NEW MATERIALS

Development of High-tensile-strength Stainless Steel Wire

Hiromu IZUMIDA, Nozomu KAWABE, Shinei TAKAMURA, Hirotsugu MORITA and Teruyuki MURAI

Austenitic stainless steel wire, which consists of a stable austenitic matrix, provides resistance to corrosion and heat and is widely used for springs. In the recent technological trend toward environmental preservation, higher tensile property has been requested for this wire in addition to the above mentioned two basic properties of stainless steel. It is considered to be difficult for conventional austenitic stainless wire to simultaneously attain high tensile strength, corrosion resistance, and heat resistance, in spite of the strong market demand. Therefore, low nickel content high-tensile-strength stainless steel wires like SUS301 and SUS631J1 have been commonly used. As a result of the instability of austenitic matrix, above high strength wires do not offer enough resistance against corrosion and heat. Sumitomo (SEI) Steel Wire Corp. has developed a new stainless steel wire to respond to the market demand. This high strength, high-corrosion-and-heat-resistant alloy wire has been developed by the integration of wire drawing technology and heat treatment technology and the addition of small amount of nitrogen into conventional SUS304 steel, for improving the stability of austenitic matrix. The developed stainless steel wire shows excellent tensile strength and resistance to corrosion and heat, and varieties of application can be expected.

1. Introduction
Austenitic stainless steel wire like stainless steel Type 302 (SUS304 in Japan, hereafter referred to as Type 302), which consists of a stable austenitic matrix, provides resistance to corrosion and heat and is widely used for springs. The specific uses of stainless steel wire are various, including springs for accessory parts of electric household appliances to which corrosion resistance is required, pump springs in shampoo or conditioner bottles, and heat-resistant springs and meshes used in cars exhaust systems. In recent years, a coexistence of high strength, high corrosion resistance, and high heat resistance is required by the market in response to the change to stainless steel wires from piano wires aimed at the elimination of chromium (VI) compounds generated by corrosion resistant surface treatment (chromic acid treatment such as zinc chromate (VI) treatment), and at the further improvement of heat resistance (high-temperature tensile strength and high-temperature sag resistance) related to the exhaust gas reduction technology of a car and further increase in tensile strength to miniaturize assemblies. While above-mentioned coexistence is strongly needed in conventional stainless steel wires, it is thought to be difficult to achieve, and the high tensile strength stainless steel Type 301 (SUS301 in Japan, hereafter referred to as Type 301) and stainless steel Type 631 (SUS631J1 in Japan, hereafter referred to as Type 631) were used generally. These are the materials that have fewer nickel amount and lower matrix (austenitic phase) stability. By wire drawing these materials, the stress induced martensite (1) with very high hardness is generated. In the case of Type 631, intermetallic compounds are precipitated by aging heat

treatment, and high tensile strength is thereby attained. Since the factors for corrosion resistance and heat resistance are lost by performing such treatment, it is far from attaining the coexistence of the characteristics. Moreover, as for the fatigue resistance of springs, there also exists an uncertainty that it is not yet proven whether the existence of a stress-induced martensite is beneficial or detrimental. (2), (3), (4) Sumitomo (SEI) Steel Wire Corp. has developed a new stainless steel wire. This high-strength, high-corrosion-and-heat-resistant alloy wire has been developed by integrating wire drawing technology with heat treatment technology and adding a small amount of nitrogen into conventional Type 302 steel, for improving the stability of austenitic matrix. In this paper, the authors report the basic properties (mainly on spring characteristic) and development concept of the new high tensile strength stainless steel wire.

2. Development concept
2-1 Chemical composition Figure 1 shows the influence of alloying elements on the 0.2% proof stress of Fe-Cr-Ni austenite steel (5). Compared with the ferrite stabilizing elements like Si and Mo that form substitutional solid solutions, the austenite stabilizing elements like C and N greatly improve the 0.2% proof stress. Table 1 shows the chemical composition of the developed material and conventional stainless steels. The developed steel uses Type 302 as the base material for the purpose of suppressing the cost. By adding N, which is an austenite stabilizing ele-

24 Development of High-tensile-strength Stainless Steel Wire

ment, the strengthening and stabilization of the matrix are achieved. Furthermore, solid solution hardening is performed for the developed steel by adding a ferrite stabilizing element like Si or Mo, which raises corrosion resistance.

