WO2011111872A1

WO2011111872A1 - High-strength steel and high-strength bolt with excellent resistance to delayed fracture, and manufacturing method therefor

Info

Publication number: WO2011111872A1
Application number: PCT/JP2011/056481
Authority: WO
Inventors: 大輔平上; 徹志千田; 敏三樽井
Original assignee: 新日本製鐵株式会社
Priority date: 2010-03-11
Filing date: 2011-03-11
Publication date: 2011-09-15
Also published as: EP2546379A1; JP5177323B2; US20120247618A1; EP2546379A4; KR101366375B1; IN2012DN05089A; CN102812145A; KR20120056879A; EP2546379B1; JPWO2011111872A1

Abstract

The disclosed steel contains, by mass: 0.10-0.55% carbon; 0.01-3% silicon; 0.1-2% manganese; and up to 1.5% vanadium and/or up to 3.0% molybdenum, with the vanadium content (V) and the molybdenum content (Mo) satisfying the relation V+½Mo > 0.4%. Said steel also contains one or more of the following: 0.05-1.5% chromium; 0.001-0.05% niobium; 0.01-4% copper; 0.01-4% nickel; and 0.0001-0.005% boron. The remainder comprises iron and unavoidable impurities. The structure of the disclosed steel is primarily tempered martensite. Said steel, which is a high-strength steel that exhibits excellent resistance to delayed fracture, is characterized by the following being formed in a surface layer thereof: (a) a nitrided layer with a thickness of at least 200 μm from the surface of the steel and a nitrogen concentration by mass that is at least 0.02% higher than that of the steel and no greater than 12.0%; and (b) a low-carbon region, at a depth between 100 μm and 1000 μm from the surface of the steel, with a carbon concentration by mass that is at most 0.9 times that of the steel and no less than 0.05%.

Description

High-strength steel material and high-strength bolt excellent in delayed fracture resistance, and manufacturing method thereof

The present invention relates to a high-strength steel material used for wire rods, PC steel rods (prestressed concrete steel rods) and the like, in particular, a high-strength steel material having excellent delayed fracture resistance and a tensile strength of 1300 MPa or more, a high-strength bolt, and production thereof It is about the method.

High-strength steels used in many machines, automobiles, bridges, and building structures are medium carbon steels with a C content of 0.20 to 0.35%, such as SCr specified in JIS G 4104 and JIS G 4105. , SCM and the like are subjected to a tempering process. However, in any steel type, if the tensile strength exceeds 1300 MPa, the risk of delayed fracture increases.
As a method for improving the delayed fracture resistance of high-strength steel, a method in which the steel structure is a bainite structure or a method in which prior austenite grains are refined is effective.
Patent Document 1 discloses a steel in which old austenite grains are refined to increase delayed fracture resistance, and Patent Documents 2 and 3 increase delayed fracture resistance by suppressing segregation of steel components. Steel is disclosed. However, it is difficult to significantly improve the delayed fracture resistance by refinement of prior austenite grains and suppression of component segregation.
The bainite structure contributes to the improvement of the delayed fracture resistance, but the formation of the bainite structure requires appropriate additive elements and heat treatment, which increases the cost of steel.
In Patent Documents 4 to 6, a pearlite structure having an area ratio of 80% or more is subjected to strong wire drawing to give a strength of 1200 N / mm ² or more and excellent delayed fracture resistance. % Of high-strength bolts are disclosed. However, the wire materials described in Patent Documents 4 to 6 are expensive due to wire drawing, and it is difficult to produce a wire having a large wire diameter.
Patent Document 7 discloses a coil spring in which the occurrence of delayed fracture after cold coiling is suppressed by using an oil tempered wire having an internal hardness of Hv550 or more. However, the product surface hardness after nitriding is Hv 900 or more, and the delayed fracture characteristics are low under high load stress such as bolts and PC steel bars, and there is a problem that delayed fracture occurs when the corrosive environment becomes more severe.
Patent Document 8 discloses a high-strength steel material excellent in delayed fracture resistance mainly composed of a tempered martensite structure obtained by nitriding a steel having a required component composition. The high-strength steel material disclosed in Patent Document 8 exhibits delayed fracture resistance even in a corrosive environment containing hydrogen.
However, in recent years, the corrosive environment has become more severe, and there is a demand for a high-strength steel material that exhibits excellent delayed fracture resistance even under severe corrosive environments.

Japanese Patent Publication No. 64-4566 JP-A-3-243744 JP-A-3-243745 JP 2000-337332 A JP 2000-337333 A JP 2000-337334 A JP-A-10-251803 JP 2009-299180 A

As described above, there is a limit to significantly increasing the delayed fracture resistance in a high strength steel material by a conventional method. As a method for improving delayed fracture resistance, there is a method in which fine precipitates are dispersed in a steel material and hydrogen is trapped in the precipitates. However, even if this method is adopted, it is difficult to effectively suppress delayed fracture when the amount of hydrogen entering from the outside is large.
In view of the above situation, the present invention provides a high-strength steel material (wire rod, PC steel bar) and high-strength bolt that exhibit excellent delayed fracture resistance even in a severe corrosive environment, and a manufacturing method for manufacturing them at low cost. The purpose is to provide.

