 1, 2, 3 and 4 car? each be mWe by the methods pf the examples ~, 2, 3 and 4 provided 'that't!'~e sM rrm_-z-hc_-L.
cooling speeds and the heat treatment temperatures are adapted to the chemical compositions and to the dimensions. irn each of the presented examples, the number ofi slugs can vary according tn the size of the finished product.
Part of the copper of the alloys ofi the present iroverocion can be replac.c~d by other elements, for example Fe, Zn or Mn, at a ratio for C'X~rTlpiC' l-Ip t0 ~in%.
Other elements s~.~ch as Nb, Cr, Mg, Zr and AI can ~Iso be present, at a ratio t.rp to several percents. These elements have among others the 1U effect of improving the spinodai hardenirog.
sum: rm ..>.f~~_v-
State of the art Alloys based on copper, nickel end tin <3re Known arld widely used. -they offer excellerlt mechanical properties and exhifJit a strolig t~Zrderair~g during strain-hardening. Their mechanical properties arc' fl.lrther improved by the known feat-acing treatment such as spinodal decormposition. For ~n alloy containing, by weigklt, 15% of nickel arld F3%
of tire (standard alloy ASTM C7?.9(~p), the mechar~ic~ll resistance earl reach 1 S00 MPa.
1!p Another favorable property o'f the Cul-Ni-5 alloys is that they offer good trik~ofogical properties, comEoarable to those o-f bronzes, while' exhibiting st~pc~rior mechanical properties.
Another advantage of these materials is Choir oxcellernt fiorrllability, combirled with 'favorable elastic properties. Moreover, these.
~~I~Uys Uffer cl goOd rE.'sl5'~clrlCC'. dgdirl5'l COrrO5lorl and arl C'XCC'lIC'nt rC'Slst~'3r'1CC' to the constraints' heat relaxa'tior~. f=or this reason, the ~r.r-Ni-Sn springs do not lose their compression force with age, even rlrlder vibrations and strong boat strossos.
Theac~ favorable properties, col~nbir~ed with good heat and ~5 electricity Cor~ldllctlvlty, moan that these materials tare widely rlsed 'for making highly reliablo connectors for telecomrnunicatiorls and 'the car indrlstry. These alloys are also ~.lsed in several switches or~d electrical or s Nl r-. r nl.. > m: ~-Z
electromechanical devices or as supports of electronic components or for making bearing friction surfaces srabjected to high charges.
The Cr.u-Be alloys can be machined fairly weft and can contend with and were outperform the mechanical properties of Cr.l-Ni-Sn alloys.
The' machinability index of the Cu-Be alloys car-~ reach 50-~0% relatively to standard ASTM C3G000 brass. Their cost is however' high and their productiorn, rrse and recycling are particularly constraining because of the ber'yllirrm's higl7 toxicity. The resistance to the constraints' heat relaxation of 'these materials is lower ~cl-~an tf~oat o~t~'the Cu-Ni-Sri for ternperat~.rres 1(7 above 150-1'75°~:.
One' inconvenience of the Cru-Ni-Sn alloys is however that they are poorly sr.lited to processes si-rch as milling, tr_~rr~iry or sliciroc~ ar is ar~y other known process. A further ir~cor~veroiertce of these n3loys is Cheir strong segiegwlior~ during cosUirog.
15 It is thus an aim of the present invention to propose ar-~ alloy associating the favorable mechanical characteiistics of alloys based on copper, nickel and tin with a good workability.
It is ~rnother aim of the present inver~liol~ to propose a method for prodecir~g a rnachinable product on the basis of Crn~Ni~sl~ free from the' 20 incorwer~icnccs of the prior art.
ft is another airt~ of 'the present irmeotion to propose a machiuable alloy combir~ir~g high elasticity arid rnechar~icnl resistance characteristics brlt free 'from berylli~rrn or 'toxic eiernervts.
A IVrr~ther airn of the present irvver~tior~ is to propose a r~nc~tl~ocf for 25 producir~d a rnachirnable product on the basis of Crl-Ni-Sn allowing the problems relative to se c3regation to be solved.
~l-hese aims are ~~chieved by the product and thc~ method that arc' the object of the independent claims of corresponding category and 5Mf-_-1-AI_-2_r'C:1 notably by a machinable product composed of an alloy camprisir~g between 1 % arid 20% by weigl'~t of Ni, between 1 % ancf 7_0% by weight of Sn, betweero 0.1 % arid 4% of Pb, the remainder being constituted essentially of Cu, having ur'~dergorve a heat homogenizing treatment comprising a step o'f~ heatirng said alloy followed by a step of cooling at a speed sufficiently slaw to prevent 'fissuring.
pet~_i_Ied..descripvtior~ ofythe inveroior~
the present irwention concerns alloys oro the basis of copper, nickel, tin and lead Obtc~rneC:l by c~ cOntrnL.roUS Or S2lTll-CUrltlr'tUUUS
C~35'tIr7C) method, a static billet casting or casting by spr~yforming. -fhe copper-nickel-tin alloys have a long solidification interval leading to a considerable segregation durirog c~s'ting. Uf the 'fo~.~r aforementioned processes, casting by sprzyformir~g, also known by the name "Osprey" method, ar-id described far exarnple ire patent FPO?_?_573? makes it a possible 20 ob'lain an almost W homoger~or~s microstructrare presc~ntinc~ 7 f1'tlnlr'1'lr'71 degree of segrecla'tlon.
