JP6259579B2 - High-strength stainless steel wire, high-strength spring, and method of manufacturing the same - Google Patents

Description

  The present invention relates to a high-strength stainless steel wire that is used as a heat-resistant steel wire material such as a heat-resistant spring or a heat-resistant rope, such as an automobile engine exhaust system component or an electrical component that requires high strength characteristics. The present invention is a precipitation hardening quasi-type that has a metal structure of an austenite (γ) phase + work-induced martensite (α ′) phase and that has fine precipitates controlled by cold working and aging heat treatment by adding Mo, Al, etc. The present invention relates to a stable austenitic high-strength stainless steel wire, particularly a high-strength heat-resistant stainless steel wire, a high-strength spring using the same, particularly a high-strength heat-resistant spring, and a method for producing the same.

  Conventionally, high strength stainless steel wires such as piano wire, SUS304, SUS301, etc. have been used as high strength spring materials. However, although the conventional spring product has sufficient strength at normal temperature, for example, in the case of a piano wire, the heat resistance sagability is 0.01 in terms of residual shear strain, which will be described later, in the warm temperature range of about 100 ° C. to 300 ° C. % Was drastically reduced to more than% and was subject to application restrictions. This tendency is the same when stainless steel wires are used. For this reason, for example, austenitic stainless steel wires to which Mo, Al, Ti, etc. are added have been proposed (Patent Documents 1 and 2). Although the heat sagability is improved by such component adjustment, conversely, the amount of work-induced martensite is small, the tensile strength is less than 1800 MPa, and the strength is insufficient, which is not sufficient as a product for high-strength springs.

  A martensitic stainless steel using precipitation hardening of Mo, Al, etc. has also been proposed (Patent Document 3). However, this stainless steel has a high C and is already martensitic after heat treatment, so it is inferior in workability, and cannot be expected to have a large work hardening, and is not sufficient as a high-strength spring product.

  Furthermore, a high strength precipitation hardening austenitic steel using precipitation hardening of Mo, Al, Cu, etc. has been proposed (Patent Document 4). However, since this stainless steel contains a large amount of Ni and Cu, the material cost is high. Further, this stainless steel suppresses work-induced martensite, and it is difficult to satisfy heat sagability.

  Thus, conventional high-strength stainless steel wires for springs cannot have both strength and heat resistance.

Japanese Patent No. 4163055 Japanese Patent Laid-Open No. 10-68050 Japanese Patent No. 3482053 Japanese Patent No. 4327601

  The problem to be solved by the present invention is a high-strength stainless steel that has sufficient high-strength characteristics and heat-resisting properties even under the temperature environment, especially on the premise of heat-resistant materials that are frequently used in the warm region, especially for heat-resistant springs. It is to provide a wire, a high-strength spring using the steel wire, and a manufacturing method thereof.

As a result of various studies to solve the above problems, in the precipitation hardening type metastable austenitic stainless steel wire,
1) Control the austenite stability and form a large amount of work-induced martensite (ausformed martensite) structure from austenite-based structure by strong working such as cold drawing before forming into a spring shape. Improving strength while maintaining ductility,
2) Ensuring ductility while maintaining strength by controlling in the range of 0.05 ≦ (C + N) ≦ 0.13,
3) Addition of Al and Mo, and by further dispersing NiAl and Mo-based fine compounds uniformly in the strongly-worked work-induced martensite structure near the steel wire surface layer by a combination of strong working and aging heat treatment conditions The conclusion was reached that it was effective to significantly increase the strength and heat sagability, and the present invention was obtained.

That is, the present invention has the following configuration.
(1) In mass%, C: 0.02 to 0.12%, and N: 0.005 to 0.03%, and 0.050% ≦ (C + N) ≦ 0.13%, Si: 0.1 to 2.0%, Mn: 0.1 to 2.0%, Ni: 6.8 to 9.0%, Cr: 12.0 to 14.4%, Mo: 1.0 to 3. High-strength stainless steel wire containing 0% and Al: 0.5-2.0%, and having excellent heat sag due to aging heat treatment composed of the balance Fe and unavoidable impurities And
The processing induced martensite generation index MdS value represented by the formula (1) is 15 to 60, and the processing induced martensite amount in the matrix is 80 to 99 vol. %, A high-strength stainless steel wire having a tensile strength of 1800-2200 MPa.
MdS = 551-462 (C + N) -9.2Si-8.1Mn-29 (Ni + Cu) -13.7Cr-18.5Mo (1)
However, the element symbol in a formula means content (mass%) of the said element.
(2) By mass%, V: 0.01 to 1.0%, Nb: 0.01 to 1.0%, Ti: 0.01 to 1.0%, W: 0.05 to 2.0 %, Ta: 0.05% to 2.0%, containing at least one kind, high strength stainless steel wire according to (1) above.
(3) It is characterized by containing at least one of Cu: 0.8% or less, Co: 0.1-2.0%, B: 0.0005-0.015% by mass%. The high-strength stainless steel wire according to (1) or (2).
(4) By mass%, further containing at least one of Ca: 0.0005 to 0.01%, Mg: 0.0005 to 0.01%, REM: 0.0005 to 0.1% The high-strength stainless steel wire according to any one of (1) to (3) above.
(5) When the stainless steel wire is held for a distance of 100 times as long as its equivalent wire diameter, and a torsion test in which one end of the stainless steel wire is twisted and rotated, the twist value that leads to breakage without vertical cracking is The high-strength stainless steel wire according to any one of (1) to (4), which has a high twisting characteristic of 5 times or more.
(6) the (1) chemical composition, strain-induced martensite amount of any one of - (4), and satisfies the MdS value, tensile strength Ri 2100~2600MPa der, particle size 50nm following NiAl A high-strength stainless steel wire characterized by comprising fine compound particles of the system .
(7) The yield strength ratio {(σ _0.2 / σ _B ) × 100} between the tensile strength (σ _B ) and its 0.2% yield strength (σ _0.2 ) is 80 to 95%, and is used for a heat resistant spring. The high-strength stainless steel wire according to any one of the above (1) to ( 5 ), which is used in the manufacturing process.
(8) The strength ratio {(σ _0.2 / σ _B ) × 100} between the tensile strength (σ _B ) and its 0.2% yield strength (σ _0.2 ) is 80 to 95%, and is used for heat resistant springs The high-strength stainless steel wire according to (6).
( 9 ) The stainless steel wire according to the above (6), the residual shear strain represented by the formula (2) at an environmental temperature of 200 ° C. is ε ≦ 0.008%. A high-strength spring excellent in heat sag resistance, comprising NiAl fine compound particles having a diameter of 50 nm or less.
Residual shear strain ε = {8ΔPD / πd ³ G} × 100 (2)
Where ΔP: load loss (N), D: center diameter of spring (mm), d: equivalent wire diameter of steel wire (mm), G: transverse elastic modulus of steel wire (N / mm ² )
( 10 ) The manufacturing method according to any one of (1) to (5) and (7) , wherein the processing is performed by performing 60 to 90% cold working on a predetermined equivalent wire diameter after a solution heat treatment. After the stainless steel wire is formed into a predetermined spring shape, it is further subjected to an aging heat treatment at a temperature of 300 to 600 ° C. to precipitate NiAl-based fine compound particles having a particle size of 50 nm or less in the steel wire matrix. A method for producing a high-strength spring with excellent heat resistance, characterized in that a high-strength spring having a residual shear strain represented by the formula (2) at an environmental temperature of 200 ° C. is ε ≦ 0.008% .
Residual shear strain ε = {8ΔPD / πd ³ G} × 100 (2)
Where ΔP: load loss (N), D: center diameter of spring (mm), d: equivalent wire diameter of steel wire (mm), G: transverse elastic modulus of steel wire (N / mm ² )
(11) the following equation (3) high-strength spring manufacturing method having excellent heat fatigue resistance according to aging heat treatment factors and characterized by applying the aging heat treatment at 100 to 10000 (10).
Aging heat treatment factor = {temperature (° C.) × treatment time (min)} / 2√ {equivalent wire diameter of spring (mm) × deployed length (mm)} (3)