The inventors of the present invention have intensively studied a method for solving the above-described problems. As a result, (a) the steel material contains a predetermined amount of V and / or Mo that forms precipitates that trap hydrogen, and (b) decarburization treatment and nitriding treatment, (b1) low carbon It has been found that when the region is formed to suppress curing, and (b2) the nitride layer is formed to prevent hydrogen from entering, the delayed fracture resistance is remarkably improved.
This invention was made | formed based on the said knowledge, The summary is as follows.
(1) By mass%, C: 0.10 to 0.55%, Si: 0.01 to 3%, Mn: 0.1 to 2%, V: 1.5% or less and Mo : Containing one or two of 3.0% or less, and the contents of V and Mo satisfy V + 1 / 2Mo> 0.4%, and Cr: 0.05 to 1.5%, One or more of Nb: 0.001 to 0.05%, Cu: 0.01 to 4%, Ni: 0.01 to 4%, and B: 0.0001 to 0.005% are contained. And the balance consists of Fe and unavoidable impurities, and the structure is a steel material whose structure is mainly tempered martensite, and in the surface layer of the steel material,
(A) a nitride layer having a thickness from the surface of the steel material of 200 μm or more and a nitrogen concentration of 12.0% by mass or less, which is 0.02% by mass or more higher than the nitrogen concentration of the steel material; and
(B) A low carbon region having a depth from the surface of the steel material of 100 μm or more and 1000 μm or less and a carbon concentration of 0.05% by mass or more and 0.9 times or less of the carbon concentration of the steel material is formed. High strength steel with excellent delayed fracture resistance.
(2) The amount of hydrogen entering the steel material is 0.5 ppm or less due to the presence of the nitride layer and the low carbon region, and the limit diffusible hydrogen content of the steel material is 2.00 ppm or more. A high-strength steel material excellent in delayed fracture resistance as described in (1).
(3) Further, the steel material is, by mass%, Al: 0.003-0.1%, Ti: 0.003-0.05%, Mg: 0.0003-0.01%, Ca: 0.00. It has excellent delayed fracture resistance according to the above (1) or (2), characterized by containing one or more of 0003 to 0.01%, Zr: 0.0003 to 0.01% High strength steel.
(4) The high strength steel material excellent in delayed fracture resistance according to any one of (1) to (3), wherein the nitride layer has a thickness of 1000 μm or less.
(5) The high strength steel material having excellent delayed fracture resistance according to any one of (1) to (4), wherein the area ratio of the tempered martensite is 85% or more.
(6) The high-strength steel material having excellent delayed fracture resistance according to any one of (1) to (5), wherein a compressive residual stress on the surface of the steel material is 200 MPa or more.
(7) The high-strength steel material having excellent delayed fracture resistance according to any one of (1) to (6), wherein the steel material has a tensile strength of 1300 MPa or more.
(8) By mass%, C: 0.10 to 0.55%, Si: 0.01 to 3%, Mn: 0.1 to 2%, V: 1.5% or less and Mo : Containing one or two of 3.0% or less, and the contents of V and Mo satisfy V + 1 / 2Mo> 0.4%, and Cr: 0.05 to 1.5%, One or more of Nb: 0.001 to 0.05%, Cu: 0.01 to 4%, Ni: 0.01 to 4%, and B: 0.0001 to 0.005% are contained. And the balance is a bolt made of steel material which is composed of Fe and unavoidable impurities, and whose structure is mainly tempered martensite, and on the surface layer of the bolt,
(A) a nitride layer having a thickness from the surface of the bolt of 200 μm or more and a nitrogen concentration of 12.0% by mass or less, which is 0.02% by mass or more higher than the nitrogen concentration of the steel material; and
(B) A low carbon region having a depth from the surface of the bolt of 100 μm to 1000 μm and a carbon concentration of 0.05% by mass or more and 0.9 times or less of the carbon concentration of the steel material is formed. A high-strength bolt with excellent delayed fracture resistance.
(9) The presence of the nitride layer and the low carbon region, the amount of hydrogen penetrating into the bolt is 0.5 ppm or less, and the limiting diffusible hydrogen amount of the bolt is 2.00 ppm or more. A high-strength bolt excellent in delayed fracture resistance as described in (8).
(10) Further, the steel material is, in mass%, Al: 0.003-0.1%, Ti: 0.003-0.05%, Mg: 0.0003-0.01%, Ca: 0.00. It has excellent delayed fracture resistance as described in (8) or (9) above, comprising one or more of 0003 to 0.01%, Zr: 0.0003 to 0.01% High strength bolt.
(11) The high-strength bolt excellent in delayed fracture resistance according to any one of (8) to (10), wherein the nitride layer of the bolt has a thickness of 1000 μm or less.
(12) The high strength bolt excellent in delayed fracture resistance according to any one of (8) to (11), wherein the area ratio of the tempered martensite is 85% or more.
(13) The high-strength bolt excellent in delayed fracture resistance according to any one of (8) to (12), wherein a compressive residual stress on the surface of the bolt is 200 MPa or more.
(14) The high strength bolt excellent in delayed fracture resistance according to any one of (8) to (13), wherein the bolt has a tensile strength of 1300 MPa or more.
(15) A method for producing a high-strength steel material having excellent delayed fracture resistance according to any one of (1) to (7),
(1) The steel material having the composition described in (1) or (3) is heated, and the carbon concentration is 0.05% by mass or more from the surface of the steel material to a depth of 100 μm or more and 1000 μm or less. Form a low carbon region of 0.9 times or less of the carbon concentration, then cooled as it is to make the steel structure a martensite-based structure,
(2) The steel material is subjected to nitriding treatment at a temperature exceeding 500 ° C. and not more than 650 ° C., and the nitrogen concentration of the steel material is 12.0% by mass or less and 0.02% by mass than the nitrogen concentration of the steel material. Production of high-strength steel material excellent in delayed fracture resistance, characterized by forming a nitride layer with a thickness of 200 μm or more from the surface of the steel material higher than the above, and having the steel material structure mainly composed of tempered martensite Method.
(16) The method for producing a high-strength steel material having excellent delayed fracture resistance according to (15), wherein the nitride layer has a thickness of 1000 μm or less.
(17) A method for producing a bolt having excellent delayed fracture resistance according to any one of (8) to (14),
(1) The bolt which processed the steel material of the component composition as described in said (8) or (10) is heated, and carbon concentration is 0.05 mass% or more from the surface of a bolt to the depth of 100 micrometers or more and 1000 micrometers or less. , Forming a low carbon region of 0.9 times or less of the carbon concentration of the steel material, then cooled as it is, the steel material structure is a martensite-based structure,
(2) The bolt is subjected to nitriding treatment at over 500 ° C. and not more than 650 ° C., and the nitrogen concentration is 12.0 mass% or less on the surface layer of the bolt, and 0.02 mass% than the nitrogen concentration of the steel material. A method for producing a high-strength bolt excellent in delayed fracture resistance, characterized in that a nitride layer having a thickness of 200 μm or more from the surface of the bolt is formed, and the steel is made of a tempered martensite-based structure. .
(18) The method for producing a high-strength bolt excellent in delayed fracture resistance according to (17), wherein the nitrided layer has a thickness of 1000 μm or less.

According to the present invention, there are provided a high-strength steel material (wire rod, PC steel bar) and high-strength bolt that exhibit excellent delayed fracture resistance even in a severe corrosive environment, and a manufacturing method capable of manufacturing them at low cost. I can.

Fig.1 (a) is a figure which shows typically the hydrogen release rate curve obtained by the hydrogen analysis by a temperature rising method.
FIG.1 (b) is a figure which shows typically the relationship between the fracture | rupture time obtained by the constant load delayed fracture test of steel materials, and the amount of diffusible hydrogen.
FIG. 2 is a diagram showing a method for obtaining the depth (thickness) of a low carbon region from a carbon concentration curve obtained by an energy dispersive X-ray fluorescence spectrometer (EDX).
FIG. 3 is a diagram showing a method for obtaining the thickness (depth) of a nitride layer from a nitrogen concentration curve obtained with an energy dispersive X-ray fluorescence spectrometer (EDX).
FIG. 4 is a view showing a test piece used for a delayed fracture test of a steel material.
FIG. 5 is a diagram showing an embodiment of the delayed fracture tester.
FIG. 6 is a diagram showing the relationship between temperature, humidity and time in a corrosion acceleration test.

