EP1600515B1 - Bleifreie Automatenkupferlegierung - Google Patents

Bleifreie Automatenkupferlegierung Download PDF

Info

Publication number
EP1600515B1
EP1600515B1 EP05017189A EP05017189A EP1600515B1 EP 1600515 B1 EP1600515 B1 EP 1600515B1 EP 05017189 A EP05017189 A EP 05017189A EP 05017189 A EP05017189 A EP 05017189A EP 1600515 B1 EP1600515 B1 EP 1600515B1
Authority
EP
European Patent Office
Prior art keywords
remainder
weight
percent
free
lead
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.)
Expired - Lifetime
Application number
EP05017189A
Other languages
English (en)
French (fr)
Other versions
EP1600515A2 (de
EP1600515B8 (de
EP1600515A3 (de
Inventor
Keiichiro Oishi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Shindoh Co Ltd
Original Assignee
Sambo Copper Alloy Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sambo Copper Alloy Co Ltd filed Critical Sambo Copper Alloy Co Ltd
Publication of EP1600515A2 publication Critical patent/EP1600515A2/de
Publication of EP1600515A3 publication Critical patent/EP1600515A3/de
Publication of EP1600515B1 publication Critical patent/EP1600515B1/de
Application granted granted Critical
Publication of EP1600515B8 publication Critical patent/EP1600515B8/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent

Definitions

  • the present invention relates to lead-free, free-cutting copper alloys.
  • copper alloys with a good machinability are bronze alloys such an the one under JIS designation H5111 BC6 and brass alloys such an the ones under JIS designations H3250-C3604 and C3771.
  • Those alloys are enhanced in machinability by the addition of 1.0 to 6.0 percent, by weight, of lead and provide an industrially satisfactory machinability. Because of their excellent machinability, those lead-contained copper alloys have been an important basic material for a variety of articles such as city water faucets, water supply/drainage metal fittings and valves.
  • lead contained therein is an environment pollutant harmful to humans. That is, the lead-containing alloys pose a threat to human health and environmental hygiene because lead is contained in metallic vapor that is generated in the steps of processing those alloys at high temperatures such as melting and casting and there is also concern that the lead contained in the water system metal fittings, valves and others made of those alloys will dissolve out into drinking water.
  • JP-A-9-316570 discloses an end bearing for a one way clutch having high wear resistance having manganese silicide type high strength brass having ⁇ 30% beta phase in its metallic structure.
  • the brass has a chemical composition comprising (1) by weight 15-37% Zn, 0.3-5.0% Mn, 0.3-3.0% Si, and the balance Cu.
  • the composition may composition one or more elements selected from the group consisting of 0.1-5% Al, 0.1-4% Ni, Co, Pb or Bi, 0.1-3% Sn or Fe, 0.05-2% Cr, Ti, V, Zr, Nb or Mo.
  • the cutting works, forgings, castings and others include city water faucets, water supply/drainage metal fittings, valves, stems, hot water supply pipe fittings, shaft and heat exchanger parts.
  • tin, aluminum and phosphorus help to reinforce the alpha phase in the matrix, thereby improving strength, wear resistance, and also machinability.
  • Tin and phosphorus disperse the alpha and gamma phases, by which the strength, wear resistance and also machinability are improved.
  • Tin in an amount of 0.3 or more percent by weight is effective in improving the strength and machinability. But if the addition exceeds 3.0 percent by weight, the ductility will fall. For this reason, the addition of tin is set at 0.3 to 3.0 percent by weight to raise the high strength feature and wear resistance in the alloy of the present invention to enhance the machinability.
  • Aluminium also contributes to improving the wear resistance and exhibits its effect of reinforcing the matrix when added in 0.2 or more percent by weight.
  • the addition of aluminium is set at 0.2 to 2.5 in consideration of improvement of machinability.
  • the addition of phosphorus disperses the gamma phase and at the same time refines the crystal grains in the alpha phase in the matrix, thereby improving the hot workability and also the strength and wear resistance. Furthermore, it is very effective in improving the flow of molten metal in casting. Such results will be produced when phosphorus is added in the range of 0.02 to 0.25 percent by weight.
  • the content of copper is set at 62 to 78 percent by weight in the light of the addition of silicon and bonding of silicon with manganese and nickel.
  • the alloy of the present invention contains at least one element selected from among 0.02 to 0.4 percent, by weight, of bismuth, 0.02 to 0.4 percent, by weight, of tellurium, and 0.02 to 0.4 percent, by weight, of selenium. Addition of these elements causes an improvement in machinability by adding at least one element selected among bismuth and other elements which are effective in raising the machinability through a mechanism different from that exhibited by silicon.
  • the alloy of the present invention is provided in which at least one element selected from bismuth, tellurium and selenium is mixed to improve further the machinability of the alloy of the present invention.
  • the addition of bismuth, tellurium or selenium in addition to silicon produces a high machinability such that complicated forms could be freely cut at a high speed.
  • the alloy of the present invention may have further improved machinability obtained by subjecting it to a heat treatment for 30 minutes to 5 hours at 400°C to 600°C.
  • the alloys of the present invention contain machinability improving elements such as silicon and have an excellent machinability because of the addition of such elements.
  • the alloys with a high copper content which have great amounts of other phases, mainly kappa phase, than alpha, beta, gamma and delta phases can further improve in machinability in a heat treatment.
  • the kappa phase turns to a gamma phase.
  • the gamma phase finely disperses and precipitates to further enhance the machinability.
  • the alloys with a high content of copper are high in ductility of the matrix and low in absolute quantity of gamma phase, and therefore are excellent in cold workability.
  • the aforesaid heat treatment is very useful.
  • those which are high in copper content with gamma phase in small quantities and kappa phase in large quantities undergo a change in phase from the kappa phase to the gamma phase in a heat treatment.
  • the gamma phase is finely dispersed and precipitated, and the machinability is improved.