N 15 C 10 5 0 0

interstitial W Mo

substitutional stabilizer substitutional stabilizer V Si Mn Co

Ni 10 Amount of alloying element / at%

Fig. 1. Influence of alloying elements on 0.2% proof stress on Fe-Cr-Ni austenite steel

Table 1. Chemical composition of developed and conventional stainless steels

(mass%)

C Developed steel

Si

Mn Cr

Ni

Cu Mo

Al 1.2

N 0.2

0.07 0.9 1.7 18.8 9.5 0.2 1.0

Type 302 (SUS304) 0.07 0.3 1.2 18.3 8.6 0.3 Type 631 (SUS631J1) 0.08 0.3 0.8 16.3 8.1 0.1

2-2 Heat treatment In order to further promote the strengthening by N addition, the temperature of low-temperature annealing, which is aimed at removing the strain induced by the coiling process, was set at a higher value than the conventional temperature. Figure 2 shows the change of tensile strength due to aging (low-temperature annealing) of the 0.55-mm-diameter developed wire and conventional stainless steel wires. When the aging time is set at 30 minutes (same as the time for low-temperature annealing after the standard coiling process), the peak

tensile strength of Type 304 wire is reached at around 370C, the temperature at which strain aging occurs, and that of Type 631 is reached at around 450C, the temperature at which an intermetallic compound NiAl is precipitated. The peak tensile strength of the developed wire is reached at around 500C, which is higher temperature compared with the above mentioned conventional stainless steel wires. Moreover, the increase in tensile strength due to age hardening is about 400 MPa for the developed wire, which is a larger value than that for Type 302, and equivalent to that for Type 631. It is thought that the above-mentioned phenomenon originates in the chemical composition of the developed material. The authors assume that the formation of a Cottrell atmosphere, which locks the edge dislocations introduced by the wire drawing process, is promoted since the developed material contains a large amount of N. Furthermore, the authors also assume that the Mo-N cluster reported by Murayama et al. is formed (6) since the developed material contains Mo. Therefore, the authors set the low-temperature annealing conditions of the developed wire as 500C for 30 minutes from the above-mentioned reason. The characteristic values of the developed material mentioned below are the values after carrying out lowtemperature annealing at 500C for 30 minutes. The annealing conditions of Type 302 and Type 316 (SUS316 in Japan here after reffered to as Type 316), which are the comparison materials, were set as 400C for 30 minutes, and that of Type 631 was set as 475C for 30 minutes. These are the manufacturers recommended conditions. 2-3 Wire drawing process The relationship between wire drawing strain and tensile strength of the developed wire and conventional wires before/after aging is shown in Fig. 3. The inclination of the graph of the as-drawn developed wire is almost the same as that of Type 302 (drawing strain less than 2.0) and smaller than that of Type 631. Type 631 that lacks phase stability most generates the stress-

Increase of 0.2% proof stress / t/in2

2500 Tensile strength / MPa 2400 (0.55) Tensile strength / MPa 2300 2200 2100 2000 1900 Type 631 (SUS631J1) Developed steel Type 302 (SUS304)

2000

1500
Developed wire (as aged) Developed wire (as drawn) Type 631 (as aged) Type 631 (as drawn) Type 302 (as tempered) Type 302 (as drawn)

1000

500 0 100 200 300 400 500 600

0.5

1.0

1.5

2.0

2.5

Strain of wire drawing / %

Aging temperature /C(for 30 min.)

Fig. 2. Increase of tensile strength of developed and conventional steels by aging

Fig. 3. Relationship between wire drawing strain and tensile strength before/after aging of developed wire and conventional stainless steel wires