It is known that hydrogen in steel is involved in delayed fracture. Further, the penetration of hydrogen into the steel occurs with corrosion in the actual environment, and the diffusible hydrogen that has entered the steel accumulates in the concentrated portion of the tensile stress, resulting in delayed fracture.
FIG. 1 (a) schematically shows a hydrogen release rate curve obtained by hydrogen analysis by a temperature raising method. As shown in FIG. 1A, the amount of diffusible hydrogen released reaches a peak around 100 ° C.
In the present invention, the sample is heated at 100 ° C./h, and the integrated value of the amount of hydrogen released between room temperature and 400 ° C. is defined as the amount of diffusible hydrogen. The amount of hydrogen released can be measured with a gas chromatograph.
In the present invention, the minimum amount of diffusible hydrogen that causes delayed fracture is referred to as the limit diffusible hydrogen amount. The amount of critical diffusible hydrogen varies depending on the type of steel.
FIG. 1B schematically shows the relationship between the rupture time and the amount of diffusible hydrogen obtained in the constant load delayed fracture test of steel. As shown in FIG. 1B, the break time is short when the amount of diffusible hydrogen is large, and the break time is long when the amount of diffusible hydrogen is small.
That is, if the amount of diffusible hydrogen is small, delayed fracture does not occur, and if the amount of diffusible hydrogen is large, delayed fracture occurs. In the present invention, a constant load delayed fracture test was performed on the steel material, and the maximum diffusible hydrogen amount that did not break for 100 hours or more was defined as the limit diffusible hydrogen amount, as shown in FIG.
Comparing the amount of intrusive hydrogen and the amount of limit diffusible hydrogen, if the amount of limit diffusible hydrogen is greater than the amount of intrusion hydrogen, delayed fracture does not occur. Conversely, if the amount of limit diffusible hydrogen is less than the amount of intrusion hydrogen , Delayed fracture occurs. Therefore, the greater the amount of critical diffusible hydrogen, the more delayed the occurrence of delayed fracture.
However, when the amount of hydrogen entering the steel material from the corrosive environment exceeds the limit diffusible hydrogen amount, delayed fracture occurs.
Therefore, in order to prevent the occurrence of delayed fracture, it is effective to suppress the penetration of hydrogen into the steel material. For example, when a nitride layer is formed on the surface of a steel material by nitriding, the amount of invading hydrogen due to corrosion is suppressed, so that delayed fracture resistance is improved.
However, when a nitride layer is formed on the surface of the steel material, the amount of critical diffusible hydrogen decreases due to the hardening of the surface layer, and the delayed fracture resistance is not improved. Therefore, the present inventors examined the component composition of the steel material on the premise that the hydrogen that has entered the steel material is trapped by the fine precipitates and made harmless in order to increase the critical diffusible hydrogen content.
As a result, the present inventors contain an appropriate amount of one or two of V and Mo, and fine precipitates composed of carbides, nitrides, and / or carbonitrides of V and Mo in the steel material. It was confirmed that the amount of critical diffusible hydrogen can be increased by precipitation.
However, on the other hand, it has also been confirmed that even if one or both of V and Mo are contained in the steel material, the delayed fracture resistance cannot be sufficiently improved.
Therefore, the present inventors have made extensive studies by paying attention to the relationship between the crystal form of fine precipitates, the amount of critical diffusible hydrogen and the amount of invading hydrogen, and as a result, the following has been found.
Hexagonal Mo carbides, nitrides, and carbonitrides have a greater effect on increasing the amount of limit diffusible hydrogen than on increasing the amount of invading hydrogen, and thus greatly contribute to the improvement of delayed fracture resistance. However, the strength improvement effect by fine precipitation is small compared with V carbide, nitride, and carbonitride of NaCl type crystal.
On the other hand, V-type carbides, nitrides, and carbonitrides of NaCl-type crystals are excellent in strength improvement effect by fine precipitation. However, the NaCl-type crystal V carbide, nitride, and carbonitride increase the critical diffusible hydrogen amount while increasing the intrusion hydrogen amount. Small compared to Mo carbides, nitrides, and carbonitrides.
That is, it is necessary to set the contents of Mo and V appropriately in order to ensure the required strength and the excellent delayed fracture resistance in the steel material.
Then, the present inventors diligently studied to set the contents of Mo and V appropriately. As a result, V: 1.5% by mass or less, Mo: 3.0% by mass or less of one or two types, and the content (% by mass) of V and Mo are V + 1 / 2Mo> 0. It has been found that if 4 mass% is satisfied, the amount of critical diffusible hydrogen is increased and excellent delayed fracture resistance can be obtained.
In addition, the inventors have studied to improve the delayed fracture resistance by reducing the hardness of the nitrided layer, subjecting the surface to decarburization treatment, and further accelerating corrosion test and exposure of the steel material subjected to nitriding treatment Tests were conducted to investigate the hydrogen penetration characteristics and delayed fracture resistance of steel materials.
As a result, when a nitride layer having a predetermined nitrogen concentration and thickness is formed on the surface of a steel material having a predetermined component composition and structure, and further, a low carbon region having a predetermined carbon concentration and depth is formed on the steel surface. It was found that the delayed fracture resistance is remarkably improved as compared with the case where only the nitride layer is formed on the steel surface.
This is because (1) the formation of the nitride layer in the low carbon region formed on the steel material surface suppressed the amount of intrusion hydrogen compared to the case of the nitride layer alone, and (2) the low carbon region on the steel material surface. This is considered to be due to a synergistic effect with the increase in the amount of critical diffusible hydrogen by suppressing excessive curing of the surface layer.
Basically, on the surface layer of a steel material having a predetermined composition and structure, (a) a thickness of 200 μm or more from the surface of the steel material, a nitrogen concentration of 12.0% by mass or less, and 0.02% by mass or more higher than the steel material A nitride layer is formed, and (b) a low carbon region having a carbon concentration of 0.05% by mass or more and a carbon concentration of 0.9 times or less of the steel material at a depth of 100 μm or more and 1000 μm from the steel surface. Then, it became clear that the amount of limit diffusible hydrogen of steel materials can be increased, and the amount of intrusion hydrogen can be reduced.
Further, the present inventors have found that compression residual stress is generated on the surface of the steel material due to heating and rapid cooling during the nitriding treatment, and the delayed fracture resistance is improved. In particular, in the case of a high-strength bolt in which strain is introduced into the surface layer by processing, the formation of a nitrided layer is promoted and the nitrogen concentration is increased, so that the delayed fracture resistance is markedly improved.
Hereinafter, the present invention will be described in detail.
The high-strength steel material and high-strength bolt of the present invention have a predetermined composition, and have a nitride layer and a low carbon region simultaneously on the surface thereof.
That is, in the surface layer of the high-strength steel material and high-strength bolt of the present invention, the nitrogen concentration is 12.0 mass% or less, 0.02 mass% or more higher than the nitrogen concentration of the steel material, and the carbon concentration is 0.05 mass%. As described above, there is a region (low carbonitriding layer) 0.9 times or less that of the steel material.
When the thickness of the nitride layer is thicker than the thickness of the low carbon region, the carbon concentration deeper than the low carbon region is equal to the carbon concentration of the steel material, and the nitrogen concentration is higher than the nitrogen concentration of the steel material.
On the other hand, when the thickness of the low carbon region is thicker than the thickness of the nitride layer, the carbon concentration is 0.05% by mass or more and 0.9% or less of the carbon concentration of the steel material below the nitride layer. The element content will have a low carbon region equivalent to steel.
First, the low carbon region will be described. In the present invention, the low carbon region is a region having a carbon concentration of 0.05% by mass or more and 0.9 times or less the carbon concentration of the high-strength steel material or high-strength bolt.
In the high-strength steel material and high-strength bolt of the present invention, a low carbon region is formed from the steel material surface to a depth of 100 μm or more and 1000 μm.
The depth and carbon concentration of the low carbon region are adjusted by the heating atmosphere, the heating temperature, and the holding time in the heat treatment for forming the low carbon region. For example, when the carbon potential of the heating atmosphere is low, the heating temperature is high, and the holding time is long, the low carbon region becomes deep and the carbon concentration in the low carbon region decreases.
If the carbon concentration in the low carbon region is less than 0.05% by mass, the lower limit of 0.10% by mass of the carbon concentration of the steel material is not more than half, and the predetermined strength and hardness cannot be ensured in the low carbon region. If the carbon concentration in the low carbon region exceeds 0.9 times the carbon concentration of the steel material, the carbon concentration in the steel material is substantially equivalent to the carbon concentration in the steel material, and the existence effect of the low carbon region is reduced.
Therefore, in the present invention, the low carbon region is defined as a region having a carbon concentration of 0.05% by mass or more and 0.9 times or less the carbon concentration of the steel material.
When the carbon concentration in the low carbon region is 0.05% by mass or more and 0.9 times or less the carbon concentration of the steel material, the increase in the surface hardness due to the formation of the nitride layer can be reduced. As a result, the hardness of the surface layer of the steel material is equal to the hardness of the steel material or lower than the hardness of the steel material, and the reduction of the critical diffusible hydrogen amount can be prevented.
The depth (thickness) of the low carbon region was set to a depth (thickness) of 100 μm or more from the surface of the steel material or bolt so as to obtain the above effect. The depth (thickness) of the low carbon region is preferably as deep (thick) as possible, but if it exceeds 1000 μm, the strength of the entire steel material or the entire bolt decreases, so the depth (thickness) of the low carbon region is 1000 μm. Is the upper limit.
Next, the nitride layer will be described. In the present invention, the nitride layer is a region having a nitrogen concentration of 12.0% by mass or less and 0.02% by mass or more higher than the nitrogen concentration of the steel material or bolt. The nitride layer is formed with a thickness of 200 μm or more from the surface of the steel material or bolt.
The thickness and nitrogen concentration of the nitride layer can be adjusted by the heating atmosphere, heating temperature, and holding time during the nitriding treatment. For example, when the concentration of ammonia or nitrogen in the heating atmosphere is high, the heating temperature is high, and the holding time is long, the nitride layer becomes thick and the nitrogen concentration of the nitride layer becomes high.
