EP3423604A1 - Zinnhaltige kupferlegierung, verfahren zu deren herstellung sowie deren verwendung - Google Patents
Zinnhaltige kupferlegierung, verfahren zu deren herstellung sowie deren verwendungInfo
- Publication number
- EP3423604A1 EP3423604A1 EP17706407.8A EP17706407A EP3423604A1 EP 3423604 A1 EP3423604 A1 EP 3423604A1 EP 17706407 A EP17706407 A EP 17706407A EP 3423604 A1 EP3423604 A1 EP 3423604A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tin
- phases
- alloy
- wear
- casting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 109
- 239000000956 alloy Substances 0.000 claims abstract description 109
- 229910052718 tin Inorganic materials 0.000 claims abstract description 109
- 229910052796 boron Inorganic materials 0.000 claims abstract description 68
- 238000005266 casting Methods 0.000 claims abstract description 57
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 57
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 52
- 239000010703 silicon Substances 0.000 claims abstract description 38
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005260 corrosion Methods 0.000 claims abstract description 28
- 230000007797 corrosion Effects 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 239000000853 adhesive Substances 0.000 claims abstract description 17
- 230000001070 adhesive effect Effects 0.000 claims abstract description 17
- 230000001976 improved effect Effects 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052745 lead Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 56
- 238000000137 annealing Methods 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000011574 phosphorus Substances 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- -1 phosphorus silicates Chemical class 0.000 claims description 26
- 238000001953 recrystallisation Methods 0.000 claims description 26
- 238000012545 processing Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 23
- 239000000155 melt Substances 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000011265 semifinished product Substances 0.000 claims description 15
- 238000007711 solidification Methods 0.000 claims description 14
- 230000008023 solidification Effects 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 238000005482 strain hardening Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000009749 continuous casting Methods 0.000 claims description 5
- 238000004512 die casting Methods 0.000 claims description 5
- 238000004870 electrical engineering Methods 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 239000011253 protective coating Substances 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 238000005495 investment casting Methods 0.000 claims description 3
- 238000011089 mechanical engineering Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 238000009527 percussion Methods 0.000 claims description 3
- 238000007528 sand casting Methods 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000000384 rearing effect Effects 0.000 claims description 2
- 239000013535 sea water Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 239000002245 particle Substances 0.000 description 61
- 239000000463 material Substances 0.000 description 49
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 29
- 230000001965 increasing effect Effects 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000011148 porous material Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000005097 cold rolling Methods 0.000 description 13
- 238000005204 segregation Methods 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000005098 hot rolling Methods 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 238000005275 alloying Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 150000004760 silicates Chemical class 0.000 description 7
- 229910008423 Si—B Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000009827 uniform distribution Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005242 forging Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- YWIHFOITAUYZBJ-UHFFFAOYSA-N [P].[Cu].[Sn] Chemical compound [P].[Cu].[Sn] YWIHFOITAUYZBJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 239000002347 wear-protection layer Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910017755 Cu-Sn Inorganic materials 0.000 description 2
- 229910017927 Cu—Sn Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 2
- 230000035508 accumulation Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 210000004197 pelvis Anatomy 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910017818 Cu—Mg Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910020944 Sn-Mg Inorganic materials 0.000 description 1
- KRJBVTKYLBPUJC-UHFFFAOYSA-N [B+3].[O-2].[Al+3].[O-2].[O-2] Chemical compound [B+3].[O-2].[Al+3].[O-2].[O-2] KRJBVTKYLBPUJC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 238000005552 hardfacing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010112 shell-mould casting Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000012791 sliding layer Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000012546 transfer Methods 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
- C22C9/02—Alloys based on copper with tin 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
- B22D21/025—Casting heavy metals with high melting point, i.e. 1000 - 1600 degrees C, e.g. Co 1490 degrees C, Ni 1450 degrees C, Mn 1240 degrees C, Cu 1083 degrees C
Definitions
- Tin-containing copper alloy Tin-containing copper alloy, process for their preparation and their
- the invention relates to a tin-containing copper alloy having excellent hot workability and cold workability, high resistance to abrasive wear, adhesive wear and fretting wear, and improved corrosion resistance and stress relaxation resistance according to the preamble of any one of claims 1 to 3, a process for the same
- copper-tin alloys Due to the alloying component tin, copper-tin alloys are characterized by a high strength and hardness. Furthermore, the copper-tin alloys are considered corrosion-resistant and seawater resistant.
- This material group has a high resistance to abrasive wear.
