WO2011013361A1

WO2011013361A1 - Treatment liquid for forming protective film for steel member having nitrogen compound layer, and compound layer protective film

Info

Publication number: WO2011013361A1
Application number: PCT/JP2010/004781
Authority: WO
Inventors: 小西知義; 池田芳宏; 別府正昭
Original assignee: 日本パーカライジング株式会社
Priority date: 2009-07-31
Filing date: 2010-07-28
Publication date: 2011-02-03
Also published as: JP5520536B2; JP2011032513A

Abstract

Disclosed is a means for preventing oxidation of a compound layer by high-frequency hardening, said compound layer having been formed on the surface of a steel material by nitriding. Specifically disclosed is a treatment liquid for forming a compound layer protective film, which is a nonaqueous treatment liquid for forming a protective film on a nitride layer for the purpose of protecting the compound, said nitride layer having been formed on a steel material after nitriding. The treatment liquid for forming a compound layer protective film is characterized by containing at least one molten metal alkoxide, metal acetylacetonate and/or metal carboxylate of a metal selected from the metal group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg and Mo.

Description

Protective film forming treatment liquid for steel member having nitrogen compound layer, and compound layer protective film

The present invention relates to a hardened steel material used as a mechanical structural component having excellent mechanical strength such as surface pressure strength, wear resistance, bending fatigue strength, a manufacturing method thereof, and a treatment liquid used therefor.

Conventionally, in order to improve mechanical strength, surface hardening treatments such as nitriding treatment (including soft nitriding treatment), carburizing and quenching, induction hardening, etc. have been applied to cast iron and steel mechanical structural parts.
Among these, a compound layer made of nitride formed on the outermost surface by nitriding treatment is known to have excellent sliding properties, wear resistance, and high seizure resistance (hereinafter referred to as nitrogen compound). Called layer effect I ). However, in general, nitriding treatment is inferior in surface pressure strength, fatigue strength, etc. compared to carburizing quenching and induction quenching. For example, when a roller pitching test is performed, the nitrogen compound layer peels from the steel substrate. There is a case. For this reason, the nitrogen compound layer was widely believed to have a negative effect in fatigue tests at high surface pressures exceeding 2 GPa. The present inventors have found that this factor is not in the compound layer itself but because the hardened layer depth of the substrate supporting the compound layer is shallow. In other words, the nitriding unit alone has insufficient the depth of the hardened layer immediately below it in order to make full use of the good slidability of the outermost compound layer.

By the way, a steel material containing nitrogen has a finer martensite structure obtained after quenching than a steel material not containing nitrogen, so that the hardness is increased, and the hardening depth is increased by improving the hardenability. It is known. That is, the nitriding treatment can also be used as a nitrogen diffusion pretreatment for forming a nitrogen diffusion layer for improving hardenability (hereinafter referred to as effect II by forming a nitrogen compound layer). That is, the characteristics that can be obtained by using this effect II are not due to the action of the nitrogen compound layer itself, but due to the action of diffused nitrogen in the steel immediately below the nitrogen compound layer generated when the nitrogen compound layer is formed. Is.
The nitrogen-containing martensite structure obtained by quenching has high surface pressure strength and high fatigue strength due to resistance to temper softening, resistance to crack initiation and growth, in addition to the above-mentioned high hardness and hardenability improvement. It has been known.

When induction hardening is performed as it is after nitriding, the quenching temperature must be at least the temperature Ac3 transformation point at which an austenite structure is formed, and is usually selected from a temperature range of 750 to 1050 ° C. The nitrogen compound layer formed at a nitriding temperature of 570 ° C. is a combination of iron and nitrogen. When reheated to 650 ° C. or higher in an air atmosphere, the nitrogen compound layer undergoes oxidation and decomposes. It is released as a gas and the nitrogen compound layer disappears. This has been reported for a long time (Non-Patent Document 1).

The combined heat treatment technique by nitriding and quenching usually uses only the effect II of the nitrogen diffusion layer obtained by nitriding, and does not use the effect I of the nitrogen compound layer formed by nitriding. That is, the nitrogen compound layer does not stop disappearing during quenching, which is a subsequent process of nitriding. There are many disclosure examples for this technology, and for example, the composite heat treatment described in Patent Documents 1 to 5 can be mentioned.

Patent Document 6 discloses a composite heat treatment method in which a nitriding treatment is performed at a temperature of 600 ° C. or higher to form a nitrogen compound layer having a thickness of 5 μm or less, followed by induction hardening to obtain a quenched member having a nitrogen compound layer having a thickness of 2 μm or less. ing. The reason why the nitriding condition is set to a high temperature of 600 ° C. or higher in the present technology is that a higher concentration of nitrogen diffusion can be expected at the deeper side of the steel material. Is a nitrogen compound layer having a low effect I. That is, the present technology also expects only the effect II by the nitrogen compound layer, and the remaining nitrogen compound layer of 2 μm or less may be omitted.

