Naturharte Kupfer-Legierungen

Legierungen wie Messinge (CuZn), Zinnbronzen (CuSn) und Neusilber (CuNiZn), bei denen die gewünschte Festigkeit durch Kaltumformung erzeugt wird, werden als naturharte Legierungen bezeichnet. Zu dieser Gruppe sind auch die Silberbronzen mit Silbergehalten von 2 bis 6 Massen-% zu zählen.

Kupfer-Zink-Legierungen (Messing)

Kupfer-Zink-Legierungen finden wegen ihrer ausreichend hohen elektrischen Leitfähigkeit, der gegenüber Kupfer höheren Festigkeit bei noch guter Verarbeitbarkeit und des günstigen Preises breite Anwendung als Kontaktträgerwerkstoffe in Schaltgeräten der Energietechnik (Table 1 und Table 2). Besonders geeignet sind die sehr gut kaltbildsamen Messinge bis 37 Massen-% Zn, die nach dem Zustandsdiagramm ausschließlich aus der α-Phase aufgebaut sind (Figure 1). Beachtenswert ist die starke Abhängigkeit der Dichte, der elektrischen Leitfähigkeit und der Festigkeitseigenschaften vom Zinkgehalt (Figure 2).

Table 1: Physikalische Eigenschaften einiger Kupfer-Zink-Legierungen

Werkstoff Bezeichnung EN UNS	Zusammensetzung [wt%]	Dichte [g/cm3]	Elektr. Leitfähigkeit		Elektr. Widerstand[μΩ·cm]	Wärmeleitfähigkeit [W/(m·K)]	Lin. Ausdehnungskoeff. [10-6/K]	E-Modul [GPa]	Erweichungstemperatur (ca. 10% Festigkeitsabfall) [°C]	Schmelzbereich [°C]
			[MS/m]	[% IACS]
CuZn5 CW500L C21000	Cu 94 - 96 Zn Rest	8.87	33	57	3.8	243	18.0	127		1055 - 1065
CuZn10 CW501L C22000	Cu 89 - 91 Zn Rest	8.79	25	43	4.0	184	18.2	125		1030 - 1045
CuZn15 CW502L C23000	Cu 84 - 86 Zn Rest	8.75	21	36	4.8	159	18.5	122	ca. 250	1005 - 1025
CuZn20 CW503L C24000	Cu 79 - 81 Zn Rest	8.67	19	33	5.3	142	18.8	120	ca. 240	980 - 1000
CuZn30 CW505L C26000	Cu 69 - 71 Zn Rest	8.53	16	28	6.3	124	19.8	114	ca. 230	910 - 940
CuZn37 CW508L C27200	Cu 62 - 64 Zn Rest	8.45	15.5	27	6.5	121	20.2	110	ca. 220	900 - 920
CuZn23Al3Co CW703R C68800	Cu 73.5 Al 3.4 Co 0.4 Zn Rest	8.23	9.8	17	10.2	78	18.2	116	ca. 280	950 - 1000

Table 2: Mechanische Eigenschaften einiger Kupfer-Zink-Legierungen

Werkstoff	Zustand	Zugfestigkeit Rm [MPa]	0,2% Dehngrenze Rp02 [MPa]	Bruchdehnung A50 [%]	Vickershärte HV	Biegeradius1) min senkrecht zur Walzrichtung	Biegeradius1) min parallel zur Walzrichtung	Federbiegegrenze σFB [MPa]	Biegewechselfestigkeit σBW [MPa]
CuZn5	R 230 R 270 R 340	230 - 280 270 -350 340 - 440	≤ 130 ≥ 200 ≥ 280	36 12 4	45 - 90 70 - 120 110 - 160	0 x t 0 x t	0 x t 0 x t	250	130
CuZn10	R 240 R 280 R 350	240 - 290 280 - 360 350 - 450	≤ 140 ≥ 200 ≥ 290	36 13 4	50 - 100 80 - 130 110 - 160	0 x t 0 x t	0 x t 0 x t	260	140
CuZn15	R 300 R 350 R 410 R 480 R 550	300 - 370 350 - 420 410 - 490 480 - 560 ≥ 550	≤ 150 ≥ 270 ≥ 360 ≥ 420 ≥ 480	16 8 3 1	85 - 120 100 - 150 125 - 155 150 - 180 ≥ 170	0 x t 0 x t 0 x t 1 x t	0 x t 0 x t 1 x t 3 x t	300	160
CuZn20	R 270 R 320 R 400 R 480	270 - 320 320 - 400 400 - 480 480 - 570	≤ 150 ≥ 200 ≥ 320 ≥ 440	38 20 5 3	55 - 105 95 - 155 120 - 180 ≥ 150	0 x t 0 x t 0 x t	0 x t 0 x t 0 x t	320	180
CuZn30	R 270 R 350 R 410 R 480	270 - 350 350 - 430 410 - 490 480 - 580	≤ 160 ≥ 200 ≥ 430 ≥ 430	40 21 9 4	95 - 125 120 - 155 150 - 180 170 - 200	0 x t 0 x t 0 x t 1 x t	0 x t 1 x t 2 x t 3 x t	330	180
CuZn37	R 300 R 350 R 410 R 480 R 550	300 - 370 350 - 440 410 - 490 480 - 560 550 - 640	≤ 180 ≥ 200 ≥ 260 ≥ 430 ≥ 500	38 19 8 3	55 - 105 95 - 155 120 - 190 ≥ 150 ≥ 170	0 x t 0 x t 0 x t 0.5 x t 1 x t	0 x t 0 x t 0 x t 1 x t 3 x t	350	190
CuZn23Al3Co	R 660 R 740 R 820	660 - 750 740 - 830 ≥ 820	≥ 580 ≥ 660 ≥ 780	10 3 2	190 - 220 210 - 240 ≥ 235	0 x t 1 x t	0 x t 2 x t	≥ 400	230