  • the materials are often force-air-cooled or water cooled depending on the forging conditions, productivity after hot working (hot extrusion, hot forging etc.), working environment and other factors.
  • those with low content of copper hereinafter called the low copper content alloy
  • the low copper content alloy are rather low in the content of the gamma phase and contain beta phase.
  • the beta phase changes into gamma phase, and the gamma phase is finely dispersed and precipitated, whereby the machinability is improved.
  • This aluminium bronze is the most excellent of the expanded copper alloys under the JIS designations with regard to strength and wear resistance.
  • No. 14006 corresponds to the naval brass alloy "JIS C 4622" and is the most excellent of the expanded copper alloys under the JIS designations with regard to corrosion resistance.
  • the chips from the cutting work were examined and classified into four forms (A) to (D) as shown in Fig. 1 .
  • the results are enumerated in Table 20 to Table 29.
  • the chips in the form of a spiral with three or more windings as (D) in Fig. 1 are difficult to process, that is, recover or recycle, and could cause trouble in cutting work as, for example, getting tangled with the tool and damaging the cut metal surface.
  • chips in the form of a fine needle as (A) in Fig. 1 or in the form of an arc as (B) will not present such problems as mentioned above and are not bulky as the chips in (C) and (D) and easy to process. But fine chips as (A) still could creep into the sliding surfaces of a machine tool such as a lathe and cause mechanical trouble, or could be dangerous because they could stick into the worker's finger, eye or other body parts.
  • the surface condition of the cut metal surface was checked after cutting work.
  • the results are shown in Table 20 to Table 29.
  • the commonly used basis for indication of the surface roughness is the maximum roughness (Rmax).
  • Rmax the maximum roughness
  • the alloys with 10 microns ⁇ Rmax ⁇ 15 microns are judged as industrially acceptable, while those with Rmax ⁇ 15 microns are taken as poor in machinability.
  • the alloys with Rmax ⁇ 10 microns are marked “o"
  • those with 10 microns ⁇ Rmax ⁇ 15 microns are indicated as " ⁇ ”
  • those with Rmax ⁇ 15 microns are represented by symbol "x”.
  • the following invention alloys are all equal to the conventional lead- contained alloys Nos 14001 to 14003 in machinability: alloy Nos. 7001 to 7030 and 8001 to 8147.
  • those invention alloys are favourably compared not only with the conventional alloys Nos. 14004 to 14006 with a lead content of not higher than 0.1 percent by weight but also Nos. 14001 to 14003 which contain large quantities of lead.
  • the alloys of the present invention were examined in comparison with the conventional alloys in hot workability and mechanical properties.
  • hot compression and tensile tests were conducted the following way.
  • test pieces two test pieces, first and second test pieces, in the same shape 15 mm in outside diameter and 25 mm in length were cut out of each extruded test piece obtained as described above.
  • the first test piece was held for 30 minutes at 700°C, and then compressed 70 percent in the direction of axis to reduce the length from 25 mm to 7.5 mm.
  • the surface condition after the compression 700°C deformability was visually evaluated.
  • the results are given in Table 20 to Table 29.
  • the evaluation of deformability was made by visually checking for cracks on the side of the test piece. In Table 20 to Table 29, the test pieces with no cracks found are marked "o", those with small cracks are indicated in " ⁇ " and those with large cracks are represented by a symbol "x".
  • the second test pieces were put to a tensile test by the commonly practised test method to determine the tensile strength, N/mm 2 and elongation, %.
  • the alloys of the present invention are equal to or superior to the conventional alloys Nos. 14001 to 14004 and No. 14006 in hot workability and mechanical properties and are suitable for industrial use.
  • the alloys of the present invention in particular have the same level of mechanical properties as the conventional alloy No. 14005, the aluminium bronze which is the most excellent in strength of the expanded copper alloys under the JIS designations, and thus have understandably a prominent high strength feature.
  • cylindrical ingots with compositions given in Tables 1-18 each 100 mm in outside diameter and 200 mm in length, were hot extruded into a round bar 35 mm in outside diameter at 700°C to produce the following test pieces: alloy Nos. 7001a to 7030a and alloys Nos. 8001a to 8147a.
  • cylindrical ingots with compositions given in Table 19 each 100 mm in outside diameter and 200 mm in length, were hot extruded into a round bar 35 mm in outside diameter at 700 C to produce the following alloy test pieces: Nos. 14001a to 14006a as second comparative examples (hereinafter referred to as the "conventional alloys'). It is noted that the alloys Nos.
  • 7001a to 7030a, Nos. 8001a to 8147a and Nos. 14001a to 14006a are identical in composition with the aforesaid copper alloys Nos. 7001 to 7030, Nos. 8001 to 8147 and Nos. 14001 to No. 14006 respectively.
  • test piece thus obtained was cut on the circumferential surface, holed and cut down into a ringshaped test piece 32 mm in outside diameter and 10 mm in thickness (that is, the length in the axial direction).
