JPS60245770A - Fe base alloy material superior in workability - Google Patents

Abstract

PURPOSE:To obtain an Fe base alloy material having superior workability and toughness by containing Ni, and Mn, Cr, Si, C, B, P by specified atomic ratios respectively therein. CONSTITUTION:The Fe base alloy material consists of 2-60atom% at least one kind of Ni and Mn, 7.5-60% Cr, 1-15% Si, 0.5-10% at least one kind among C, B and P, and the balance Fe substantially. The alloy is obtained by heating, melting, then cooling rapidly and solidifying, etc. said compsn. material. The alloy material has superior workability, high tensile strength, good toughness and corrosion resistance, etc. and the electromagnetic characteristic, etc. are also good. Said material is useful for various industrial material, composite material, fiber, resistor for heat generator, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an Fe-based alloy material with excellent workability.

Conventionally, steel materials containing Ni and Cr.

Examples include Ni-Cr steel and stainless steel. In particular, as is well known, there are many types of stainless steel.

Each has corrosion resistance, weather resistance, oxidation resistance, and weldability.

Excellent cold workability, machinability, work hardening properties, etc.

Widely used in various chemical industries, architecture, turbines, aircraft, vehicles, etc. However, even stainless steel is austenitic and ferritic.

There are martensitic types, precipitation hardening types, etc., and each has advantages and disadvantages. For example, martensitic stainless steel has a low Cr content of about 13 atomic percent, even though it has high strength and hardness.

In addition, since the carbon content is as high as about 3 at %, it is inferior in corrosion resistance to austenitic and ferritic stainless steels, and is also inferior in formability such as deep drawing and cold forming. Next, although austite stainless steel has excellent corrosion resistance, it has poor tensile strength.

The strength was as low as about 60 g/mm'', and even if it was work hardened, it could not achieve a very high strength.

In addition, grain refinement treatment is performed to improve toughness and workability, but unlike ordinary steel, orstenitic stainless steel has difficulty in grain refinement through heat treatment, and hot processing Therefore, the crystal grains of the molded product tend to become extremely coarse. Further, although ferritic stainless steel is cheaper than austenitic stainless steel, it is disadvantageous in terms of workability or corrosion resistance.

On the other hand, ACr (AlloyC
(asting intensity) standard (2) or HKw4 are known, but these steels are usually produced by casting, resulting in low productivity.1 Their properties also include a large amount of C and a structure containing coarse carbides. Therefore, the creep ductility or thermal fatigue properties are significantly inferior to those of 5US347 and the like.

In addition, metal materials that exhibit high tensile strength of 300 kg/mm" or more include piano wire and maraging steel. However, these piano wire and maraging steel have
Since it contains coarse carbides and precipitates, hot and cold working steps to impart work hardening etc. are complicated,
Maraging steel is difficult to make into wire rod. In addition, piano wires tend to break easily due to insufficient ductility of the drawn wire material, and in particular, it is completely impossible to manufacture ultrafine wires of 30 μm or less.

Furthermore, Japanese Patent Publication No. 54-39338 discloses a method for manufacturing a thin continuous steel wire. This is Fe −
It is a C-5i-Mn-0 based alloy, and the appropriate amount ranges of Si and Mn are limited in order to solidify it in a cooling medium.

For example, 97.7Fe -0,7Si -0,4Mn-1
,2G, 93.5Fe-2,35i 1.2Mn-
It has been reported that several types of examples such as 3G were able to form steel wires. Since solid silica precipitates are formed when the ejected molten metal stream contacts the cooling medium, this oxidation product is
It is stated that it acts as an anabolic initiator and a solid promoter.

Particularly thin continuous copper wires can be obtained. preferred S
The amount of i is about 1 to 6 at%, and the amount of Mn is about O to 1.5 at%.
It is clearly stated that it is within the range of That is, the above report does not describe the characteristics of the manufactured copper wire at all, but merely reports on the alloy composition that can be manufactured.