¹⁾ t: Banddicke max 0,5 mm

Nachteile der Kupfer-Zink-Legierungen sind die mit steigendem Zinkgehalt zunehmende Neigung zur Spannungsrisskorrosion und das im Vergleich zu anderen Kupferlegierungen schlechte Spannungsrelaxationsverhalten.

Von den Sondermessingen kommt vor allem CuZn23Al3Co als Kontaktträgerwerkstoff zum Einsatz. Dieser Werkstoff erreicht wesentlich höhere Festigkeitswerte als die Standard-Messinge. Obwohl CuZn23Al3Co zu den naturharten Legierungen gerechnet wird, erreicht er bei geeigneter Anlassbehandlung eine ausgeprägte Festigkeitszunahme.

Figure 1 Zustandsdiagramm Kupfer-Zink für den Bereich 0 bis 60 Massen-% Zink

Figure 2 Festigkeitseigenschaften von Messing in Abhängigkeit vom Kupfergehalt (Kaltumformung 0 und 50%)

Figure 3 Verfestigungsverhalten von CuZn36 durch Kaltumformung

Figure 4 Erweichungsverhalten von CuZn36 nach 3h Glühdauer und einer Kaltumformung von 25%

Figure 1: Zustandsdiagramm Kupfer-Zink für den Bereich 0 bis 60 Massen-% Zink

Figure 2: Festigkeitseigenschaften von Messing in Abhängigkeit vom Kupfergehalt (Kaltumformung 0 und 50%)

Figure 3: Verfestigungsverhalten von CuZn36 durch Kaltumformung

Figure 4: Erweichungsverhalten von CuZn36 nach 3h Glühdauer und einer Kaltumformung von 25%

Kupfer-Zinn-Legierungen (Zinnbronze)

Because of their good elastic spring properties and formability the copper-tin alloys CuSn6 and CuSn8 are standard materials for spring contact elements in electrome-chanical components such as connectors, switches, and relays Table 3 and Table 4. Besides these other alloys such as CuSn4 and CuSn5 and the multi-metal tin bronze CuSn3Zn9 have significant usage – mainly in North America. Figure 6 shows the copper rich side of the phase diagram for the CuSn system. The mechanical property values achieved by cold forming are superior to these of the brass alloys Figure 7. They increase significantly with increasing Sn content. The work hardening and softening behavior are shown for the example of CuSn8 in Figure 8 and Figure 9. The stress relaxation properties for CuSn alloys are good for up to 100°C, deteriorate however quickly for temperatures above 150°C.