- the copper-tin alloys ensure good sliding properties and a high fatigue strength, resulting in their excellent suitability for sliding elements and sliding surfaces in engine and vehicle construction and in general mechanical engineering. Often the copper-tin alloys for sliding bearing applications to improve the
- Copper-tin alloys are widely used in the electronics and telecommunications industries. They often have sufficient electrical conductivity and good to very good spring properties. The Setting the spring properties requires sufficient cold workability of the materials.
- percussion instruments made of copper-tin alloys are preferably produced on account of their special sound properties.
- the copper-tin materials tend to be particularly strong due to their wide solidification interval
- the element phosphorus is added to the copper-tin alloys to deoxidize the melt sufficiently. However, phosphorus extends that
- Cooling rate the hot working of the material at 720 to 920 ° C take place.
- the document DE 704 398 A discloses the description of a method for producing copper-tin alloy fittings comprising 6 to 14% by weight of Sn, more than 0.1% by weight of P, preferably 0.2 to 0 , 4 wt .-% P, which may be replaced by silicon, boron or beryllium included.
- the copper-tin alloy comprises about 91.2 wt% Cu, about 8.5 wt% Sn, and about 0.3% P.
- the moldings are homogenized at a temperature below 700 ° C. until the tin and phosphorus-enriched eutectoids are dissolved.
- the Schwingreibverschl salt in the jargon also called fretting, is a Reibverschl composition that occurs between oscillating contact surfaces.
- fretting is a Reibverschl corrosion.
- Material damage can significantly lower the local strength in the wear zone, in particular the fatigue strength. From the damaged component surface can go out Schwinganrisse, the
- Plain bearing built a high voltage, which is further increased by the thermal strains and the dynamic shaft loads in modern engines. Due to the geometry changes of the sliding bearing due to the voltage increase micro-movements of the sliding bearing relative to the bearing receptacle are possible. The cyclic relative movements with less Vibration width at the contact surfaces between bearing and bearing support lead to vibration friction wear / fretting corrosion / fretting of the slide bearing back. The result is the initiation of cracks and ultimately the Reibdauerbruch of the plain bearing.
- Reibkorrosions of connectors on the material side can be improved.
- a contact material of a silver, palladium or palladium-silver alloy containing 20 to 50% by weight of tin, indium and / or antimony is applied to a support made of bronze.
- the silver and / or palladium content ensures corrosion resistance.
- the oxides of tin, indium and / or antimony increase the wear resistance.
- the Consequences of a fretting corrosion are encountered.
- Crystallization nuclei present or is formed in the melt only a small number of nuclei, so is a coarse grained, seigerungsreiches and often dendritic solidification microstructure. It is called a copper alloy with 0, 1 to 25 wt .-% calcium and 0, 1 to 15 wt .-% boron, which can be added to the grain refining of the melt of copper materials. In this way, with the addition of crystallizers, a uniform and fine-grained solidification microstructure is produced in copper alloys.
- Phosphorus succeeds in lowering the relatively high base melt temperature in terms of processing technology.
- High-temperature materials of the systems Ni-Si-B and Ni-Cr-Si-B are especially the alloying elements boron and silicon for the strong lowering of the
- the lowering of the base melt temperature by the addition of boron is used for copper-tin materials, which are used as build-up welding material
- US Pat. No. 3,392,017 A discloses an alloy containing up to 0.4% by weight of Si, from 0.02 to 0.5% by weight of B, from 0.1 to 1.0% by weight of P, 4 to 25 wt .-% Sn and a remainder Cu disclosed.
- the addition of boron and a very high content of phosphorus of greater than or equal to 0.1 wt .-% should hereby the self-fluxing properties of the hardfacing and the
- the document DE 102 08 635 B4 describes the processes in a diffusion solder joint in which intermetallic phases are present. By diffusion soldering parts with a different coefficient of thermal expansion are to be connected to each other. With thermomechanical loading of this solder joint or during the soldering process itself, large voltages occur at the
- particles of boron silicates or phosphorus silicates can be used due to their
- a starting material may be used that has been prepared by conventional casting methods without the urgent need to carry out spray compacting or strip casting.
- the copper-tin alloy should be free of gas and shrinkage pores and stress cracks and should be characterized by a uniform distribution of the Sn-rich ⁇ phase present in relation to the Sn content of the alloy.
- the cast state of the copper-tin alloy does not necessarily have to be homogenized by means of a suitable annealing treatment in order to be able to produce sufficient hot workability.
- the casting material should be characterized by a high strength, a high hardness and a high corrosion resistance.