In 'this process, a metal billet is obtained by contirmrarrs depositing of artdmized droplets. "I'E~Ze segredatioo carp take place only on the scale' of the ator~iz~d droplets. The clif'fusior~ distarvces reqceired 'for dir~~inishing the segregation are th~.ls shortened. Irn the Case wl' corotine.roces or semi-7_0 cor-~tinuot-rs casting, the segregation is stronger than with 'the sprayforming process, br-et it remair-~s sr-efficiently reduced to void an excessive fragility of tEte alloy. ~~fhe static billet casting leads to a strong segrc~c~ation that can be elimir~a~ted only by a prolorycd heat processing.
Lead being essen'tiolly insol~rble in 'the other metals of the alloy, 75 the prodLlct obt~in~d will comprise lead particles dispersed in a Cry-Ni--sn matrix. Drjring the machining operations, floe lead has a It.rbricating effect and facilitates the fragrz~er~tation of the slivers.
The quantity of fend introd~.rced in the alloy depernds ora 'the degree of rnachrnabllity that one streves to achieve. Geroerally, a qr.ranti'ty of 3o lead up to several percents by weight can be introduced Wlt~lUUt the alloy's mechanical properties at normal tc~mpc~ratr-ere being modified. lwlowever, an~r: one.-z-her above 'the lead melting point (327 °C), the liquid lead strongly weakens the alloy. Alloys containing lead are thus difficult to make, on the one hand because they have a very strongly pronounced tendency towards fissuring and, Ur'1 the other hand, because they can exhibit a two-phased crystallographic strrscture containing are undesirable weakening phase.
°fhe method of the present invention makes it possible to produce a rr~achirzabfe Cu-Ni-Sr~~Pb prodr.lct contairrir2g up to several percents by weigh~l of lead, without it fissuring during fabrication, and having excellent mechanical properties, The ratio of lead cc~n vary between 0.1 % and 4% by weight, preferably between 0,7.% and .3% by weigf7~t, even more preferably between 0.5% and 1.5% by weight.
After smelting in the foundry, the production methods can be decomposed In slrCCe55ive Sll-lgs: far the first slug, two cases must be considered according to whether the product is manufactured by contir,uor.~s casting at small dianoeter or by static billet casting, sprayforming, semi~continirous or contirmoras casting at large dir~me-cer.
'T'he pr-odt.rcts of the invention are characterized by their excc~llc~nt rnachinability, wf'~ich is c3reater than that of Cr.r-Be .~Iloys. The machirrability index of the inventive alloys exceeds X30% relatively to standard AS~rM
?0 C36000 brass and can even reach ~~0%.
First-sl~.y-g:
Alloys obtained by contim.rous sm~3lf-diameter thread casting, c.g.
of 25mm or less, urodergo a heat homogenizing irea~er7ren~l or a step of cold deformration by harnrneriry followed by a horr,oger~izir~g t~r,d 75 recrystailization treatment. 'fire temperatr.rre of the heat tremurnere mast be within the range where the alloy is arse-phased. Cooling after ll7e heat treatment must occur at a speed sirfficier~tly slow to prevent fissnriry of tire alloy drre to internal cor~s~trair~~ts generated by the temperature differences d~.iring cooling, and st~f-licier~~lly fast -to limit the: formation of r~ two-phased 30 strncturc~. If the speed is too slow, a considerable yrantity of secorod phase s nn r_ rm--z-ro:: r a carp appear. ~hhis second phase is very fragile and greatly reduces the alloy's deformability. The critical cooling speed reqraired to avoid the formation of too large a quantity of second phase will depend on the alloy's chemistry and is grea'ter'for a higher quantity of nic!<c~l and tin.
Moreover, during cooling, transitory internal constraints r'~re generated within the alloy. They are linked to t~mperat~.ire differences between the surface and the center of the product. If these constraints exceed the alloy's resistance, the la'c'ier will 'fiss~~re arid is roo longer ~.rsable.
Ir7terrval constraints dr.re to cooling are all 'the higher the more the prodract's diameter is large. The critical cooling speeds to avoid fissuring thus depend on 'the product's diameter. This problem is even more acute wi't~5 Cu-Ni-5n-Pb alloys since above its ~rreltiog temperature of 327°C, lead strongly w~al<ens the alloy.
In the method of the present irvverotior~, cooling after heat treatment occc.rrs at a predetermined speed -taking into acco~~r~'t the alloy's chemistry and the transversal dimerosior-~, or diameter, of the produc't. -1-he cooling speed must be at the same tirrre sr.rfficiently slow to prevent fiss~~ring and sufficiently great to prevent too large a qr.rantity of fragilizir~g phase to form.
Unrir~g rnanufacturc~ of a large-diameter prodt.ict, 'the in'ter'nal corostrariro'ts due to 'floe temperature differences are greater Chars irv a small-dimensioro product, or~d the cooling speed mast conseqr.rently be limited. At the same tune, strong propor'tior~s of Ni arid Sn promote the formation of a fragilizing phase and require a fv3ster cooling.
z5 Alloys ohtained by sprayforrnirog, static billet casting or sc~mi~~
corotimaor-rs casting undergo a hot extrusio~o 'lreatmerot. ~f-his is also the caso for con'tir~e-roras casting if the product is of I~~rge diameter. Cooling during extrusion rz~ust be svafficiently slow to prevent fissurirog and srnf'Ficier~tly fast to limit the formation of a fragilizing secorrci phase. Alterroalively, if cooling during extrr.rsion is too slow, heat homogenizing arnd recrys'tallizatior~
snn r-rm--z-r~~_ r treatments as explained l7ere above for the case of small-diameter continuous-casting products mt.~st follow extrusion.
