JP5258928B2 - Hardening method of steel member, hardened steel member and hardened surface protective agent - Google Patents

Description

  The present invention relates to a surface hardening treatment technology for machine structural parts having excellent mechanical strength such as surface pressure strength, wear resistance, and bending fatigue strength.

  In order to improve mechanical strength, surface hardening treatments such as nitriding treatment, soft nitriding treatment, carburizing and quenching, and induction hardening are performed on mechanical structural parts of cast iron and steel. Among these, it is known that the nitride layer formed on the outermost surface by nitriding treatment has excellent sliding resistance, is resistant to wear, and has high seizure resistance. However, the conventional nitriding treatment or soft nitriding treatment has a hardened layer depth shallower than carburizing and induction hardening, and there is room for improvement in surface pressure strength, fatigue strength, and the like. Therefore, in recent years, a composite curing process has been developed that takes advantage of the characteristics of nitrogen and that is subjected to induction quenching to deepen the curing depth, increase the surface pressure strength, and increase the fatigue strength after nitriding or soft nitriding.

  However, for example, in Patent Documents 1 to 4, the composite treatment is performed by utilizing the characteristics of the quenched structure in the nitrogen diffusion layer obtained by nitriding treatment, that is, by utilizing the surface pressure by utilizing temper softening resistance and crack generation resistance. The improvement of strength and fatigue strength is expected, and use of a nitride layer (compound layer) formed by nitriding is not found. Rather, in the above publication, high frequency processing conditions for actively decomposing and disappearing the nitride layer are studied. That is, in induction hardening after nitriding, the quenching temperature needs to be at least the temperature Ac1 transformation point at which the austenite structure is formed, and is usually selected from a temperature range of 750 to 1050 ° C. The nitride layer formed at a nitriding temperature of 570 ° C. is a combination of iron and nitrogen. When re-heated to 650 ° C. or higher, it is oxidized and decomposed, and nitrogen in the nitride layer is released as nitrogen gas on the outermost surface. Then, as a result of diffusion inside, the nitride layer disappears. This has been reported for a long time (Non-Patent Document 1).

  As a technique for solving such a problem of damage or disappearance of the nitride layer by high-temperature heating by directly quenching the nitride layer formed on the surface by nitriding treatment, Further, Patent Document 5 discloses a method of coating and quenching a gas nitriding / ion nitriding inhibitor, carburizing inhibitor, and antioxidant containing silicon oxide as a component at a thickness of 1 to 3 mm.

However, in this method, even if the oxidation phenomenon during heating can be prevented, a thick film of 1 mm or more is required and the thermal conductivity is low, so that the cooling rate during quenching becomes insufficient, and the desired fine martensite. It was difficult to obtain the hardness. Moreover, since such a surface film has a high frictional resistance, it has to be removed after the quenching treatment, and the production efficiency is not sufficient.
Patent No. 3193320 Japanese Patent No. 3327386 Japanese Patent No. 3145517 JP-A-7-90364 JP 58-96815 Heat treatment Vol.16 No.4 P206 1976

  Therefore, the present invention solves these problems of the prior art, and not only prevents the hard nitride layer from being damaged and decomposed during quenching, but also identifies the nitride layer without reducing the cooling rate during quenching. The purpose is to obtain a good slidability without removing the protective layer, and to improve the hardness and mechanical strength to obtain surface pressure strength and fatigue strength. And

In the method of impregnating or coating a hardened surface protective agent on the surface before quenching the steel member having a hard nitride layer formed on the surface, the present inventors have a film thickness of several μm or less (with an adhesion amount). several thousand mg / m ² or less) even allows nitride layer protection during quenching, there is no problem on the cooling rate during quenching, and quenching the surface protection slidability without removing the protective layer after quenching is not reduced Intensive experiments were conducted on the composition of the agent.

  As a result, a quenching surface protective agent comprising a ceramic precursor containing at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo and Al is conventionally known. It is found that even a thin coating of a few μm or less that is not known shows a good nitride protection effect, and shows good sliding performance without removing the protective film after heat treatment. It has been found that the nitride protective effect is further improved by including one selected from Mg, Y, Sc and Ba.