On the other hand, JP-A-56-3651 reports that Lh-type gold intermetallic compounds have toughness. In this alloy composition, at least one of Ni and Mn is 3.9 to 67.
0 atom %, AI 7.2 to 22.5 atom %, C 0.
7 to 11.0 at%, or 0.7 to 11.0 at% of C and 0.8 at% or less of N, and the remainder is Fe, and most of it is between Ll□ type molding. The compound is formed and C
Or, it is an intermetallic compound material in which most of C and N are dissolved in the intermetallic compound. In addition, the above alloy (:r,
It is stated that at least one of MO and W can be added at 7.4 atomic % or less, and it is also possible to substitute 42.0 atomic % or less with Ni and MnfGo, and in addition, Ti,
At least one of Ta, Zr, Nb and Si is 3
．． A trace amount of Cr, Mo can be added as long as it is 8 at% or less.
, W+Go, Ti, Ta+ Zr+ Nb and S
Even if i is added, most of the LIZ type mold intermetallic compound is formed, and most of C or C and N are dissolved in the intermetallic compound. .

This intermetallic compound material has an ordered structure due to its low Cr (7.4 atomic % or less), high I content, and high C content.

This intermetallic compound material now has an antiphase region and exhibits toughness, but this intermetallic compound material has toughness only within the above composition range, and when the AI amount is less than 7.2 at%, ,
L1g type mold compound is not formed and the strength is low, and at 22.5 atomic % or more, L1g type mold compound is formed, but the stickiness is significantly reduced and it becomes brittle. Regarding the amount of Ni, if it is less than 3.9 atomic %, the toughness will be significantly impaired due to the formation of carbides. On the other hand, at 65.5 atomic% or more, Fe,
It forms C and loses its stickiness. As for the C content, if it is less than 0.7 at%, the quenching effect cannot be achieved and Ll□
The mold cannot form intermetallic compounds and becomes brittle. 1
At 1.0 atom%.

Even with rapid cooling, it is difficult to prevent the precipitation of Fe and C.

It loses its ductility significantly and becomes brittle. Thus, this L1□ intermetallic compound material has toughness only within the composition range,
If the composition was outside the above range, carbide precipitation, etc. would immediately occur, the toughness would be completely lost, and the material would be unsuitable for practical use. In addition, although the Ll-type intermetallic compound material made of this alloy composition has toughness, it is difficult to undergo I drawing, rolling, heat treatment, etc., and there is little improvement in mechanical properties through processing. I can't wait. For example, the above-mentioned Lh type intermetallic compound material, Fe59.8Ni16.4A114.2C9,6, which has the highest breaking strength of about 175 kg/mm''
As mentioned earlier, the compositional alloy material contains many antiphase boundaries and has fine antiphase regions, so it does not undergo work hardening at all.

Even after some post-treatment, the breaking strength and
It was not possible to improve the yield strength at all. In addition, since this intermetallic compound material has a non-equilibrium phase, 600
When heat treatment is performed at about ℃, lhr.

The anti-phase boundary suddenly disappears, and the fine anti-phase region that is essential for providing toughness disappears.
It becomes an L12 type intermetallic compound in the equilibrium phase.

It lost its ductility, became completely brittle, and was a highly thermally unstable material. Furthermore, this intermetallic compound material has a type of boundary called an antiphase boundary within one grain, and since it is an extremely high carbon material, its corrosion resistance is also quite poor.

That is, it currently has an extremely high tensile strength of 300 kg/mm2 or more, as well as corrosion resistance and heat resistance.

There is no material that has excellent fatigue resistance and is easy to process.

Therefore, the present inventors have conducted extensive research with the aim of providing an Fe-based alloy material that has excellent workability and toughness through refinement of crystal grains and uniform dispersion of ultra-fine precipitates. As a result, when an Fe-based alloy with a specific composition is rapidly solidified from a molten state, it is possible to achieve all of the above objectives, and it is also an alloy material that has excellent corrosion resistance, heat resistance, fatigue resistance, etc., and is also useful electromagnetically. Heading 1
The invention has been completed.

That is, in the present invention, at least one of Ni and Mn is 2
~60 at%, 7.5 to 60 at% of Cr, 1 to 15 at% of St, 0.5 to 10 at% of at least one of C, B, and P, and the remainder is substantially composed of Fe. Fe-based alloy material with excellent workability, and at least one of Ni and Mn is 2 to 60 atomic %, and Cr is 7.5 to 60 atomic %.
At %, St is 0.25 to 15 atomic %, at least one of C, B and P is 0.5 to 10 atomic %,
AI is 0.02 to 0.5 at%, and the balance is substantially F.
It is an Fe-based alloy material with excellent workability.