As described above, in fatigue strength at high surface pressure, there has been a widespread misconception that the nitrogen compound layer is rather detrimental, so there is almost no technology that tries to combine the effects I and II with the nitrogen compound. It is. The problem of the damage and disappearance of the nitride layer due to high-temperature heating by induction-hardening the nitride layer formed on the surface by such nitriding treatment as it is is solved and both the effects I and II are attempted. As a non-technical technique, there is a method in which a gas nitriding / ion nitriding inhibitor containing silicon oxide as a component, a carburizing inhibitor, and an antioxidant are coated on the surface after nitriding treatment to a thickness of 1 to 3 mm, followed by quenching. Patent Document 7 discloses this.

However, in this method, even if the oxidation phenomenon during heating can be prevented, since the thermal conductivity is low due to the thick film of 1 mm or more, the cooling rate during quenching necessary for martensitic transformation becomes insufficient. It was actually difficult to obtain the desired fine martensite.

Further, in Patent Document 8 to be used for both effects I and II, a hard nitride layer is formed on the surface of a steel material, and further, Ti, Zr, Hf, V, Nb, Ta, Cr, W are formed thereon. A hardened steel member is disclosed in which an inorganic compound layer containing at least one metal oxide selected from the group consisting of Mo and Al is formed.

This patent relates to a “quenched surface protective agent” using neutral to alkaline water as a solvent, but is not necessarily sufficient for preventing oxidation of the nitrogen compound layer. In some cases, the surface layer was oxidatively decomposed.
Patent No. 3193320 Japanese Patent No. 3327386 Japanese Patent No. 3145517 JP-A-7-90364 JP 2007-154254 A JP 2007-77411 A JP 58-96815 JP 2008-038220 Heat treatment Vol.16 No.4 P206 1976

In view of the above problems, the present invention investigates and elucidates the mechanism by which the nitrogen compound layer obtained by nitriding treatment causes oxidation during the subsequent high-frequency heat treatment, and develops an effective antioxidant that prevents it. Therefore, it is an object of the present invention to provide a method for producing a quenched steel material, a steel material, and a treatment liquid used therefor that prevent oxidation by induction quenching of a compound layer formed on the surface of the steel material by nitriding.

In the present invention (1), Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, coated as a dry solid state on a nitride layer formed after nitriding treatment on a steel material, A compound layer protective film containing at least one metal selected from the group consisting of W, Al, Sr, Zn, Mg, and Mo, wherein the compound layer protective film is formed from a non-aqueous treatment liquid. It is formed in a range of 0.05 to 3 g / m ² in total, and is heated for 0.3 to 5 seconds until reaching a predetermined heating temperature to be performed thereafter, and the reached temperature is 750 to 860 ° C. It is a compound layer protective film that suppresses decomposition of the compound layer during induction hardening.

The present invention (2) is a non-aqueous treatment liquid for forming a protective film according to claim 1 for protecting the nitride on a nitride layer formed after nitriding treatment on a steel material, At least one dissolved metal selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo A compound layer protective film-forming treatment solution containing an alkoxide, metal acetylacetonate and / or metal carboxylate.

In the present invention (3), the treatment liquid is selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo. At least one dissolved metal alkoxide selected from: metal acetylacetonate and / or metal carboxylate and / or Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Dispersed particles having an average particle diameter of 4 to 40 nm including at least one selected from the group consisting of Al, Sr, Zn, Mg, and Mo; and Si, Ti, Zr, Hf, V, Ta, Ca, And dispersed particles having an average particle diameter of 40 to 400 nm including at least one selected from the group consisting of Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo. ,in front In the compound layer protective film-forming treatment solution of the invention (2), the ratio of the mass occupied by the dry solid state to the mass occupied by the latter as the dry solid state is 1:10 to 10: 1 is there.

The present invention (4) is the compound layer protective film-forming treatment liquid according to the invention (2) or (3), wherein the treatment liquid contains 0.1 to 400 g / L of at least one amine. is there.

According to the present invention (5), in the steel material having a nitride layer formed on the surface by nitriding treatment, the compound layer protective film formed from the treatment liquid according to any one of the inventions (2) to (4) is the nitride. In a state where it is formed on the layer, it is heated for 0.3 to 5 seconds until reaching a predetermined heating temperature, and subjected to induction hardening processing at which the reaching temperature is 750 to 860 ° C. It is a hardened steel material.