Table 3: Physical Properties of Copper-Tin Alloys

Material Designation EN UNS	Composition [wt%]	Density [g/cm3]	Electrical Conductivity		Electrical Resistivity [μΩ·cm]	Thermal Conductivity [W/(m·K)]	Coeff. of Linear Thermal Expansion [10-6/K]	Modulus of Elasticity [GPa]	Softening Temperature (approx. 10% loss in strength) [°C]	Melting Temp Range [°C]
			[MS/m]	[% IACS]
CuSn4 CW450K C51100	Sn 3.5 - 4.5 P 0.01 - 0.4 Cu Rest	8.85	12.0	20	8.3	118	18.0	120	ca. 260	960 - 1060
CuSn5 CW451K C51000	Sn 4.5 - 5.5 P 0.01 - 0.4 Cu Rest	8.85	10.0	17	10.0	96	18.0	120	ca. 260	940 - 1050
CuSn6 CW452K C51900	Sn 5.5 - 7.0 P 0.01 - 0.4 Cu Rest	8.80	9.0	15	11.1	75	18.5	118	ca. 280	910 - 1040
CuSn8 CW453K C52100	Sn 7.5 - 8.5 P 0.01 - 0.4 Cu Rest	8.80	7.5	13	13.3	67	18.5	115	ca. 320	875 - 1025
CuSn3Zn9 CW454K C42500	Zn 7.5 - 10 Sn 1.5 - 3.5 P 0.2 Ni 0.2 Cu Rest	8.75	12	28	6.2	120	18.4	126	ca. 250	900 - 1015

Table 4: Mechanical Properties of Copper-Tin Alloys

Material	Hardness Condition	Tensile Strength Rm [MPa]	0,2% Yield Strength Rp02 [MPa]	Elongation A50 [%]	Vickers Hardness HV	Bend Radius1) perpendicular to rolling direction	Bend Radius1) parallel to rolling direction	Spring Bending Limit σFB [MPa]	Spring Fatigue Limit σBW [MPa]
CuSn4	R 290 R 390 R 480 R 540 R 610	290 - 390 390 - 490 480 - 570 540 - 630 ≥ 610	≤ 190 ≥ 210 ≥ 420 ≥ 490 ≥ 540	40 13 5 4 2	70 - 100 115 - 155 150 - 180 170 - 200 ≥ 190	0 x t 0 x t 0 x t 0 x t	0 x t 0 x t 0 x t 1 x t	420	200
CuSn5	R 310 R 400 R 490 R 550 R 630 R 690	310 - 390 400 - 500 490 - 580 550 - 640 630 - 720 ≥ 690	≤ 250 ≥ 240 ≥ 430 ≥ 510 ≥ 600 ≥ 670	45 17 10 6 3	75 - 105 120 - 160 160 - 190 180 - 210 200 - 230 ≥ 220	0 x t 0 x t 0 x t 0 x t 1 x t	0 x t 0 x t 0 x t 1 x t 2 x t	460	220
CuSn6	R 350 R 420 R 500 R 560 R 640 R 720	350 - 420 420 - 520 500 - 590 560 - 650 640 - 730 ≥ 720	≤ 300 ≥ 260 ≥ 450 ≥ 500 ≥ 600 ≥ 690	45 20 10 7 4	80 - 110 125 - 165 160 - 190 180 - 210 200 - 230 ≥ 220	0 x t 0 x t 0 x t 0 x t 1 x t	0 x t 0 x t 0 x t 1 x t 2 x t	480	230
CuSn8	R 370 R 450 R 540 R 600 R 660 R 740	370 - 450 450 - 550 540 - 630 600 - 690 660 - 750 ≥ 740	≤ 300 ≥ 280 ≥ 460 ≥ 530 ≥ 620 ≥ 700	50 23 15 7 4	90 - 120 135 - 175 170 - 200 190 - 220 210 - 240 ≥ 230	0 x t 0 x t 0 x t 1 x t 2 x t	0 x t 0 x t 0 x t 1 x t 2 x t	520	240
CuSn3Zn9	R 320 R 380 R 430 R 510 R 580 R 660	320 - 380 380 - 430 430 - 520 510 - 600 580 - 690 ≥ 660	≤ 230 ≥ 200 ≥ 330 ≥ 430 ≥ 520 ≥ 610	25 18 6 3 4	80 - 110 110 - 140 140 - 170 160 - 190 180 - 210 ≥ 200	0 x t 0 x t 0 x t 0 x t 1 x t	0 x t 0 x t 0 x t 1 x t 2 x t	500	210

¹⁾ t: Strip thickness max. 0.5 mm

Figure 5 Softening of CuZn36 after 3 hrs annealing after 50% cold working)

Figure 6 Phase diagram of the Cu-Sn system for the range of 0 – 30 wt% Sn)

Figure 7 Mechanical properties of tin bronze depending on the tin content (cold working 0 and 50%)