First, to explain the first alloy material of the present invention, Ni
and Mn are among the elements essential for stabilizing the austenite phase having toughness.

At least one of Ni and Mn is required in an amount of 2 to 60 atomic %.

Preferably it is 3 to 50 atom%. If the content of at least one of Ni and Mn is less than 2 atomic % or more than 60 atomic %, a large amount of coarse precipitates are formed, resulting in decreased toughness, brittleness, and reduced workability. Cr has the function of stabilizing the austenite phase by coexisting with Ni and Mn, but 7.5 to 60 at % of Cr is required.

Preferably it is 7.5 to 50 at%. If the Cr content is less than 7.5 at%, ductility and toughness will decrease, resulting in poor workability, and if it is more than 60 at%, unevenly coarsened precipitates will precipitate, resulting in brittle workability. Gender disappears.

Sj is rapidly solidified from a molten state and directly shaped into a ribbon.

St is an element that imparts moldability necessary for obtaining tape-like and thin wire-like materials, and the content of St is required to be 1 to 15 at%, preferably 2 to 14 at%. St is 1 atomic%
If it is less than 15 at %, it will be difficult to rapidly solidify the molten metal and directly obtain ribbon-shaped, tape-shaped, or thin wire-shaped materials, and if it is more than 15 at %, St compounds will be produced, resulting in decreased toughness and workability. do. This Si improves the toughness and hardness of the alloy material obtained by rapid solidification, and when processing such as cold rolling or cold drawing to improve the mechanical properties,
In particular, deformation-induced martensitic transformation occurs from the low deformation rate region.

Significant improvements in strength and toughness are seen. It is necessary that at least one of C, B and P is 0.5 to 10 atomic %, preferably 0.5 to 8 atomic %, and in particular, C is essential as an austenite phase forming element, and C, B, and P have the effect of rapid cooling, and become carbides, borides, and phosphides, respectively, which are uniformly dispersed in the matrix and play the role of composite reinforcement, and are essential elements for obtaining high strength. Become. However, if at least one of these C, B, and P is less than 0.5 at%, it will be difficult to obtain a non-equilibrium phase when rapidly solidified, and if it is more than 10 at%, the precipitates will become coarse. It becomes brittle and has poor workability, making it unusable.

Next, to explain the second alloy material, the second alloy is:
The amount of Si in the first alloy was able to be reduced to 0.25 atomic % by adding 1-t-0.02 to 0.5 atomic %. That is, if the St content in the first alloy is less than 1 atomic %, the physical properties of the molten metal will change as described above, and the wettability with ceramics etc. that is the material of the nozzle will increase, making it difficult to eject the molten metal from the nozzle hole. In addition, the direct moldability during rapid cooling and solidification is extremely reduced, making it difficult to directly produce continuous ribbon-shaped, tape-shaped, and thin wire-shaped materials. , preferably 0.03 to 0.6 at%, the wettability between the molten metal and the nozzle material ceramic decreases,
The molten metal can be spouted smoothly from the nozzle hole, and at the same time, the direct moldability during rapid cooling and solidification, which deteriorates due to the low Si content, has been improved, resulting in a continuous ribbon shape.

Materials in the form of tapes and wires can be obtained.

By adding 81, Si can be reduced to 0.25 atomic %, preferably 0.5 atomic %. Si is 0.
If it is less than 25 at%, even if AI is added, it will not be possible to directly obtain a continuous ribbon-like, tape-like, or thin wire-like material by rapid solidification, and if it is more than 15 at%, St compounds will be produced, and the toughness and workability will deteriorate. descend. Also, AI is 0
．． If the amount is less than 0.02 at %, the physical properties of the molten metal cannot be improved, and the direct moldability during rapid cooling and solidification is also poor.