The present invention (6) is an application process in which a steel material having a nitride layer formed on the surface by nitriding treatment is prepared, and the treatment liquid according to any one of the inventions (2) to (4) is applied onto the nitride layer. A protective film forming step of drying the treatment liquid after the application step and forming a compound layer protective film on the nitride layer; and after the protective film forming step, 0.3 to 5 seconds until a predetermined heating temperature is reached. A method for producing a hardened steel material, comprising: heating and induction hardening with an ultimate temperature of 750 to 860 ° C.

According to the protective film forming treatment liquid for protecting a compound layer of a steel member having a metal nitrogen compound layer of the present invention from high-temperature oxidative decomposition, and the compound layer protective film, the protective layer forming film of the present invention is formed on the compound layer obtained by nitriding treatment. By forming the compound layer protective film, it is possible to effectively suppress oxidative decomposition of the compound layer due to subsequent induction hardening. The steel member obtained by the present invention maintains the mechanical strength, sliding resistance, wear resistance and the like based on the characteristics of the compound layer as a result of the remaining compound layer having good sliding characteristics. Furthermore, steel members whose hardenability has been improved by the diffused nitrogen can obtain a deep hardening depth and high hardness by induction hardening, and therefore have high mechanical strength in terms of surface pressure strength, wear resistance, and bending fatigue strength. It can be suitably used for machine structural parts that require strength.

The steel material to which the present invention is applied is not particularly limited, and examples thereof include carbon steel, low alloy steel, medium alloy steel, high alloy steel, cast iron and the like. A preferable material in terms of cost is carbon steel, low alloy steel, or the like. For example, carbon steel for machine structural use (S20C to S58C) is suitable as carbon steel, and nickel chrome steel (SNC 236 to 836), nickel chrome molybdenum steel (SNCM 220 to 815), chrome, etc. as low alloy steel. Molybdenum steel (SCM 415 to 445, 822), chromium steel (SCr 415 to 445), manganese steel for mechanical structure (SMn 420 to 443), manganese chrome steel (SMnC 420, 443) and the like are suitable. For these steel materials, it is not always necessary to use a tempered steel material (H material) whose hardenability is ensured by tempering, and a tempered steel material that has not been tempered and remains in a ferrite-pearlite structure may be used. Further, in the present invention, although alloy steel tends to have higher surface hardness, a sufficiently deep hardening depth can be obtained even with carbon steel because of the effect of improving the hardenability of effect II by nitrogen. Further, in the present invention, due to the effect II by nitrogen, it is not always necessary to use tempered steel, and even a non-tempered steel of ferrite-pearlite structure can provide sufficient mechanical strength.

In the present invention, the nitrogen compound layer on the surface of the steel material is obtained by a surface hardening treatment that diffuses active nitrogen on the surface of the steel material to generate a hard and stable nitride. Although it is not particularly limited as long as it is a nitrogen compound layer, it is usually composed mainly of Fe as a base material component, and a nitride containing Ti, Zr, Mo, W, Cr, Mn, Al, Ni, C, B, Si, etc. It is preferable that it is a layer. As a method for forming the nitrogen compound layer, a nitrogen compound layer having an effect I, such as salt bath nitriding treatment such as tuftride treatment, isonite treatment, and pulsonite treatment, gas soft nitriding treatment, ion nitriding treatment, plasma nitriding treatment, and nitrogen immediately below the nitrogen compound layer Any nitriding method can be used as long as it is a method in which a region in which is diffused. The nitriding heat treatment temperature for forming the nitrogen compound layer for achieving the effect I is preferably 600 ° C. or lower, more preferably 580 ° C. or lower, and further preferably 570 ° C. or lower. Although the thickness of the nitrogen compound layer obtained at a processing temperature exceeding 600 ° C. is increased, the effect I can no longer be expected because the hardness decreases. In addition, although a minimum is not specifically limited, For example, it is 350 degreeC.
The thickness of the nitrogen compound layer obtained by nitriding before induction hardening is not particularly limited, but it is usually sufficient if it is formed with a thickness of 1 to 30 μm, more preferably 2 to 20 μm, and even more preferably 3 ~ 15 μm.

In the present invention, after forming the nitrogen compound layer on the steel material, a protective film is formed using a non-aqueous treatment liquid for protecting the nitrogen compound layer. This treatment liquid is a non-aqueous treatment liquid, and a metal group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo It is preferable to contain at least one dissolved metal alkoxide, metal acetylacetonate and / or metal carboxylate selected from among the above. The non-aqueous treatment liquid in the present invention refers to a solvent having a single phase and a water content of 30% by mass or less in the solvent.