SEI TECHNICAL REVIEW NUMBER 60 JUNE 2005 25

induced martensite even after being lowly processed, and therefore is susceptible to hardening. This means that Type 631 tends to lose toughness during the wire drawing or coiling process and requires extremely careful handling. Moreover, because the wire drawing strain is 2.0 or more, it turns out that the inclination of the graph of the developed material becomes a little smaller than that of Type 302. This originates in the fact that the stress-induced martensite is generated also in Type 302 at the wire drawing strain of 2.0 or more. This indicates that the developed materials matrix phase (austenite) is stable even after a large drawing strain is introduced. The comparison of tensile strength after aging shows that the developed wire exhibits the improvement in strength that is equivalent to that of above mentioned Type 631. The effect of age-hardening is related to the strain introduced by wire drawing. It is found out that the effect of aging is large when the drawing strain is large. It is thought that this is because the amount of edge dislocations, which are required for forming a Cottrell atmosphere, increases as the strain aging, which is the strengthening mechanism of the developed wire, proceeds. It is also thought that the formation of Mo-N clusters also has some influence. 2-4 Microstructure The optical microscope image of the hard-drawn developed wire (the reduction by wire drawing is 90%) is shown in Photo 1. This photograph is an optical image of the horizontal section of the developed wire that was electrolytically etched after polishing. Photo 1 shows that the developed material maintains an austenitic single phase even after being hard drawn, and that neither precipitates nor second phase exists. This shows the high stability of the matrix of the developed material.

eter size and tensile strength of the developed wire and conventional wires after aging. The numerical values for the developed wire are the actual measurement values after age hardening, and those for the conventional wires were the values calculated based on the JIS standard tensile strength value of stainless steel wire. Generally, a steel wire has a tendency that its tensile strength increases as wire size becomes smaller. In all ranges of wire sizes, it was found that the tensile strength of the developed wire is higher than that of Type 302, and is equivalent to the maximum limit of that of Type 631.

2600 2500 Tensile strength / MPa 2400 2300 2200 2100 2000 1900 1800 0.0 0.5 1.0 Type 631 Type 302
Developed wire Type 631 Type 302

Deve

loped

wire

1.5

2.0

2.5

3.0

Wire diameter size / mm

Fig. 4. Relation between wire diameter size and tensile strength of developed wire and conventional wires after aging

3-2 Fatigue strength The results of the Hunter-type rotating bending fatigue tests for the developed wire and conventional wires with 1.0 mm wire diameter are shown in Fig. 5. A comparison of the fatigue limit for 1 107 cycles shows that the developed wire has a higher fatigue limit than conventional wires.

1100 1000 900 800 700 600 500 400 300 200 104 Stress amplitude / MPa
Developed wire Type 302 Type 631

Developed wire Type 302 Type 631

5m

105

106

107

Number of cycles to failure

Photo 1. Optical microscope image of hard-drawn developed wire (reduction by wire drawing: 90%, horizontal section, electrolytic etching)

Fig. 5. Result of Hunter-type rotating bending fatigue test (1.0)

3. Mechanical properties of developed wire

3-1 Tensile strength Figure 4 shows the relationship between wire diam-

3-3 Heat resistance (high-temperature tensile strength and high-temperature sag resistance) Figure 6 shows the high-temperature tensile strengths of the developed wire and conventional wires with 1.0 mm wire diameter. In all steel wires, tensile

26 Development of High-tensile-strength Stainless Steel Wire

strength decreases as temperature rises. However, while the rapid fall of tensile strength is observed at above 400C in Type 302 and Type 631, the rapid change is not seen in the developed wire at 600C and under. This means that the developed wire has a high level of hightemperature tensile strength. High-temperature sag resistance is one of the properties required for heat-resistant springs. High-temperature sag is a phenomenon in which the free length of a spring changes after a load is applied under high temperature. It causes a problem that predetermined stress or predetermined displacement cannot be obtained. The high-temperature sag resistance of the developed wire and conventional wires are shown in Fig. 7. The illustration in the upper part of Fig. 7 is the schematic diagram of sag resistance test. Strain was added to the specimens so that a torsion stress of 500 MPa was

applied at room temperature. After the specimens were kept in an electric furnace for 24 hours at 400C under a constant strain, they were cooled to room temperature, and their residual strains were measured. As is clear from Fig. 7, the high-temperature sag resistance of the developed wire is equivalent to or higher than that of the Type 631 wire. 3-4 Polarization curve (corrosion resistance) Figure 8 shows the polarization measurement results of the developed wire and conventional wires with 1.0 mm wire diameter. As is clear from the result, the critical current density of the developed material is lower than those of the conventional materials. Moreover, when the potential is scanned in the positive direction, there is a point at which the current (about 0) increases suddenly. This indicates that the passivation surface layer formed under an acid atmosphere was torn as the voltage increased. The potential at which the current starts to rise rapidly is called the pitting potential,