If AI is more than 0.5 at%, there is no effect of improving the physical properties of the molten metal. By adding a small amount of AI, Si
This reduces the hardness of the material obtained by rapid cooling and solidification, which contributes to the reduction of running costs such as die wear loss, and also improves the electrical conductivity, making it possible to improve the quality of conductive parts. Reduces energy loss when used as

In the case of a low Ni content, a low Cr content, and a low C content, the alloy material of the present invention has a structure in which ultrafine precipitates are uniformly dispersed in a mixed phase of a lath martensite phase and a trace amount of austenite phase. As the amounts of , Ni, Cr and C increase, the lath martensite phase decreases and the austenite phase increases. As described above, the alloy material of the present invention has high breaking strength, good toughness, and excellent workability due to the effects of the lath martensite phase and uniformly dispersed ultrafine precipitates. In particular, when processing by drawing, rolling, heat treatment, etc. is applied, the austenite phase is induced by processing.

It can cause martensitic transformation and dramatically improve toughness. Improvement of toughness 2 strength by wire drawing, rolling, etc. is achieved when at least one of Ni and Mn is 3
~40 at%, Cr at 7.5-30 at%, Si
is 3 to 14 atomic %, at least one of C, B and P is 0.5 to 6 atomic %, the balance is Fe, and at least one of Ni and Mn is 3 to 40 atomic %,
Cr: 7.5 to 3.0 at%, St: 0.5 to 14 at%, at least one of C, B, and P; l! l(
0.5 to 66 atoms, and 0.03 to 0.5 at% of AI.

A composition range in which the remainder is Fe is most preferred. In the above composition range, the alloy material of the present invention in particular has extremely excellent workability, and the austenite phase present in the above composition range is metastable and easily undergoes deformation-induced martensitic transformation due to strong deformation. in a state. That is, the alloy material of the present invention within the above composition range has ultrafine precipitates uniformly dispersed in a two-phase mixture of a lath martensite phase and an austenite phase, and a lath martensite phase or an austenite phase single phase structure. structure, has high toughness,
By further processing, the material undergoes processing-induced martensitic transformation, allowing for cold drawing of, for example, 85% or more, and a high breaking strength of about 400 kg/mm2 or more. Moreover, when heat treatment is applied as described above, the non-equilibrium state suddenly changes to the equilibrium state.

Ll□ type mold metal compound that becomes completely brittle 1976
-3651), the alloy material of the present invention is
When heat treatment is applied, ultrafine precipitates with a diameter of approximately 0.03 μm or less are precipitated in a uniformly dispersed state on the dislocations of lath martensite during the transition from a non-equilibrium state to an equilibrium state, so precipitation hardening occurs. , is effective in improving toughness. Since the non-equilibrium state cannot reach the equilibrium state due to precipitation, the toughness is not impaired at all.
Although it is in a non-equilibrium state, it is extremely stable thermally, completely overturning the conventional wisdom of non-equilibrium phases. In particular, this diameter of approximately 0.
The precipitation hardening effect due to ultrafine precipitates of 0.03 μm or less is remarkable in the low Ni, low Cr, and low C regions including the lath martensite phase, where Ni is 3 to 20 at%.

A composition range in which Cr is 7.5 to 25 atomic%, Si is 1 to 7 atomic%, a small amount of C1B and P (one is 0.5 to 4 atomic%, and the remainder is substantially Fe). and Ni
is 3 to 20 at%, Cr is 7.5 to 25 at%, S
i is 1 to 7 atomic%, at least one of C, B and P
is 0.5 to 4 at%, and 81 is 0.03 to 0.5 at%.

A composition range in which the remainder is substantially Fe is most preferable,
Further, the heat treatment conditions are preferably 9, for example, 450 to 700°C for about 1 hour. In this case, the tensile breaking strength tends to decrease under heat treatment conditions exceeding 700°C, but at 900°C
Even after being heat-treated for 1 hour, the tensile strength at break is still as high as about 273 that of the original rapidly solidified material.

In addition, nine alloy materials of the present invention include Nb, Ta, Ti, M
o, V.

When one or more elements selected from the group consisting of W and Cu are added in an amount of 5 at % or less, the toughness of the quenched material is improved by solid solution hardening, and the corrosion resistance and oxidation resistance are improved. +Nb+Ta+T within the composition range where the precipitation hardening effect is significant, that is, within the range of heat treatment conditions.
When one or more elements selected from the group consisting of i, Mo+V, W, and Cu are added in an amount of 5 at % or less, precipitation hardening becomes more significant.

However, it shows even higher breaking strength and toughness.

If more than 5 at % was added, the rapidly solidified material became dangerous.

In addition, in the above alloy system, impurities such as S, Sn, In, and As are present in ordinary industrial materials.