  The precipitation hardening type high-strength stainless steel wire excellent in heat sag resistance according to the present invention has a high work-induced martensite (α ′) amount and a predetermined tensile strength at the wire drawing stage. In addition, the high-strength stainless steel wire of the present invention is formed into a spring shape and then subjected to an aging heat treatment to promote formation of fine compounds, particularly precipitation of fine compounds uniformly dispersed in the steel wire surface layer. It is possible to impart high strength and heat sagability particularly in a warm region. As a result, it is possible to provide a high-strength spring product having high strength and excellent heat sagability that has been difficult to achieve at the same time. Therefore, the high-strength stainless steel wire of the present invention is suitable for high-strength springs that require particularly strict quality characteristics.

  In addition, according to the invention of the spring manufacturing method, it can be carried out within the range of normal low-temperature heat treatment, and can be carried out stably without any special cost increase due to continuation.

FIG. 1A shows an example of an enlarged photograph of a fracture surface by a torsion test. FIG. 1A shows a good torsion fracture surface, and FIG. 1B shows a fracture surface torsionally cracked. Explanatory drawing explaining the measuring method of a spring characteristic. The microscope picture which shows an example of the production | generation state of the precipitation compound by aging heat processing. FIG. 4A is an example of a diagram showing changes in tensile strength with aging heat treatment temperature, and FIG. 4B is a diagram showing changes in residual shear strain characteristics.

As described above, the stainless steel wire of the present invention is
% By mass, C: 0.02 to 0.12%, and N: 0.005 to 0.03%, and 0.05% ≦ (C + N) ≦ 0.13%, Si: 0.1 -2.0%, Mn: 0.1-2.0%, Ni: 6.8-9.0%, Cr: 12.0-14.4%, Mo: 1.0-3.0%, And Al: 0.5 to 2.0%, composed of the balance Fe and inevitable impurities, and a processing-induced martensite (α ′) production index represented by the formula (1) (hereinafter simply referred to as “production index”) The MdS value is 15-60,
In the matrix, 80-99 vol. It is a high-strength stainless steel wire excellent in heat sag resistance, characterized in that it contains a processing-induced α ′ amount of 1% and has a tensile strength of 1800-2200 MPa. The high-strength stainless steel wire of the present invention is particularly suitable as a high-strength heat-resistant stainless steel wire, for example, for use in a spring wire, particularly in a warm region where the environmental temperature is 100 to 300 ° C.

MdS = 551-462 (C + N) -9.2Si-8.1Mn-29 (Ni + Cu) -13.7Cr-18.5Mo (1)
However, the element symbol in a formula means content (mass%) of the said element. In addition, for an element that does not contain an element necessary for the calculation or whose content is unknown, 0 is substituted as the content of the element.

The form is not particularly limited, and for example, it is frequently used as a thin wire for secondary processing of, for example, a wire diameter of 6 mm or less, more specifically about 0.05 to 3 mm as a normal wire, and the shape is also a round wire. In addition, for example, it can be used as a non-circular wire such as a flat wire or a square wire. However, the present invention is not limited to this and can be applied in various forms. As described above, since the stainless steel wire of the present invention also includes a wire having a non-circular cross-sectional shape, the wire diameter display in that case is, for example, an equivalent wire diameter (d calculated from its arbitrary cross-sectional area) (d ).
In this embodiment, the description will be focused on the case where the round wire is used as a target, but instead of this, for example, a rolling process or a combined process combined with the wire drawing process may be employed.

  Further, the stainless steel wire has a precipitation hardening function for precipitating and distributing fine compound particles in the matrix by aging heat treatment performed in the final stage. In the present invention, precipitation elements such as Al and Mo are added to the composition so that the precipitation hardening function is exhibited, and N and C are added in appropriate amounts. By uniformly dispersing and precipitating NiAl, Mo-based compound particles in the work-induced martensite phase in the vicinity of the steel wire surface layer that has been strongly processed under the drawing conditions such as cold drawing and cold rolling, This makes it possible to provide high-strength heat-resistant spring products that are strong and have excellent heat resistance.