If the nitrogen concentration in the nitride layer is higher than the nitrogen concentration in the steel material, the amount of hydrogen entering the steel material from the corrosive environment can be reduced, but the difference between the nitrogen concentration in the nitride layer and the nitrogen concentration in the steel material is less than 0.02% by mass. And the effect of reducing the amount of intrusion hydrogen cannot be sufficiently obtained. Therefore, the nitrogen concentration of the nitrided layer is set to a concentration higher than the nitrogen concentration of the steel material by 0.02% by mass or more.
On the other hand, if the nitrogen concentration exceeds 12.0% by mass, the hardness of the nitrided layer increases excessively and becomes brittle, so 12.0% by mass was made the upper limit.
Corrosion occurs when a nitride layer is formed on the steel surface with a nitrogen concentration of 12.0 mass% or less, 0.02 mass% or more higher than the nitrogen concentration of the steel material, and a depth of 200 μm or more from the surface. The amount of hydrogen entering the steel from the environment is greatly reduced.
The nitrided layer was limited to a thickness (depth) of 200 μm or more from the surface of the steel material or bolt so that the above effect was obtained. The upper limit of the thickness of the nitrided layer is not particularly specified, but if it exceeds 1000 μm, the productivity is lowered and the cost is increased, so 1000 μm or less is preferable.
The depth (thickness) of the low carbon region formed in the high-strength steel material or high-strength bolt of the present invention can be determined from the carbon concentration curve from the surface of the steel material or bolt.
Polishing the cross section of a steel material or bolt having a low carbon region and a nitride layer on the surface layer, an energy dispersive X-ray fluorescence analyzer (hereinafter sometimes referred to as “EDX”), or a wavelength dispersive X-ray fluorescence analyzer ( Hereinafter, the carbon concentration in the depth direction from the surface is measured by performing a line analysis.
FIG. 2 shows a method for obtaining the depth (thickness) of the low carbon region from the carbon concentration curve obtained by EDX. That is, FIG. 2 is a diagram showing the relationship between the distance from the steel material surface and the carbon concentration obtained by measuring the carbon concentration in the depth direction from the surface using EDX.
As shown in FIG. 2, the carbon concentration increases as the distance (depth) from the steel surface increases. This is because a low carbon region is formed on the steel surface by decarburization.
In the region not affected by the decarburization treatment, the carbon concentration is substantially constant (average carbon concentration a). The average carbon concentration a is a carbon concentration in a region not affected by the decarburization process, and is equivalent to the carbon amount of the steel material before the decarburization process.
Therefore, in the present invention, the chemical analysis value of the carbon concentration of the steel material is used as a reference value for determining the depth of the low carbon region.
As shown in FIG. 2, the range in which the carbon concentration from the steel surface to the required depth is lower by 10% (a × 0.1) or more than the average carbon concentration a (0.9 times or less the carbon concentration of the steel material) The depth (thickness) of the low carbon region can be evaluated by determining the distance (depth) from the steel material surface at the boundary in the depth direction of the range.
The thickness (depth) of the nitride layer can be determined from the change in the nitrogen concentration from the surface of the steel material or bolt as in the low carbon region. Specifically, the cross section of a steel material or bolt having a low carbon region and a nitride layer on the surface layer is polished, and line analysis is performed by EDX or WDS to measure the nitrogen concentration in the depth direction from the surface.
FIG. 3 shows a method for determining the thickness (depth) of the nitride layer from the nitrogen concentration curve obtained with an energy dispersive X-ray fluorescence spectrometer (EDX). That is, FIG. 3 is a diagram showing the relationship between the distance from the steel material surface and the nitrogen concentration obtained by measuring the nitrogen concentration in the depth direction from the surface using EDX.
As the distance (depth) from the steel material surface increases, the nitrogen concentration decreases, but the carbon concentration is substantially constant (average nitrogen concentration) in a region not affected by nitriding treatment.
The average nitrogen concentration is a nitrogen concentration in a range not affected by the nitriding treatment, and is equivalent to the nitrogen amount of the steel material before the nitriding treatment. Therefore, in the present invention, the chemical analysis value of the nitrogen concentration of the steel material is used as a reference value for determining the thickness of the nitride layer.
As shown in FIG. 3, a range in which the nitrogen concentration from the steel surface to the required depth is 0.02% by mass or more of the average nitrogen concentration is determined, and from the steel surface at the boundary in the depth direction of the range. By obtaining the distance (depth), the thickness (depth) of the nitride layer can be evaluated.
The depth of the low carbon region and the thickness of the nitrided layer are obtained by simply averaging the values measured at any five points in the cross section of the steel material or bolt.
Note that the carbon concentration and the nitrogen concentration of the steel material may be obtained by measuring the carbon concentration and the nitrogen concentration at a position sufficiently deeper than the depth of the low carbon region and the nitrided layer, for example, at a depth of 2000 μm or more from the surface. Good. Alternatively, an analytical sample may be collected from a position at a depth of 2000 μm or more from the surface of the steel material or bolt, and obtained by chemical analysis.
In the high-strength steel material according to the present invention, as described above, (1) the formation of a nitride layer in the low carbon region formed on the steel material surface suppresses the amount of intruded hydrogen, and (2) the steel material surface By forming the low carbon region, the delayed fracture resistance is remarkably improved by a synergistic effect with the increase in the amount of critical diffusible hydrogen.
According to the inventors' investigation, the presence of a nitride layer and a low carbon region on the surface layer of the steel material suppresses the amount of hydrogen entering the steel material to 0.5 ppm or less, and the limit diffusible hydrogen content of the steel material Can be increased to 2.00 ppm or more.
Next, the reason for limiting the component composition of the steel material will be described. Hereinafter,% related to the component composition means mass%.
C: C is an essential element for securing the strength of the steel material. If it is less than 0.10%, the required strength cannot be obtained, and if it exceeds 0.55%, ductility and toughness are lowered and delayed fracture resistance is also lowered, so C is 0.10 to 0.00. 55%.
Si: Si is an element that increases strength by solid solution strengthening. If it is less than 0.01%, the effect of addition is insufficient, and if it exceeds 3%, the effect is saturated, so Si was made 0.01 to 3%.
Mn: Mn is an element not only for deoxidation and desulfurization but also for increasing the hardenability by lowering the transformation temperature of the pearlite structure or the bainite structure in order to obtain a martensite structure. If it is less than 0.1%, the effect of addition is insufficient. If it exceeds 2%, it segregates at the grain boundary during austenite heating, embrittles the grain boundary, and deteriorates the delayed fracture resistance. Was 0.1 to 2%.
The high-strength steel material or high-strength bolt of the present invention contains one or two of V and Mo in order to improve delayed fracture resistance.
V: V is an element for precipitating carbides, nitrides, and / or carbonitride fine precipitates in the steel material. This fine precipitate captures the hydrogen that has entered the steel material, renders it harmless, and acts to increase the amount of critical diffusible hydrogen. Moreover, the fine precipitate contributes to the strength improvement of the steel material.
V is an element that contributes to improving the strength by lowering the transformation temperature of the pearlite structure or bainite structure to enhance the hardenability and the softening resistance during the tempering treatment.
If V exceeds 1.5%, the solution temperature for precipitation strengthening becomes high, and the force for trapping hydrogen is saturated, so it was made 1.5% or less. If V is less than 0.05%, the effect of improving the strength due to the precipitation of fine precipitates cannot be obtained sufficiently, so 0.05% or more is preferable.
Mo: Mo is an element that precipitates carbides, nitrides, and / or carbonitride fine precipitates in the steel material. This fine precipitate captures the hydrogen that has entered the steel material, renders it harmless, and acts to increase the amount of critical diffusible hydrogen. Moreover, the fine precipitate contributes to the improvement of the delayed fracture resistance by increasing the critical diffusible hydrogen amount while contributing to the strength improvement of the steel material.
Mo is an element that contributes to the improvement of strength by lowering the transformation temperature of the pearlite structure and bainite structure to increase the hardenability and the softening resistance during the tempering treatment.
If Mo exceeds 3.0%, the solution temperature for precipitation strengthening becomes high, and the force for capturing hydrogen is saturated, so it was made 3.0% or less. If Mo is less than 0.4%, the effect of increasing the amount of critical diffusible hydrogen cannot be sufficiently obtained due to the precipitation of fine precipitates.
V + 1 / 2Mo: In the present invention, Mo and V need to satisfy V + 1 / 2Mo> 0.4%. If V and Mo satisfy the above formula, the amount of V that increases not only the amount of limit diffusible hydrogen but also the amount of invading hydrogen is relatively small with respect to the amount of Mo. Delayed fracture resistance can be obtained.
The high-strength steel material or high-strength bolt of the present invention is one or two kinds of Cr, Nb, Cu, Ni, and B as long as the excellent delayed fracture resistance is not excluded for the purpose of improving the strength. You may contain the above.
Cr: Cr is an element that lowers the transformation temperature of the pearlite structure or bainite structure to increase the hardenability, and increases the softening resistance during the tempering process, thereby contributing to the improvement of the strength. If it is less than 0.05%, the effect of addition cannot be sufficiently obtained, and if it exceeds 1.5%, the toughness is deteriorated, so Cr is made 0.05 to 1.5%.
Nb: Nb, like Cr, is an element that contributes to improving strength by increasing hardenability and temper softening resistance. If it is less than 0.001%, the effect of addition is not sufficiently obtained, and if it exceeds 0.05%, the effect of addition is saturated, so Nb was made 0.001 to 0.05%.
Cu: Cu is an element that contributes to improving the hardenability, increasing the temper softening resistance, and improving the strength due to the precipitation effect. If it is less than 0.01%, the effect of addition cannot be sufficiently obtained. If it exceeds 4%, grain boundary embrittlement occurs and the delayed fracture resistance deteriorates, so Cu was made 0.01 to 4%.
Ni: Ni is an element that increases the hardenability and is effective in improving ductility and toughness that decrease with increasing strength. If it is less than 0.01%, the effect of addition is not sufficiently obtained, and if it exceeds 4%, the effect of addition is saturated, so Ni was made 0.01 to 4%.