  In addition, as a result of cross-sectional composition analysis of the quenched film by EPMA or the like, these films exist as the upper layer of the nitride film, and some of them are combined or reacted with the nitride and bonded firmly to protect and slide. The present invention was completed on the assumption that the effect was enhanced.

That is, in the “hardened steel member” of the present invention, the first invention is that a hard nitride layer is formed on the surface of the steel material, and further, Ti, Zr, Hf, V, Nb, Ta, Cr are formed thereon. An inorganic compound layer containing at least one metal oxide selected from the group consisting of W, Mo, and Al is formed. A second invention is the first invention, wherein the inorganic compound layer containing the metal oxide further contains at least one selected from Ca, Mg, Y, Sc and Ba. Further, in the third invention, the hard nitride layer is at least one nitride selected from Fe, Ti, Zr, Mo, W, Cr, B, and Si. It is the second invention. In a fourth aspect of the invention, the inorganic compound layer contains at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo and Al, in terms of the metal It is any one of said 1st invention-said 3rd invention contained in the range of 1-2000 mg / m < ² > in total. A fifth invention is any one of the first to fourth inventions, wherein the steel member is a mechanical structural component used in a high surface pressure region.

  Further, the “method for quenching steel member” and the method for producing quenched steel member according to the present invention include a steel material having a hard nitride layer on the surface, Ti, Zr, Hf, V, Nb, Ta, A liquid containing a ceramic precursor containing at least one element selected from the group consisting of Cr, W, Mo, and Al (for example, selected from oxides, hydrated oxides, ions, complex ions) A solution containing a ceramic precursor containing the element as at least one state) and then performing a quenching treatment, and the quenching treatment is preferably induction quenching, and includes the ceramic precursor. The liquid (for example, the solution) further contains at least one element selected from Ca, Mg, Y, Sc, and Ba (for example, oxide, hydrated oxide, ion, complex ion). At least containing the element as one state of) is preferably selected from among.