3000
Developed wire Type 302 Type 631

Electric current density (A/cm2)

2500 Tensile strength / MPa

2.0

Solution: 5%H2SO4+3%NaCl Test temp.: 35C Sweep rate: 2 V/hr

2000

1.0

Type 302 Type 631 Type 316 Developed wire

1500

1000

0.0 -1.0 -0.5 0.0 0.5 1.0

500

Electric potential (V vs SCE)

200

400 Test temp. / C

600

800

Fig. 8. Results of polarization measurement

Fig. 6. High-temperature tensile strength of developed wire and conventional wires

Developed wire In an electric furnace at 400C (High) Sag resistance (Low) Residual shear strain (amount of sag) /% Fix one end 0.20 Twist at a constant strain Schematic diagram of heat resistance test 0.10 Type 302 100mm

0 Type 302 Type 631 Specimen(1.0) Developed wire

Type 631

1mm

Fig. 7. High-temperature sag resistance of developed wire and conventional wires (test temp.: 400C, strain: 500 MPa torsion stress at R.T., time: 24 hours)

Photo 2. Appearance photographs after salt-spray fog test (at 35C for 500 hours, 5% salt solution)

SEI TECHNICAL REVIEW NUMBER 60 JUNE 2005 27

and it is supposed that this value is high when corrosion resistance is high. This measurement data clearly indicates that the pitting potential of the developed wire is higher than that of the conventional corrosion-resistant Type 316 stainless steel wire. The appearances of the developed wire and conventional stainless steel wires after the salt-spray fog test (at 35C for 500 hours, 5% salt solution) are shown in Photo 2. Unevenness that is at a level of corrosion pitch is not observed in all specimens. However, the comparison of the discoloration due to rust shows that the extent of discoloration is greater in the order of Type 631>Type 302> the developed material, and this result proves that the developed wire has a high corrosion resistance.

4. Conclusions
From the above evaluation results, the relationship between tensile strength and corrosion resistance of the developed wire and conventional wires are described in schematic form in Fig. 9. The developed wire has a tensile strength equivalent to that of conventional highstrength stainless steel Type 631, and has a corrosion resistance equivalent to that of conventional high-corrosion resistant stainless steel Type 316. That is, unlike conventional stainless steel wires, the developed wire allows both high corrosion resistance and high tensile strength to exist at a higher dimension. The developed wire is commercialized as Super DOLCE by Sumitomo (SEI) Steel Wire Corp. from the end of 2003. The developed wire is expected to be used widely in the fields of corrosion resistance and high tensile strength.

Photo 3. Heat-resistant springs for exhaust systems of cars

(1) (2) (3) (4) (5) (6)

References C.Bathias, Pelloux: Trans Met. 4(1973)5, p.1265. French: Trans ASTM 21(1933)p.899. Koyama, et al.: JSSR Transactions Vol.25(1985), P.1-7. Research committees in JSSR organization: JSSR Transactions Vol.46(2001), P.41-65. K.J.Irvin et al.: JISI, 199(1961), 153. Murayama et al.: CAMP-ISIJ, Vol.12(1999)p.458.

Titanium Developed wire State of solution treatment

Corrosion resistance

Type 316

Dolce

Type 302 Type 631

Type 430 Type 410 Piano wire 1000MPa 1500MPa Tensile strength at R.T. 2000MPa

Fig. 9. Relationship between tensile strength and corrosion resistance

28 Development of High-tensile-strength Stainless Steel Wire

Contributors

H. IZUMIDA
Assistant Manager, Metals & Inorganic Materials Technology R&D Department, Electronics & Materials R&D Laboratries

N. KAWABE
Assistant General Manager, Metals & Inorganic Materials Technology R&D Department, Electronics & Materials R&D Laboratries

S. TAKAMURA
Group Leader, Precision Wire Engineering Department, Precision Wire Division, Sumitomo (SEI) Steel Wire Corp.

H. MORITA
Senior Engineer, Precision Wire Engineering Department, Precision Wire Division, Sumitomo (SEI) Steel Wire Corp.

T. MURAI
Chief Engineer, Precision Wire Engineering Department, Precision Wire Division, Sumitomo (SEI) Steel Wire Corp.

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