  • the test piece was then fitted around a free-rotating shaft, and a roll 48 mm in outside diameter placed in parallel with the axis of the shaft was urged against the test piece under a load of 50 kg.
  • the roll was made of stainless steel under the JIS designation SUS 304.
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 7001 ⁇ ⁇ 138 ⁇ 670 18 7002 ⁇ ⁇ 136 ⁇ 712 20 7003 ⁇ ⁇ 132 ⁇ 783 23 7004 ⁇ ⁇ 138 ⁇ 736 21 7005 ⁇ ⁇ 136 ⁇ 785 23 7006 ⁇ ⁇ 139 ⁇ 700 24 7007 ⁇ ⁇ 138 ⁇ 707 23 7008 ⁇ ⁇ 131 ⁇ 805 22 7009 ⁇ ⁇ 136 ⁇ 768 19 7010 ⁇ ⁇ 135 ⁇ 718 23 7011 ⁇ ⁇ 137 ⁇ 677 23 7012 ⁇ ⁇ 134 ⁇ 800 21 7013 ⁇ ⁇ 133 ⁇ 819 22 7014 ⁇ ⁇ 138 ⁇ 641 21 7015 ⁇ ⁇ 134 ⁇ 764 23 7010 ⁇ ⁇ 129 ⁇ 759 20 7017
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 7021 ⁇ ⁇ 130 ⁇ 754 24 7022 ⁇ ⁇ 134 ⁇ 780 23 7023 ⁇ ⁇ 133 ⁇ 765 22 7024 ⁇ ⁇ 135 ⁇ 772 23 7025 ⁇ ⁇ 138 ⁇ 687 24 7026 ⁇ ⁇ 135 ⁇ 718 24 7027 ⁇ ⁇ 136 ⁇ 742 18 7028 ⁇ ⁇ 138 ⁇ 785 20 7029 ⁇ ⁇ 134 ⁇ 703 23 7030 ⁇ ⁇ 135 ⁇ 820 18 Table 22 No.
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700 °C deformability tensile strength (N/mm 2 ) elongation (%) 8001 ⁇ ⁇ 132 ⁇ 655 15 8002 ⁇ ⁇ 129 ⁇ 708 17 8003 ⁇ ⁇ 127 ⁇ 768 20 8004 ⁇ ⁇ 128 ⁇ 785 18 8005 ⁇ ⁇ 131 ⁇ 714 16 8006 ⁇ ⁇ 134 ⁇ 680 16 8007 ⁇ ⁇ 132 ⁇ 764 17 8008 ⁇ ⁇ 130 ⁇ 673 16 8009 ⁇ ⁇ 132 ⁇ 759 18 8010 ⁇ ⁇ 132 ⁇ 751 15 8011 ⁇ ⁇ 134 ⁇ 767 17 8012 ⁇ ⁇ 128 ⁇ 796 18 8013 ⁇ ⁇ 129 ⁇ 784 18 8014 ⁇ ⁇ 129 ⁇ 802 17 8015 ⁇ ⁇ 133 ⁇ 679 15 8016 ⁇ ⁇ 130 ⁇ 706 16 80
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 8021 ⁇ ⁇ 134 ⁇ 765 16 8022 ⁇ ⁇ 132 ⁇ 770 16 8023 ⁇ ⁇ 131 ⁇ 746 18 8024 ⁇ ⁇ 132 ⁇ 816 19 8025 ⁇ ⁇ 129 ⁇ 159 18 8026 ⁇ ⁇ 130 ⁇ 726 17 8027 ⁇ ⁇ 133 ⁇ 703 17 8028 ⁇ ⁇ 132 ⁇ 737 18 8029 ⁇ ⁇ 129 ⁇ 719 20 8030 ⁇ ⁇ 133 ⁇ 645 23 8031 ⁇ ⁇ 129 ⁇ 764 22 8032 ⁇ ⁇ 131 ⁇ 790 19 8033 ⁇ ⁇ 133 ⁇ 674 20 8034 ⁇ ⁇ 131 ⁇ 748 23 8035 ⁇ ⁇ 129 ⁇ 777 22 8036 ⁇ ⁇ 131 ⁇ 725 23 80
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 8041 ⁇ ⁇ 128 ⁇ 735 23 8042 ⁇ ⁇ 127 ⁇ 822 18 8043 ⁇ ⁇ 131 ⁇ 780 18 8044 ⁇ ⁇ 126 ⁇ 726 21 8045 ⁇ ⁇ 128 ⁇ 766 22 8046 ⁇ ⁇ 127 ⁇ 712 23 8047 ⁇ ⁇ 128 ⁇ 674 21 8048 ⁇ ⁇ 129 ⁇ 753 24 8049 ⁇ ⁇ 127 ⁇ 768 22 8050 ⁇ ⁇ 132 ⁇ 691 17 8051 ⁇ ⁇ 131 ⁇ 717 17 8052 ⁇ ⁇ 128 ⁇ 739 21 8053 ⁇ ⁇ 128 ⁇ 730 22 8054 ⁇ ⁇ 127 ⁇ 735 20 8055 ⁇ ⁇ 134 ⁇ 818 15 8056 ⁇ ⁇ 132 ⁇ 812 16
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 8061 ⁇ ⁇ 129 ⁇ 705 21 8062 ⁇ ⁇ 131 ⁇ 690 22 8063 ⁇ ⁇ 133 ⁇ 811 18 8064 ⁇ ⁇ 131 ⁇ 746 17 8065 ⁇ ⁇ 133 ⁇ 652 19 8066 ⁇ ⁇ 130 ⁇ 758 19 8067 ⁇ ⁇ 129 ⁇ 734 19 8068 ⁇ ⁇ 131 ⁇ 710 17 8069 ⁇ ⁇ 131 ⁇ 767 20 8070 ⁇ ⁇ 131 ⁇ 753 18 8071 ⁇ ⁇ 129 ⁇ 792 19 8072 ⁇ ⁇ 131 ⁇ 736 21 8073 ⁇ ⁇ 130 ⁇ 767 22 8074 ⁇ ⁇ 132 ⁇ 679 19 8075 ⁇ ⁇ 134 ⁇ 728 17 8076 ⁇ ⁇ 133 ⁇ 795 16 8077
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 8081 ⁇ ⁇ 132 ⁇ 706 23 8082 ⁇ ⁇ 130 ⁇ 768 23 8083 ⁇ ⁇ 128 ⁇ 774 25 8084 ⁇ ⁇ 129 ⁇ 765 22 8085 ⁇ ⁇ 130 ⁇ 729 23 8086 ⁇ ⁇ 133 ⁇ 687 24 8087 ⁇ ⁇ 131 ⁇ 798 20 8088 ⁇ ⁇ 132 O 699 23 8089 ⁇ ⁇ 130 ⁇ 740 21 8090 ⁇ ⁇ 132 ⁇ 782 18 8091 ⁇ ⁇ 129 ⁇ 763 22 8092 ⁇ ⁇ 130 ⁇ 680 22 8093 ⁇ ⁇ 131 ⁇ 655 23 8094 ⁇ ⁇ 128 ⁇ 714 21 8095 ⁇ ⁇ 132 ⁇ 638 24 8096 ⁇ ⁇ 128 ⁇ 889 22 8097 ⁇
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 8101 ⁇ ⁇ 131 ⁇ 685 18 8102 ⁇ ⁇ 132 ⁇ 690 21 8103 ⁇ ⁇ 133 ⁇ 744 17 8104 ⁇ ⁇ 130 ⁇ 726 17 8105 ⁇ ⁇ 133 ⁇ 751 19 8106 ⁇ ⁇ 130 ⁇ 752 21 8107 ⁇ ⁇ 131 ⁇ 760 21 8108 ⁇ ⁇ 132 ⁇ 748 22 8109 ⁇ ⁇ 130 ⁇ 807 18 8110 ⁇ ⁇ 133 ⁇ 739 16 8111 ⁇ ⁇ 132 ⁇ 717 17 8112 ⁇ ⁇ 134 ⁇ 763 20 8113 ⁇ ⁇ 129 ⁇ 745 22 8114 ⁇ ⁇ 132 ⁇ 722 20 8115 ⁇ ⁇ 130 ⁇ 706 17 8116 ⁇ ⁇ 133 ⁇ 684 19 8117
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 8121 ⁇ ⁇ 130 ⁇ 788 20 8122 ⁇ ⁇ 131 ⁇ 755 22 8123 ⁇ ⁇ 127 ⁇ 711 21 8124 ⁇ ⁇ 130 ⁇ 763 20 8125 ⁇ ⁇ 131 ⁇ 687 18 8126 ⁇ ⁇ 134 ⁇ 706 17 8127 ⁇ ⁇ 128 ⁇ 730 22 8128 ⁇ ⁇ 130 ⁇ 702 23 8129 ⁇ ⁇ 132 ⁇ 727 21 8130 ⁇ ⁇ 130 ⁇ 701 24 8131 ⁇ ⁇ 129 ⁇ 745 22 8132 ⁇ ⁇ 132 ⁇ 749 21 8133 ⁇ ⁇ 130 ⁇ 826 18 8134 ⁇ ⁇ 128 ⁇ 770 20 8135 ⁇ ⁇ 129 ⁇ 828 17 8136 ⁇ ⁇ 129 ⁇ 746 20 8137
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 8141 ⁇ ⁇ 131 ⁇ 687 22 8142 ⁇ ⁇ 130 ⁇ 635 20 8143 ⁇ ⁇ 129 ⁇ 710 23 8144 ⁇ ⁇ 130 ⁇ 662 24 8145 ⁇ ⁇ 128 ⁇ 728 23 8146 ⁇ ⁇ 129 ⁇ 753 21 8147 ⁇ ⁇ 130 ⁇ 709 24 Table 30 No.
  • wear resistance weight loss by wear (mg/100000rot.) 7001a 1.3 7002a 0.8 7003a 0.9 7004a 1.4 7005a 1.3 7006a 1.7 7007a 1.8 7008a 1.2 7009a 0.8 7010a 2.4 7011a 1.9 7012a 1.2 7013a 1.1 7014a 2.7 7015a 1.4 7016a 1.3 7017a 1.6 7018a 1.4 7019a 1.9 7020a 1.5
  • No. wear resistance weight loss by wear (mg/100000rot) 7021a 1.3 7022a 0.9 7023a 1.2 7024a 1.0 7025a 2.3 7026a 1.7 7027a 1.8 7028a 1.1 7029a 1.5 7030a 1.4 Table 32 No.
  • wear resistance weight loss by wear 8021a 1.0 8022a 1.4 8023a 1.4 8024a 0.8 8025a 1.2 8028a 1.4 8027a 1.9 8028a 0.9 8029a 1.4 8130a 2.2 8131a 2.1 8132a 1.0 8133a 2.4 8134a 1.4 8135a 1.2 8136a 1.5 8137a 1.3 8138a 0.8 8139a 1.4 8140a 1.5 Table 34 No.
  • wear resistance weight loss by wear 8061a 1.6 8062a 1.9 8063a 1.2 8064a 1.7 8065a 2.0 8068a 1.4 8067a 1.5 8068a 1.2 8069a 0.9 8070a 1.0 8071a 1.7 8072a 1.9 8073a 1.6 8014a 1.6 8075a 1.8 8076a 0.8 8077a 1.3 8078a 1.2 8079a 1.4 8080a 1.3 Table 36 No.
  • wear resistance weight loss by wear 8121a 1.0 8122a 1.0 8123a 1.2 8124a 0.8 8125a 1.1 8126a 0.9 8127a 1.3 8128a 1.4 8129a 1.3 8130a 1.5 8131a 1.2 8132a 1.3 8133a 0.8 8134a 1.0 8135a 0.8 8136a 1.3 8137a 1.1 8138a 0.9 8139a 1.2 8140a 1.0 Table 39 No. wear resistance weight loss by wear (ng/100000rot ) 8141a 1.4 8142a 1.8 8143a 1.6 8144a 1.9 8145a 1.1 8146a 1.2 8147a 1.4 Table 40 No. rear resistance weight loss by wear (ng/100000rot.) 14001a 500 14002a 620 14003a 520 14004a 450 14005a 25 14006a 600