- a further processing which includes an annealing or a hot forming and / or cold working with at least one annealing, is a fine-grained structure with high strength, high hardness, high stress relaxation and corrosion resistance, high electrical conductivity and a high degree of complexity
- the invention includes a high strength tin-containing copper alloy excellent in hot workability and cold workability
- Al-containing and B-containing phases, Si-containing and B-containing phases and / or Anlagenüngseducationen and / or mixed compounds of the two phases which as boron silicates and / or Borphosphorsilikate and / or
- Grain boundary segregations are formed, which cause damage to the structure in the form of cracks in thermal and / or mechanical stress of the casting, which can lead to breakage.
- the structure after casting is still free of gas pores and shrinkage pores and stress cracks.
- the alloy is in the cast state.
- the invention includes a high strength tin-containing copper alloy having excellent hot workability and cold workability
- Al-containing and B-containing phases, Si-containing and B-containing phases and / or addition compounds and / or mixed compounds of both phases which as boron silicates and / or Borphosphorsilikate and / or
- the Sn-rich ⁇ phase is preferably at least 1% by volume.
- the ⁇ -phase with up to 40 vol .-% is distributed evenly in island form uniformly in the structure. If the Sn content of the alloy is between 9.0 and 13.0% by weight, the island shape of the ⁇ phase, which is present in the microstructure with up to 60% by volume, changes into the network form. This ⁇ mesh is also distributed very uniformly in the structure of the alloy. In the range of the Sn content of 13.0 to 7.0 wt .-%, the ⁇ -phase is present with up to 80 vol .-% almost exclusively in the form of a uniform network in the structure. At an Sn content of the alloy of 17.0 to 23.0 wt .-% is the
- Al-containing and B-containing phases, Si-containing and B-containing phases and / or their addition compounds and / or mixed compounds which are formed as aluminum borides and silicon borides and / or as addition compounds and / or mixed compounds of the aluminum borides and silicon borides hereinafter referred to as hard particles. They take over in the melt of the alloy according to the invention the function as
- Crystallization nuclei during solidification and cooling As a result, it is no longer necessary to supply so-called foreign nuclei to the melt, whose uniform distribution in the melt can only be ensured inadequately.
- the cast state of the invention has a very uniform microstructure with a fine distribution of the ⁇ phase in the form of uniformly and densely arranged islands and / or in the form of a uniformly dense network.
- Accumulations of Sn-rich ⁇ -phase known as so-called reverse block segregations and / or as
- Grain boundary segregations are formed, can not be observed in the cast structure of the invention.
- the elements boron, silicon, aluminum and phosphorus cause a reduction of the metal oxides.
- Crystallization nuclei a uniform structure with a fine distribution of the structural components with different Sn content.
- Hard particles ensure, in particular, the boron silicates and / or borophosphosililicates which form during the solidification of the melt and / or
- the alloy according to the invention may be subjected to further processing by annealing or by hot working and / or cold working together with at least one annealing.
- annealing or by hot working and / or cold working together with at least one annealing.
- Borosilicate and / or Borphosphorsilikaten and / or alumina boron silicates and / or alumina Borphosphorsilikaten and with the phosphorus silicates bring about an adjustment of the thermal expansion coefficients of the Sn-poor and Sn-rich phases could also during the process of
- Aluminum oxides which takes place in the material during hot forming.
- the silicates and hard particles require during the
- Recrystallization was manifested in the possible lowering of the necessary recrystallization temperature, which additionally facilitates the adjustment of a fine-grained microstructure of the alloy according to the invention.
- Alloy allows higher degrees of cold working, whereby particularly high values for the tensile strength R m , the yield strength R p o, 2 and the hardness can be adjusted can.
- the height of the parameter R p0 , 2 is for the sliding elements and guide elements in internal combustion engines, valves, turbochargers,
- the Sn content of the invention is within the limits of between 4.0 and 23 wt%.
- a tin content of less than 4.0 wt .-% would result in low strength values and hardness values.
- the running properties would be insufficient in a sliding load.
- the resistance of the alloy to the abrasive and adhesive wear would not meet the requirements.
- the toughness properties of the alloy according to the invention would rapidly deteriorate, causing the
- the alloy according to the invention has a hard phase component which, due to the high hardness, contributes to an improvement in the material resistance to abrasive wear.
- Silicate phases together with the aluminum oxides, also play the role of a wear-protecting and / or corrosion-protecting coating on the components.
- the alloy of the present invention ensures a combination of the properties of wear resistance and corrosion resistance.
- the invention is outstandingly suitable for use as a sliding element and connector, since it has a high degree of resistance to sliding wear and the Schwingreibverschl formulate / fretting.