Once the 'first sfe~g has been made, 'the final rnachinable product must be either ob'tair~ed directly by one or several cold deformation operations, e.g. by rolling, wire-drawing, stretch-forming or- any other cold deformation process, or obeairoed by one or several successive slt.rgs.
5ycc.~SSiveslugs:
from the first slug, the followiry slugs are obtained by oroe or several cold deformation operations followed by a heat recrystaliiz~tion 30 treatmervt. '1"he temperature of the recrystallization treatment must be within the range where 'the alloy is one-phased. Coolirng after the heat treatment mtast have a speed st~'f'ficier~tly slow to prevent fissuring but always sufficierotly fast. to limit 'the 'forrna'lior~ of a two-phased s'lrurtt_tre.
'l~~hrot.rgh successive slr.rgs, thC'_ slZe Of the product is redrmed. From the las~c slug, the fiir~ol product is obtained by one or several cold deforr~~atior~
opc~ratior~s.
The mech<3nical properties of the alloy oi.~tain~c~ corn be snbseqetewtly increased by a spinad~~l decomposition heat treatr'aoerot. -1-iois trezornewt cao 'take place before the final machining or after the latter.
70 f-ierewfter, examples of rz~ethods ~~nd of rn7chinable prodt.rcts according to the preserot ir~ver7~tior~ will be presented. Ira the following examples, the cooling ternperotures refer to thc~ enter of the prodt.rct.
F. x ~-rz~_p 1-c---1-The chemical corrrposition of tt~e alloy in this c~xamp(e is given by table 1:
snnrr nl -z-hc:-r c~~~e 1 CompUrlerlt ~rbpOrtibrv. (by WeLC~ht~
Cll ren'lalnder Ni 7.5%
5n 5%
Pb 1 Mn 0.1%-1%
other <_0.5%
Manganese is introduced in the composition as deoxidizer, It is however possible to use ir~ste~d other eiemerr'ts or deVICes preventing the alloy from oxidizing.
This ailoy carp be cast according to the different methods merotior~ed furtk7er above. Irr this example, this alloy is obtained by contirvitous billet cas'tirng with a diameter of lFiUmm.
F_i_rst__sly,lg: the' billets are extri.aded for example to o diameter of l 8mrz~. At the exit of the extrctsior~ die, the' alloy is cooled by ~
strea~'n o'f compressed air allowing a cooling speed of 50°C/rnir~ to 300°Clmin to be achieved, as rneasr.rred a't the cer~'ler of 'the alloy. This speed is sufficic~ntfy slow to avoid fissuring and sufficiently fast to limi't'the 'formation of a fragilizing S(?COrld pklc7se, cooling by water spray ccm also be r.rsed, possibly allowing cooling sp~c~ds of .300°Clmin to 1000°Clmin to be achieved without fissuring of the material. Other means for reaching a suitable cooling speed car? also be l.~sed. If cooling at the exit of the extrrrsior~ die' is not sr~fficiet~tly fast, a too great a proportion of second pi~ase care form, tf~e alloy will have 'to ttrldergo o horr~oc~er~ization treatrnerl'l with 'the sarme characteristics for the cooling speed at a tempera'tr_rre wi'tl'~in the rar~de where the alloy is 2U one-phased, i.e. betweero 690°C anc3 92()'C for tk7e cornpositiorn of table 1.
S_c~co»c~ slug: the material of the first slag of a diameter ofi 1 t3mm is rolle;~d to a diamc~t~r of 13mm thin ar~n~aled ire a through-'type fe.rrnace or removable cover f~.irnacc. For the alloy with the chemical cornpositioro ofi exar7iple 1, the annealing temper~~trirc~ must be comprised betweero 59U~C
7.5 and 9?0°C. A cooling spc~c~d on the order of 10°Clmin is sufficient to limit the formation of second phase' for this compasitior~ and this diameter of s ran:w n n-z-sm-l3mm, Furthermore, water spray cooling at speed of 300°Clmin tQ
3000°C/mir~ allows fissuring to be prevented and the formation of a fragilizing secorod phase to be limited.
Fi-r~is_h_ir~~: the rrraterial of tile second slag is wire-drawr-~ or stretch-formed to a diameter of 8mm to obtain a machir~able product. A
spinodal decomposition ~CreaOrner~~l is finally perforrmed on the machinable produce or orr the rnachiroed pieces to obtairo optimal mechanical propertres.
F_x,~ m_EOl ~..
The chemical composition of the alloy ire this example is given by table Z:
Table z Component Proportion (by weight) Cu rernairrder In this exacmple, this Ni 9% alloy is obtained by continuous 5n 0% 15 thread castirog with a di~rz~eter of Pb 1 Mrl 0,1 %-1 % 18mrZ~.
Imp~iri~ties <0.5%
I-irs 5~~ag: the thread ~.mdergoes a homogenization treatrnent in a tf~rough-type fv_irn~ce at a temperotrire between 700°C and 970°C, corresponding to the one~phase ,~0 mange of thc~ chemical composition of exarT~ple 7. A cooling speed between 100°Clrnin and 1000°Clr~~rir~ allows fissuring to be prevented arod the proportion of fragilizir~g second phase to be limited. Such cooling speeds can for- exarrrple be achieved by usiry compressed air, water spray or a gaslwater excharngirog cooler.