Landscapes

  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Powder Metallurgy (AREA)
  • Conductive Materials (AREA)
  • Adornments (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Claims (6)

  1. Bleifreie, schnittige Kupferlegierung, enthaltend:
    62 bis 78 Gew.-% Kupfer, 2,5 bis 4,5 Gew.-% Silizium; wenigstens ein Element ausgewählt aus [der Gruppe] 0,3 bis 3,0 Gew.-% Zinn, 0,2 bis 2,5 Gew.-% Aluminium, und 0,02 bis 0,25 Gew.-% Phosphor;
    wenigstens ein Element ausgewählt aus [der Gruppe] 0,7 bis 3,5 Gew.-% Mangan und 0,7 bis 3,5 Gew.-% Nickel; optional wenigstens ein Element ausgewählt aus [der Gruppe] 0,02 bis 0,4 Gew.-% Bismut, 0,02 bis 0,4 Gew.-% Tellur und 0,02 bis 0,4 Gew.-% Selen;
    wobei der restliche Gew.-%-Gehalt Zink ist und worin die Metall-Struktur der schnittigen Kupferlegierung wenigstens eine Phase gewählt aus γ(gamma)-Phase und κ(kappa)-Phase besitzt.
  2. Bleifreie, schnittige Kupferlegierung nach Anspruch 1, wobei dann, wenn diese auf einer ringförmigen Oberfläche mit einer Drehmaschine, die mit einem geraden Drehspitzmeißel ausgestattet ist, mit einem Spanwinkel von -8 (minus 8) und einer Zerspangeschwindigkeit von 50m/min, einer Schneidtiefe von 1,5 mm, einem Vorschub von 0,11 min/Umdrehung spanabhebend bearbeitet wird, Späne ergibt, die eine oder mehrere Formen ausgewählt aus der Gruppe Bogenform oder feine Nadelform haben.
  3. Bleifreie, schnittige Kupferlegierung nach einem der vorhergehenden Ansprüche, die einer Wärmebehandlung von 30 Minuten bis 5 Stunden bei 400 bis 600° C ausgesetzt wird.
  4. Verfahren zur Herstellung einer bleifreien, schnittigen Kupferlegierung, die eine Metall-Struktur hat, die wenigstens eine Phase, gewählt aus γ(gamma)-Phase und k(kappa)-Phase besitzt, wobei das Verfahren das Legieren von Kupfer und Silizium in einer Menge von 62 bis 78 Gew.-% Kupfer; 2,5 bis 4,5 Gew.-% Silizium umfasst;
    sowie von wenigstens einem Element ausgewählt aus Zinn, Aluminium und Phosphor in einer Menge von 0,3 bis 3,0 Gew.-% Zinn, 0,2 bis 2,5 Gew.-% Aluminium und 0,02 bis 0,25 Gew.-% Phosphor;
    von wenigstens einem Element ausgewählt aus Mangan und Nickel in einer Menge von 0,7 bis 3,5 Gew.-% Mangan, und 0,7 bis 3,5 Gew.-% Nickel;
    optional von wenigstens einem Element ausgewählt aus Bismut, Tellur und Selen in einer Menge von 0,02 bis 0,4 Gew.-% Bismut, 0,02 bis 0,4 Gew.-% Tellur und 0,02 bis 0,4 Gew.-% Selen; wobei der restliche Gew.-%-Gehalt Zink ist.
  5. Verfahren nach Anspruch 4, wobei das Silizium als eine Cu-Si-Legierung beigefügt wird.
  6. Verfahren nach einem der Ansprüche 4 oder 5, wobei die genannte bleifreie, schnittige Legierung einer Wärmebehandlung von 30 Minuten bis 5 Stunden bei 400 bis 600° C ausgesetzt wird.
EP05017189A 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung Expired - Lifetime EP1600515B8 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP28859098 1998-10-12
JP28859098A JP3734372B2 (ja) 1998-10-12 1998-10-12 無鉛快削性銅合金
EP98953071A EP1045041B1 (de) 1998-10-12 1998-11-16 Bleifreie automatenkupferlegierung

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP98953071A Division EP1045041B1 (de) 1998-10-12 1998-11-16 Bleifreie automatenkupferlegierung

Publications (4)