B: B is an element that suppresses grain boundary fracture and is effective in improving delayed fracture resistance. Further, B is an element that segregates at the austenite grain boundary and remarkably increases the hardenability. When the content is less than 0.0001%, the effect of addition cannot be sufficiently obtained. When the content exceeds 0.005%, B carbide or Fe carbon boride is generated at the grain boundary, and grain boundary embrittlement occurs, resulting in delay resistance. Since the fracture characteristics deteriorate, B is set to 0.0001 to 0.005%.
The high-strength steel material and high-strength bolt of the present invention are one or two of Al, Ti, Mg, Ca, and Zr as long as the excellent delayed fracture resistance is not excluded for the purpose of refining the structure. It may contain seeds or more.
Al: Al is an element that forms oxides and nitrides, prevents coarsening of austenite grains, and suppresses deterioration of delayed fracture resistance. If it is less than 0.003%, the effect of addition is insufficient, and if it exceeds 0.1%, the effect of addition is saturated. Therefore, Al is preferably 0.003 to 0.1%.
Ti: Ti, like Al, is an element that forms oxides and nitrides to prevent coarsening of austenite grains and suppress deterioration of delayed fracture resistance. If it is less than 0.003%, the effect of addition is insufficient, and if it exceeds 0.05%, Ti carbonitride is coarsened during rolling or processing, or during heat treatment, and the toughness is reduced. Ti is preferably 0.003 to 0.05%.
Mg: Mg has deoxidation and desulfurization effects, and forms Mg oxide, Mg sulfide, Mg-Al, Mg-Ti, Mg-Al-Ti complex oxides and sulfides, etc. An element that prevents coarsening of austenite grains and suppresses deterioration of delayed fracture resistance. If it is less than 0.0003%, the effect of addition is insufficient, and if it exceeds 0.01%, the effect of addition is saturated. Therefore, Mg is preferably 0.0003 to 0.01%.
Ca: Ca has a deoxidizing and desulfurizing effect, and also forms Ca oxide, Ca sulfide, Al, Ti, Mg composite oxide and composite sulfide to prevent austenite grain coarsening. It is an element that suppresses the deterioration of delayed fracture resistance. If it is less than 0.0003%, the effect of addition is insufficient, and if it exceeds 0.01%, the effect of addition is saturated. Therefore, Ca is preferably 0.0003 to 0.01%.
Zr: Zr forms Zr oxide, Zr sulfide, composite oxide or composite sulfide of Al, Ti, Mg, Zr, etc., prevents austenite grains from coarsening, and deteriorates delayed fracture resistance. It is an element to suppress. If it is less than 0.0003%, the effect of addition is insufficient, and if it exceeds 0.01%, the effect of addition is saturated, so Zr is preferably 0.0003 to 0.01%.
Next, the structure of the high-strength steel material and the high-strength bolt of the present invention (hereinafter sometimes referred to as “the steel structure of the present invention”) will be described. Since the steel structure of the present invention is mainly tempered martensite, it has a good ductility and toughness even when the tensile strength is 1300 MPa or more.
In the steel structure of the present invention, the area ratio of tempered martensite in the low carbon region and the region excluding the nitrided layer is 85% or more, and the balance is a structure composed of one or more of retained austenite, bainite, pearlite, and ferrite. Is preferred.
The area ratio of tempered martensite is the deeper of the depth at which the carbon concentration is constant in the carbon concentration curve shown in FIG. 2 and the depth at which the nitrogen concentration is constant in the nitrogen concentration curve shown in FIG. Measure with
For example, the area ratio of tempered martensite may be measured at a depth of 2000 μm or more from the surface of the steel material or bolt, or at a site that is 1/4 of the thickness or diameter of the steel material.
In addition, the area ratio of martensite can be obtained by observing the C cross section of a steel material using an optical microscope and measuring the area of martensite per unit area. Specifically, the C cross section of the steel material is polished and etched with a nital etchant, the area of martensite in five fields in the range of 0.04 mm ² is measured, and the average value is calculated.
Further, in the steel material of the present invention, the compressive residual stress on the steel material surface is generated by heating and rapid cooling during the nitriding treatment, thereby improving delayed fracture resistance. When the compressive residual stress is 200 MPa or more, the delayed fracture resistance is improved. Therefore, the compressive residual stress on the surface of the steel of the present invention is preferably 200 MPa or more.
The compressive residual stress can be measured using an X-ray residual stress measuring device. Specifically, the residual stress on the steel material surface is measured, and then the steel material surface is etched by 25 μm by electropolishing to measure the residual stress in the depth direction. It is preferable to measure three arbitrary points and use the average value.
In the steel material in which the low carbon region and the nitride layer are not formed on the surface layer, when the tensile strength is 1300 MPa or more, the occurrence frequency of delayed fracture is remarkably increased. Therefore, when the tensile strength is 1300 MPa or more, the delayed fracture resistance of the steel material of the present invention in which the low carbon region and the nitride layer are formed on the surface layer is remarkably excellent.
Although the upper limit of the tensile strength of the steel of the present invention is not particularly limited, it is technically difficult to exceed 2200 MPa at the present time, and therefore, the upper limit is 2200 MPa. In addition, what is necessary is just to measure a tensile strength based on JISZ2241.
Manufacturing method Next, the manufacturing method of this invention steel material is demonstrated.
The manufacturing method of the steel material of the present invention includes a decarburization process in which a decarburization process is performed by heating a steel material (wire material, PC steel rod, steel material processed into a predetermined shape) having a required component composition, and a decarburized steel material. And quenching the steel structure into a martensite-based structure, and a nitriding process in which the quenched steel material is subjected to nitriding treatment at over 500 ° C. and below 650 ° C.
Note that the structure of the steel material of the present invention becomes a structure mainly composed of tempered martensite by the nitriding step.
In the decarburization step, the steel material of the present invention is decarburized, and the carbon concentration is 0.05% or more and 0.9 times or less of the carbon concentration of the steel material from the surface of the steel material to a depth of 100 μm or more and 1000 μm or less. To do. For example, the atmosphere of the heating furnace can be weakly decarburized by adjusting the concentration of methane gas to form a low carbon region.
The heating temperature in the decarburization treatment is preferably Ac ₃ to 950 ° C. By heating to Ac ₃ or higher, the steel structure becomes austenite, decarburization from the surface layer is promoted, and a low carbon region can be easily formed.
The upper limit of the heating temperature is preferably 950 ° C. from the viewpoint of suppressing coarsening of crystal grains and improving delayed fracture resistance. The holding time at the heating temperature is preferably 30 to 90 minutes. By maintaining at the above heating temperature for 30 minutes or more, the depth of the low carbon region can be sufficiently secured and the steel structure can be made homogeneous. Considering productivity, the holding time at the heating temperature is preferably 90 minutes or less.
In the quenching step, the heated steel material is cooled to a martensite-based structure. The heated steel material may be quenched with oil as it is.
Since the area ratio of tempered martensite is preferably 85% or more in the steel structure of the present invention, the area ratio of martensite after quenching is preferably 85% or more.
In order to ensure an area ratio of martensite of 85% or more in the quenching step, it is preferable to set the cooling rate in the range of 700 to 300 ° C. to 5 ° C./s or more during quenching. If the cooling rate is less than 5 ° C / s, the area ratio of martensite may be less than 85%.
In the nitriding step, nitriding treatment is performed on a steel material whose steel structure is mainly martensite and a low carbon region is formed on the surface layer. By nitriding, a nitride layer having a thickness from the steel surface of 200 μm or more and a nitrogen concentration of 12.0% or less and 0.02% or more higher than the nitrogen concentration of the steel material is formed. Tempering is performed to make the steel structure a structure mainly composed of tempered martensite and to precipitate fine precipitates that capture hydrogen.
In the method for producing a steel material of the present invention, since the steel material contains one or both of V and Mo, fine carbides, nitrides, and / or carbonitrides (fine particles) that act to trap hydrogen in the nitriding step. Precipitate).
The nitriding treatment is performed, for example, by heating a steel material in an atmosphere containing ammonia or nitrogen. The nitriding treatment is preferably held at 500 ° C. or higher and 650 ° C. or lower for 30 to 90 minutes. If the nitriding temperature exceeds 650 ° C., the strength of the steel material decreases, so the nitriding temperature is set to 650 ° C. or lower.
If the nitriding temperature is 500 ° C. or less, fine precipitates are not sufficiently precipitated, so the nitriding temperature is set to be over 500 ° C. Further, if the temperature of the nitriding treatment exceeds 500 ° C., the time required for diffusion of nitrogen from the steel material surface is shortened, the treatment time is shortened, and the productivity is increased.
If the nitriding time is less than 30 minutes, the depth of the nitrided layer may not reach 200 μm or more from the surface, so the nitriding time is preferably 30 minutes or longer. Although the upper limit of the nitriding time is not specified, since the nitriding temperature is high in the present invention, a sufficiently thick nitride layer can be formed even in 90 minutes or less.
In the nitriding step, a general nitriding method such as a gas nitriding method, a gas soft nitriding method, a plasma nitriding method, or a salt bath nitriding method can be used.
Next, a method for producing the high-strength bolt of the present invention (hereinafter sometimes referred to as “the bolt of the present invention”) will be described.
The manufacturing method of the bolt according to the present invention includes a processing step for processing the steel material according to the present invention into a bolt, a decarburizing step for heating and decarburizing the bolt, cooling the heated bolt, and It consists of a quenching process with a site-based structure and a nitriding process in which the quenched bolt is nitrided at a temperature of more than 500 ° C. and 650 ° C. or less.
In the nitriding process, the steel structure of the bolt becomes a structure mainly composed of tempered martensite.
In the processing step, for example, a wire material that is a steel material may be cold-forged and rolled into a bolt shape.
Since the manufacturing method of the bolt of the present invention differs from the manufacturing method of the steel material of the present invention only in the processing step of processing the steel material into a bolt shape, the description of the other steps is omitted.
In the method for producing the steel material of the present invention and the method for producing the bolt of the present invention, it is preferable to rapidly cool the range from 500 to 200 ° C. at a cooling rate of 10 to 100 ° C./s after nitriding. By the rapid cooling after the nitriding treatment, the compressive residual stress on the surface of the steel material or bolt can be set to 200 MPa or more. Due to the presence of this compressive residual stress, the delayed fracture resistance is further improved.