  In general, it is well known that austenitic stainless steel is work-hardened by cold working, and one of the factors is the influence of work-induced martensite phase induced by working. However, the amount of induced generation varies greatly depending on the balance of the component composition of each element constituting this and the processing conditions. For example, with a stable SUS316 stainless steel, the amount of induced martensite produced is only a few percent even when normal processing is performed. On the other hand, in the present invention, the production of martensite induced by cold working is actively promoted, the production amount is adjusted to be increased to 80 to 99 vol%, and the tensile strength of the steel wire itself is adjusted. One of the features is that the strength is increased to 1800 to 2200 MPa in a cold working state such as wire drawing.

And as a further means of improving the heat-resistant sagability in the spring product together with its high strength characteristics, the composition of each component is set so as to promote the production of the amount of work-induced martensite that becomes the precipitation nuclei of fine precipitates. Stainless steel adjusted so that the generation index MdS value is 15 to 60 is drawn as a balance index under specific processing conditions.
The MdS value means a temperature at which 50% of the structure is transformed into a martensite phase when 30% tensile deformation is applied to the stainless steel. This is to be grasped in relation to the component elements.

  Thereby, the amount of work-induced martensite at the time of wire drawing can be increased, which contributes to higher strength.

  The reason why the MdS value is set in the above range in the present invention is that when the MdS value is less than 15, the stabilization of the austenite phase increases, and the amount of work-induced martensite after wire drawing decreases to less than 80 vol%, Not only does it become difficult to increase the strength, but the amount of precipitation strengthening associated with the aging heat treatment at 300 to 600 ° C. is also reduced, and the heat sagability is also deteriorated. On the other hand, when the MdS value exceeds 60, excess work-induced martensite exceeding 99 vol% is generated by a predetermined wire drawing process, the toughness after wire drawing is lowered, and the productivity is inferior. More preferably, the range of the MdS value is 20-50.

  By adjusting the components as described above, the stainless steel wire of the present invention can achieve a work-induced martensite amount of 80 to 99 vol%, and each characteristic can be improved. In other words, if the amount of processing-induced α ′ (martensite) in the matrix is less than 80 vol%, the necessary high strength characteristics cannot be obtained even if aging heat treatment is performed on the spring product, and conversely if it exceeds 99 vol%. Lack of organizational stability and hardly satisfy corrosion resistance and toughness. It is also expected to be inferior in spring fatigue resistance. The amount of processing-induced martensite is preferably 83 vol% or more, and more preferably 85 vol% or more. Further, the processing induced martensite amount is preferably 95 vol% or less, more preferably 90 vol% or less.

[Measurement of martensite content]
For the measurement of the amount of martensite, various methods such as a method using a ferrite scope, a magnetic method, and a method using X-rays can be employed for a specimen arbitrarily collected from a stainless steel wire. For example, the latter magnetic method For example, the Japan Iron and Steel Institute “Iron and Steel” (81-S1163) and many others are described.

In the present invention, the processing-induced α ′ amount was calculated using the following equations (4) to (6) after measuring the saturation magnetization value of the wire at 1.0 × 10 ⁴ Oe with a DC magnetometer.
Processing-induced α ′ amount (vol.%) = Σ _s / σ _s (bcc) × 100 (4)
σ _s : Saturation magnetization value (T), σ _s (bcc): 100% α ′ transformation saturation magnetization value (calculated value)
σ _s (bcc) = 1.83-0.030Cr _eq (5)
Cr _eq = Cr + 1.8Si + Mo + 0.5Ni + 0.9Mn + 3.6 (C + N) + 1.25P + 2.91S + 1.85Al (6)

Thus, the stainless steel wire has a high strength characteristic in which the tensile strength (σ _B ) in the cold drawn state is 1800 to 2200 MPa. The tensile strength can be measured, for example, according to JIS-Z2241, and if the property is less than 1800 MPa, the strength property cannot be significantly improved even by subsequent aging heat treatment, and if the strength is increased to exceed 2200 MPa, the spring There are problems in terms of quality, such as increasing the variation of the spring shape at the molding stage and easily inducing brittle fracture. More preferable tensile strength is 1900-2100 MPa.

On the other hand, when the steel wire that has been cold-drawn according to the present invention is subjected to an aging heat treatment, the strength characteristics are further improved dramatically, and a preferable value of 2100 to 2600 MPa in tensile strength is obtained depending on the conditions of the aging heat treatment. It is done. Therefore, for applications where the spring-shaped product is used in a straight state, such as for a microshaft, a straight spring treatment is performed following the wire drawing process, and this is subjected to continuous aging heat treatment as it is to provide a long spring material. It can also be. This can further enhance the mechanical properties in the wire state. In addition, these processes can be performed continuously.
The present invention includes other forms of stainless steel wire that has been subjected to aging heat treatment after cold drawing. The tensile strength in that case is 2100-2600 MPa, the more preferable lower limit of tensile strength is 2200 MPa, and the more preferable upper limit is 2500 MPa. The aging heat treatment conditions for the steel wire can be set as appropriate so that the tensile strength after the aging heat treatment is in the above range, but as an example, aging heat treatment conditions after spring forming can be mentioned as described later. .

Further, the yield strength ratio {(σ _0.2 / σ _B ) × 100} to the 0.2% yield strength (σ _0.2 ) obtained together with the tensile strength (σ _B ) is preferably 80 to 95%. Such a stainless steel wire is effective as a heat-resistant spring material that has high strength and improves fatigue fracture. If the yield ratio is less than 80%, the predetermined elastic characteristics cannot be obtained, and if it exceeds 95%, the yield during severe spring processing may be adversely affected. A more preferable lower limit of the yield strength ratio is 83%, and a more preferable upper limit is 91%.