- the effect of hard particles as crystallization nuclei and recrystallization nuclei, as a wear carrier and the effect of Al oxides and silicate phases for the purpose of corrosion protection can only reach a technically significant level in the alloy according to the invention if the silicon content is at least 0.05% by weight. %, the aluminum content is at least 0.01 wt .-% and the boron content is at least 0.005 wt .-%. If, on the other hand, the Si content exceeds 2.0% by weight and / or the Al content is 1.0% by weight and / or the B content is 0.6% by weight, this leads to a Deterioration of casting behavior. The too high content of hard particles would make the melt significantly thicker. In addition, reduced toughness properties of the
- the Si content in the limits of 0.05 to 1, 5 Wt .-% and in particular from 0.5 to 1, 5 wt .-% evaluated.
- the advantageous Al content of the alloy according to the invention is from 0.1 to 0.8% by weight.
- the content of 0.01 to 0.6 wt .-% is considered advantageous.
- the content of boron has proven to be particularly advantageous from 0.1 to 0.6% by weight.
- Alloy of the invention between 0.3 and 10.
- a ratio Si / B of 1 to 10 and further from 1 to 6 has proved to be advantageous.
- the precipitation of the hard particles influences the viscosity of the melt of the alloy according to the invention. This circumstance also underlines why it may not be waived to add phosphorus. Phosphor causes the melt, despite the content of hard particles is sufficiently thin liquid, which is of great importance for the pourability of the invention.
- the content of phosphorus of the alloy according to the invention is 0.001 to 0.08 wt .-%. A P content in the range of 0.001 to 0.05 wt .-% is advantageous.
- the sum of the element contents of the elements silicon, boron and phosphorus is advantageously at least 0.5% by weight. Machining of semi - finished products and components from the Conventional copper-tin and copper-tin-phosphorus wrought alloys in particular with an Sn content of up to about 9 wt .-% is due to
- Machining area of the machine must be removed.
- the hard particles in whose regions, depending on the Sn content of the alloy, the element tin and / or the ⁇ phase crystallized or precipitated, serve as chip breakers.
- the tin-containing alloy which is why the semi-finished products and components made of the alloy according to the invention have a better machinability.
- Copper alloys consist of (in% by weight):
- the tin-containing copper alloy may consist of (in% by weight):
- the tin-containing copper alloy may consist of (in% by weight):
- the Sn-rich O phase is uniformly arranged in island form up to 40% by volume.
- the element tin and / or the ⁇ phase is usually crystallized in the regions of the hard particles and / or encapsulates these.
- the castings of these embodiments have excellent hot workability at the working temperature in the range of 600 to 880 ° C.
- the significant increase in strength and hardness after the hot stamping process step can be used for components that do not require cold working to produce.
- an accelerated cooling, advantageously in water, take place after hot working.
- the hard particles precipitated in the microstructure act in the thermal
- Recrystallization nuclei By means of this further processing step, it is possible to set a structure with a grain size up to 20 pm.
- the favoring of the recrystallization mechanisms by the hard particles allows a lowering of the recrystallization temperature so that a structure with a particle size of up to 10 ⁇ m can be produced.
- By a multi-stage manufacturing process of cold forming and annealing and / or by an appropriate reduction of the recrystallization temperature it is even possible to adjust the size of the crystallites in the material structure to less than 5 pm.
- the mechanical properties of some embodiments stand
- values for the tensile strength R m of over 700 to 800 MPa, values for the yield strength R p0 , 2 can be achieved by over 600 to 700 MPa.
- the toughness properties of the embodiments are at a very high level. This fact is expressed by the high values for the elongation at break A5.
- Copper alloys consist of (in% by weight):
- the tin-containing copper alloy may consist of (in% by weight):
- microstructure of these embodiments of the invention is characterized by a content of the ⁇ -phase of up to 60 vol .-%, this phase in
- Island shape and network shape is uniformly distributed in the structure.
- the element tin and / or the ⁇ -phase is usually crystallized in the areas of the hard particles and / or encapsulates them.
- the castings of these embodiments have excellent hot workability at the working temperature in the range of 600 to 880 ° C.
- Hot forming very fine grain before Due to the high strength values of the hot-worked state, its cold workability is limited. This can be significantly improved by an annealing after the hot forming process at the temperature of 200 to 880 ° C with a duration of 10 minutes to 6 hours.
- the hard particles precipitated in the microstructure act in the thermal
- Recrystallization through the hard particles allows a lowering of the recrystallization temperature, so that a microstructure with a further reduced particle size can be generated.
- the fine grain of the microstructure can be further optimized.
- Copper alloys consist of (in% by weight):
- the tin-containing copper alloy may consist of (in% by weight):
- Hot forming very fine grain before Due to the high strength values of the hot-worked state, its cold workability is severely limited.