The “quenched surface protective agent” of the present invention is a ceramic containing at least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo and Al. A liquid containing a precursor (for example, a solution containing a ceramic precursor containing the element in at least one state selected from oxides, hydrated oxides, ions, and complex ions), and the ceramic precursor (For example, the solution) further contains at least one element selected from Ca, Mg, Y, Sc, and Ba (for example, among oxides, hydrated oxides, ions, and complex ions). It is more preferable that the element is contained as at least one state selected from: Here, in addition to a type that can be used as it is, a concentrated type that is diluted with a solvent at the time of use and a dry type that is added with a solvent are also included in the concept of “quenched surface protective agent” (however, it can be used as it is below) Type)).
Specifically, the present invention relates to the following aspects.
(1) A hard nitride layer is formed on the surface of the steel material, and at least selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo and Al as the upper layer A hardened steel member, wherein an inorganic compound layer containing one kind of metal oxide is formed.
(2) The quenched steel member according to (1), wherein the inorganic compound layer containing the metal oxide further contains at least one selected from Ca, Mg, Y, Sc, and Ba.
(3) The hardened steel member according to (1) or (2), wherein the hard nitride layer is at least one nitride selected from Fe, Ti, Zr, Mo, W, Cr, B, and Si. .
(4) The inorganic compound layer includes at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo, and Al, in total in terms of the metal. The hardened steel member according to any one of (1) to (3), which is contained in the range of 1 to 2000 mg / m ² .
(5) The quenched steel member according to (1) to (4), wherein the steel member is a machine structural component used in a high surface pressure region.
(6) A steel material having a hard nitride layer on the surface contains at least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo and Al. A method for quenching a steel member, wherein the quenching treatment is performed after contacting the liquid containing the ceramic precursor to be cured.
(7) The method for quenching a steel member according to (6), wherein the liquid containing the ceramic precursor further contains at least one element selected from Ca, Mg, Y, Sc, and Ba.
(8) The method for quenching a steel member according to (6) or (7), wherein the quenching treatment is induction quenching.
(9) A steel material having a hard nitride layer on the surface contains at least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo and Al A method for producing a hardened steel member, comprising: bringing into contact with a liquid containing a ceramic precursor to be subjected to hardening treatment.
(10) The method for producing a quenched steel member according to (9), wherein the liquid containing the ceramic precursor further contains at least one element selected from Ca, Mg, Y, Sc, and Ba.
(11) The method for producing a quenched steel member according to (9) or (10), wherein the quenching treatment is induction quenching.
(12) A liquid containing a ceramic precursor containing at least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo, and Al. Quenching surface protective agent.
(13) The quenching surface protective agent according to (12), wherein the liquid containing the ceramic precursor further contains at least one element selected from Ca, Mg, Y, Sc, and Ba.
In particular, the present invention relates to the following embodiments.
(A1) Steel member before quenching treatment, and a hard nitride layer is formed on the surface of the steel member by a nitrogen diffusion treatment, and Ti, Zr, Hf, V are further formed on the hard nitride layer. A ceramic precursor layer is formed by applying a ceramic precursor containing at least one element selected from the group consisting of Nb, Ta, Cr, W, Mo, and Al. Steel member to be used.
(A2) The steel member according to (A1), wherein the ceramic precursor layer further contains at least one selected from Ca, Mg, Y, Sc and Ba.
(A3) The ceramic precursor layer contains at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo, and Al in terms of the total metal equivalent. The steel member of (A1) or (A2) which is contained in the range of 1 to 2000 mg / m ² .
(A4) The hard nitrided layer is formed by a process selected from a salt bath nitriding process, a gas soft nitriding process, an ion nitriding process, and a plasma nitriding process, and any one of (A1) to (A3) Steel member.
(A5) (i) At least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo, and Al for a steel material having a hard nitride layer on the surface (A1) to (A4) manufactured by a method including: a step of applying a liquid containing a ceramic precursor containing the element of (ii); and a step of (ii) removing a solvent of the liquid containing the ceramic precursor. ) Any steel member.
(A6) The steel member according to (A5), wherein the liquid containing the ceramic precursor further contains at least one selected from Ca, Mg, Y, Sc, and Ba.
(A7) The steel member of (A5) or (A6), wherein the solvent of the liquid containing the ceramic precursor is neutral to alkaline.
(A8) A hard nitrided steel member obtained by quenching a steel member of any one of (A1) to (A7) and formed on the surface of the steel member by nitrogen diffusion treatment Steel members with physical layers.
(A9) The steel member of (A8), which is a machine structural component used in a high surface pressure region.
(A10) The steel member of (A9), which is a shaft, gear, piston, shaft or cam.
(A11) The steel member according to any one of (A8) to (A10), wherein the quenching process is performed at 800 to 850 ° C.
(A12) The steel member of (A8) to (A11), wherein the quenching treatment is induction hardening.

  According to the quenched steel member of the present invention, a method of quenching a steel member, a method of manufacturing a quenched steel member, and a quenching surface protective agent, it is possible to prevent damage and decomposition of the hard nitride layer during quenching with an unprecedented thin film, Quenching is possible without reducing the cooling rate during quenching, and high hardness and mechanical strength can be obtained. In addition, since good slidability can be obtained without removing the protective layer, mass productivity and practicality can be improved as compared with conventional techniques.

  First, each element of the “hardened steel member” according to the present invention will be described in detail. First, the steel material to which the present invention is applied is not particularly limited, and examples thereof include carbon steel, low alloy steel, high alloy steel, and cast iron. Particularly preferred materials are high carbon carbon steel, low alloy steel and the like.

  The hard nitride layer on the surface of the steel material in the present invention is not particularly limited as long as it is a nitride layer formed by surface treatment of steel (nitrogen diffusion treatment, CVD, PVD, etc.), Fe, Ti, Zr, Mo , W, Cr, B and Si are preferably at least one nitride layer selected from Si, and Fe is most preferable from the viewpoint of mass productivity. As a method for forming the hard nitride layer of Fe, any nitriding method such as salt bath nitriding treatment such as tuftride treatment or pulsonite treatment, gas soft nitriding treatment, ion nitriding treatment or plasma nitriding treatment is preferable. The formation of the hard nitride layer other than Fe is preferably performed by a method such as PVD such as plasma CVD, sputtering, or ion plating.