[Torsion test 1]
Further, as another test method for evaluating the spring workability, it can also be performed with a twist characteristic by the following twist test. The twisting property is the number of times until a test piece taken from the stainless steel wire is held for a distance of 100 times the equivalent wire diameter and broken by twisting and rotating one end side. For example, in the case of a cold-worked stainless steel wire, if the number of twists (twist value) has a high twist characteristic of 5 times or more, for example, about 5 to 10 times or more without vertical cracking It can be widely used for various spring products. And in the steel wire which has been subjected to such aging heat treatment, and in which the yield strength ratio exceeds 95%, the twisting property is limited to a few times or is liable to cause vertical cracks. For this reason, for example, as a coil spring, the yield may be adversely affected in severe spring processing in which the ratio D / d of the wire diameter (d) to the average coil diameter (D) is 4 times or less. That is, although spring forming is possible regardless of the twist value, a steel wire showing a twist value of 5 times or more without vertical cracking is preferable for spring forming, and more preferably 6 times or more.

[Torsion test 2]
This torsion test is described in, for example, JIS-G4314, and the toughness of the stainless steel wire can be observed by observing the fracture surface in this torsion test.
FIG. 1 shows an example thereof. FIG. 1A shows a substantially uniform fracture surface, whereas FIG. 1B shows a torsion crack in a part of the transverse cross section, indicating that a brittle fracture occurred. In the case of a good fracture surface like the former, the number of twists can be satisfied.

Next, the reasons for limiting the constituent elements of the stainless steel wire targeted by the present invention will be described.
In the present invention, unless otherwise noted, the element content means mass%.

  C is added in an amount of 0.02% or more (the following is all by mass%) in order to obtain high strength after wire drawing. However, if added over 0.12%, not only does it become sensitized and the corrosion resistance deteriorates, but also the manufacturability deteriorates, so the upper limit is made 0.12%. Preferably, it is less than 0.10%, and a more preferable range is 0.04 to 0.09%.

  N is an element that contributes to strength, and forms carbonitride and has the effect of refining crystal grains of the material before cold working during solution heat treatment, so 0.005% or more is added. However, if added over 0.03%, formation of coarse nitrides such as AlN and deterioration of ductility occur, and the manufacturability deteriorates remarkably. Therefore, the upper limit is made 0.03%. The minimum with preferable N content is 0.01%, and a preferable upper limit is 0.025%.

  C and N are both interstitial elements, and have the effect of generating strain, forming solid solution strengthening that acts on strengthening, forming a Cottrell atmosphere and fine carbonitride, and fixing dislocations in the metal structure. In order to obtain these effects, 0.05% or more of C + N is added. However, if C + N exceeds 0.13%, ductility deteriorates, so the upper limit is made 0.13%. A preferable range is 0.08 to 0.11%.

  Si is deoxidized, so 0.1% or more is added. However, the addition exceeding 2.0% not only saturates the effect but also deteriorates manufacturability, so the upper limit is made 2.0%. A preferable range is 0.3 to 1.0%.

  Mn is added in an amount of 0.1% or more for deoxidation. However, if added over 2.0%, the corrosion resistance is deteriorated and the processing-induced α 'amount is reduced, not only the strength is lowered, but also the heat sag is deteriorated, so the upper limit is made 2.0%. A preferable range is 0.5 to 1.5%.

  Ni is added in an amount of 6.8% or more in order to ensure the ductility of the material and obtain an appropriate amount of work-induced martensite by wire drawing. However, if added over 9.0%, the MdS value decreases, the amount of work-induced martensite decreases, the strength decreases, and the heat sag resistance also deteriorates. Therefore, the upper limit is made 9.0%. A preferable range is more than 7.0% and 8.5% or less, more preferably 7.5 to 8.2%.

  Cr is added in an amount of 12.0% or more to ensure corrosion resistance and to obtain an appropriate amount of work-induced martensite. However, if it is added in excess of 14.4%, the MdS value is lowered and the amount of work-induced martensite is lowered, not only the strength is lowered, but also the heat sagability is degraded. Therefore, the upper limit is made 14.4%. A preferable range is 13.0 to 14.0%.

  Mo dissolves in the austenite matrix and increases the hardness of the matrix, and further reduces heat sag due to temperature rise during use. Furthermore, it is effective for finely depositing Mo-based fine metal clusters in work-induced martensite by aging heat treatment at 300 to 600 ° C. when manufacturing springs, thereby increasing strength and improving heat resistance. It is an element, and 1.0% or more is added. However, if added over 3.0%, the effect is saturated and the MdS value is lowered, so that the amount of work-induced martensite is lowered and the strength is lowered, and the heat sagability is also degraded. Therefore, the upper limit is made 3.0%. A preferable range is 1.5 to 2.6%, more preferably 1.7% to 2.3%.

  Al is used to improve heat resistance and sag resistance by finely precipitating fine NiAl-based intermetallic compounds in work-induced martensite by aging heat treatment, for example, at 300 to 600 ° C. when manufacturing springs. It is an effective element and 0.5% or more is added. However, even if added over 2.0%, the effect is saturated and manufacturability deteriorates. Therefore, the upper limit is made 2.0%. A preferable range is 0.7 to 1.5%, more preferably 0.9% to 1.2%.

  The stainless steel wire is composed of these constituent elements, and the components are adjusted so that the MdS value is 15 to 60, and the balance Fe and some (for example, O: 0.001 mixed in the production of normal stainless steel) -0.01%, Zr: 0.0001-0.01%, Sn: 0.001-0.1%, Pb: 0.00005-0.01%, Bi: 0.00005-0.01%, Zn: 0.0005 to 0.01%, etc., including materials contained in raw materials and refractories, etc. in total of 2.0% or less) is allowed to be contained.

  In addition to the above constituent elements, the present invention may further contain any of the following third elements.