Publication Number Publication Date
EP1600515A2 EP1600515A2 (de) 2005-11-30
EP1600515A3 EP1600515A3 (de) 2005-12-14
EP1600515B1 true EP1600515B1 (de) 2008-07-30
EP1600515B8 EP1600515B8 (de) 2008-10-15

Family

ID=17732235

Family Applications (5)

Application Number Title Priority Date Filing Date
EP05017189A Expired - Lifetime EP1600515B8 (de) 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung
EP05017190A Expired - Lifetime EP1600516B1 (de) 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung
EP05017191A Expired - Lifetime EP1600517B1 (de) 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung
EP98953071A Expired - Lifetime EP1045041B1 (de) 1998-10-12 1998-11-16 Bleifreie automatenkupferlegierung
EP05075421.7A Expired - Lifetime EP1559802B1 (de) 1998-10-12 1998-11-16 Bleifrei Automatenkupferlegierung

Family Applications After (4)

Application Number Title Priority Date Filing Date
EP05017190A Expired - Lifetime EP1600516B1 (de) 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung
EP05017191A Expired - Lifetime EP1600517B1 (de) 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung
EP98953071A Expired - Lifetime EP1045041B1 (de) 1998-10-12 1998-11-16 Bleifreie automatenkupferlegierung
EP05075421.7A Expired - Lifetime EP1559802B1 (de) 1998-10-12 1998-11-16 Bleifrei Automatenkupferlegierung

Country Status (8)

Country Link
EP (5) EP1600515B8 (de)
JP (1) JP3734372B2 (de)
KR (1) KR100352213B1 (de)
AU (1) AU744335B2 (de)
CA (1) CA2314144C (de)
DE (4) DE69832097T2 (de)
TW (1) TW421674B (de)
WO (1) WO2000022182A1 (de)