25 Ser_o~yc~ slug: the rnateriol of the first slug of a diarr~e~ter of lF3mm is rolled, wire-drawn or stretch-'formed co a diameter of l3r~nm then oranealed in za through-type furnace at a temperature conoprised between 700°C and 920°C. WiOir a diameter o~F l3mrn and the chemical composition snntrm...o.io.:r c3 of table ~, a cooling speed betweero 100°Clrnin to 3000°Clrnin allows the formation of a second phase to be limited while avoiding fissuring.
Third-s!_rrg: the material of 'the second slug at a diameter of l3rnm is rolled, wire-drawn or stretch-formed to a diameter of 10mm then a annealed in a throragh-type 'furnace or tempering furnace at a temperature comprised betweero 700°C anc9 920°C. With a diameter of 10mm and the chemical composiliora ov table 2, a cooling sped betweew100°Clmin to 15000°Umin allows the formation of a second phase to be limited withor.rt any fissurirog being created.
1() Fo~.irth-sl-a.yg: the material of the tl7ird slug a~t a diameter of l0mm is rolled, wire-drawn or stretch-formed 'to a dizo~neter of 7mm then annealed ire a through-'type 'furnace or tempering furr~.-~ce at a temperatrare comprised betweerv '700"C arod 920"C. With a diameter of 7mm and the Chemic7l Cor'npositiorl of table 2, a cooling speed between 100°C/min to 15 20000"Clmin allows the forrz~atior~ of a fragiiizing SecUrld phase to be limited withor.rt any fissr.rrir~g being created.
f:yivftf~ slug: the material of the fourth slug at a diarzieter of 7a~m is rollecJ, wire-drawn or stretch-formed to a diameter of 5mrz~ then ar~r~ealed irr a tfirorrgh~type f«rnac~ or t~mpcrirlg furnace at a ternperatnre 20 comprised b.ntwc~c~n 700"C armJ 9z0"C. lNitl~ a diameter of 5rnrn arnd ~lhe chervical composition of table z, a coalir~d speed between 100°Clmirr to 30000"C/r~~ir~ allows the for matioro of a fragilizing second phase to be limited withornt ar~y fi5surir~g being created. A cooling speed on the order of 15000°Clrniro can be acP~ieved by tempering in appropriate fluids.
25 Sixtp_sliig: the material of the fifth sl~.rg at a diarz~eter of 5mm is rolled, wire-drawn or stretch-formed to a diameter of 3mm, ar~r~ealed in a through-type furnace or tempering fr.rrnace at a temperat~.rre comprised betweern 700"C arid 92_0°C, then cooled at a cooling speed comprised belweer~ 100°Clrnin to 40000"C/rr~in.
sMr_nnc_-z-ro: r SeverytPy.sl_r.i.~: the material of the sixth slag aU a diameter of 3mm is rolled, wire-drawn or stretch-formed to a diameter o~f zmm, annealed ire a through-type furnace or tempering furnace at a ternperatr.rre comprised between 700°C and 920°C, then cooled at a cooling sped comprised 5 between 100°Clmin to 40000"Clmin.
Eigtyth slug: Ohe material of the seventh slug at ~3 diameter of 7mm is rolled, wire-drawn or stretch-formed to a diameter of 1,60mm, annealed in a through-type ~furr~ace or tempering furnace at a temperature com~~rised between 700°C and 920°C, and then cooled at a cooling speed 1U cornprised between 100°C/min to 500UU°Clr~nin.
f~irpishing: 'the material of the eighth slug is rolled, wire-drawn or strotch~formed to a diameter of lrnm to obtain a m~ichinable product. A
spinodal decomposition treatrnewt is finally performed on the m7chiroable product or on the machined pieces to obtain optimal rrrec.hanic~~l properties.
1 he "AS I M 'lest method for rnachin<~bility" test proposes a method for determiroirag ~cF~e rnachinability index relatively to standard Cu7r~39f~b3, or c:3f~000 brass. "fhe machinability index of the alloy according tc~ this aspect of the invention is better by F30%.
LxampLe 3 The chemical CUrllpOSltlOrl Of thc~ alloy ire this example is the sar~c~
as that of the secorvd example given by table 2_. In this example, the alloy is obtained by COiltlr~lllOUS C~~Stll'1C~ at a diameter of ?..5mm.
Fi_rst___sf_r,ag: the thread cast at a diameter of ?5mrrr is hammered to z5 a diameter of 1Umm. The hammering allows the material to deform with a considerabie redaction rate without prior heat homogenizing treatment.
Wi~lh tlois method, a high remainder ratio of fragilizing second phase can be Oolerated at this stage. The second phase carp reach a volume ratio orr the orc9er of 50%_ snnc rnr, z-nc:r After hammering, the thread at a diameter of l6mm undergoes homogenizing and recrystallization treatment in a thrm.rgh~~typc~ furnace.
The terr~perature of the heat treatment must be comprised between 7p0°C
and 9~0°C. The following cooling will take place at a speed comprised beUween 100°C/min and 300o°C/r7~ir~. These cooling speeds make it possible to prevent ~fissrtrir7g ar7d to limit the ratio of second phase for a product of this diameter arid of this corn position. 5tich speeds carp be obtained by using compressed air, w~rler spray or gaslwater exchangers.
F-in_ist~ing: the materizol of the first slug is wire-drawn or stretch-formed to a diameter of 1Ornm to ok~tain a machinabfe product. A spinodal deCOmpositiorl treatment is finally performed on the machinzble product or oro the machined pieces to obtairo optimal mechanical properties.
