Materials Transactions, Vol. 49, No. 7 (2008) pp.

1656 to 1660 #2008 The Japan Institute of Metals

Eects of Cold Drawing and Annealing on Mechanical Properties and Microstructure of Co-Cr-Mo-Ni-Fe Alloys for Surgical Implants
Yoshimitsu Okazaki
National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8564, Japan
The eects of cold drawing and annealing on the mechanical properties and microstructure of 0.06C and 0.12C-Co-Cr-Mo-Ni-Fe alloys were examined. The 0.2% proof strength (0.2%PS ) and ultimate tensile strength (UTS ) of the cold-drawn 0.06C alloy increased proportionally as the reduction in area increased, whereas the total elongation (T. E.) decreased linearly. The 45% cold-drawn alloys showed the following 0.2%PS , UTS , T. E., and reduction of area (R. A.): for the 0.06C alloy 1174 125 MPa, 1549 23 MPa, 10 1%, and 36 5%; for the 0.12C alloy, 1223 57 MPa, 1623 23 MPa, 12 2%, and 44 4%, respectively. In the 45% cold-drawn 0.12C alloy, M6 C carbide precipitates were observed in the dislocation network, which was caused by cold drawing. M6 C carbide precipitates were also observed in the grain and grain boundary in the 0.06C and 0.12C alloys annealed from 950 to 1200 C. The matrix was the -phase; no "- or  -phase was observed. As annealing temperature increased, the 0.2%PS and UTS of the annealed alloys decreased gradually, while the T. E. increased linearly. Approximately 70% T. E. was obtained by annealing at 1100 C for the 0.06C alloy, and at 1200 C for the 0.12C alloys. [doi:10.2320/matertrans.MRA2007275] (Received November 7, 2007; Accepted April 8, 2008; Published June 25, 2008) Keywords: microstructure, mechanical property, cobalt-chromium-molybdenum-nickel-iron alloy, annealing, cold drawing

1.

Introduction

Distinctive alloys for surgical devices include Co-Cr-MoNi-Fe alloys specied by ISO 5832-8. Their comprehensive features, such as excellent elasticity, excellent ductility, high mechanical strength, and good cold workability, have led to Co-Cr-Mo-Ni-Fe alloys gaining considerable attention as metallic materials for orthopedic implants, particularly for stents and stent grafts.16) Thereby, the use of Co-Cr-Mo-NiFe alloys for orthopedic and vascular implants has become common in recent years. Now the focus is on the development of the manufacturing process of such alloys. To develop a manufacturing process for Co-Cr-Mo-Ni-Fe alloys, it is important to investigate the eects of cold drawing and heat treatment on the mechanical properties and microstructure of these alloys. However, there are only a few valuable in-depth research studies of Co-Cr-Mo-Ni-Fe alloys in spite of the above attention. In this study, the eects of cold drawing and heat treatment were examined mechanically and microstructurally by the following methods: a tensile test at room temperature to evaluate the mechanical properties, and X-ray diraction analysis, optical microscopy and transmission electron microscopy to observe microstructural changes. 2. Experimental Methods

was subjected to thermal treatment at 1200 C for 10 h, and then hot-forged into rod specimens. The rod was heated preliminarily at 1200 C for 15 min and then quenched in water. The water-quenched rods were cold-drawn by 45% reduction in area (cold-drawn 0.12C). Some of the colddrawn rods were annealed separately at 1050, 1100, 1130, 1150, 1200 and 1220 C for 5, 15, and 30 min, and quenched in water (annealed 0.12C). Table 1 shows the detailed chemical compositions of the alloys. 2.2 Tensile tests To investigate the eects of cold drawing and annealing on mechanical properties, tensile test at room temperature was performed in accordance with the Japanese Industrial Standard (JIS) H 4600. Specimens of each alloy (diameter: 8 mm, gauge length: 40 mm) were pulled at a crosshead speed of 1 mm/min. When the proof strength reached 0.2%, it was changed to 2.5 mm/min until the specimen fractured. The means of the tensile test parameters (i.e., 0.2% proof strength, ultimate tensile strength, total elongation, and reduction in area) and standard deviations were calculated values of three measurements. Microscopic observation and X-ray diraction analysis The microstructures of the cold-drawn and annealed alloys were evaluated by optical microscopy, transmission electron microscopy (TEM) and X-ray diraction analysis. Specimens for microscopic observation were cut from the sample alloys, covered with epoxy resin, and then polished with waterproof emery paper from 120 to 2400 grit under running water. The sample surfaces were nished by bu cleaning using a high-quality SiO2 (OP-S) suspension and etched. A Nikon upright microscope was used for microscopic observation. Specimens for TEM were prepared by electrolytic polishing with a 95% methanol+5% perchloric acid solution. TEM was carried out with a Hitachi, Ltd. H-800 microscope equipped with an EDX (Horiba, Ltd. EMAX-2200) system. 2.3