  The inorganic compound layer in the present invention exists on the hard nitride layer on the surface of the steel material and is selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo, and Al. It is preferable that at least one metal oxide is contained as a main component and further contains at least one selected from Ca, Mg, Ba, Y and Sc as an optional component. The former main component is excellent in oxidation resistance and nitride forming ability, and a preferable optional component can be expected to improve the physical properties and stability of crystals.

  Here, the inorganic compound layer containing at least one metal oxide selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo, and Al is a nitride of the metal. It is preferable that it is further included. When the inorganic compound layer contains these metal nitrides, improvement in hardenability and slidability can be expected. In addition, when the ceramic precursor containing the metal is applied and hardened on the hard nitride layer, since the nitride is stable with respect to the metal, a part of the metal is hard nitride during the quenching. Reacts with nitrogen coming from the layer to form nitrides. Therefore, in this case, the inorganic compound layer containing the metal oxide essentially contains nitride.

The inorganic compound layer preferably contains at least one essential metal selected from the metal group in an amount of 1 to 2000 mg / m ^{2 in} terms of the metal. If the total metal conversion is less than 1 mg / m ² , the protective effect of the nitride layer is insufficient, and if it exceeds 2000 mg / m ² , the slidability and adhesion deteriorate, which is not preferable. In addition, although the said numerical value in this specification is the said metal amount in the said layer after the said inorganic compound layer was formed, this numerical value is in the ceramic precursor liquid made to adhere to the steel surface before quenching. It is the same as the amount of metal. Further, the amount of the optional metal is preferably about 20% or less of the essential metal.

  Next, the use of the “quenched steel member” according to the present invention will be described. The quenched steel member according to the present invention is preferably used in a high pressure region, and a preferable range of surface pressure is about 0.5 Mpa to 3.5 Mpa. Moreover, the shape of a steel member and a component kind are not specifically limited, For example, a shaft, a gearwheel, a piston, a shaft, a cam etc. can be mentioned.

  Next, “a method for quenching a steel member” and “a method for producing a quenched steel member” according to the present invention will be described. This method includes an application process of applying a ceramic precursor-containing liquid to a steel material having a hard nitride layer on the surface, and a quenching process of quenching the steel material to which the liquid is applied. In addition, this method may include the drying process for removing the solvent of the ceramic precursor liquid applied to the steel member surface etc., for example. In this case, it is preferable to perform the said drying process before quenching, and methods, such as natural drying and heat drying, are not ask | required.

  Here, first, the application process will be described. Before quenching, a steel material having a hard nitride layer (for example, a layer containing iron nitride) on the surface is made of Ti, Zr, Hf, V, Nb, Ta, Cr, W A ceramic precursor containing at least one element selected from the group consisting of Mo and Al as at least one state selected from an oxide, a hydrated oxide, an ion, and a complex ion It is preferred to contact the solution. Here, it is more preferable that the solution further contains an element selected from Ca, Mg, Y, Sc and Ba in addition to these elements. The contact method is not particularly limited, and for example, spraying, dipping, brushing, flow coating, roll coating, electrolytic deposition and the like are possible.

  Next, the quenching process will be described. This process is not particularly limited, and examples thereof include salt bath quenching, flame quenching, and induction quenching, and induction quenching is most preferable. Here, as quenching conditions, for example, in the case of a low alloy steel material, quenching is generally set to 900 to 930 ° C. which is 50 to 60 ° C. higher than the austenitizing temperature of the material. Since it has been applied, in the case of induction hardening capable of rapid heating, it is more preferable to set the temperature to 800 to 850 ° C.