Exymple 4 The chemical composition of the alloy in this example is givero by table 3:
Table 3 Component Proportion (by weight) Ct.i remainder Ni 15%
Sri B%
f' k~ 1 ~/
Mn 0.~%..1%
Irllpl.lrItIC'S<0.5%
This alloy can be cast ~ccordir~g to the differewe methods mentioned here above. !r~ this example, this alloy is obtairoeci by sprayforming billets whose diameter is 240mm.
7. Q First_sl_y.g.: the billets arc' extruded for example to a diameter of ZOmm. If the billets' dimensional irregr.il~ritics are too great, a turning step can be necessary before extrr.rsior~. At the exit of the extrusion die, the alloy is cooled by water spray allowing a cooling speed of 300°Clmin to 3000"C/min to be achieved, as measr.rred at the center of the alloy. This snrrr--r-nr.-z-r~~l 1z speed is sufficiently slow to avoid fissuring and sufficiently fast to limit the formation o~f a fragilizing second phase. If cooling at the exit of the extrusion die is clot sufficiently fast, a too great a proportion of second phase carp form. The alloy will then have to undergo a homogenization treatment wiOh the same characteristics for the cooling speed at a temperature within the range where the alloy is one-phased, i.e. beOween 780°C and 920°C for the composition of Uable 3.
Secor~c~,_sly.~g: the material of the first sing at a diameter of 20mrt~
is i~ammc~red to a diameeer o~f 1 1 mm then annealed iro a through-type furnace. For the alloy with the chemical compositioro of example 3, the annealing temperature mast be comprised l~e~tween 780°c~ and 920°C. With a diameter of 1 1 mm end the chemical composition of table 3, a cooling speed comprised bctwe~rr 300°Clmin and 15000°C/min allows the presence of second phase to be lirmited while avoiding fissuring. Use of~ harnmering allows considerable strain-hardening rates to be achieved, e~er~ with a fragile material. With ehis rnPthod, the r-emair~der rate of fragilizing second phase cars be higher ti~an with rolling, wire-drawing or stretch-forrr,irrg methods. Il carp reach values on the order of 50% by volume.
Thi_rd___sI_y_gy the material of the s~cor~d slug at a diameter of 1lmm Z0 is hammered to a diameter of 6,5mm then arvr~ealed iro a ~through,~type furnace or tempering furnace at a temperature comprised between 780°C
and 970"C. With ~3 di<imeter of f,5mm 'the alloy of table 3 allows cooling speeds between 300°Clmin to 70000°Cl~~nirv without any fissr.rring. These speeds oilow the ratio of fragilizind second phase to be limited.
7S Finishing: the material of the third slug is wire-drawn or stretch-~formed to a diameter of 4rnrY~ to obtain a rnachinable product. n spinodal decomposition treatmenO is ~finaily performed on the rnacP~ir~able product or on the machirved pieces 'to obtain optimal mechanical properties.
sMr_ rai_-z-rec-r COO~In(~'_test Samples of the inventive alloy have beero subjected 'to 'test o'f 'fast cooling to determine the occurrence of fisstaring. 'fhe chemical corrtposition of the allay in this test is given by table 2.
The samples were subjected to a heat ~~reatmer~t at a temperature of 800°C and 'then cooled quickly by immersion in a tempering fl~.tid (EXXON XD90) and in water.
I=or each cooling, the cooling sped, in °Clmin, was measured with a -thermocouple at the center of the sample. The presence of fissuring was verified by a traction test.
Tabic 5 i diameOerlmm traction traction test test X~'~O 'l"ate 24000 C7 63000 x U 16000 O 4~35d0 8 12000 O 33000 x 10.8 8300 O -13 6500 Olx 2300 _...._._ -......
(O - st.lccess I
xu failu.lre) The test permits to observe ~thwt'the diame'cers up to about 1Umm can tolerate a coolirvg irt a tempering fluid. Water tsampering, on thc~ other hand, always leads to o fissuring of the sample, ancf this trp to a minimal diarz~eter of 4rorn.
I-or srreall~dimer~sion products of Ctn~Ni~Sn~f'b, cooling speeds c7reoter than 24000°C/min can be used. In this case, water terrrpering can be efficient if the prOdlJCt~S 5170-' IS slIffICICntIy small to limit the transitory internal constraints and thus prevent fissuring from forr,~ing.
The maGhinable prodtacts of the examples 1, 2, 3 and 4 car? each be mWe by the methods pf the examples ~, 2, 3 and 4 provided 'that't!'~e sM rrm_-z-hc_-L.
cooling speeds and the heat treatment temperatures are adapted to the chemical compositions and to the dimensions. irn each of the presented examples, the number ofi slugs can vary according tn the size of the finished product.
Part of the copper of the alloys ofi the present iroverocion can be replac.c~d by other elements, for example Fe, Zn or Mn, at a ratio for C'X~rTlpiC' l-Ip t0 ~in%.
Other elements s~.~ch as Nb, Cr, Mg, Zr and AI can ~Iso be present, at a ratio t.rp to several percents. These elements have among others the 1U effect of improving the spinodai hardenirog.
sum: rm ..>.f~~_v-
Claims (35)
1. Production method of a metallic product composed of an alloy comprising between 1% and 20% by weight of Ni, between 1% and 20% by weight of Sn, between 0.1% and 4% of Pb, the remainder being constituted essentially of Cu, the method comprising a heat treatment comprising as step of heating said alloy followed by a cooling step at a speed sufficiently slow to prevent fissuring.