  The first group includes V, Nb, Ti, W, and Ta. These elements each form fine carbonitrides to refine crystal grains and increase strength, and also improve heat resistance. Contributes to The effect is as follows: V: 0.01 to 1.0% (preferably 0.05 to 0.6%), Nb: 0.01 to 1.0% (preferably 0.05 to 0.4%), Ti: 0.01 to 1.0% (preferably 0.02 to 0.2%), W: 0.05 to 2.0% (preferably 0.05 to 0.5%), Ta: 0.0. It becomes possible by addition of any one or more of 0.5 to 2.0% (preferably 0.1 to 0.5%), but if added exceeding each upper limit, the carbonitride becomes coarse and manufacturability Reduce. Therefore, it is more preferable to carry out the operation within the preferable range described above.

  Similarly, the second group enhances incidental effects such as corrosion resistance, toughness, and workability of the stainless steel wire, and allows addition of any of the following elements as necessary.

  Cu is an element effective for improving the corrosion resistance, and is added as necessary. However, if added over 0.8%, the work hardening becomes small and softens, and also the heat sag is reduced, so the upper limit is made 0.8% or less. A preferable range is 0.1 to 0.6%.

  Co is added in an amount of 0.1% or more as necessary to ensure ductility and improve heat resistance. However, if added over 2.0%, the strength is lowered and the heat resistance is deteriorated, so the upper limit is made 2.0%. A preferred range is 0.5% to 1.5%.

  Further, B is added in an amount of 0.0005% or more as necessary in order to improve the hot manufacturability and toughness of the stainless steel. However, if added over 0.015%, boride is generated, and conversely, the toughness is lowered and the manufacturability is deteriorated. Therefore, the upper limit is made 0.015%. A preferred range is 0.001 to 0.01%.

  Further, Ca, Mg, and REM are selected as the third group. These elements can be contained for deoxidation, and if necessary, Ca: 0.0005 to 0.01%, Mg: 0.0005 to 0.01%, REM: 0.0005 to 0.1% Add one or more. However, if it is added in excess of each upper limit, coarse inclusions are produced and productivity is lowered.

  Moreover, in this invention, it is also preferable to adjust from a viewpoint of hot workability and ductility by making P and S into a specific range as another element. As the allowable range, P is 0.015 to 0.045% and S is 0.0001 to 0.01%. However, excessive reduction causes cost increase. Then, it becomes a factor of quality deterioration, such as a nonmetallic inclusion. Each of these groups can be added alone, or any two or more groups can be selected and added.

  The stainless steel wire of the present invention configured as described above is, for example, cast a slab having the predetermined component composition, hot-rolled into a lot wire, and then cold work or solution heat treatment between the processes. It is possible to obtain a stainless steel wire having a target wire diameter by reducing the diameter while repeating the above. The cold working includes the wire drawing and rolling, and for example, continuous wire drawing using a drawing die or a roller die, or rolling using a rolling roller is adopted. In particular, the cold working after the final solution heat treatment is adopted. In the inter-processing, the total processing rate is preferably 60 to 90%. As a result, it is possible to realize the processing-induced α ′ amount and tensile strength in the matrix defined in the present invention, and it is possible to realize the twist value and yield strength ratio of the stainless steel wire similarly defined in the present invention. Preferably, the final cold total working rate is within a relatively suppressed range of about 65 to 85%, more preferably 70 to 83%.

  Further, as a more preferable form of these cold working, for example, the processing temperature is adjusted so that the surface temperature of the steel wire on the final finishing die and the final roll entrance is 70 ° C. or less (preferably 10 to 50 ° C.), and the final It is preferable that the processing rate in the finishing die or final rolling is 20% or less, preferably 10% or less, and surface layer uniform strong processing is performed. Thereby, heat-resistant settling property can further be improved.

  The mechanism by which the heat-resistant sagability is further improved by controlling the surface temperature of the steel wire on the entry side of the final finishing die and the processing rate in the final finishing die or final rolling is not known at this time. However, when the inventors controlled these conditions and when not controlled, the steel wires were each subjected to aging heat treatment, and after aging heat treatment, the vicinity of the surface layer of the steel wire was observed and compared, and the above conditions were controlled. In the case, it was found that the fine compound was uniformly distributed. From this, it can be inferred that the more even precipitation of the fine compound in the vicinity of the steel wire surface layer affects the further improvement of the heat sagability.

Further, if necessary, it is also effective to improve the yield by imparting Ni plating or the like to the surface of the wire to enhance the lubricity.
In addition, the said process rate is shown by the change rate of the cross-sectional area of this stainless steel wire accompanying the process, and is calculated by following Formula.
Processing rate (%) = {(cross-sectional area before processing−cross-sectional area after processing) / cross-sectional area before processing} × 100

[Spring product manufacturing method]
Next, the invention relating to the spring product of the present invention will be described. The spring product is formed by the stainless steel wire having any one of the above-described structures into various shapes such as a coil spring, a torsion spring, and a linear spring. Furthermore, the spring characteristics can be improved by performing an aging heat treatment described later. Since the spring characteristics are premised on the use in the warm region in the present invention, the ambient temperature is set based on 200 ° C. in particular, and the residual shear strain at that temperature is 0.008% or less. .

  As shown in FIG. 2, for example, as shown in FIG. 2, the spring characteristic is deformed to a height corresponding to an arbitrary stress (for example, 400 MPa), heated and held under predetermined environmental test conditions, taken out, and tested. It may be indicated by the load loss obtained by dividing the load difference of the load load corresponding to the spring height before and after by the load load before the test.

  However, in this method, the value varies depending on the spring shape and is not necessarily standard. Therefore, in the present invention, the residual shear strain rate is used instead, and the ambient temperature is 200 ° C. as described above. Is set.