Next, examples of the present invention will be described. The conditions in the examples are one example of conditions used for confirming the feasibility and effects of the present invention, and the present invention is based on this one example of conditions. It is not limited. The present invention can adopt various conditions as long as the object of the present invention is achieved without departing from the gist of the present invention.
(Example)
Molten steel having the composition shown in Table 1 was cast according to a conventional method, and the slab was hot worked to obtain a steel material (wire). The steel was heated to Ac ₃ to 950 ° C., cooled as it was, and quenched.
During heating, the atmosphere in the heating furnace was controlled to be weakly decarburized, and quenching was oil-cooled so that the cooling rate in the range of 700 to 300 ° C. was 5 ° C./s or more. The depth of the low carbon region was adjusted by the carbon potential of the furnace atmosphere, the heating temperature and the holding time.

Thereafter, the steel material was subjected to nitriding treatment to form a nitrided layer by gas soft nitriding. After nitriding, the range of 500 to 200 ° C. was quenched at the cooling rate shown in Table 2 (cooling rate after tempering). 1 to 25 high strength steel materials were obtained.
The nitriding treatment was performed at a temperature shown in Table 2 with an ammonia volume ratio in the treatment gas atmosphere of 30 to 50% and a treatment time of 30 to 90 minutes.
The thickness of the nitride layer was adjusted by changing the heating temperature and holding time. The nitrogen concentration of the nitride layer was adjusted by changing the ammonia volume ratio in the processing gas atmosphere.