- annealing after the hot forming process at the temperature of 200 to 880 ° C with a duration of 10 minutes to 6 hours the
- the hard particles precipitated in the microstructure act in the thermal
- Recrystallization nuclei By means of this further processing step, it is possible to set a microstructure with a particle size of up to 35 ⁇ m. By favoring the recrystallization mechanisms by the hard particles, it is possible to lower the recrystallization temperature so that a microstructure having a grain size of up to 25 ⁇ m can be produced. The net-like arrangement of the ⁇ phase in the microstructure is retained.
- Recrystallization it is even possible to adjust the size of the crystallites in the material structure to less than 10 pm.
- the tin-containing copper alloy may consist of (in% by weight):
- a very dense network of the ⁇ -phase which is uniformly arranged in the cast structure with up to 98% by volume, is a feature of these embodiments of the invention.
- the microstructure may increasingly have dendritic structural components which, however, due to the very small distance between the so-called dendrite arms, also have a net-like character.
- the element tin and / or the ⁇ phase is usually crystallized in the regions of the hard particles and / or encapsulates these. Due to the uniformity of the dense ⁇ mesh, the castings of these embodiments also exhibit excellent hot workability at the working temperature in the range of 600 to 880 ° C.
- the alloying element tin contributes in particular to the formation of a so-called tribo layer between the sliding partners. Especially under mixed friction conditions, this mechanism is significant when the emergency running characteristics of a
- the tribo layer leads to the reduction of the purely metallic contact surface between the sliding partners, whereby a welding or seizing of the elements is prevented.
- Boron silicates and / or Borphosphorsilikaten and / or alumina boron silicates and / or alumina boron phosphors and of phosphorus silicates and aluminum oxides These compounds still reinforce the tribo layer, resulting in an increased adhesive wear resistance of the sliding elements of the alloy according to the invention.
- the hard particles cause a higher temperature stability of the microstructure of the copper alloy according to the invention.
- the element zinc can be added to the tin-containing copper alloy according to the invention with a content of 0.1 to 2.0% by weight. It has been found that the alloying element zinc, depending on the Sn content of the alloy, increases the proportion of Sn-rich phases in the invention, whereby strength and hardness increase. However, no evidence was found that adding zinc has a positive effect on the uniformity of the microstructure as well as on further reducing the content of pores and cracks in the microstructure. Obviously, the relative influence of the combined alloy content on boron, silicon and phosphorus predominates. Under 0, 1 wt .-% Zn a strength and hardness increasing effect could not be observed. At Zn contents above 2.0 wt%, the toughness properties of the alloy were lowered to a lower level. In addition, the deteriorated
- the invention may be added to a zinc content in the range of 0.5 to 1, 5 wt .-%.
- a zinc content in the range of 0.5 to 1, 5 wt .-%.
- the addition of the alloying elements iron and magnesium can be done individually or in combination.
- the alloy according to the invention may contain from 0.01 to 0.6% by weight of Fe. In this case, up to 10% by volume of Fe borides, Fe phosphides and Fe silicides and / or Fe rich particles are present in the microstructure. Furthermore, it comes in the structure for the formation of addition compounds and / or mixed compounds of Fel o-containing phases and the Al-containing and B-containing phases, Si-containing and B-containing phases and / or Si-Al-B phases. These phases and compounds contribute to increase the strength, hardness, heat resistance, the
- the tin-containing copper alloy may have low levels of lead. Just acceptable and lying above the impurity limit are lead contents up to 0.25 wt .-%. In a particularly preferred
- the tin-containing copper alloy is free of lead, except for any unavoidable impurities.
- Compressive strength of the sliding layer is increased.
- One aspect of the invention relates to an advantageous method of further processing the as-cast or hot-worked condition or the annealed cast condition or annealed hot-worked condition comprising performing at least one cold working.
- the hard particles are embedded in the metallic base. In further embodiments of the invention are still in the metallic
- Base mass precipitated Fe and / or Mg-containing phases added.
- the alloy according to the invention Due to the uniform and fine-grained structure with extensive freedom from pores, freedom from cracks and freedom from segregation and the content of hard particles, the alloy according to the invention already has a high degree of strength, hardness, ductility, complex wear resistance and as-cast condition
- Treatment temperatures for tempered steels (hardening 820 to 860 ° C, tempering 540 to 660 ° C, DIN EN 10083-1) in the heat treatment range of
- Sliding elements and guide elements in internal combustion engines, valves, turbochargers, transmissions, exhaust aftertreatment systems, lever systems, brake systems and components can already be found in the casting formats in strip form, sheet form, plate form, bolt form, wire form, rod form, tubular form or profile shape
- Joint systems, hydraulic units or in machinery and equipment of general engineering can be produced.