  The residual shear strain ε is defined as the shear strain rate that remains when a given spring is deformed by applying a certain load or torque, and then the load or torque is removed. 7). That is, for example, in the case of a compression coil spring, the predetermined compression load is applied to the coil spring shown in FIG. 2, and the spring height is displaced from S to S1. While maintaining this state, it is heated to 200 ° C. Then it is cooled to room temperature and the compression load is released. The spring height when the compression load is released is S0, and the load loss (ΔP) is calculated using the load when the spring height returns from S1 to S0. Specifically, when the spring height S1 when the compression load shown in FIG. 2 is applied is set to a predetermined set height, the spring having the height S0 after being heated and cooled with the predetermined compression load, Measure the load necessary to displace each spring up to the height of S1 with a spring of a height S before heating with a compression load of, and calculate the difference between the necessary loads. This is the load loss (ΔP). Then, the residual shear strain ε is calculated from the following equation (7) using the load loss. From this residual shear strain ε, heat sagability can be evaluated.

Residual shear strain ε = {8ΔPD / πd ³ G} × 100 (7)
△ P: Load loss (N)
D: Center diameter of the spring (mm) ··· As shown in Fig. 2, the distance between the center points of the opposing steel wires.
d: Equivalent wire diameter of steel wire (mm)
G: transverse elastic modulus of steel wire (N / mm ² ) (MPa)

  In an excellent spring product having a residual shear strain of 0.008% or less, there is an advantage that, for example, a heat setting process, which is conventionally performed in order to reduce functional deterioration during use, can be omitted, and a more preferable residual shear strain is 0. .005% or less is set.

  In order to enhance such spring characteristics, for example, the spring product is heat-treated at a predetermined temperature in advance, and an aging heat treatment is performed to precipitate fine compound particles uniformly in the structure of the stainless steel wire, particularly in the vicinity of the surface layer. Is recommended. In the aging heat treatment, for example, a heating time of about 3 minutes to 10 hours is set in a temperature range of 300 to 600 ° C. Thereby, for example, a fine and hard compound as shown in FIG. 3 can be formed and distributed, and as a result, the residual shear strain of the high-strength spring defined in the present invention can be realized. It is desired that the compound precipitation to be formed is adjusted in advance so that the stainless steel wire is particularly strongly processed into a precipitation hardening type.

As a more preferable condition for the aging heat treatment, for example, as shown in the aging heat treatment factor of the following formula (3), the set temperature and the heating time are related depending on the volume and form of the spring product. Is preferably adjusted to 150 to 3000.
Aging heat treatment factor = {temperature (° C.) × treatment time (min)} / 2√ {equivalent wire diameter of spring (mm) × deployed length (mm)} (3)
The developed length is the total length of the stainless steel wire constituting the spring product, and by such aging heat treatment, the desired compound is precipitated in the matrix, and the material characteristics are improved.

  In that case, if the heating temperature of the aging heat treatment is less than 300 ° C., sufficient compound formation cannot be obtained even when heated for a long time, and if it exceeds 600 ° C., the wire is softened and the strength tends to decrease, so that 400 is more preferable. Treatment at about ~ 580 ° C is recommended. In addition, since the precipitation state of the compound varies depending on the heating time, and the particle size and density change, it is preferable to perform heating for at least 3 minutes. Including the situation, the appropriate range is set by the equation (3). A more preferable appropriate range is 400 to 550 ° C.

  In addition, since the compound is very fine, it is difficult to define its existence in detail in most of the above aging heat treatment condition range, and it can be confirmed with a three-dimensional atom probe or a transmission electron microscope. it can. In particular, since the aging heat treatment temperature is high and the compound grows gradually as it becomes longer, the presence of the compound can be confirmed with a transmission electron microscope under the treatment conditions near the upper limit.

  For example, FIG. 3 shows 600 ° C. × 30 min. The cross section of the stainless steel wire obtained by the aging heat treatment was enlarged at a high magnification, and a fine compound of NiAl having an average particle size of 50 nm or less was precipitated in the martensite matrix at a high density, and the electrons In the line diffraction image, it is also confirmed that the compound has a B2 structure. In addition, the average particle diameter is shown, for example by the average value of the diameter of each compound particle confirmed in the arbitrary observation visual field of this diffraction image, and a more optimal particle diameter is 20 nm or less.

  FIG. 3 a) is a bright-field image of a transmission electron microscope of a thin film of material, showing an image of a work-induced martensite structure. b) shows a diffraction image of the region (a material obtained by Fourier transform of the material). In addition to the BCC structure of processing-induced martensite, the presence of NiAl having a B2 structure as shown in d) can be confirmed. c) shows a dark field image in which only a precipitate of NiAl having a B2 structure is projected. The compound particles tend to be distributed more uniformly by controlling the surface temperature of the steel wire with the final finishing die and the processing rate in the final finishing die or the final rolling.

  As described above, the compound greatly depends on the heating temperature and heating conditions, the processing conditions and constituent elements of the steel wire, and for example, the reaction is accelerated by high-temperature heating or long-time heating, and can be increased in size and density. . Therefore, it is desirable to carry out the treatment while conducting a preliminary test so as to obtain a desired compound formation state.

  Since the spring product obtained by the present invention has high strength and excellent heat resistance, preheating adjustment (heat setting) before using the spring, which has been carried out with other conventionally used stainless steel wires or piano wires, etc. Cost reduction due to omission of the process can be expected, and the use of piano wire as described above is suitable for heat-resistant springs in the warm region where the characteristics are slightly degraded. In addition, its application range is expanded, for example, application to heat-resistant applications for general high-temperature environments of 400 ° C or higher is expected.

  Hereinafter, the present invention will be further described by examples.

<Manufacture of stainless steel wire>
Table 1 shows the chemical components of the stainless steel used as an example, and also shows the comparative materials. In both Tables 1 and 2, numerical values outside the scope of the present invention are underlined.

  Steels of these chemical components are melted in a vacuum melting furnace, cast into a slab of φ178 mm, the slab is made into a steel bar of φ62 mm by hot forging, and then a hot extrusion simulator (heated at 1250 ° C., A wire rod having a diameter of 10.7 mm was obtained by extrusion. Thereafter, solution treatment and pickling were performed, and the wire was drawn to φ5.5 mm to obtain a wire.