In this treatment solution, at least one selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo. The concentration containing the dissolved metal alkoxide, metal acetylacetonate and / or metal carboxylate is a concentration that allows the compound layer protective film to have a predetermined adhesion amount depending on the coating method and the number of repeated coatings. For example, the content may be 0.5 to 100 g / L.

The treatment liquid of the present invention is at least selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo. 1 dissolved metal alkoxide, metal acetylacetonate and / or metal carboxylate and / or Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn , Dispersed particles having an average particle size of 4 to 40 nm including at least one selected from the group consisting of Mg and Mo, Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb , Cr, W, Al, Sr, Zn, Mg and Mo, and dispersed particles having an average particle size of 40 to 400 nm including at least one selected from the group consisting of Mo, Mo and Mo. shape And mass occupied as the ratio of the mass occupied latter as a dry solid state between 1:10 and 10: 1. In addition, the average particle diameter in this specification can be measured, for example using the particle size distribution measuring apparatus by a dynamic light scattering method.
Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg and Mo decompose and oxidize the nitrogen compound layer during high-frequency heating performed thereafter. It is the main component of the protective film to prevent, and its oxide is thermally and chemically stable. In particular, Si, Ti, Zr, Ce, Cr, W, Al, and Mo are more preferable because the diffusion rate of ions in these metal compounds is small.

The main components of the protective film, Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo are film forming components and stress relaxation components. It is preferable to be composed of two. The film forming component is at least one selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo. Seed dissolved metal alkoxide, metal acetylacetonate and / or metal carboxylate, and / or Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Dispersed particles having an average particle diameter of 4 to 40 nm including at least one selected from the group consisting of Zn, Mg, and Mo are preferable.
The stress relaxation component of the protective film is selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo. It is preferable to contain dispersed particles having an average particle diameter of 40 to 400 nm including at least one kind.
For example, oxides, hydroxides, nitrides, fluorides, carbonates, and phosphate compounds can be used as the dispersed particles of the film forming component and the stress relaxation component. Oxide particles are particularly preferable.

Even if only the stress relaxation component alone is applied, the average particle size is large, so that the film forming property is poor, and the continuity and adhesion as a film are weak, so that the action as a protective film may be insufficient.
When only the film forming component is applied, a continuous film can be formed on the nitrogen compound layer, but the stress in the protective film caused by large volume shrinkage during drying cannot be relieved, and the protective film may crack or peel. is there.
For the above reasons, the film forming component and the stress relaxation component are both incorporated into the film and formed, and the mass ratio of the two in the dry solid state (the dry solid state in the protective film before quenching) is 1:10 to 10 When it is set to 1, the action as a protective film for the nitrogen compound layer is most enhanced. More preferably, it is 1: 5 to 5: 1, and still more preferably 1: 3 to 3: 1. Here, the “dried solid state” in the claims and the present specification refers to an oxide equivalent value assuming that all of the metal-containing components as raw materials are oxides. In practice, there may be components that volatilize or exist in other forms or remain in the form of raw material components. However, the `` dry solid state '' in the claims and the specification is only It is an assumed value (theoretical value) on a raw material basis.

As described above, the technique described in Japanese Patent Application Laid-Open No. 2008-038220 is not necessarily sufficient for preventing the oxidation of the nitrogen compound layer. Depending on the situation, a part of the surface layer of the nitrogen compound layer is oxidatively decomposed after high-frequency heating. There was a case. As a result of earnest investigations by the inventors, the role required of the protective film is not only to prevent decomposition and oxidation of the nitrogen compound layer that occurs during high-frequency heating performed after the formation of the protective film, but first of all. Furthermore, it has been found that it is essential to prevent decomposition and oxidation of the nitrogen compound layer when forming the protective film itself. Although the nitrogen compound layer has higher corrosion resistance than the iron base itself, it decomposes and oxidizes when it is heated to 50 ° C or higher, especially during wet semi-drying, until the treatment solution is applied and fixed and dried as a protective film. Cheap. When wet with a temperature load of about 50 to 200 ° C, it is wet, so in some cases, decomposition and oxidation of the nitrogen compound layer occur compared to the case of high-frequency heating load with a dry protective film performed at 750 to 860 ° C. It becomes easy.
From the point of protection of the nitrogen compound layer, it was found that decomposition and oxidation of the compound layer are effectively suppressed when the solvent of the treatment liquid is a non-aqueous organic solvent. Although the mechanism is not clear, especially in the case of an organic solvent, the polarity is lower than that of water, and since it is easy to volatilize and has a short wet time, dissolution of the nitrogen compound layer seems to be suppressed. In the present invention, the non-aqueous processing liquid is composed of a single phase solvent, and the water content in the solvent is 30% by mass or less, more preferably 10% by mass or less, and further preferably 2% by mass. % Or less. The non-aqueous solvent is not particularly limited as long as it dissolves metal alkoxide, metal acetylacetonate, and / or metal carboxylate, and examples thereof include non-polar hydrocarbons such as hexane, octane, benzene, toluene, and tetralin. In addition, for example, acetylacetone, methanol, ethanol, propanol, propionic acid, ethyl acetate, butyl acetate and the like can be used. These may be used alone or in combination of two or more depending on the type of metal alkoxide, metal acetylacetonate, or metal carboxylate.