Figure 8 Strain hardening of CuSn8 by cold working

Figure 9 Softening of CuSn8 after 3 hrs annealing after 50% cold working

Figure 5: Softening of CuZn36 after 3 hrs annealing after 50% cold working

Figure 6: Phase diagram of the Cu-Sn system for the range of 0 – 30 wt% Sn

Figure 7: Mechanical properties of tin bronze depending on the tin content (cold working 0 and 50%)

Figure 8: Strain hardening of CuSn8 by cold working

Figure 9: Softening of CuSn8 after 3 hrs annealing after 50% cold working

Copper-Nickel-Zinc Alloys (German Silver)

Despite its lower electrical conductivity, the good spring properties, high corrosion resistance, and the good workability make copper-nickel-zinc alloys a frequently used spring contact carrier in switches and relays. As illustrated in the phase diagram the most commonly used materials are in the α -range which means that they are single-phase alloys Figure 10. The formability and strength properties of german silver are comparable to those of the copper-tin alloys. The work hardening and softening behavior is illustrated on the example of CuNi12Zn24 in Figure 11 and Figure 12.

The relaxation behavior of Cu-Ni-Zn alloys is superior to the one for the tin bronzes. Additional advantages are the very good weldability, brazing properties, and the high corrosion resistance of these copper-nickel-zinc alloys.

Table 5: Physical Properties of Copper-Nickel-Zinc Alloys

Material Designation EN UNS	Composition [wt%]	Density [g/cm3]	Electrical Conductivity		Electrical Resistivity [μΩ·cm]	Thermal Conductivity [W/(m·K)]	Coeff. of Linear Thermal Expansion [10-6/K]	Modulus of Elasticity [GPa]	Softening Temperature (approx. 10% loss in strength) [°C]	Melting Temp Range [°C]
			[MS/m]	[% IACS]
CuNi12Zn24 CW403J C75700	Cu 63- 66 Ni 11 - 13 Mn 0.5 Fe 0.3 Zn Rest	8.67	4.4	7	30	42	18	125	ca. 400	1020 - 1065
CuNi18Zn20 CW409J C76400	Cu 60 - 63 Ni 17 - 19 Mn 0.5 Fe 0.3 Zn Rest	8.73	3.3	5	23	33	17.7	135	ca. 440	1055 - 1105
CuNi18Zn27 CW410J C77000	Cu 53 - 56 Ni 17 - 19 Mn 0.5 Fe 0.3 Zn Rest	8.70	3.3	5	23	32	17.7	135	ca. 440	1050 - 1100

Table 6: Mechanical Properties of Copper-Nickel-Zinc Alloys

Material	Hardness Condition	Tensile Strength Rm [MPa]	0,2% Yield Strength Rp02 [MPa]	Elongation A50 [%]	Vickers Hardness HV	Bend Radius1) perpendicular to rolling direction	Bend Radius1) parallel to rolling direction	Spring Bending Limit σFB [MPa]	Spring Fatigue Limit σBW [MPa]
CuNi12Zn24	R 360 R 430 R 490 R 550 R ≥ 610	360 - 430 430 - 510 490 - 580 550 - 640 ≥ 580	≤ 230 ≥ 230 ≥ 400 ≥ 480 ≥ 580	35 8 6 3 2	80 - 110 110 - 150 150 - 180 170 - 200 ≥ 190	0 x t 0 x t 0 x t 0 x t	0 x t 0 x t 0 x t 0 x t	480	210
CuNi18Zn20	R 380 R 450 R 500 R 580 R ≥ 640	380 - 450 450 - 520 500 - 590 580 - 670 ≥ 640	≤ 250 ≥ 250 ≥ 410 ≥ 510 ≥ 600	27 9 5 2	85 - 115 115 - 160 160 - 190 180 - 210 ≥ 220	0 x t 0 x t 0 x t 0 x t	0 x t 0 x t 0 x t 0 x t	520	220
CuNi18Zn27	R 390 R 470 R 540 R 600 R ≥ 700	390 - 470 470 - 540 540 - 630 600 - 700 ≥ 700	≤ 280 ≥ 280 ≥ 450 ≥ 550 ≥ 680	30 11 5 2	90 - 120 120 - 170 170 - 200 190 - 220 ≥ 220	0 x t 0 x t 0 x t 0 x t	0 x t 0 x t 0 x t 1 x t	550	250

¹⁾ t: Strip thickness max. 0.5 mm

Figure 10 Copper rich region of the ternary copper-nickel-zinc phase diagram with indication of the more commonly available german silver materials

Figure 11 Strain hardening of CuNi12Zn24 by cold working

Figure 12 Softening of CuNi12Zn24 after 3 hrs annealing after 50% cold working

Copper rich region of the ternary copper-nickel-zinc phase diagram with indication of the more commonly available german silver materials

Figure 11: Strain hardening of CuNi12Zn24 by cold working

Figure 12: Softening of CuNi12Zn24 after 3 hrs annealing after 50% cold working

Copper-Silver-(Cadmium) Alloys (Silver Bronze)

Besides the low-allowed CuAg0.1 other copper materials with higher silver contents (2-6 wt%) are also used as contacts carrier materials. Some of them contain additionally 1.5 wt% Cd. The phase diagram Figure 13 shows that in principle the CuAg alloys can be precipitation hardened, but the possible increase in mechanical strength is rather small.