Families Citing this family (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8506730B2 (en) 1998-10-09 2013-08-13 Mitsubishi Shindoh Co., Ltd. Copper/zinc alloys having low levels of lead and good machinability
US7056396B2 (en) 1998-10-09 2006-06-06 Sambo Copper Alloy Co., Ltd. Copper/zinc alloys having low levels of lead and good machinability
JP3459623B2 (ja) * 2000-08-08 2003-10-20 京和ブロンズ株式会社 無鉛青銅合金
JP4496662B2 (ja) 2001-04-20 2010-07-07 株式会社豊田自動織機 斜板式圧縮機における斜板
US20040234412A1 (en) * 2002-09-09 2004-11-25 Keiichiro Oishi High-strength copper alloy
JP4522736B2 (ja) * 2004-03-30 2010-08-11 株式会社キッツ 金型鋳造用銅基合金とこの合金を用いた鋳塊・製品
US20070169854A1 (en) 2004-08-10 2007-07-26 Sanbo Shindo Kogyo Kabushiki Kaisha Copper-based alloy casting in which grains are refined
BRPI0516067B1 (pt) * 2004-10-11 2014-10-14 Diehl Metall Stiftung & Co Kg Liga de cobre/zinco/silício, e seu processo de produção
KR100631041B1 (ko) 2005-03-04 2006-10-04 주식회사 풍산 절삭성 및 가공성이 우수한 쾌삭황동합금
ES2294604T3 (es) 2005-07-28 2008-04-01 Gebr. Kemper Gmbh + Co. Kg Metallwerke Procedimiento de fabricacion de piezas fundidas en cobre, con tendencia a la migracion reducida.
WO2007013428A1 (ja) * 2005-07-28 2007-02-01 San-Etsu Metals Co., Ltd. 銅合金押出材およびその製造方法
ATE557108T1 (de) 2005-09-22 2012-05-15 Mitsubishi Shindo Kk Kupferautomatenlegierung mit sehr wenig blei
JP4951517B2 (ja) 2005-09-30 2012-06-13 三菱伸銅株式会社 溶融固化処理物並びに溶融固化処理用銅合金材及びその製造方法
EP1798298B2 (de) 2005-12-14 2016-05-04 Gebr. Kemper GmbH + Co. KG Metallwerke Verwendung einer migrationsarmen Kupferlegierung sowie Bauteile aus dieser Legierung
EP1801250B1 (de) 2005-12-22 2017-11-08 Viega Technology GmbH & Co. KG Migrationsarme Bauteile aus Kupferlegierung für Medien oder Trinkwasser führender Gewerke
JP2008095918A (ja) * 2006-10-16 2008-04-24 Yamaha Marine Co Ltd サーモエレメント及びこのサーモエレメントを用いたサーモスタット装置
EP2014964B1 (de) 2007-06-05 2011-11-23 R. Nussbaum AG Armatur
JP2009007657A (ja) * 2007-06-29 2009-01-15 Joetsu Bronz1 Corp 無鉛快削性銅合金並びに連続鋳造用無鉛快削性銅合金
JP5320638B2 (ja) * 2008-01-08 2013-10-23 株式会社Ｓｈカッパープロダクツ 圧延銅箔およびその製造方法
CN101235448B (zh) * 2008-02-22 2010-10-13 中南大学 一种无铅易切削硅石墨黄铜
CN101440444B (zh) * 2008-12-02 2010-05-12 路达(厦门)工业有限公司 无铅易切削高锌硅黄铜合金及其制造方法
DE102009015186A1 (de) * 2009-03-31 2010-10-14 Viega Gmbh & Co. Kg Fitting zum Anschluss eines Rohres
JP5326114B2 (ja) 2009-04-24 2013-10-30 サンエツ金属株式会社 高強度銅合金
EP2290114A1 (de) 2009-08-04 2011-03-02 Gebr. Kemper GmbH + Co. KG Metallwerke Wasserführendes Bauteil
TWI398532B (zh) 2010-01-22 2013-06-11 Modern Islands Co Ltd Lead-free brass alloy
CN101787461B (zh) * 2010-03-02 2014-11-19 路达(厦门)工业有限公司 一种环保型锰黄铜合金及其制造方法
JP2011214095A (ja) * 2010-03-31 2011-10-27 Joetsu Bronz1 Corp 鋳造用無鉛快削黄銅合金
JP2011214094A (ja) * 2010-03-31 2011-10-27 Joetsu Bronz1 Corp 無鉛快削黄銅合金
EP2614167B1 (de) 2010-09-10 2017-04-12 Raufoss Water & Gas AS Messinglegierung mit silizium und arsen sowie herstellungsverfahren dafür
CN102321827B (zh) * 2011-09-25 2013-01-09 宁波市鄞州锡青铜带制品有限公司 一种高导电率低锡青铜带的制备方法
KR101340487B1 (ko) * 2011-09-30 2013-12-12 주식회사 풍산 쾌삭성 무연 구리합금 및 이의 제조방법
JP5763504B2 (ja) * 2011-11-11 2015-08-12 三菱伸銅株式会社 銅合金製の転造加工用素材及び転造加工品
DE102012013817A1 (de) 2012-07-12 2014-01-16 Wieland-Werke Ag Formteile aus korrosionsbeständigen Kupferlegierungen
US8991787B2 (en) 2012-10-02 2015-03-31 Nibco Inc. Lead-free high temperature/pressure piping components and methods of use
ES2704430T3 (es) 2012-10-31 2019-03-18 Kitz Corp Aleación de latón que presenta capacidad de reciclaje y resistencia a la corrosión
JP5778736B2 (ja) 2013-10-04 2015-09-16 ファナック株式会社 モータ冷却用の冷却管継手、および冷却管継手を備えるモータ冷却装置
EP2960350B1 (de) 2014-06-27 2017-11-29 Gebr. Kemper GmbH + Co. KG Metallwerke Kupfergusslegierung
JP6868761B2 (ja) * 2015-12-17 2021-05-12 パナソニックＩｐマネジメント株式会社 流体用開閉弁及びそれを用いた空気調和機
TWI598452B (zh) * 2016-01-21 2017-09-11 慶堂工業股份有限公司 具優異熔鑄性之無鉛快削黃銅合金及其製造方法和用途
JP6391204B2 (ja) 2016-08-15 2018-09-19 三菱伸銅株式会社 快削性銅合金加工材、及び、快削性銅合金加工材の製造方法
JP2018156771A (ja) * 2017-03-16 2018-10-04 住友電装株式会社 雌端子
US11155909B2 (en) 2017-08-15 2021-10-26 Mitsubishi Materials Corporation High-strength free-cutting copper alloy and method for producing high-strength free-cutting copper alloy
KR101969010B1 (ko) 2018-12-19 2019-04-15 주식회사 풍산 납과 비스무트가 첨가되지 않은 쾌삭성 무연 구리합금
CN109930025A (zh) * 2019-03-22 2019-06-25 广东出入境检验检疫局检验检疫技术中心 一种无铅环保易切削黄铜材料
JP7180488B2 (ja) * 2019-03-25 2022-11-30 三菱マテリアル株式会社 銅合金丸棒材
WO2020261666A1 (ja) 2019-06-25 2020-12-30 三菱マテリアル株式会社 快削性銅合金、及び、快削性銅合金の製造方法
CN113348260B (zh) 2019-06-25 2022-09-16 三菱综合材料株式会社 易切削铜合金及易切削铜合金的制造方法
KR102623143B1 (ko) 2019-06-25 2024-01-09 미쓰비시 마테리알 가부시키가이샤 쾌삭성 구리 합금 주물, 및 쾌삭성 구리 합금 주물의 제조 방법
KR102914924B1 (ko) 2019-12-11 2026-01-19 미쓰비시 마테리알 가부시키가이샤 쾌삭성 구리 합금, 및 쾌삭성 구리 합금의 제조 방법
KR20240145044A (ko) 2019-12-11 2024-10-04 미쓰비시 마테리알 가부시키가이샤 쾌삭성 구리 합금, 및 쾌삭성 구리 합금의 제조 방법
DE102020127317A1 (de) 2020-10-16 2022-04-21 Diehl Metall Stiftung & Co. Kg Bleifreie Kupferlegierung sowie Verwendung der bleifreien Kupferlegierung
GB2614752B (en) 2022-01-18 2024-07-31 Conex Ipr Ltd Components for drinking water pipes, and method for manufacturing same
WO2024090037A1 (ja) 2022-10-28 2024-05-02 日本碍子株式会社 鉛フリー快削ベリリウム銅合金
KR102799468B1 (ko) * 2022-12-08 2025-04-25 주식회사 대창 절삭성이 우수한 저실리콘계 무연 황동 합금