Even if small amounts of sb, o, N, etc. are present, this does not pose any problem in achieving the present invention.

In order to manufacture the alloy material of the present invention, the above alloy composition is used and heated and melted in an atmosphere or in a vacuum.

This may be rapidly solidified. The rapid cooling method is 5
There are various methods such as liquid quenching method such as single roll method, double roll method, and rotating liquid spinning method (Japanese Patent Application Laid-open No. 16501-1982).
6) is particularly effective. Also.

The plate-shaped alloy can also be manufactured by a piston-anvil method, a splat quenching method, or the like. The liquid quenching method described above (
Single roll method, double roll method, two-rotation submerged spinning method) is approximately 104
It has a cooling rate of ~10'℃/sec, and the piston anvil method and sub-sotoquenching method have a cooling rate of approximately 10
Since it has a cooling rate of 5 to 106° C./sec, by applying these rapid cooling methods, it is possible to efficiently rapidly solidify it.

When manufacturing ribbon materials, tape materials, and thin wire materials using such single roll method, double roll method, and rotating liquid spinning method, slits with a width of about 1 to 3 mm or pores with a diameter of 0.
The molten metal stream must be ejected onto the cooling medium through a nozzle of the order of 1 to 0.5 mm.

However, since the above-mentioned conventional Ll□ type mold intermetal compound material contains AI at a very high concentration, when it is melted in a normal argon gas atmosphere, a large amount of slag is generated, and this slag When the molten metal passes through the slits and nozzle holes, pulsations occur in the molten metal flow, resulting in large irregularities in the ribbon thickness, wire diameter, etc. Namely.

Ll□ type mold intermetallic compound containing a large amount of %AI, which is easy to form into slag, completely lacks uniformity in its thinning and wire rod formation.

The alloy material of the present invention, which contains Si, which is less likely to become a slag than AI, can easily produce a uniform continuous wire.

The alloy material of the present invention can be subjected to continuous cold working, and its dimensional accuracy and mechanical properties can be dramatically improved by rolling and wire drawing.

In particular, thin wire-shaped materials can be easily processed by applying a 2wA pressure and rolling reduction rate of 8.
It is possible to produce high-strength ultrafine wires with a wire diameter of 5% or more and a wire diameter of 0.01 mm or less.

Further, it is also possible to add heat treatment such as annealing during the processing process as necessary. The high speed and simple process of this liquid quenching method reduce manufacturing costs when producing the alloy material of the present invention.

It also has the effect of saving energy.

Furthermore, when the rapidly solidified material is heat-treated at a low temperature of about 100 to 400°C, the elongation of the alloy material of the present invention increases significantly by approximately 2 to 5 times. The rolling and wire drawing processes described in 2.
Running costs such as die wear can be significantly reduced.

The alloy material of the present invention thus obtained is as follows.

It has excellent workability, exhibits extremely high tensile strength of 400 kg/mm'' or more, and good toughness, and also has the following excellent properties.

Although the alloy material of the present invention has a high C content and a martensitic structure after cold drawing, the corrosion resistance is comparable to that of stainless steel, and if the optimum alloy composition is selected, It began to exhibit high corrosion resistance that surpassed that of stainless steel.

Furthermore, the alloy material of the present invention is resistant to high-temperature oxidation in the atmosphere, and its various properties do not deteriorate at all even after being exposed to high temperatures of about 700° C. in the atmosphere.

Furthermore, since the alloy material of the present invention becomes a martensitic structure after cold drawing, +Hc is 30 to 150'Oe, B
When r is 10 to 17 kg, the material changes to an electromagnetically semi-hard material with high squareness. For example, 68Fe −1ONi −]O
In the alloy composition of Cr-8St-3C-IMo,
The alloy material of the present invention that has been cold drawn to a reduction rate of 90% has a HC of 600e.

It is an excellent semi-hard material with a Br of 15 KG and very high squareness, and when it is further heat treated at 400°C for about 1 hour, the Br and squareness are significantly improved. The alloy material of the present invention has excellent toughness, strength, and hardness.

It can be said that this material is extremely superior in one respect to conventional semi-hard materials.

Furthermore, the alloy material of the present invention also has good fatigue resistance.