- semi-finished products and components with complicated geometry and increased mechanical properties can be used for these applications
- the invention is suitable for the metal objects in constructions for the rearing of marine organisms (aquaculture).
- Another aspect of the invention includes use of the tin-containing copper alloy for propellers, blades,
- Ship propellers and hubs for shipbuilding for water pump housings, oil pumps and fuel pumps, for guide wheels, impellers and impellers for pumps and water turbines, for gears, worm wheels, helical gears and for pressure nuts and spindle nuts, as well as for marine, chemical and pipe joints, seals and connecting bolts Industry.
- cymbals so-called cymbals of high quality are made of tin-containing copper alloys by means of hot forming and at least one annealing, before they are usually brought by means of a bell or a shell in the final form. The basins are then annealed again before their final machining takes place.
- Variants of the pelvis for example ride cymbals, hi-hat, crash cymbals, China cymbals, splash cymbals and effect cymbals, therefore require a particularly advantageous hot workability of the material, which is ensured by the alloy according to the invention.
- different structural proportions may be used for the ⁇ phase and for the hard particles in a very wide range can be adjusted. In this way it is already possible on the alloy side, to act on the sound of the pelvis. Further important embodiments of the invention will be explained with reference to Tables 1 to 11. Cast blocks of the tin-containing copper alloy according to the invention were produced by chill casting. The chemical composition of the casts is shown in Tab.
- Table 1 shows the chemical composition of alloy variant 1. This material is characterized by an Sn content of 7.35 wt.%, An Si content of 0.74 wt.%, An Al content of 0.34 wt.%, A boron content of 0, 33 wt .-% and a P content of 0.015 wt .-% and a balance copper characterized.
- the structure of embodiment 1 is characterized by a very uniform, insular distribution of a relatively small proportion of the ⁇ phase (1, about 20% by volume) and the hard particles 2 in the copper mixed crystal 3 (FIG. 1). ,
- the hardness of this type of alloy is 108 HB (Table 2).
- Alloy variant 2 can be seen. This material contains, in addition to 15.09 wt .-% Sn and 0.027 wt .-% P, the other elements Si (0.80 wt .-%), Al (0.54 wt .-%), boron (0.24 wt .-%) and a remainder copper.
- Table 3 Chemical Composition of Working Example 2 (in wt.
- the invention is inter alia characterized in that the structure in the casting state with increasing Sn content of the alloy, depending on the casting / cooling process, consists of increasing proportions of ⁇ -phase.
- the ⁇ phase is present with a significantly higher content (up to 70% by volume).
- This structure is shown in Fig. 3 in 200-fold and from Fig. 4 in 500-fold magnification.
- the reference numeral 1 the Sn-rich ⁇ -phase arranged in a netlike manner in the structure is characterized in each case.
- hard particles 2 which are coated with tin and / or the Sn-rich oil phase, can be seen.
- Labeled by the reference numeral 3 is the
- Microstructure component of copper mixed crystal is Microstructure component of copper mixed crystal.
- One aspect of the invention relates to a method for producing strips, sheets, plates, bolts, wires, rods, tubes and profiles from the tin-containing copper alloy according to the invention with the aid of
- the alloy according to the invention can also be subjected to further processing.
- this enables the production of certain and often complicated geometries.
- the demand for an improvement of the complex operating properties of the materials especially for wear-stressed components and for construction and fasteners in electronics / electrical engineering is met, as it in the corresponding machinery, engines, transmissions, units, structures and equipment to a strongly increasing stress on the system elements.
- the further processing of the cast state can advantageously the Performing at least one hot working in the temperature range of 600 to 880 ° C.
- the forging processes are suitable to produce near-net shape components with partly complicated geometry.
- a further advantageous possibility of further processing the cast state or the hot-formed state or the annealed cast state or the annealed hot-formed state comprises performing at least one cold forming.
- At least one annealing treatment can be carried out in one
- Temperature range from 200 to 880 ° C with the duration of 10 minutes to 6
- a flash annealing in a temperature range of 200 to 650 ° C with a duration of 0.5 to 6 hours.
- a further processing can be selected, which comprises at least one cold forming or the combination of at least one hot working and at least one cold forming in conjunction with at least one annealing in a temperature range of 200 to 800 ° C with the duration of 10 minutes to 6 hours and a recrystallized
- Relaxation annealing in the temperature range from 200 to 650 ° C for a period of 0.5 to 6 hours.