2.1 Heat treatment 0.06C and 0.12C-Co-Cr-Mo-Ni-Fe alloys, as described in the ISO 5832-7 standard, were prepared by vacuum-induction melting. A 0.06C alloy ingot (90 kg) was maintained at 1200 C for 0.5 h. The ingot was hot-forged into rod specimens. The rods were separately annealed for 0.5 h at 950 or 1050 C, followed by cold-drawing (cold-drawn 0.06C). Plot measurements of 30, 37, 40 and 45% reductions in area were conducted for evaluation. Some of the 45% 0.06C colddrawn rods were again annealed separately at 950, 980, 1000, 1050 and 1100 C for 0.5 h, and then quenched in water (annealed 0.06C). Meanwhile, a 0.12C alloy ingot (50 kg)

Eects of Cold Drawing and Annealing on Mechanical Properties and Microstructure of Co-Cr-Mo-Ni-Fe Alloys for Surgical Implants Table 1 Cr 0.06C 0.12C 19.33 20.77 Mo 6.74 7.88 Ni 16.65 14.51 Chemical compositions (mass%) of Co-Cr-Mo-Ni-Fe alloys. C 0.06 0.12 Mn 1.78 1.27 Si 0.47 0.85 P 50.005 0.005 S 0.0006 0.0025 Be 50.001 0.001 Co 40.1 39.7

1657

Fe Bal. Bal.

1800

70

(a)
UTS/MPa
1600 1400 1200
UT S

(b)
60

Total Elongation (%)

50 40 30 20 10 0

0.2%PS /MPa,

1000 800 600 400 200

0.2 %P S

: 950C : 1050C

UTS 950C 1050C

0.2%

10 15 20 25 30 35 40 45 50 55

10 15 20 25 30 35 40 45 50 55

Reduction in Area (%)

Reduction in Area (%)

Fig. 1 Eects of cold drawing on 0.2% proof strength (0.2%PS ), ultimate tensile strength (UTS ) and total elongation of 0.06C Co-Cr-NiMo-Fe alloy after annealing at 950 or 1050 C for 0.5 h.

Precipitates were also analyzed by electron beam diraction and EDX analyses. For X-ray diraction analysis with RINT1500 (Rigaku Corp.), the surface of each sample was bu-cleaned. The diraction patterns were measured under the following conditions: Cu K X-ray source; tube voltage, 40 kV; tube current, 0.02 A; and scanning rate (2), 2 /min. The lattice constant of the precipitates was carefully calculated as follows: The silicon powder (NIST, 640C) used for X-ray diraction analysis was thinly spread onto the bu-cleaned sample surface as at as possible, according to the specications of the testing manual. Scanning rate (2) and sampling step were set at 2 /min and 0.01 , respectively. To ensure the precise calculation of the lattice constant, the tested peak values were corrected by comparison with the standard peak values of Si. 3. 3.1 Experimental Results and Discussion

Table 2 Mechanical properties of annealed and cold-drawn Co-Cr-Mo-NiFe alloys. 0.2%PS /MPa UTS /MPa T.E.(%) R.A.(%) 0.06C 45% Cold-drawn 1174 125 1549 23 10 1 Annealed Annealed 350 10 493 34


36 5 70 4 44 4 49 3

796 6 999 8

70 2 59 12

0.12C 45% Cold-drawn 1223 57

1623 23 12 2

Annealing conditions: 0.06C, 1100 C for 30 min; 0.12C, 1130 C for 5 min.

Eects of cold drawing on mechanical properties and microstructure Figure 1 shows the eect of cold drawing on the 0.2%PS , UTS , and T. E of the 0.06C alloys annealed at 950 or 1050 C for 0.5 h. With an increase in the reduction in area, the 0.2%PS and UTS of the 0.06C alloy increased linearly, while the T. E. decreased linearly. A marked variation was observed in that UTS increased from approximately 900 to 1500 MPa by 45% reduction while T. E. decreased to approximately 10%. Table 2 summarizes the mechanical properties of the 45% cold-drawn alloys. As the table shows, both of the 45% colddrawn alloys exhibited sucient UTS (over 1500 MPa) as a material for implants. The optical micrograph of the 0.12C alloy cold-drawn by 45% reduction in area is shown in Fig. 2(a); a microstructure