Compared to conventional stainless steel wire and piano wire, it has a higher fatigue limit and is a material that is resistant to fatigue, and is a material with sufficiently high reliability when used as a structural material.

As described above, the alloy material of the present invention has excellent workability, high tensile strength, good toughness and corrosion resistance, oxidation resistance, heat resistance, fatigue resistance, and has good electromagnetic properties. Because of its high resistance, it is widely used in various industrial materials, composite materials, materials for filters and strainers, heating resistors, fibers for sound absorbing materials, etc. It is also useful as material for rafting relays, switching relays, etc. very good in terms of It is a material with extremely high utility value that is unparalleled to conventional materials.

Next, the present invention will be specifically explained using examples.

Examples 1-44. Comparative Examples 1 to 35 Fe-(Ni
+ Mn) -Cr-(si, AI)-(C+ P+
B) (Nb+Ta+Ti, Mo, LW,
After melting the Cu) based alloy in an argon gas atmosphere, the pore diameter was 0.13 at an argon gas injection pressure of 3.5 kg/cm".
By mm ruby spinning nozzle? A continuous thin wire having a circular cross section was produced by jetting it into rotating cooling water of 2.5 cm depth and temperature of 6° C. formed in a cylindrical drum with an inner diameter of 500 mm rotating at 280 rpm and rapidly solidifying it.

At this time, the distance between the spinning nozzle and the rotating cooling liquid level was maintained at 11, and the angle between the molten metal flow jetted from the spinning nozzle and the rotating cooling liquid level was 65°.

In addition, the structure of this thin wire was observed by X-ray diffraction, the top and transmission electron microscopy, and the 180' contact bendability was also investigated.

Next, this fine wire was subjected to continuous cold drawing using a commercially available diamond die without intermediate annealing.

Furthermore, we also investigated the improvement in tensile strength at break when the thin wire was heat treated at 550° C. for 1 hour before cold drawing.

The breaking strength of these samples was measured at room temperature using an Instron type tensile tester at a speed of 4.17 x 10-'5e.
It was measured under the conditions of c-'.

The results are summarized in Table 11 and Table 2.

The symbols in the structure column of fine lines after rapid solidification in Table 1 are as follows:
γ: Austenite phase, α: Lath martensite phase, α
; Ferrite phase, A; Coarse precipitates, B; Diameter approximately 0
．． It refers to ultrafine, uniformly dispersed precipitates of about 1 μm or less.

Example 1. 2.10.11.12.13.15.16
．． 18°19, 20.21.23.24.25.27.
28.29.31.33゜34, 35.36.37.3
The alloy material No. 8 has a lath martensite phase or uniformly dispersed ultrafine precipitates.

It was strengthened and showed high strength even as a rapidly cooled material (thin wire after rapidly solidified). Furthermore, when the austenite phase in these alloy materials of the present invention is subjected to strong deformation due to cold drawing, it undergoes 3 deformation-induced martensitic transformation, and the temperature is approximately 400 k.
It now has a high strength of the order of g/mmz.

However, the Ll□ type intermetal compound material of Comparative Examples 28 and 29 could only be wire-drawn to a reduction rate of about 20 to 40, and when wire-drawn beyond that, breakage occurred frequently.
This is because it is impossible to process and does not cause work hardening even if processed.

There was almost no improvement in mechanical properties such as breaking strength.

Also, Example 3. 4', 5. 6. 7. 8. 9
．． 13°1? , 22.26.30.32 alloy materials are Nb+ Tar Tt+Mo, V, H and Cu
By adding a small amount of
m'' tensile strength at break was improved.Furthermore, continuous cold drawing could be performed up to a high reduction rate, and the material had a tensile strength at break equal to or higher than that of a material without additives.

However, Comparative Examples 1, 2, 3, 4, 5, 6, 7゜8,
9.10.11.12.13.14.15.17.1B
, 20゜21, 23.24.26.27 are out of the appropriate range, so one structure is in a state where coarse carbide is precipitated, and it is brittle and cannot be wire-drawn, so it cannot be used for practical use. It was something that I didn't do.

In Comparative Examples 16, 19, 22, 25, and 30, Al and St, which are essential for improving the physical properties of the moldable molten metal, and C, B, and P, which are essential for rapid solidification, are out of the appropriate range.

A wire-like sample could not be obtained.