The treatment liquid of the present invention preferably further contains 0.1 to 400 g / L of amines. More preferably, it is 0.5 to 200 g / L, and still more preferably 1 to 100 g / L. The amines also have high adsorptivity to the surface of the nitrogen compound layer until the dried compound layer protective film is fixed from the treatment liquid, and effectively suppress the dissolution of the compound layer. It has in processing liquid. These amines also have an effect of suppressing oxidation / decomposition of the nitrogen compound layer during high-frequency heating. As a mechanism for this, the present inventors have released nitrogen during high-frequency heating, and the nitrogen is on the nitrogen compound layer side. I guess to spread. These amines only need to be compatible with the organic solvent of the treatment liquid used. For example, ammonia, urea, methylamine, ethylamine, trimethylamine, triethylamine, triethanolamine, N, N-diisopropylethylamine, piperidine, piperazine Morpholine, pyridine, 4-dimethylaminopyridine, ethylenediamine, tetramethylethylenediamine, hexamethylenediamine, aniline, catecholamine, phenethylamine, and the like can be used. Any of these can be decomposed or volatilized when heated.

In the treatment liquid of the present invention, an antifoaming agent or a surfactant called a wettability improver for obtaining a uniform film on the surface to be coated, a thickener, and other organic / inorganic additions are appropriately supplemented. It can also be added.

The method for applying the treatment liquid is not particularly limited, and dip coating, spin coating, spraying, brushing, and the like can be used. The coating drying / firing temperature at the time of application is preferably 60 to 550 ° C., more preferably 100 to 400 ° C., and further preferably 120 to 300 ° C. The heating time may be 30 seconds to 60 minutes, for example, and it may be sufficiently solidified, dried and fixed by exposure to the atmosphere. The atmosphere during drying is preferably an inert atmosphere, but may be an air atmosphere. Depending on the shape of the steel part, in order to avoid the severe condition where the wet state is maintained at the liquid reservoir for a long time, air-drying is performed at room temperature or below 50 ° C, and then firing at a predetermined temperature is adopted. Also good. Further, in order to obtain a predetermined film thickness, coating and drying may be repeated a plurality of times to adjust the film thickness.

In the present invention, the compound layer protective film is formed by coating Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, and the like on a nitride layer formed after nitriding treatment on a steel material as a dry solid state. Containing at least one metal selected from the group consisting of Cr, W, Al, Sr, Zn, Mg, and Mo, and 0.05 to 3 g / m ^{2 in} total in terms of the metal Formed in range. More preferably, it is 0.1 to 1 g / m ² .
Protective effect of total nitride layer is less than 0.05 g / ^{m 2} of the metal basis is insufficient, also already effective economically undesirable to saturate it exceeds 30000 mg / ^{m 2.} When the total metal deposition amount is 30000 mg / m ² , the film thickness is about 2 to 4 μm, which is overwhelmingly thinner than Patent Document 7 covering a millimeter-order film and does not impair hardenability. It is thick.

As induction hardening performed after forming the compound layer protective film, it is subjected to induction heating by heating for 0.3 to 5 seconds so as to reach a predetermined heating temperature set at 750 to 860 ° C. After reaching a predetermined temperature, it is immediately cooled by a coolant, whereby a fine martensitic structure containing nitrogen can be obtained. Regarding the heating temperature, a more preferable heating temperature is 770 to 840 ° C., and a further preferable heating temperature is 780 to 830 ° C. The heating time is more preferably 0.8 to 3 seconds, and further preferably 1 to 2 seconds.
Although heating is performed at 750 ° C. or lower, nitrogen is contained, at this temperature, the material is not sufficiently austenitic, and thus quenching is insufficient. When the heating exceeds 860 ° C., the effect of the compound layer protective film is no longer effective, and the decomposition of the compound layer can no longer be suppressed, and excessive residual austenite tends to be generated in the martensite structure immediately below the compound layer. It is not preferable. Even if the heating time is 0.3 seconds or less, nitrogen is diffused, but it is not sufficiently austenitized, resulting in insufficient quenching. A heating time exceeding 5 seconds is not preferable because the effect of the heating time is almost saturated and the function of the compound layer protective film is lowered.
By using the compound layer protective film of the present invention, the nitrogen compound layer is sufficiently suppressed from oxidation and decomposition even when the atmosphere during high-frequency heating is in the air. If equipment can be introduced, the atmosphere during high-frequency heating may be a vacuum atmosphere, an inert atmosphere with argon gas or nitrogen gas, a low oxygen atmosphere, a hydrocarbon-based reducing atmosphere, an ammonia gas atmosphere, or the like. it can.
When the treatment is large at the time of high-frequency heating, a multistage temperature raising method including preheating can be appropriately performed. After quenching by high-frequency heating, tempering treatment may be performed under appropriate conditions in the same manner as a normal quenching technique.