- the hot-worked state of Alloy Variation 1 had sufficient cold workability.
- the implementation of an annealing treatment in the temperature range of 600 to 880 ° C with the duration of 3 hours proved to be advantageous.
- the hot-rolled plates were cold-rolled with a cold forming ⁇ of about 85% crack-free.
- the cold-rolled strips were annealed at the temperature of 280 ° C for a period of 2 hours.
- the characteristic values of the thus relaxed bands are shown in Tab. 6.
- the bands of the alloy possess sufficient toughness properties for which the value for the elongation at break A5 represents the measure.
- Embodiment 1 in the final state (Production 1)
- the strips of alloy variant 1 were annealed after the first cold rolling at 680 ° C for 3 hours. Subsequently, the cold rolling of the strips was carried out with a cold forming ⁇ of about 60%. To the After completion of the production, the belts were thermally relaxed at various temperatures between 280 and 400 ° C with a duration of 2 and 4 hours. The characteristic values of the resulting material states are listed in Tab.
- Table 7 Structural characteristics and mechanical characteristics of the strips of the embodiment 1 in the final state (production 2)
- the temperature of the annealing was reduced to 450 ° C. after the first cold forming. After the three-hour annealing at this temperature, the cold rolling of the strips with the cold forming ⁇ of about 30%. The final two-hour
- the second part of the 7,04 mm cold-rolled strips, designated 2-B, was made by means of a cyclic annealing and annealing process
- the structure is already after the first cold rolling in a uniform form with a particle size of 20 to 25 ⁇ before.
- the toughness properties can be further improved by means of an annealing treatment in the temperature range of 200 to 650 ° C.
- an annealing treatment in the temperature range of 200 to 650 ° C.
- Figure 5 the structure of the embodiment 2 after a three-hour annealing at 500 ° C is shown.
- the ⁇ -phase (dark colored) is distributed extremely uniformly in the structure of the material. Further reduction of the ⁇ -phase fraction is achieved by annealing at 600 ° C / 3h ( Figure 6).
- the hard particles are more completely contained in the ⁇ -phase regions with respect to the casting state. This underlines the function of the hard particles as crystallization / precipitation nuclei also in the thermomechanical
- Table 10 Grain size and hardness of the cold-rolled and subsequently annealed strips 2-A (according to manufacturing step 4 in Tab. 9) from the exemplary embodiment 2
- the alloy according to the invention has a Sn content of 4 to 23% Sn over the entire range
- Hard particles encased in tin and / or the Sn-rich ⁇ phase are copper mixed crystal consisting of low-tin a-phase
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Abstract
Description
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DE102016002604.9A DE102016002604A1 (de) | 2016-03-03 | 2016-03-03 | Zinnhaltige Kupferlegierung, Verfahren zu deren Herstellung sowie deren Verwendung |
PCT/EP2017/000189 WO2017148568A1 (de) | 2016-03-03 | 2017-02-10 | Zinnhaltige kupferlegierung, verfahren zu deren herstellung sowie deren verwendung |
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EP3423604A1 true EP3423604A1 (de) | 2019-01-09 |
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US (1) | US20190062876A1 (de) |
EP (1) | EP3423604B1 (de) |
JP (1) | JP6679742B2 (de) |
KR (1) | KR20180121889A (de) |
CN (1) | CN108699631B (de) |
DE (1) | DE102016002604A1 (de) |
MX (1) | MX2018010583A (de) |
WO (1) | WO2017148568A1 (de) |
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US10918171B2 (en) * | 2016-07-26 | 2021-02-16 | Ykk Corporation | Copper alloy fastener element and slide fastener |
CN111687407B (zh) * | 2020-07-28 | 2022-07-26 | 鞍山大族激光技术有限公司 | 一种磷铜工件激光熔覆用铜粉及熔覆方法 |