Steel materials (wires) shown in Table 1 were processed into bolts and manufactured No. In the same process as the high-strength steel materials (wires) 1 to 25, the production No. 26 to 40 high-strength bolts were obtained. The nitriding treatment was performed in the temperature range shown in Table 3, and after the nitriding treatment, the range of 500 to 200 ° C. was rapidly cooled at the cooling rate shown in Table 3 (cooling rate after tempering).

Production No. No. 1 to 25 high strength steel (Table 2) and production No. Tempered martensite ratio, tensile strength, low carbon region depth, nitrided layer thickness, compressive residual stress, amount of penetrating hydrogen, amount of critical diffusible hydrogen, and delayed fracture resistance of high-strength bolts of 26 to 40 (Table 3) The characteristics were measured by the method shown below. The results are also shown in Table 2 and Table 3.
Tempered Martensite Ratio Tempered martensite ratio No. 1 to 25 high strength steel and production No. The C section of 26 to 40 high-strength bolts was polished and etched with a nital etchant, and using an optical microscope, the area of martensite with 5 visual fields in the range of 0.04 mm ² was measured. did.
Production No. No. 1 to 25 high strength steel and production No. In the high-strength bolts of 27 to 41, the remaining structure of the tempered martensite was one or more of retained austenite, bainite, pearlite, and ferrite.
Tensile strength The tensile strength was measured according to JIS Z 2241.
Low carbon region depth and nitride layer thickness No. 1 to 25 high strength steel and production No. The cross-sections of 26 to 40 high-strength bolts were polished, and the carbon concentration and the nitrogen concentration in the depth direction from the surface were measured at any five locations in the longitudinal direction using EDX.
The depth (thickness) of the region where the carbon concentration is 0.9 times or less the carbon concentration of the steel material ((carbon concentration in the low carbon region / carbon concentration in the steel material) ≦ 0.9) is expressed as “low carbon region depth. The depth (thickness) of the region where the nitrogen concentration is 0.02% or more higher than the nitrogen concentration of the steel material (nitrogen concentration of the nitride layer−nitrogen concentration of the steel material ≧ 0.02) is referred to as “nitride layer thickness”. did.
The depth of the low carbon region and the thickness of the nitride layer were average values of values measured at arbitrary five locations in the longitudinal direction.
Compressive residual stress The compressive residual stress of the surface was measured using an X-ray residual stress measuring apparatus. Production No. 1 to 25 high-strength steel materials and production no. After measuring the residual stress on the surface of 26 to 40 high-strength bolts, the surface was etched by 25 μm by electrolytic polishing, and the residual stress in the depth direction was measured. The compressive residual stress was an average value of values measured at three arbitrary locations.
Limiting diffusible hydrogen content and delayed fracture resistance No. 1 to 25 high strength steel and production No. A delayed fracture specimen having the shape shown in FIG. 4 was produced from 26 to 40 high-strength bolts, and hydrogen was allowed to enter. For the hydrogen intrusion, an electrolytic hydrogen charging method was used, and the charge current was changed to change the amount of intruding hydrogen as shown in Tables 2 and 3.
In order to prevent the escape of diffusible hydrogen, the surface of the delayed fracture test piece into which hydrogen had penetrated was subjected to Cd plating and left at room temperature for 3 hours to homogenize the hydrogen concentration inside the test piece.
Thereafter, using a delayed fracture tester shown in FIG. 5, a constant load delayed fracture test was performed in which a tensile load of 90% of the tensile strength was applied to the test piece 1. In the testing machine shown in FIG. 5, when applying a tensile load to the test piece 1, the balance weight 2 is arranged at one end of the lever having the fulcrum 3 as a fulcrum, and the test piece 1 is arranged at the other end. The test was conducted.
And as shown in FIG.1 (b), the maximum value of the diffusible hydrogen amount of the test piece 1 which did the constant load delayed fracture test for 100 hours or more and did not fracture | rupture was made into the limit diffusible hydrogen amount. Regarding the amount of diffusible hydrogen in test piece 1, the delayed fracture test piece was heated at 100 ° C./h, and the integrated value of the amount of hydrogen released between room temperature and 400 ° C. was measured with a gas chromatograph.
Comparing the amount of intrusion hydrogen and the amount of critical diffusible hydrogen for delayed fracture, if the amount of critical diffusible hydrogen is greater than the amount of intruded hydrogen, delayed fracture does not occur. When the amount of hydrogen is small, delayed fracture occurs.
Therefore, the delayed fracture resistance indicates “no delayed fracture” when the intrusion hydrogen amount shown in Table 2 and Table 3 is less than the limit diffusible hydrogen amount, and when the intrusion hydrogen amount is equal to or greater than the limit diffusible hydrogen amount. It was evaluated that there was delayed fracture.
Intrusion hydrogen amount The intrusion hydrogen amount is determined according to the production no. No. 1 to 25 high strength steel and production No. Test pieces of 26 to 40 high-strength bolts were prepared, and 30 cycles of the corrosion acceleration test using the temperature / humidity / time pattern shown in FIG. 6 were performed.
After removing the corrosion layer on the surface of the test piece by sand blasting, hydrogen analysis was performed by a temperature rising method, and the amount of hydrogen released from room temperature to 400 ° C. was measured to determine the amount of invading hydrogen.
As shown in Table 2, the production No. of the invention example. 1 to 15 high-strength steel materials have a low carbon region depth of 100 μm or more and a nitrided layer thickness of 200 μm or more, all of which have a tensile strength of 1300 MPa or more and an intrusion hydrogen amount of 0.5 ppm or less. The amount of ionic hydrogen was 2.00 ppm or more and the amount of invading hydrogen was less than the limit diffusible hydrogen amount, indicating “no delayed fracture”.
In addition, production No. Each of the high strength steel materials 1 to 15 had a tempered martensite ratio of 50% or more, and was a tempered martensite-based structure. In addition, production No. All the high strength steel materials 1 to 15 had a compressive residual stress of 200 MPa or more.
On the other hand, as shown in Table 2, the production No. No. 16 high-strength steel material is an example in which the amount of C, the amount of Si and the amount of Mn are small and the strength is low.
Production No. No. 17 has a large amount of C. No. 18 has a large amount of Mn. No. 19 has a large amount of Cr. No. 21 has a large amount of Cu. No. 22 has a large amount of B. No. 20 is an example in which the amount of critical diffusible hydrogen is low because “V + 1 / 2Mo” is low, resulting in “with delayed fracture”.
In addition, production No. No. 23 is an example in which the heating time for quenching is short, the depth of the low carbon region is less than 100 μm, the amount of critical diffusible hydrogen is low, and “delayed fracture occurs”. Production No. No. 24 is an example in which the time for the nitriding treatment is short, the nitrided layer thickness is less than 200 μm, the amount of invading hydrogen is large, and “delayed fracture occurs”.
Production No. In No. 25, since the concentration of ammonia in the nitriding gas was lowered, the difference in nitrogen concentration with the steel material was 0.01% by mass in the region from the surface to a depth of 200 μm, and the amount of invading hydrogen was large. This is an example.
As shown in Table 3, the production numbers of the invention examples. High strength bolts of 26 to 40 have a low carbon region depth of 100 μm or more, a nitrided layer thickness of 200 μm or more, all of which have a tensile strength of 1300 MPa or more, an intrusion hydrogen amount of 0.5 ppm or less, and limit diffusion. The amount of ionic hydrogen was 2.00 ppm or more and the amount of invading hydrogen was less than the limit diffusible hydrogen amount, indicating “no delayed fracture”.
Production No. Each of the high-strength bolts of 26 to 40 had a tempered martensite ratio of 50% or more, a tempered martensite-based structure, and a compressive residual stress of 200 MPa or more.
From Table 2 and Table 3, only the point which processed the steel material (wire) into the volt | bolt is manufacture No.2. Production No. different from 1-15 high strength steel. The high strength bolts of 26 to 40 (the high strength bolts of production No. 26 to 40 correspond to the high strength steel materials of production Nos. 1 to 15) are more intruded hydrogen than the high strength steel materials. It can be seen that the amount is suppressed.