  Then, using this as a raw material, it is processed into a soft wire having a wire diameter of 2.2 mm while repeatedly performing cold wire drawing and solution heat treatment, and then into a hard wire having a wire diameter of φ1.0 mm in the final cold wire drawing. Therefore, the final total wire drawing rate was 80%. The processed steel wire has a 1.2 μm thick Ni plating layer formed on the surface, and the surface reduction rate (processing rate) of the final drawing wire dies is 8-25%. This was performed by adjusting the temperature to 0 to 80 ° C.

Each of the example materials according to the present invention can be processed with a small diameter without any problem, and has a tensile strength of 1800 to 2200 MPa (N / mm ² ), a proof stress ratio of 80 to 95%, and a high strength of 5 or more twists. A thin wire was obtained, and the amount of processing-induced martensite was 80 to 95 vol%.

  The tensile strength and 0.2% proof stress are measured according to JIS-Z2241, the martensite amount is measured by the magnetic method described in [Measurement of Martensite Amount], and the twist value is the [Torsion Test 1], [ The results are shown in Tables 3 and 4 above.

<Verification of aging characteristics>
Next, in order to see the change in characteristics of each stainless steel wire due to aging heat treatment, each sample after the final wire drawing of Example 1 having the components shown in Table 1 or Table 2 was cut to a length of 150 mm. Was subjected to an aging heat treatment at 500 ° C. for 30 minutes. The aging heat treatment factor according to the equation (3) is 612.

  And the tensile strength of the steel wire after an aging heat treatment, yield strength, yield strength ratio, twist value, and rigidity were evaluated. The results are shown in Tables 3 and 4 above. The rigidity was evaluated by the torsion pendulum method.

  The steel wires subjected to the aging heat treatment of the example materials according to the present invention had excellent high strength characteristics with a tensile strength of 2100 to 2600 MPa, a proof stress ratio of 80 to 95%, and a rigidity of 77000 MPa or more. As a result of microscopic observation of the arbitrary cross section, a precipitated compound composed of NiAl particles having an average particle diameter of about 3 to 10 nm was confirmed as in FIG.

  In addition, about the twist value, when performing the aging heat processing, the vertical crack generate | occur | produced at the time of twisting 5 times in any steel wire.

<Verification of spring products>
Next, in order to further verify the effect of Example 2, using each stainless steel wire before aging heat treatment, average coil diameter: 7 mm, effective number of coils: 4.5 mm, spring free length: 25 mm, unfolded length : 100 mm compression coil spring was coiled and similarly subjected to aging heat treatment at 500 ° C. for 30 minutes to evaluate the heat resistance of the actual spring product. The heat sagability was measured under the conditions described in [Method for producing spring product] at 200 ° C. under the condition of applying a compressive stress of 600 MPa and holding for 96 hours.

  The results are listed in Tables 3 and 4 above, and it was confirmed that all of the examples have a residual shear strain of 0.008% or less, high strength and excellent heat resistance. On the other hand, in the comparative material, No. Except for 51, the same shear strain characteristics are greatly reduced, and the effect of the present invention is recognized. No. No. 51 had a small residual shear strain, but had insufficient strength.

  About manufacturability, when cracking, disconnection, or breakage occurred during wire rod rolling, wire drawing, or spring processing, it was evaluated as unmanufacturable. The product of the present invention could be manufactured to a spring product without any problem.

<Effect of aging conditions>
Next, in order to see the influence of the aging heat treatment conditions of the stainless steel wire and spring material, the steels A and D of the present invention steel in Table 1 and the AP steel of the comparative steel in Table 2 are referred to as the “stainless steel wire of Example 1”. Before the aging heat treatment manufactured with the steel wire as cold-drawn with a diameter of φ1.0 mm manufactured according to the method described in the above and the steel wire as cold-drawn according to the method described in “Verification of spring products” in Example 3 above. Each of the coil springs was subjected to an aging heat treatment at a temperature of 250 to 650 ° C. for 2 minutes to 10 hours. Then, the tensile strength of the steel wire after the aging heat treatment and the heat sagability of the coil spring were evaluated. The partial results are shown in Table 5 and FIG.

  The tensile strength has a peak especially at a temperature of 450 to 550 ° C., and is somewhat softened at 600 ° C. Similarly, the residual shear strain is almost 0.008% or less. In the temperature range increased up to around 600 ° C., it was recognized that the characteristics were slightly deteriorated. Further, when the aging heat treatment factor was about 150 to 825, the residual strain characteristic was 0.005% or less, which was very preferable.

 Next, the A and D steels listed in Table 1 were drawn by the method described in Example 1 and a soft wire with a wire diameter of φ1.8 mm was used as a raw material, and a metal soap lubricant was applied to the surface. Then, following the thinning to a hard fine wire with a wire diameter of 1.0 mm by a cold wire drawing device, the solid flat wire is finally pressed to a thickness of 0.2 mm by cold rolling with a multi-stage rolling device. Manufactured. In this rolling process, an optimum cooling method was adopted so that the surface temperature of the steel wire on the entrance side of the final finishing roll was 45 ° C.

The total processing rate after the solution heat treatment was 83%, and it was confirmed that there was no trouble such as material cracking or disconnection associated with the multi-stage cold rolling processing, and that there was good workability.
Then, in order to evaluate the characteristics of the spring product using the flat wire, after removing the lubricant adhering to the surface, an aging heat treatment was performed at 500 ° C. for 30 minutes as in Example 2, and the flattening before and after the heat treatment was performed. The characteristics of the lines were evaluated.
The results are shown in Table 6.