The materials of the alloys of Examples 39 to 44 are Nb, Ta+
By adding a small amount of Ti+Mo+v, W, and Cu, the tensile strength at break is improved by solid solution hardening.

When the tempering treatment is performed, in addition to the ultrafine precipitates that existed in the thin wire after rapid solidification, even more ultrafine precipitates with a diameter of about 0.03 μm or less are uniformly dispersed. The tensile strength at break is further improved. Materials manufactured by liquid quenching have almost no component segregation.

The precipitates produced by heat treatment are even finer than the precipitates produced during rapid solidification, so the alloy material of the present invention does not transform into an equilibrium phase even after heat treatment and loses its stickiness at all. It didn't become brittle.

On the other hand, Comparative Example 35 is a non-equilibrium Ll□ type mold intermetallic compound material obtained by three-liquid quenching. As it changes to the equilibrium phase, it becomes completely kneeling,
It was a thermally unstable material.

Examples 45-50. Comparative Example 36.0f In order to investigate the corrosion resistance of Fe-Ni-Cr-(AI+Si)-C-Mo alloy, approximately 0.08 to 0.13 mm was measured using the same equipment and conditions as in Example-1.
A thin wire having a wire diameter of 0 was manufactured, and the 3-average corrosion degree was determined using a corrosion resistance measurement method based on an AC impedance method (AC impedance corrosion resistance measuring device manufactured by Riken Denshi).

What is this corrosion resistance measurement method using the AC impedance method?
The sample is immersed in the target corrosive liquid as an electrode.

This is an accelerated test in which electricity is applied intermittently between electrodes for a certain period of time, and the amount of corrosion is determined from the resistance value (References: Shibe Haruyama, Toru Mizuryu: Metal Physics Seminar, vol. 4.
Na2.1979 etc.).

The results are shown in Table-3.

The alloy materials of Examples 45 to 50 are: Ni+ Cr+ S
It had excellent corrosion resistance due to various synergistic effects such as improved corrosion resistance due to elements such as i+ AI + Mo, hardening of fine crystal grains, and uniform concentration of component elements due to rapid liquid cooling. Further, even when subjected to strong working by cold drawing, no deterioration in corrosion resistance was observed at all.

However, although Comparative Example 36 is a piano wire that has been commonly used in the past, it has no corrosion resistance at all even when subjected to a corrosion test with rust preventive oil attached, and furthermore, the tensile rupture strength is also different from that of the alloy material of the present invention. It was very low in comparison. Moreover, the stainless steel wire of Comparative Example 37 is as follows.

Compared to the alloy material of the present invention, the corrosion resistance was inferior and the tensile strength at break was 1/4 or less.

Examples 51-55. Comparative Example 38.39 Fe-Ni-Cr-C-M. In order to study the fatigue resistance of the alloy, a thin wire having a wire diameter of approximately 0.03 mm was manufactured using the same equipment and conditions as in Example-1.

For the fatigue resistance test, a roller bending fatigue testing machine was used to apply surface strain to the fine wire shown in Table 2-4 with a roller, and measure the relationship between the number of bends until breakage and the surface strain. In the following, a so-called fatigue limit, which is a limit that does not break even after being bent 107 times or more, is set.

The results are shown in Table-4.

The alloy materials of Examples 51 to 55 are materials with higher toughness and excellent fatigue resistance due to the effects of long, fibrous crystal grains, ultrafine precipitates, deformation-induced martensite, etc. It became clear that.

Comparative Examples 38 and 39 are commercially available piano wires and stainless steel wires, respectively, and their fatigue limits are lower than the alloy materials of the present invention.
It could not be said that the material had excellent fatigue resistance.

Claims (1)

[Claims] (1) At least one of Ni and Mn is 2 to 60 atom%
in. Cr is 7.5 to 60 at%, Si is 1 to 15 at%
in. F with excellent workability, in which at least one of C, B, and P is 0.5 to 10 atomic %, and the remainder is substantially Fe.
e-based alloy material. (At least one of 218i and Mn is 2 to 60 atomic%
in. Cr is 7.5 to 60 at%, St is 0.25 to 15
In atomic %, at least one of C, B and P is 0.
5 to 10 at%, and 0.02 to 0.5 at%. An Fe-based alloy material with excellent workability, the remainder of which is essentially Fe.