When the processed product according to the present invention is incorporated as a machine part after a series of heat treatments, the compound layer protective film may or may not be removed and can be selected as necessary. The removal of the protective film of the compound layer can be easily performed because the hardness is lower than that of the compound layer, and can be appropriately performed by, for example, lapping, emery paper polishing, buffing, shot blasting, shot pinning, or the like.

After the high frequency heating, the nitrogen compound layer remains with the compound layer protective film of the present invention, but the nitrogen compound layer does not necessarily remain 100% of the state of the compound layer before the high frequency heating, and the minimum film thickness is 1 μm or more. The layer thickness should just be ensured. More preferably, it is 2 μm or more, and more preferably 3 μm or more. When the oxidized layer of the nitrogen compound layer is present on the surface layer, it is brittle and low in hardness. Therefore, when the above-described compound layer protective film removal operation step is performed, most of the protective layer is removed together with the protective film. Become.

A hard layer containing a fine martensite structure containing nitrogen having a nitrogen compound layer having a thickness of 1 to 30 μm on the surface and having a hardness distribution gradually decreasing from directly below to the inside by the composite heat treatment as described above. In addition, the hardness of the nitrogen compound layer is HV630 or more in terms of Vickers hardness, and the hardness region exceeding HV550 of the hard layer containing a fine martensite structure is 200 μm or more, preferably 400 μm or more, more preferably 600 μm or more in terms of the distance from the surface. A steel material having an existing hardness distribution can be obtained. In addition, although an upper limit is not specifically limited, For example, it is 1.5 mm.

By the above-described treatment of the present invention, a mechanical component having both effects I and II of the nitrogen compound layer is obtained. That is, the machine part subjected to the treatment of the present invention has high slidability and seizure resistance due to the nitrogen compound layer formed on the outermost surface, and high temper softening resistance due to the nitrogen-containing fine martensite structure. It has crack resistance / crack growth resistance, surface pressure resistance, high fatigue strength, and deep cure depth.

The quenching by induction heating by the composite heat treatment according to the present invention is 750 to 860 ° C., and the quenching temperature is sufficiently lower than the induction quenching and carburizing quenching usually performed at temperatures exceeding 900 ° C. This is extremely advantageous in terms of thermal deformation and cracking, and enables a significant reduction in the post-cutting process for adjusting the dimensional accuracy performed after general induction hardening or carburizing and quenching.
As described above, the steel material to which the present invention is applied is not necessarily required to use a tempered steel because of the effect of improving the hardenability of the effect II caused by nitrogen. Sufficient mechanical strength can be obtained even with steel. Further, although alloy steel tends to have a slightly higher surface hardness, a sufficiently deep hardening depth can be obtained even with inexpensive carbon steel due to the effect II of nitrogen. For example, carbon steel for mechanical structures such as S45C is a heat treatment material having a hardness profile with sufficient hardness and sufficient depth. Further, even S45C is not necessarily a tempered material, and even if the heat treatment of the present invention is applied to a steel member having a non-tempered ferrite-pearlite structure, sufficient martensitic transformation occurs, and sufficient mechanical properties are obtained. It can be a heat-treated machine part with high strength.
As described above, the application of the present invention improves the mechanical strength of the parts, reduces the cutting process and switches to inexpensive materials, thereby reducing the size and weight of the entire mechanical parts by downsizing the parts, and nitriding and induction hardening. It is possible to reduce the actual cost by surplus to compensate for the cost increase due to the combined processing.

As a replacement for the quenching method by induction quenching of the present invention, the compound layer protective film of the present invention is formed after nitriding treatment by, for example, laser quenching by short-time heating for a few seconds at the most, or impact quenching for a short heating of several milliseconds. When the obtained parts are quenched, the nitride layer is sufficiently protected, and the steel base portion under the layer can obtain a quenched structure corresponding to the used quenching technique.