  Here, the metal in the ceramic precursor applied to the steel member surface is tempered and ceramicized through an oxide formation process when the metal is not in the form of an oxide in the quenching step. As described above, since the metal is more stable in the form of nitride than in the form of oxide, the metal reacts with nitrogen from the nitride layer during the quenching process, and the metal Nitride is also formed.

  Next, the “quenched surface protective agent” used in the above method according to the present invention is at least selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo and Al. A solution containing a ceramic precursor containing one element in at least one state selected from an oxide, a hydrated oxide, an ion, and a complex ion is preferable. Among these metals, Ti, Zr, Hf, V, Nb, Ta, W, Mo, and Al oxides, hydrated oxides, ions, or complex ions are preferable as the main component. It is more preferable to add Mg, Ba, Y, and Sc oxides, hydrated oxides, ions, or complex ions. Moreover, as a solvent of the liquid (for example, solution) containing a ceramic precursor, it is preferable to use water as a main solvent from a safety surface, and in order to prevent corrosion of steel members, it should be neutral to alkaline. More preferred. In addition, although the solid content concentration of a solution is not specifically limited, 0.1-10 wt% is preferable.

  Here, as a manufacturing method (a method for preparing a ceramic precursor solution) of the “quenched surface protective agent” according to the present invention, as a metal compound raw material, the metal salt such as nitrate, acetate, oxalate, metal alkoxide, etc. Can be suitably used. These metal compound raw materials may be used as diluted in a solvent as they are, but may be used as a dispersion sol of oxides or hydrated oxides by hydrolysis, heat crystallization, or the like. Commercially available metal oxide sols can also be used. In addition, the quenching surface protective agent of the present invention preferably further includes other organic / inorganic additive components such as a sol dispersant and stabilizer, a wettability improver, and a thickener.

  Embodiments of the present invention will be described below with reference to examples. However, the scope of the present invention is not limited to the following examples.

<Example 1>
SCM440 tempered material with a diameter of 8 mm and a length of 12 mm was used as the base material, and after degreasing and cleaning this surface, salt bath soft nitriding treatment in a molten salt bath at 570 ° C. for 2 hours (tuftride treatment: Nippon Parkerizing Co., Ltd.) And a compound layer made of iron nitride having a thickness of 12 μm was formed on the surface of the steel material.

The steel material with the iron nitride layer formed on the surface is dip-coated with a 4% concentration titanium oxide neutral water dispersion sol (Pal Titanium 5603: Anatase + Amorphous Sol, manufactured by Nihon Parkerizing Co., Ltd.). After removing, it was dried at 180 ° C. The amount of Ti deposited was measured with a fluorescent X-ray analyzer and found to be 150 mg / m ² .

  In this way, the steel material on which the iron nitride layer formed with the inorganic compound layer containing titanium oxide is further heated at a rate of about 150 ° C./sec using an induction hardening device to generate a high frequency of 850 ° C. × 3 seconds. In addition, it was immediately cooled with water and quenched.

<Example 2>
A tempered material (SCM440) having a diameter of 20 mm and a length of 40 mm was used as a base material. After degreasing and cleaning this surface, soft nitriding treatment (tuftride treatment: Nippon Parkerizing Co., Ltd.) at 570 ° C. for 2 hours in a molten salt bath And a compound layer made of iron nitride having a thickness of 10 μm was formed on the surface of the steel material.

The steel material having an iron nitride layer formed on the surface in this manner was further brushed with a coating solution containing 8% concentration of ammonium zirconium carbonate (Daiichi Rare Element Chemical Co., Ltd.) and yttrium oxide. And dried. The adhesion amount of Zr and Y as measured by a fluorescent X-ray analyzer, Zr is 850 mg ^{/ m} 2, Y was 50 mg / ^{m 2.}

The steel material on which the iron nitride layer formed with the inorganic compound layer made of oxide containing zirconium and yttrium in this way was further applied with a high frequency of 800 ° C. × 5 seconds using the same induction hardening apparatus as in Example 1. Immediately cooled with water and quenched.