Here, the tensile strength was evaluated by the tensile test method in the same manner as in Example 1. Residual shear strain characteristics were evaluated as changes at a return angle when a twist stress was applied to both ends of the flat wire having a predetermined length as a characteristic at a temperature of 200 ° C. as in Example 3.
Further, the residual shear strain of the flat wire was calculated using the load loss, elastic modulus, and cross-sectional area in the same manner as in the case of the spring. In the case of a flat wire, unlike the case of a spring, the load loss is a distance set arbitrarily within a range of, for example, about 5 to 50 times the width of the flat flat wire, and the distance between both ends The difference in the load required to obtain the same twist angle was used for the flat wire twisted, heated and held and released by applying a predetermined stress and the flat wire at the beginning of the test.
As can be seen from this result, the stainless steel flat wire has excellent mechanical properties that can be used as a spring material for, for example, a wave spring. Also, the surface properties were preferable because a bright surface with excellent smoothness was obtained with the fine crystal grains.

  As described above, the high-strength spring using the stainless steel wire according to the present invention increases the amount of work-induced martensite with a tensile strength of 1800 to 2200 MPa in the wire drawing state, and thereafter The spring characteristics associated with aging heat treatment are greatly improved, and the strength and heat resistance are also excellent, so this is applied to, for example, compression, tension coil springs, torsion springs, and other various spring products, It can be used as a spring product with excellent heat resistance.

  Specific applications are suitable for use in heat-resistant springs for household appliances, including spring products used in warm regions such as around the engine of automobiles and electrical systems, etc. For example, it can be used for various high-strength heat-resistant linear products such as for high-strength ropes, heat-resistant shafts, and heat-resistant pins used in heat-resistant and high-temperature regions, and is industrially useful.

Claims (11)

% By mass, C: 0.02 to 0.12%, and N: 0.005 to 0.03%, and 0.050% ≦ (C + N) ≦ 0.13%, Si: 0.1 -2.0%, Mn: 0.1-2.0%, Ni: 6.8-9.0%, Cr: 12.0-14.4%, Mo: 1.0-3.0%, And Al: 0.5% to 2.0%, a high-strength stainless steel wire that has excellent heat sag by being subjected to an aging heat treatment composed of the balance Fe and inevitable impurities,
The processing induced martensite generation index MdS value represented by the formula (1) is 15 to 60, and the processing induced martensite amount in the matrix is 80 to 99 vol. %, A high-strength stainless steel wire having a tensile strength of 1800-2200 MPa.
MdS = 551-462 (C + N) -9.2Si-8.1Mn-29 (Ni + Cu) -13.7Cr-18.5Mo (1)
However, the element symbol in a formula means content (mass%) of the said element.   Further, V: 0.01 to 1.0%, Nb: 0.01 to 1.0%, Ti: 0.01 to 1.0%, W: 0.05 to 2.0%, Ta The high-strength stainless steel wire according to claim 1, comprising at least one of 0.05 to 2.0%.   The composition further comprises at least one of Cu: 0.8% or less, Co: 0.1-2.0%, and B: 0.0005-0.015%. The high-strength stainless steel wire according to 1 or 2.   It is characterized by containing at least one of Ca: 0.0005-0.01%, Mg: 0.0005-0.01%, REM: 0.0005-0.1% by mass%. The high-strength stainless steel wire according to any one of claims 1 to 3.   The stainless steel wire is held for a distance of 100 times as long as its equivalent wire diameter, and when it is subjected to a torsion test in which one end of the stainless steel wire is twisted and rotated, the twist value to break without vertical cracking is 5 times or more. The high-strength stainless steel wire according to any one of claims 1 to 4, which has a high twisting property. Component composition according to any one of claims 1 to 4, deformation-induced martensite amount, and satisfies the MdS value, tensile strength Ri 2100~2600MPa der, fine compounds of the following NiAl-based particle size 50nm A high-strength stainless steel wire characterized by comprising particles . The yield strength ratio {(σ _0.2 / σ _B ) × 100} between the tensile strength (σ _B ) and its 0.2% yield strength (σ _0.2 ) is 80 to 95%, and is used for heat resistant springs. Item 6. The high-strength stainless steel wire according to any one of Items 1 to 5 .   Tensile strength (σ _B ) And its 0.2% yield strength (σ _0.2 ) Yield ratio {(σ _0.2 / Σ _B ) × 100} is 80 to 95%, and is used for heat-resistant springs. The high-strength stainless steel wire according to claim 6. It is comprised with the stainless steel wire of Claim 6, and the residual shear strain represented by (2) Formula in environmental temperature 200 degreeC is (epsilon) <= 0.008%, and the particle size of 50 nm or less is in the matrix of a steel wire. A high-strength spring having excellent heat-sagging characteristics, comprising NiAl-based fine compound particles.
Residual shear strain ε = {8ΔPD / πd ³ G} × 100 (2)
Where ΔP: load loss (N), D: center diameter of spring (mm), d: equivalent wire diameter of steel wire (mm), G: transverse elastic modulus of steel wire (N / mm ² ) The stainless steel wire according to any one of claims 1 to 5 and 7, which is manufactured by performing cold working at a total working rate of 60 to 90% on a predetermined equivalent wire diameter after solution heat treatment. After forming into a spring shape, NiAl-based fine compound particles having a particle size of 50 nm or less are precipitated in the matrix of the steel wire by further performing an aging heat treatment at a temperature of 300 to 600 ° C., and at an environmental temperature of 200 ° C. (2) A method for producing a high-strength spring excellent in heat sag resistance, comprising producing a high-strength spring having a residual shear strain represented by the formula ε ≦ 0.008%.
Residual shear strain ε = {8ΔPD / πd ³ G} × 100 (2)
Where ΔP: load loss (N), D: center diameter of spring (mm), d: equivalent wire diameter of steel wire (mm), G: transverse elastic modulus of steel wire (N / mm ² ) The method for producing a high-strength spring having excellent heat sag resistance according to claim 10 , wherein the aging heat treatment with an aging heat treatment factor of the following formula (3) is 100 to 10,000.
Aging heat treatment factor = {temperature (° C.) × treatment time (min)} / 2√ {equivalent wire diameter of spring (mm) × deployed length (mm)} (3)