2. Method according to claim 1, wherein the speed of said cooling step is sufficiently high to limit the formation of a two-phased structure.
3. Method according to claim 1 or 2, wherein said cooling step occurs at a predetermined cooling speed depending on the alloy's chemical composition and on the size of said metallic product.
4. Method according to claim 1 or 2, wherein said heat treatment is followed by a step of cold deformation by rolling, wire-drawing, stretch forming or hammering.
5. Method according to claim 4, comprising a recrystallization step followed by a cooling step at a speed sufficiently slow to prevent fissuring.
6. Method according to claim 1, wherein said heat treatment is performed in a through-type furnace.
7. Method according to claim 1, comprising an initial step of continuous casting.
8. Method according to claim 7, comprising a hammering step after said continuous casting.
9. Method according to claim 1, comprising an initial step of static billet casting or a step of sprayforming billet casting, or a stop of semi-continuous billet casting, followed by an extrusion step,
10. Method according to claim 1, wherein said heat treatment tales places at a temperature comprised between 690°C and 920°C.
11. Method according to claim 1, wherein the transversal dimension of said metallic product during said heat treatment is comprised between 1 mm and 100mm.
12. Method according to claim 1, wherein the transversal dimension of said metallic, product during said heat treatment is comprised between 5mm and 50mm.
13. Method according to claim 1, wherein the transversal dimension of said metallic product during said heat treatment is comprised between 10mm and 20mm.
14. Method according to claim 1, wherein said cooling step of said heat treatment has a cooling speed comprised between 10°C/min and 24000°C/min.
15. Method according to claim 1, wherein said cooling step of said heat treatment has a cooling speed comprised between 10°C/min and 4000°C/min.
16. Method according to claim 1, wherein said cooling step of said heat treatment has a cooling speed comprised between 100°C/min and 1500°C/min.
17. Method according to claim 1, wherein said cooling step of said heat treatment has a cooling speed comprised between 100°C/min and 1000°C/min.
18. Method according to claim 1, comprising a step of wire-drawing or stretch-forming or hammering or rolling.
19. Method according to claim 1, comprising a step of spinodal hardening.
20. Method according to claim 1, wherein said alloy comprises between 6% and 8% of Ni, between 4 and 6% of Sn and between 0.5 and 2% of Pb,
21. Method according to claim 1, wherein said alloy comprises between 8% and 10% of Ni, between 5 and 7% of Sn and between 0.5 and 2% of Pb.
22. Method according to claim 1, wherein said alloy comprises between 14% and 16% of Ni, between 7 and 9% of Sn and between 0.5 and 2% of Pb.
23. Method according to claim 1, comprising up to 10% of one or more of the following elements: Zr, Nb, Cr, AI, Mg.
24. Product from the method of claim 1.
25. Machinable product, composed of an alloy comprising between 1 % and 20% by weight of Ni, between 1 % and 20% by weight of Sn, between 0.1 % and 4% of Pb, the remainder being constituted essentially of Cu, having undergone a heat treatment comprising a step of heating said alloy followed by a cooling step at a speed sufficiently slow to prevent fissuring.
26. Machinable product according to claim 25, wherein said alloy comprises between 6% arod 8% of Ni, between 4 and 6% of Sn and between 0.5 and 2% of Pb.
27. Machinable product according to claim 25, wherein said alloy comprises between 8% and 10% of Ni, between 5 and 7% of Sn and between 0.5 and 2% of Pb.
28. Machinable product according to claim 75, wherein said alloy comprises between 14% and 16% of Ni, between 7 and 9% of Sn and between 0.5 and 2% of Pb.
29. Machinable product according to claim 25, wherein said homogenizing treatment is performed in a through-type furnace.
30. Machinable product according to claim 25, wherein said heat treatment is followed by a step of cold deformation by rolling, wire-drawing, stretch-forming or hammering and a recrystallization step followed by a cooling step at a speed sufficiently slow to prevent fissuring.
31. Machinable product according to claim 25, wherein the spend of said cooling step is sufficiently high to limit the formation of a two-phased structure.
32. Machinable product according to claim 25, wherein said heal treatment takes places at a temperature comprised between 690°C
and 920°C.
and 920°C.
33. Machinable product according to claim 75, wherein the transversal dimension of said metallic product during said heat treatment is comprised between 1mm and 100mm.
34. Machinable product according to claim 25, wherein said cooling step of said heat treatment has a cooling speed comprised between 10°C/min and 24000°C/min.
35. Machinable product according to claim 25, wherein said cooling step of said heat treatment has a cooling speed comprised between 10°C/min and 4000°C/min.
35. Machinable product according to claim 25, wherein said cooling step of said heat treatment has a cooling speed comprised between 100°C/min and 1500°C/min.
37. Machinable product according to claim 25, wherein said cooling step of said heat treatment has a cooling speed comprised between 100°C/min and 1000°C/min.
38. Machinable product according to claim 25, comprising a step of spinodal hardening.
39. Machinable product according to claim 25, comprising up to 10% or more of the following elements: Fe, Zn, Mn and/or up to 5% or more of the following elements: Zr, Nb, Cr, Al, Mg.
40. Machinable product, composed of an alloy comprising between 8% and 10% of Ni, between 5 and 7% of Sn and between 0.5%
and 2% of Pb, the remainder being constituted essentially of Cu.
41. Machinable product according to claim 40, characterized by a machinability index greater than 80%.
42. Machinable product according to claim 40, containing up to 10% or more of the following elements; Fe, Zn, Mn and/or up to 5% or more of the following elements: Zr, Nb, Cr, Al, Mg.