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB352639A (en) * 1930-02-13 1931-07-16 Hirsch Kupfer & Messingwerke Improvements in and relating to copper-silicon-zinc alloys
CH148824A (de) * 1930-03-31 1931-08-15 Hirsch Kupfer & Messingwerke Verfahren zur Herstellung von Kokillengruss- und Spritzgussteilen.
US1954003A (en) * 1930-03-31 1934-04-10 Vaders Eugen Copper alloy for chill and die casting
GB354966A (en) * 1930-05-24 1931-08-20 Hirsch Kupfer & Messingwerke The method of manufacturing bells
US2237774A (en) * 1940-07-23 1941-04-08 Chase Brass & Copper Co Treating silicon copper-base alloys
FR1031211A (fr) * 1951-01-19 1953-06-22 Alliage utilisable dans l'art dentaire
DE1558470A1 (de) * 1967-02-02 1970-03-19 Dies Dr Ing Kurt Fliesspressteil
US3736131A (en) * 1970-12-23 1973-05-29 Armco Steel Corp Ferritic-austenitic stainless steel
US3900349A (en) * 1974-01-18 1975-08-19 Anaconda Co Silicon brass resistant to parting corrosion
GB1443090A (en) * 1974-03-25 1976-07-21 Anaconda Co Silicon brass resistant to partin corrosion-
JPS5696040A (en) * 1979-12-28 1981-08-03 Seiko Epson Corp Exterior decorative part material for casting
JPS61133357A (ja) * 1984-12-03 1986-06-20 Showa Alum Ind Kk 加工性および耐焼付性にすぐれた軸受用Ｃｕ合金
JPS62297429A (ja) * 1986-06-17 1987-12-24 Nippon Mining Co Ltd 耐食性に優れた銅合金
JPH0368731A (ja) * 1989-08-08 1991-03-25 Nippon Mining Co Ltd ラジエータープレート用銅合金および銅合金材の製造法
JPH09143598A (ja) * 1995-11-22 1997-06-03 Chuetsu Gokin Chuko Kk 加熱装置用黄銅合金材料
JP3956322B2 (ja) * 1996-05-30 2007-08-08 中越合金鋳工株式会社 ワンウェイクラッチ用エンドベアリング及びその他の摺動部品
FR2765243B1 (fr) * 1997-06-30 1999-07-30 Usinor Acier inoxydable austenoferritique a tres bas nickel et presentant un fort allongement en traction

Also Published As

Publication number Publication date
DE69838115T2 (de) 2008-04-10
EP1600516A3 (de) 2005-12-14
WO2000022182A1 (en) 2000-04-20
CA2314144C (en) 2006-08-22
EP1600515A2 (de) 2005-11-30
EP1600517B1 (de) 2009-02-18
AU744335B2 (en) 2002-02-21
DE69838115D1 (de) 2007-08-30
TW421674B (en) 2001-02-11
EP1600517A2 (de) 2005-11-30
EP1600515B8 (de) 2008-10-15
JP2000119775A (ja) 2000-04-25
EP1600516B1 (de) 2007-07-18
EP1045041B1 (de) 2005-10-26
EP1045041A1 (de) 2000-10-18
EP1600515A3 (de) 2005-12-14
DE69832097D1 (de) 2005-12-01
DE69832097T2 (de) 2006-07-06
EP1559802A1 (de) 2005-08-03
DE69839830D1 (de) 2008-09-11
DE69840585D1 (de) 2009-04-02
EP1559802B1 (de) 2014-01-15
JP3734372B2 (ja) 2006-01-11
EP1600517A3 (de) 2005-12-14
KR20010033073A (ko) 2001-04-25
AU1054199A (en) 2000-05-01
KR100352213B1 (ko) 2002-09-12
EP1045041A4 (de) 2003-05-07
CA2314144A1 (en) 2000-04-20
EP1600516A2 (de) 2005-11-30

Similar Documents

Publication Publication Date Title
EP1600515B1 (de) Bleifreie Automatenkupferlegierung
US6413330B1 (en) Lead-free free-cutting copper alloys
EP1502964B1 (de) Automatenlegierung auf Kupferbasis
US20150044089A1 (en) Copper/zinc alloys having low levels of lead and good machinability
JP3335002B2 (ja) 熱間加工性に優れた無鉛快削黄銅合金
CA2619357C (en) Free-cutting copper alloy containing very low lead
US7056396B2 (en) Copper/zinc alloys having low levels of lead and good machinability
EP2333126B1 (de) Messinglegierungen mit hoher Spannungskorrosionsbeständigkeit und Herstellungsverfahren dafür
SI9520012A (en) Lead-free 6xxx aluminum alloy
JP4620963B2 (ja) 黄銅およびその製造方法ならびにこれを用いた部品
JP3693994B2 (ja) 鉛低減快削性銅合金
JP2003277855A (ja) 無鉛快削黄銅合金材及びその製造方法
HK1061049A (en) A lead-free and free cutting brass alloy material and a process for preparing the same

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

17P Request for examination filed

Effective date: 20050808

AC Divisional application: reference to earlier application

Ref document number: 1045041

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FI FR GB IT SE

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE FI FR GB IT SE

AKX Designation fees paid

Designated state(s): BE DE FI FR GB IT SE

17Q First examination report despatched

Effective date: 20070125

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AC Divisional application: reference to earlier application

Ref document number: 1045041

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FI FR GB IT SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: MITSUBISHI SHINDOH CO., LTD.

REF Corresponds to:

Ref document number: 69839830

Country of ref document: DE

Date of ref document: 20080911

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080730

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20090506

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081030

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 69839830

Country of ref document: DE

Representative=s name: BISCHOF & PARTNER RECHTSANWAELTE PARTNERSCHAFT, DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 18

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20171127

Year of fee payment: 20

Ref country code: DE

Payment date: 20171205

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20171130

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69839830

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20181115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20181115