containing a high strain was seen. Figure 2(b) shows an optical micrograph of the 0.12C alloy annealed at 1130 C for 5 min; the recrystallized structure was seen in the annealed structure. TEM images of the 45% cold-drawn 0.12C alloy are shown in Fig. 3. Assefpour-Dezfuly et al. observed M23 C6 carbide and the "-phase in Co-Cr-Mo-Ni-Fe (Co: 40, Cr: 20, Ni: 15, Mo: 7, Mn: 2, C: 0.1, Fe: bal.) alloy aged at 800 C after cold working.7) In the 45% cold-drown alloy in our study, M6 C carbide precipitates were observed in the grain containing a dislocation network produced by cold drawing; no "-phase is observed in the X-ray diraction analysis. M6 C carbide precipitates were observed in the grain and grain boundary in the 0.06C and 0.12C alloys annealed from 950 to 1200 C. Eect of annealing temperature on mechanical properties Figure 4 shows the eects of annealing temperature and carbon content on the mechanical properties of the alloys. The 0.2%PS and UTS of the 0.12C and 0.06C alloys decreased gradually with annealing temperature; on the other hand, the T. E. increased linearly with annealing tem3.2

1658

Y. Okazaki

(a)

(b)

100 m
Fig. 2

100 m

Optical micrographs of 45% cold-drawn (a) and annealed (1130 C for 5 min) (b) 0.12C Co-Cr-Mo-Ni-Fe alloys.

(a)

(c) M6C
200 111 111

1 m Counts

(d)
Mo Cr Si Cr Co Fe Ni Cu Ni

perature. Extending annealing time slightly decreased the 0.2%PS and UTS of the 0.12C alloys and increased the T. E. as well. A T. E. of approximately 70% was obtained by annealing at 1100 C for 0.06C, and at 1200 C for 0.12C alloys. This pronounced elongation may be obtained owing to the -phase that contained a small amount of M6 C carbide and no "-phase. In another study, a 40Co-20Cr-7Mo15Ni-16Fe alloy tubing is cold-worked up to 45% crosssectional reduction. It has been reported that T. E. increases with annealing temperature, and a T. E. of approximately 55% is achieved in annealing of 1175 C for 10 min.3) 3.3 Microstructure of annealed alloy Figure 5 shows optical micrographs of 0.12C alloys annealed at 1100, 1150 and 1200 C for 5 min. By increasing annealing temperature, microstructural recrystallization and an increase in the grain size of the recrystallized structure were seen. Many precipitates were also observed at the grain boundaries and in the grains. Figure 6 shows the X-ray diraction pattern of the 45% cold-drawn 0.12C alloy. The alloy mainly consisted of the (fcc)-phase. Figure 7 shows the X-ray diraction patterns of the 45% cold-drawn 0.12C alloy annealed at 1130 C for 5 min. M6 C (a 1:0995 0:002 nm) carbide was observed with the (fcc)-phase
80

(b)

keV

250 nm

Fig. 3 TEM images of 45% cold-drawn 0.12C Co-Cr-Mo-Ni-Fe alloy. (c) Diraction pattern of precipitate indicated by arrow in (b). (d) EDX pattern of M6 C carbide.

1200

UTS/MPa

1000 800

UTS 15 min

5 min

70 60 30 min

T. E.(%)

30 min

50 40 30 15 min 5 min

0.2%PS /MPa,

0.2%PS
600 15 min 400 30 min 200 0 900 5 min

0.12C 0.06C

0.06C

0.12C

20 10

1000

1100

1200

1300

0 900

1000

1100

1200

1300

Annealing Temperature, T / C

Annealing Temperature, T / C

Fig. 4 Eects of carbon content and annealing temperature on 0.2% proof strength (0.2%PS ), ultimate tensile strength (UTS ) and total elongation (T. E.) of Co-Cr-Mo-Ni-Fe alloys.

Eects of Cold Drawing and Annealing on Mechanical Properties and Microstructure of Co-Cr-Mo-Ni-Fe Alloys for Surgical Implants

1659

(111)

(200)

Intensity (CPS)

750

500 M6C(422) M6C(440) M6C(442) M6C(733) M6C(822) M6C(400) M6C(331)

M6C(511)

(220)

(a)

(b)

1000

M6C(533)

M6C(551)

250

100 m

100 m

0 20

30

40

50

60

M6C(731)

70

80

(c)

2 (deg)

Fig. 7 X-ray diraction pattern of 0.12C-Co-Cr-Mo-Ni-Fe alloy annealed at 1130 C for 5 min.