35. Machinable product according to claim 25, wherein said cooling step of said heat treatment has a cooling speed comprised between 100°C/min and 1500°C/min.
37. Machinable product according to claim 25, wherein said cooling step of said heat treatment has a cooling speed comprised between 100°C/min and 1000°C/min.
38. Machinable product according to claim 25, comprising a step of spinodal hardening.
39. Machinable product according to claim 25, comprising up to 10% or more of the following elements: Fe, Zn, Mn and/or up to 5% or more of the following elements: Zr, Nb, Cr, Al, Mg.
40. Machinable product, composed of an alloy comprising between 8% and 10% of Ni, between 5 and 7% of Sn and between 0.5%
and 2% of Pb, the remainder being constituted essentially of Cu.
41. Machinable product according to claim 40, characterized by a machinability index greater than 80%.
42. Machinable product according to claim 40, containing up to 10% or more of the following elements; Fe, Zn, Mn and/or up to 5% or more of the following elements: Zr, Nb, Cr, Al, Mg.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2004/050449 WO2005108631A1 (en) | 2004-04-05 | 2004-04-05 | Free-cutting, lead-containing cu-ni-sn alloy and production method thereof |
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| Publication Number | Publication Date |
|---|---|
| CA2561903A1 true CA2561903A1 (en) | 2005-11-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CA002561903A Abandoned CA2561903A1 (en) | 2004-04-05 | 2004-04-05 | Machinable copper-based alloy and production method |
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| Country | Link |
|---|---|
| US (1) | US20070089816A1 (en) |
| EP (1) | EP1737991A1 (en) |
| JP (1) | JP2007531824A (en) |
| KR (1) | KR20070015929A (en) |
| CN (1) | CN1961089A (en) |
| AU (1) | AU2004319350B2 (en) |
| BR (1) | BRPI0418718A (en) |
| CA (1) | CA2561903A1 (en) |
| IL (1) | IL178448A (en) |
| MX (1) | MXPA06011498A (en) |
| NO (1) | NO20064876L (en) |
| NZ (1) | NZ550305A (en) |
| WO (1) | WO2005108631A1 (en) |
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| DE102006027844B4 (en) * | 2005-06-22 | 2019-10-31 | Wieland-Werke Ag | Copper alloy based on copper and tin |
| US20070253858A1 (en) * | 2006-04-28 | 2007-11-01 | Maher Ababneh | Copper multicomponent alloy and its use |
| RU2508415C2 (en) * | 2009-04-08 | 2014-02-27 | Свиссметал-Юмс Швайцерише Металлверке Аг | Copper-based alloy treated by cutting, and method for its production |
| CN106435250A (en) * | 2009-04-08 | 2017-02-22 | 瑞士金属-Ums瑞士金属加工有限公司 | Machinable copper base alloy and production method thereof |
| CN101709407B (en) * | 2009-11-06 | 2011-09-28 | 江阴新华宏铜业有限公司 | Preparation method of ferrimanganic copper-nickel tube |
| US20110226219A1 (en) * | 2010-03-17 | 2011-09-22 | Caterpillar Inc. | Fuel lubricated pump and common rail fuel system using same |
| US9181606B2 (en) | 2010-10-29 | 2015-11-10 | Sloan Valve Company | Low lead alloy |
| CN102615491B (en) * | 2011-01-31 | 2015-05-20 | 肖克建 | Processing method for copper material |
| CN102304642B (en) * | 2011-08-26 | 2012-10-24 | 河南科技大学 | Cast wear-resistant tin bronze alloy and preparation method thereof |
| CN102321826B (en) * | 2011-08-26 | 2012-10-03 | 河南科技大学 | Extruded high-tin bronze alloy and preparation method thereof |
| JP2015531829A (en) * | 2012-08-22 | 2015-11-05 | バオシダ スイスメタル アーゲーＢａｏｓｈｉｄａ Ｓｗｉｓｓｍｅｔａｌ Ａｇ | Machinable copper alloy for electrical connectors |
| JP6340408B2 (en) * | 2013-03-14 | 2018-06-06 | マテリオン コーポレイション | Ultra high strength copper-nickel-tin alloy |
| CN107354414B (en) * | 2013-03-15 | 2019-11-29 | 美题隆公司 | Metastable alloy and product with uniform grain size |
| JP6190674B2 (en) * | 2013-09-09 | 2017-08-30 | 古河電気工業株式会社 | Copper alloy sheet and manufacturing method thereof |
| DE112015001296T5 (en) | 2014-03-17 | 2016-12-29 | Materion Corporation | High strength, homogeneous copper-nickel-tin alloy and manufacturing process |
| CN104388743A (en) * | 2014-11-05 | 2015-03-04 | 无锡阳工机械制造有限公司 | Brine corrosion resistant alloy |
| CN104388742A (en) * | 2014-11-05 | 2015-03-04 | 无锡阳工机械制造有限公司 | Brine corrosion resistant alloy |
| CN104372200A (en) * | 2014-11-14 | 2015-02-25 | 无锡阳工机械制造有限公司 | Brine-corrosion-resistant alloy |
| CN105483430B (en) * | 2016-01-29 | 2017-11-14 | 罗仙花 | A kind of preparation method of high intensity high filtration flux Cu alloy material |