Next, the use of the hardened steel material according to the present invention will be described. The hardened steel member according to the present invention is suitable for those used in a high load / high surface pressure region. The shape and part type of the steel member are not particularly limited, and examples thereof include shafts, gears, pistons, shafts, cams, and the like, which are suitable for transmission-related parts and powertrain parts for automobiles and construction machinery.

Hereinafter, embodiments of the present invention will be described with reference to examples, but the scope of the present invention is not limited to the following examples.

<Example 1>
SCM440 tempered material having a diameter of 8 mm and a length of 50 mm was used as a base material, and after degreasing and cleaning the surface, salt bath soft nitriding treatment at 560 ° C. for 1 hour in a molten salt bath (Isonite treatment: Nippon Parkerizing Co., Ltd.) And a nitrogen compound layer mainly composed of iron nitride having a thickness of about 7 μm was formed on the surface of the steel material.

Isopropyl alcohol as the main solvent, alcohol-dispersed silica sol having an average particle size of 5 to 40 nm (“Colcoat P” manufactured by Colcoat Co.) as the film-increasing component is 20 g / L as silica (9.3 g / L as Si), stress As a relaxing component, isopropyl alcohol-dispersed silica sol having an average particle size of 70 to 100 nm (“IPA-ST-ZL” manufactured by Nissan Chemical Industries, Ltd.) as silica is 5 g / L (Si is 2.3 g / L), and monomethylamine is 5 g / L. Each of the treatment liquids containing was prepared. The treatment liquid was applied to the substrate using a dip coating method, and after removing the excess liquid, the process of drying at 50 ° C. × 10 minutes was repeated twice, and finally, baking was performed at 200 ° C. for 10 minutes. When the amount of Si deposited on the substrate was measured with a fluorescent X-ray analyzer, the amount of deposited Si was 310 mg / m ² . In this protective film, the ratio of the film-forming component / stress-relaxing component was 4 for the calculated silica-forming component and the stress-relaxing component.

In this way, for the steel material in which the compound layer protective film containing silica is formed on the nitrogen compound layer, the heating is stopped immediately after reaching 860 ° C. in 0.8 seconds after the start of heating using an induction hardening apparatus. Then, it was cooled and quenched. Later, the steel surface was shot blasted to remove only the compound layer protective film.

<Example 2>
S45C tempered material having a diameter of 8 mm and a length of 50 mm was used as a base material. After degreasing and cleaning this surface, salt bath soft nitriding treatment (Isonite treatment: Nippon Parkerizing Co., Ltd.) at 560 ° C. in a molten salt bath for 2 hours And a nitrogen compound layer mainly composed of iron nitride having a thickness of about 13 μm was formed on the surface of the steel material.

A treatment solution containing isopropyl alcohol as a main solvent, titanium tetraisopropoxide as a film-increasing component as titanium oxide, 40 g / L (24 g / L as Ti), and 10 g / L of triethylamine was prepared. The treatment liquid was applied to the substrate using the dip coating method, and after removing the excess liquid, the process of drying at 150 ° C. × 30 minutes was repeated 5 times, and finally, baking was performed at 300 ° C. for 10 minutes. When the amount of Ti deposited on the substrate was measured with a fluorescent X-ray analyzer, the amount deposited as Ti was 510 mg / m ² .

In this way, the steel material in which the compound layer protective film containing titanium oxide is formed on the nitrogen compound layer is further heated immediately after reaching 820 ° C. in 1.0 second after the start of heating using an induction hardening apparatus. After stopping, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.

<Example 3>
An S45C non-refined material (ferrite / pearlite structure) having a diameter of 8 mm and a length of 50 mm was used as a base material. After degreasing and cleaning this surface, salt bath soft nitriding treatment (Isonite) at 560 ° C. for 1 hour in a molten salt bath Treatment: manufactured by Nihon Parkerizing Co., Ltd.) and water-cooled to form a nitrogen compound layer mainly composed of iron nitride having a thickness of about 12 μm on the steel surface.

Isopropyl alcohol-dispersed silica sol having an average particle size of 40 to 100 nm as a stress relaxation component (Nissan Chemical Industries, Ltd.) using ethanol as a main solvent, tetraethoxysilane as a film thickening component as silica (4.7 g / L as Si), and stress relaxation component A treatment solution containing 40 g / L of silica (“IPA-ST-UP”) manufactured by the company (18.7 g / L as Si) was prepared. This treatment liquid was applied to the substrate using a dip coating method, and after removing excess liquid, baking was performed at 320 ° C. for 10 minutes. When the Si adhesion amount on the substrate was measured with a fluorescent X-ray analyzer, the adhesion amount as Si was 160 mg / m ² . In this protective film, the ratio of the film-forming component / stress-relaxing component was 0.3 for the calculated silica-forming component and the stress-relaxing component.