DE102020004652B3 (de) * | 2020-07-31 | 2021-12-16 | Wieland-Werke Aktiengesellschaft | Verfahren zur Herstellung eines Gleitelements |
CN114262853A (zh) * | 2021-11-23 | 2022-04-01 | 太仓市林源电线电缆有限公司 | 一种电工铜线的多重冷却低应力退火工艺 |
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DE581507C (de) | 1928-03-10 | 1933-07-28 | Bruno Sachs | Verfahren zum Warmpressbarmachen von Kupfer und Zinn enthaltenden Legierungen |
DE704398C (de) | 1935-04-06 | 1941-03-29 | Caro Werk Ges M B H | Verfahren zur Herstellung von Formstuecken aus Bronze (Kupfer-Zinn-Legierungen) |
US2128955A (en) | 1937-11-26 | 1938-09-06 | American Brass Co | Hot workable phosphor bronze |
AT165091B (de) * | 1946-02-08 | |||
US3392017A (en) | 1965-04-15 | 1968-07-09 | Eutectic Welding Alloys | Welding consumable products |
CA1031558A (en) * | 1973-08-27 | 1978-05-23 | Ppg Industries, Inc. | Electroconductive, corrosion resistant high silicon alloy |
DE2536166A1 (de) | 1975-08-13 | 1977-03-03 | Olin Corp | Kupferlegierung |
DE3627282A1 (de) | 1986-08-12 | 1988-02-18 | Sueddeutsche Kalkstickstoff | Legierung zur kornfeinung von kupferwerkstoffen |
JPS6345342A (ja) * | 1986-08-13 | 1988-02-26 | Furukawa Electric Co Ltd:The | 高力伝導性銅合金 |
DE3932536C1 (en) | 1989-09-29 | 1990-08-09 | W.C. Heraeus Gmbh, 6450 Hanau, De | Wear resistant contact material - in which is applied to support comprising copper alloy and non-noble metal contg. silver, palladium or palladium-silver alloy |
DE4126079C2 (de) | 1991-08-07 | 1995-10-12 | Wieland Werke Ag | Bandgießverfahren für ausscheidungsbildende und/oder spannungsempfindliche und/oder seigerungsanfällige Kupferlegierungen |
DE19756815C2 (de) | 1997-12-19 | 2003-01-09 | Wieland Werke Ag | Kupfer-Knetlegierung, Verfahren zur Herstellung eines Halbzeuges daraus und deren Verwendung |
US6346215B1 (en) * | 1997-12-19 | 2002-02-12 | Wieland-Werke Ag | Copper-tin alloys and uses thereof |
KR100371128B1 (ko) * | 2000-07-25 | 2003-02-05 | 한국통산주식회사 | 고강도 선재 및 판재용 구리(Cu)-니켈(Ni)-주석(Sn)-알루미늄(Al), 실리콘(Si), 스트론튬(Sr), 티타늄(Ti), 보론(B) 합금 |
DE10208635B4 (de) | 2002-02-28 | 2010-09-16 | Infineon Technologies Ag | Diffusionslotstelle, Verbund aus zwei über eine Diffusionslotstelle verbundenen Teilen und Verfahren zur Herstellung der Diffusionslotstelle |
EP1862560A4 (de) * | 2005-03-02 | 2013-09-18 | Furukawa Electric Co Ltd | Kupferlegierung und herstellungsverfahren dafür |
JP4068626B2 (ja) * | 2005-03-31 | 2008-03-26 | 日鉱金属株式会社 | 電子材料用Cu−Ni−Si−Co−Cr系銅合金及びその製造方法 |
DE102007010266B3 (de) | 2007-03-02 | 2008-07-31 | Tyco Electronics Amp Gmbh | Zugentlastung |
WO2009047919A1 (ja) * | 2007-10-10 | 2009-04-16 | Toto Ltd. | 鋳造性に優れた無鉛快削性黄銅 |
US7928541B2 (en) * | 2008-03-07 | 2011-04-19 | Kobe Steel, Ltd. | Copper alloy sheet and QFN package |
AT511196B1 (de) | 2011-06-14 | 2012-10-15 | Miba Gleitlager Gmbh | Mehrschichtlagerschale |
-
2016
- 2016-03-03 DE DE102016002604.9A patent/DE102016002604A1/de not_active Withdrawn
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2017
- 2017-02-10 KR KR1020187024136A patent/KR20180121889A/ko not_active Application Discontinuation
- 2017-02-10 EP EP17706407.8A patent/EP3423604B1/de active Active
- 2017-02-10 WO PCT/EP2017/000189 patent/WO2017148568A1/de active Application Filing
- 2017-02-10 JP JP2018544499A patent/JP6679742B2/ja active Active
- 2017-02-10 CN CN201780014996.3A patent/CN108699631B/zh active Active
- 2017-02-10 MX MX2018010583A patent/MX2018010583A/es unknown
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WO2017148568A1 (de) | 2017-09-08 |
EP3423604B1 (de) | 2021-04-07 |
JP6679742B2 (ja) | 2020-04-15 |
CN108699631B (zh) | 2020-08-04 |
US20190062876A1 (en) | 2019-02-28 |
DE102016002604A1 (de) | 2017-09-07 |
CN108699631A (zh) | 2018-10-23 |
KR20180121889A (ko) | 2018-11-09 |
MX2018010583A (es) | 2018-11-09 |
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