| CN105734471B (en) * | 2016-05-12 | 2017-09-29 | 中国兵器工业第五九研究所 | A kind of Ultra-fine grain copper material homogenizes preparation method |
| EP3273307A1 (en) * | 2016-07-19 | 2018-01-24 | Nivarox-FAR S.A. | Part for clock movement |
| EP3273306A1 (en) * | 2016-07-19 | 2018-01-24 | Nivarox-FAR S.A. | Part for clock movement |
| CN106119581A (en) * | 2016-07-29 | 2016-11-16 | 柳州豪祥特科技有限公司 | A kind of preparation technology of powdered metallurgical material |
| CN106086492B (en) * | 2016-07-29 | 2018-10-02 | 柳州豪祥特科技有限公司 | The preparation process of copper based powder metallurgy material |
| CN106065444B (en) * | 2016-07-29 | 2018-10-02 | 柳州豪祥特科技有限公司 | The method that powder metallurgic method prepares corronil material |
| CN106345811A (en) * | 2016-09-01 | 2017-01-25 | 史汉祥 | Method for manufacturing brass rod wire |
| BE1025772B1 (en) * | 2017-12-14 | 2019-07-08 | Metallo Belgium | Improvement in copper / tin / lead production |
| CN109750184B (en) * | 2019-03-08 | 2020-11-03 | 金华市程凯合金材料有限公司 | Preparation method of high-fine-grain atomized copper alloy powder |
| JP7433262B2 (en) | 2020-03-30 | 2024-02-19 | 日本碍子株式会社 | Method for manufacturing Cu-Ni-Sn alloy and cooler used therein |
| JP7433263B2 (en) | 2021-03-03 | 2024-02-19 | 日本碍子株式会社 | Manufacturing method of Cu-Ni-Sn alloy |
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| US1535542A (en) * | 1923-02-15 | 1925-04-28 | Scovill Manufacturing Co | Nonferrous alloy |
| GB540795A (en) * | 1940-04-22 | 1941-10-30 | Leonard Bessemer Pfeil | Improvements in the heat treatment of metal alloys |
| AU465605B2 (en) * | 1971-08-11 | 1975-10-02 | Toyo Valve Co., Ltd | Copper rase alloy |
| US4142918A (en) * | 1978-01-23 | 1979-03-06 | Bell Telephone Laboratories, Incorporated | Method for making fine-grained Cu-Ni-Sn alloys |
| US4406712A (en) * | 1980-03-24 | 1983-09-27 | Bell Telephone Laboratories, Incorporated | Cu-Ni-Sn Alloy processing |
| CA1238309A (en) * | 1984-02-09 | 1988-06-21 | Nareshchandra J. Kar | Copper-based spinodal alloy bearings |
| JPH02129328A (en) * | 1988-11-09 | 1990-05-17 | Nishidai Densen Kogyo Kk | Free-cutting spinodal copper alloy |
| FR2661922B1 (en) * | 1990-05-11 | 1992-07-10 | Trefimetaux | COPPER ALLOYS WITH SPINODAL DECOMPOSITION AND PROCESS FOR OBTAINING SAME. |
| DE4121994C2 (en) * | 1991-07-03 | 1995-06-08 | Wieland Werke Ag | Process for producing a copper-nickel-tin alloy and its use |
| JP3579122B2 (en) * | 1995-04-12 | 2004-10-20 | 株式会社宮本工業所 | Storage tank for aluminum dross |
| JPH08283889A (en) * | 1995-04-14 | 1996-10-29 | Chuetsu Gokin Chuko Kk | High strength and high hardness copper alloy |
| DE69941805D1 (en) * | 1998-02-24 | 2010-01-28 | Taiho Kogyo Co Ltd | BEARING FOR INTERNAL COMBUSTION ENGINE |
-
2004
- 2004-04-05 WO PCT/EP2004/050449 patent/WO2005108631A1/en active Application Filing
- 2004-04-05 CN CNA2004800432423A patent/CN1961089A/en active Pending
- 2004-04-05 BR BRPI0418718-0A patent/BRPI0418718A/en not_active Application Discontinuation
- 2004-04-05 KR KR1020067020938A patent/KR20070015929A/en not_active Application Discontinuation
- 2004-04-05 AU AU2004319350A patent/AU2004319350B2/en not_active Ceased
- 2004-04-05 EP EP04725712A patent/EP1737991A1/en not_active Withdrawn
- 2004-04-05 NZ NZ550305A patent/NZ550305A/en not_active IP Right Cessation
- 2004-04-05 JP JP2007506666A patent/JP2007531824A/en active Pending
- 2004-04-05 MX MXPA06011498A patent/MXPA06011498A/en unknown
- 2004-04-05 CA CA002561903A patent/CA2561903A1/en not_active Abandoned
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- 2006-10-03 US US11/542,508 patent/US20070089816A1/en not_active Abandoned
- 2006-10-04 IL IL178448A patent/IL178448A/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20070015929A (en) | 2007-02-06 |
| NO20064876L (en) | 2006-12-21 |
| EP1737991A1 (en) | 2007-01-03 |
| NZ550305A (en) | 2010-07-30 |
| IL178448A0 (en) | 2007-02-11 |
| AU2004319350B2 (en) | 2010-07-08 |
| MXPA06011498A (en) | 2007-03-21 |
| JP2007531824A (en) | 2007-11-08 |
| WO2005108631A1 (en) | 2005-11-17 |
| CN1961089A (en) | 2007-05-09 |
| AU2004319350A1 (en) | 2005-11-17 |
| BRPI0418718A (en) | 2007-09-11 |
| US20070089816A1 (en) | 2007-04-26 |
| IL178448A (en) | 2011-06-30 |
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