In this way, for the steel material in which the compound layer protective film containing silica is formed on the nitrogen compound layer, the heating is stopped immediately after reaching 820 ° C. in 1.0 second after the start of heating using the induction hardening apparatus. Then, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.

<Comparative Example 1>
SCM440 tempered material having a diameter of 8 mm and a length of 50 mm was used as a base material, and after degreasing and cleaning the surface, salt bath soft nitriding treatment at 560 ° C. for 1 hour in a molten salt bath (Isonite treatment: Nippon Parkerizing Co., Ltd.) And a nitrogen compound layer mainly composed of iron nitride having a thickness of about 7 μm was formed on the surface of the steel material. Without applying the compound layer protective film to this, after reaching 860 ° C. in 0.8 seconds after the start of heating using an induction hardening apparatus, heating was immediately stopped, cooling was performed, and quenching was performed.

(Evaluation test)
The steel material subjected to these treatments was cut with a microcutter, embedded in a resin, and cross-sectional observation was performed with a metal microscope. Moreover, cross-sectional hardness measurement was performed using this embedded sample using a micro Vickers hardness tester.

Table 1 shows a list of evaluation results. The effective curing depth in the table is the depth (mm) from the surface of the portion having a hardness of Hv550 or higher. For example, FIGS. 1, 2 and 3 show cross-sectional photographs of Example 1, Example 2 and Comparative Example 1, respectively. FIG. 4 shows the cross-sectional hardness distribution of Example 3.

From Table 1, in Examples 1 to 3 of the present invention, the nitrogen compound layer on the surface remains 1 μm or more even after induction hardening. In Comparative Example 1 without the compound layer protective film, it was observed that the entire surface was oxidized as shown in FIG.

Cross-sectional photograph of nitrogen compound layer after quenching of steel material of Example 1 Cross-sectional photograph of nitrogen compound layer after quenching of steel of Example 2 Cross-sectional photograph of nitrogen compound layer after quenching of steel of Comparative Example 1 Example 3 Cross-sectional hardness distribution of steel

Claims

Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn coated as a dry solid state on a nitride layer formed after nitriding treatment on a steel material , A compound layer protective film containing at least one metal selected from the group consisting of Mg and Mo, and the compound layer protective film is 0.05 in total in terms of metal from a non-aqueous processing liquid. Formed in a range of ˜3 g / m 2 , and then heated for 0.3 to 5 seconds until reaching a predetermined heating temperature to be performed thereafter, and when the induction temperature is 750 to 860 ° C., A compound layer protective film characterized by suppressing decomposition.
A non-aqueous treatment liquid for forming a protective film according to claim 1 for protecting a nitride on a nitride layer formed after nitriding treatment on a steel material, wherein Si, Ti, Zr, Hf V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg and Mo, at least one dissolved metal alkoxide selected from the metal group, metal acetylacetonate, and A compound layer protective film-forming treatment liquid characterized by containing a metal carboxylate.
The treatment liquid is at least one selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo. Dissolved metal alkoxide, metal acetylacetonate and / or metal carboxylate and / or Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg And dispersed particles having an average particle diameter of 4 to 40 nm including at least one selected from the group consisting of Mo, Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr , W, Al, Sr, Zn, Mg and Mo, and dispersed particles having an average particle size of 40 to 400 nm including at least one selected from the group consisting of W, Al, Sr, Zn, Mg and Mo. And a mass occupied by the ratio of the mass of the latter occupied as a dry solid state 1:10 to 10: characterized in that it is a 1, compound layer protective film formation treatment solution according to claim 2.
The compound layer protective film-forming treatment liquid according to claim 2 or 3, wherein the treatment liquid contains 0.1 to 400 g / L of at least one amine.
A steel material having a nitride layer formed on the surface thereof by nitriding, wherein the compound layer protective film formed from the treatment liquid according to any one of claims 2 to 4 is formed on the nitride layer. A hardened steel material that has been subjected to induction hardening at a temperature of 750 to 860 ° C. for 0.3 to 5 seconds until reaching a predetermined heating temperature.
A steel material having a nitride layer formed on the surface by nitriding is prepared, and an application step of applying the treatment liquid according to any one of claims 2 to 4 on the nitride layer, and drying the treatment liquid after the application step A protective film forming step for forming a compound layer protective film on the nitride layer, and after the protective film forming step, heating is performed for 0.3 to 5 seconds until a predetermined heating temperature is reached. A method for producing a quenched steel material, comprising: induction hardening at 860 ° C.