Copper-silver alloys have good spring properties and compared to other spring materials have a high electrical conductivity Table 7 and Table 8. The mechanical strength values in the strongly worked condition are comparable to those of the copper-tin alloys. Work hardening and softening behavior are shown for the example of CuAg2 (Figs. 13 – 15). For the relaxation behavior the silver bronzes are superior to German silver and tin bronze.

Because of their good spring properties combined with high electrical conductivity silver bronzes are suitable for the use contact springs in relays under higher current loads. Taking advantage of their high temperature stability they are also used as current carrying contacts in high voltage switchgear and as electrode material for resistance welding.

Table 7: Physical Properties of Selected Copper-Silver-(Cadmium) Alloys

Material Designation EN UNS	Composition [wt%]	Density [g/cm3]	Electrical Conductivity		Electrical Resistivity [μΩ·cm]	Thermal Conductivity [W/(m·K)]	Coeff. of Linear Thermal Expansion [10-6/K]	Modulus of Elasticity [GPa]	Softening Temperature (approx. 10% loss in strength) [°C]	Melting Temp Range [°C]
			[MS/m]	[% IACS]
CuAg2 not standardized	Ag 2 Cu Rest	9.0	49	85	2.0	330	17.5	123	ca. 330	1050 - 1075
CuAg2Cd1,5 not standardized	Ag 2 Cd1,5 Cu Rest	9.0	43	74	2.3	260	17.8	121	ca. 350	970 - 1055
CuAg6 not standardized	Ag 6 Cu Rest	9.2	38	66	2.4	270	17.5	120		960 - 1050

Table 8: Mechanical Properties of Selected Copper-Silver-(Cadmium) Alloys

Material	Hardness Condition	Tensile Strength Rm [MPa]	0,2% Yield Strength Rp02 [MPa]	Elongation A50 [%]	Vickers Hardness HV	Bend Radius1) perpendicular to rolling direction	Bend Radius1) parallel to rolling direction	Spring Bending Limit σFB [MPa]	Spring Fatigue Limit σBW [MPa]
CuAg2	R 280 R 380 R 450 R 550	280 - 380 380 - 460 450 - 570 ≥ 550	≤ 180 ≥ 300 ≥ 420 ≥ 500	30 6 3 1	50 - 110 100 - 140 130 - 165 ≥ 160	0 x t 0 x t 1 x t	0 x t 0 x t 1 x t	400	190
CuAg2Cd1,5	R 300 R 380 R 480 R 600	300 - 380 380 - 490 480 - 620 ≥ 600	≤ 190 ≥ 310 ≥ 440 ≥ 550	30 8 3 1	55 - 110 100 - 145 130 - 170 ≥ 160	0 x t 0 x t 1 x t	0 x t 0 x t 1 x t	440	220
CuAg6	R 320 R 400 R 500 R 650	320 - 400 400 - 510 500 - 660 ≥ 650	≤ 210 ≥ 330 ≥ 460 ≥ 610	30 6 3 1	70 - 120 110 - 150 145 - 175 ≥ 175	0 x t 0 x t 1 x t	0 x t 0 x t 1 x t	460	230

¹⁾ t: Strip thickness max. 0.5 mm

Figure 13 Phase diagram of copper-silver for the range of 0 – 40 wt% silver

Figure 14 Strain hardening of CuAg2 by cold working

Figure 15 Softening of CuAg2 after 1 hr annealing after 40% cold working

Figure 16 Softening of CuAg2 after 1 hr annealing after 80% cold working

Figure 13: Phase diagram of copper-silver for the range of 0 – 40 wt% silver

Figure 14: Strain hardening of CuAg2 by cold working

Figure 15: Softening of CuAg2 after 1 hr annealing after 40% cold working

Figure 16: Softening of CuAg2 after 1 hr annealing after 80% cold working

Referenzen

Referenzen