I M6C(511) / I (111) (%)

100 m
Fig. 5 Optical micrographs of 0.12C Co-Cr-Mo-Ni-Fe alloys annealed at 1100 C (a), 1150 C (b), and 1200 C (c) for 5 min.

0.12C 15 min 5 min

2 0.06C 30 min 1

Intensity (CPS) 10 4

6 5 4 3 2 1 0 20

(111)

0 900 1000 1100 1200 1300

Annealing Temperature, T / C
Fig. 8 Eects of annealing temperature and carbon content on the intensity ratio (%) of (511) plane for M6 C carbide to (111) plane for (fcc) phase [I M6 C(511)/I (111)100] obtained by X-ray diraction analysis.

30

40

50

(200)

60

70

80

90

2 (deg)

Fig. 6 X-ray diraction pattern of 0.12C Co-Cr-Mo-Ni-Fe alloy colddrawn by 45%.

matrix. Figure 8 shows the eects of annealing temperature and carbon content on the ratio of intensity. The intensity ratio was dened according to the following relation: the ratio of intensity(%)=(intensity of (511) plane for M6 C carbide)/(intensity of (111) plane for phase)100. The intensity ratios of 0.12C and 0.06C alloys decreased linearly with annealing temperature, and they were close to zero at approximately 1070 and 1220 C, respectively. Figures 9 and 10 show TEM images of the 0.12C alloy annealed at 1130 C for 5 min. As shown in Fig. 9(a), the dislocation network produced by cold drawing disappeared, and many precipitates were observed at the grain boundaries and in the grains. The diraction pattern conrmed that the carbide particle at the grain boundary, indicated by the arrow in Fig. 9(b), was M6 C carbide. In the EDX pattern of M6 C carbide, the counts

of Mo, Cr and Co were markedly high, whereas the Ni and Fe counts were relatively high (Fig. 9(d)). The precipitates in the grain were also M6 C carbide (Fig. 10). Moreover, a small amount of M6 C carbide precipitated in the alloy annealed at 1200 C for 5 min. The results of the series of experiments have proven the excellent cold workability of Co-Cr-Mo-Ni-Fe alloy. This evidence presumably implicates the particular suitability of such alloys as materials for coronary stents. 4. Conclusions

We examined the eects of cold drawing and annealing on the mechanical properties and microstructure of Co-CrMo-Ni-Fe alloys. The 0.2%PS and UTS of the cold-drawn 0.06C alloy increased linearly as the reduction in area increased, whereas the T. E. decreased linearly. The 45% cold-drawn 0.12C alloy showed 0.2%PS , UTS , T. E., and R. A. of 1223 57 MPa, 1623 23 MPa, 12 2%, and 44 4%, respectively. In the 45% cold-drawn 0.12C alloy, M6 C carbide precipitates were observed in the dislocation

M6C(755) 90

1660

Y. Okazaki

(a)

(c) M6C
220 400 220

(a)

(c)
220 133 313

1 m

(d)
Counts
Mo Cr Si Co

(d) M6C
Counts 1 m

(b)

(b)

Fe Cr Ni Cu Ni

Mo Si

Cr

Co

Fe Cr Ni

Cu

keV

keV

250 nm

Fig. 9 (a) TEM image of 0.12C Co-Cr-Mo-Ni-Fe alloy annealed at 1130 C for 5 min. (b) TEM image of precipitate at grain boundary. (c) Diraction pattern of precipitate at grain boundary. (d) EDX pattern of M6 C carbide.

250 nm
Fig. 10 (a) TEM image of 0.12C Co-Cr-Mo-Ni-Fe alloy annealed at 1130 C for 5 min. (b) TEM image of precipitate in grain. (c) Diraction pattern of precipitate in grain indicated by arrow in (b). (d) EDX pattern of M6 C carbide.

network caused by cold drawing. The T. E. of the annealed alloys after 45%-cold drawn increased linearly, whereas the 0.2%PS and UTS decreased. A very high T. E., approximately 70%, was obtained by annealing at 1100 C for the 0.06C alloy, and at 1200 C for the 0.12C alloy. Because of their excellent cold workability, Co-Cr-Mo-Ni-Fe alloys are suitable materials for coronary stents. In TEM images of the 0.06C and 0.12C alloys annealed from 950 to 1200 C, the dislocation network produced by cold drawing disappeared, and M6 C carbide precipitates were observed at grain boundaries and in grains. The matrix was the -phase; no "- or  -phase was observed. The images suggest that the pronounced elongation may be due to the -phase contains a small amount of M6 C carbide and no "-phase.

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