As described above, according to the present invention, high-strength steel materials (wire rods, PC steel rods) and high-strength bolts that exhibit excellent delayed fracture resistance even in severe corrosive environments, and these can be manufactured at low cost. A manufacturing method can be provided. Therefore, the present invention has extremely high applicability in the steel material manufacturing and use industries.

1 test piece 2 balance weight 3 fulcrum

Claims

% By mass
C: 0.10 to 0.55%,
Si: 0.01 to 3%,
Mn: 0.1-2%
In addition,
V: 1.5% or less and Mo: 3.0% or less of 1 type or 2 types, and the contents of V and Mo are
V + 1 / 2Mo> 0.4%
Meet, and
Cr: 0.05 to 1.5%,
Nb: 0.001 to 0.05%,
Cu: 0.01 to 4%,
Ni: 0.01 to 4%, and
B: 0.0001 to 0.005%
One or more of the following, the balance is made of Fe and unavoidable impurities, the structure is a steel material mainly composed of tempered martensite,
On the surface layer of the steel material,
(A) a nitride layer having a thickness from the surface of the steel material of 200 μm or more and a nitrogen concentration of 12.0% by mass or less, which is 0.02% by mass or more higher than the nitrogen concentration of the steel material; and
(B) A low carbon region having a depth from the surface of the steel material of 100 μm or more and 1000 μm or less and a carbon concentration of 0.05% by mass or more and 0.9 times or less of the carbon concentration of the steel material is formed. High strength steel with excellent delayed fracture resistance.
The amount of hydrogen entering the steel material is 0.5 ppm or less due to the presence of the nitrided layer and the low carbon region, and the limit diffusible hydrogen content of the steel material is 2.00 ppm or more. High strength steel with excellent delayed fracture resistance as described.
Furthermore, the said steel material is the mass%,
Al: 0.003 to 0.1%,
Ti: 0.003 to 0.05%,
Mg: 0.0003 to 0.01%
Ca: 0.0003 to 0.01%,
Zr: 0.0003 to 0.01%
The high-strength steel material excellent in delayed fracture resistance according to claim 1 or 2, characterized by containing one or more of the following.
The high-strength steel material having excellent delayed fracture resistance according to any one of claims 1 to 3, wherein the nitride layer has a thickness of 1000 µm or less.
The high strength steel material having excellent delayed fracture resistance according to any one of claims 1 to 4, wherein an area ratio of the tempered martensite is 85% or more.
6. The high-strength steel material excellent in delayed fracture resistance according to any one of claims 1 to 5, wherein a compressive residual stress on the surface of the steel material is 200 MPa or more.
The high-strength steel material having excellent delayed fracture resistance according to any one of claims 1 to 6, wherein the steel material has a tensile strength of 1300 MPa or more.
% By mass
C: 0.10 to 0.55%,
Si: 0.01 to 3%,
Mn: 0.1-2%
In addition,
V: 1.5% or less and Mo: 3.0% or less of 1 type or 2 types, and the contents of V and Mo are
V + 1 / 2Mo> 0.4%
Meet, and
Cr: 0.05 to 1.5%,
Nb: 0.001 to 0.05%,
Cu: 0.01 to 4%,
Ni: 0.01 to 4%, and
B: 0.0001 to 0.005%
1 or 2 or more of the following, the balance is made of Fe and inevitable impurities, the structure is a bolt processed steel material that is a tempered martensite-based structure,
On the surface of the bolt,
(A) a nitride layer having a thickness from the surface of the bolt of 200 μm or more and a nitrogen concentration of 12.0% by mass or less, which is 0.02% by mass or more higher than the nitrogen concentration of the steel material; and
(B) A low carbon region having a depth from the surface of the bolt of 100 μm to 1000 μm and a carbon concentration of 0.05% by mass or more and 0.9 times or less of the carbon concentration of the steel material is formed. A high-strength bolt with excellent delayed fracture resistance.
9. The amount of hydrogen penetrating into the bolt is 0.5 ppm or less due to the presence of the nitride layer and the low carbon region, and the limiting diffusible hydrogen content of the bolt is 2.00 ppm or more. High strength bolt with excellent delayed fracture resistance as described.
Furthermore, the said steel material is the mass%,
Al: 0.003 to 0.1%,
Ti: 0.003 to 0.05%,
Mg: 0.0003 to 0.01%
Ca: 0.0003 to 0.01%,
Zr: 0.0003 to 0.01%
The high-strength bolt excellent in delayed fracture resistance according to claim 8 or 9, characterized by containing one or more of the following.
The high-strength bolt excellent in delayed fracture resistance according to any one of claims 8 to 10, wherein the nitride layer has a thickness of 1000 µm or less.
The high-strength bolt excellent in delayed fracture resistance according to any one of claims 8 to 11, wherein the area ratio of the tempered martensite is 85% or more.
The high-strength bolt excellent in delayed fracture resistance according to any one of claims 8 to 12, wherein a compressive residual stress on the surface of the bolt is 200 MPa or more.
The high strength bolt excellent in delayed fracture resistance according to any one of claims 8 to 13, wherein the bolt has a tensile strength of 1300 MPa or more.
A method for producing a high-strength steel material having excellent delayed fracture resistance according to any one of claims 1 to 7,
(1) The steel material having the composition according to claim 1 or 3 is heated to a depth of 100 μm or more and 1000 μm or less from the surface of the steel material, the carbon concentration is 0.05 mass% or more, and the carbon concentration of the steel material is Form a low carbon region of 0.9 times or less, then cooled as it is, the steel structure is a martensite-based structure,
(2) The steel material is subjected to nitriding treatment at a temperature exceeding 500 ° C. and not more than 650 ° C., and the nitrogen concentration of the steel material is 12.0% by mass or less and 0.02% by mass than the nitrogen concentration of the steel material. Production of high-strength steel material excellent in delayed fracture resistance, characterized by forming a nitride layer with a thickness of 200 μm or more from the surface of the steel material higher than the above, and having the steel material structure mainly composed of tempered martensite Method.
The method for producing a high-strength steel material having excellent delayed fracture resistance according to claim 15, wherein the nitride layer has a thickness of 1000 μm or less.
A method for producing a bolt excellent in delayed fracture resistance according to any one of claims 8 to 14,
(1) A bolt obtained by processing a steel material having the component composition according to claim 8 or 10 is heated to have a carbon concentration of 0.05% by mass or more from the surface of the bolt to a depth of 100 μm or more and 1000 μm or less. Forming a low carbon region of 0.9 times or less of the carbon concentration of, and then cooling as it is, the steel structure becomes a martensite-based structure,
(2) The bolt is subjected to nitriding treatment at over 500 ° C. and not more than 650 ° C., and the nitrogen concentration is 12.0 mass% or less on the surface layer of the bolt, and 0.02 mass% than the nitrogen concentration of the steel material. A method for producing a high-strength bolt excellent in delayed fracture resistance, characterized in that a nitride layer having a thickness of 200 μm or more from the surface of the bolt is formed, and the steel is made of a tempered martensite-based structure. .
The method for producing a high-strength bolt excellent in delayed fracture resistance according to claim 17, wherein the nitride layer has a thickness of 1000 μm or less.