<Example 3>
SCM440 tempered material with a diameter of 8 mm and a length of 12 mm was used as the base material, and after degreasing and cleaning this surface, soft nitriding treatment was performed in a molten salt bath at 570 ° C. for 2 hours (Tufftride treatment: manufactured by Nihon Parkerizing Co., Ltd.) Then, an iron nitride layer having a thickness of 12 μm was formed on the steel surface.

The steel material having the iron nitride layer formed on the surface in this manner was further brush-coated with alumina sol (alumina sol 200 manufactured by Nissan Chemical Industries, Ltd.) having a concentration of 10%, and then dried. It was 1300 mg / m < ² > when Al adhesion amount was measured with the fluorescent X ray analyzer.

  Thus, about the steel material which formed the iron nitride layer in which the inorganic compound layer containing an aluminum oxide was formed, using the same induction hardening apparatus as Example 1, the high frequency of 850 degreeC * 3 second was added, and it immediately water-cooled. And hardened.

<Example 4>
SCM440 tempered material with a diameter of 8 mm and a length of 12 mm was used as the base material, and after degreasing and cleaning this surface, soft nitriding treatment was performed in a molten salt bath at 570 ° C. for 2 hours (Tufftride treatment: manufactured by Nihon Parkerizing Co., Ltd.) Then, an iron nitride layer having a thickness of 12 μm was formed on the steel surface.

The steel material having the iron nitride layer formed on the surface in this manner was further dip coated with a coating solution containing 3% ammonium molybdate and 2% ammonium tungstate, and then dried. When the adhesion amounts of Mo and W were measured with a fluorescent X-ray analyzer, Mo was 150 mg / m ² and W was 100 mg / m ² .

  In this way, a high frequency of 800 ° C. × 5 seconds was applied to the steel material on which the iron nitride layer formed with the inorganic compound layer made of oxide containing tungsten and molybdenum was further applied using the same induction hardening apparatus as in Example 1. Immediately cooled with water and quenched.

<Example 5>
A tempered material (SCM440) having a diameter of 20 mm and a length of 40 mm was used as a base material. After degreasing and cleaning this surface, soft nitriding treatment (tuftride treatment: Nippon Parkerizing Co., Ltd.) at 570 ° C. for 2 hours in a molten salt bath And an iron nitride layer having a thickness of 10 μm was formed on the surface of the steel material.

The steel material having the iron nitride layer formed on the surface was further dip-coated with a hydrated chromium oxide (III) sol (prepared by reducing chromic acid) having a concentration of 0.8% and then dried. The amount of Cr deposited was measured with a fluorescent X-ray analyzer and found to be 25 mg / m ² .

  Thus, about the steel material which formed the iron nitride layer which formed the inorganic compound layer containing chromium oxide, using the same induction hardening apparatus as Example 1, the high frequency of 850 degreeC x 3 second was added, and it immediately water-cooled. And hardened.

<Example 6>
SCM440 tempered material with a diameter of 8 mm and a length of 12 mm was used as the base material, and after degreasing and cleaning this surface, soft nitriding treatment was performed in a molten salt bath at 570 ° C. for 2 hours (Tufftride treatment: manufactured by Nihon Parkerizing Co., Ltd.) Then, an iron nitride layer having a thickness of 12 μm was formed on the steel surface.

The steel material having the iron nitride layer formed on the surface in this manner was further dip coated with a coating agent solution containing a 3% concentration of peroxotitanate sol and 0.2% calcium oxalate, and then dried at 250 ° C. When the adhesion amounts of Ti and Ca were measured with a fluorescent X-ray analyzer, Ti was 310 mg / m ² and Ca was 40 mg / m ² .

  Thus, about the steel material which formed the iron nitride layer which formed the inorganic compound layer which consists of an oxide containing Ti and Ca, using the same induction hardening apparatus as Example 1, the high frequency of 800 degreeC x 5 second was added. Immediately cooled with water and quenched.

<Example 7>
A tempered material (SCM440) having a diameter of 20 mm and a length of 40 mm is used as a base material. After degreasing and cleaning the surface, the surface is treated with an ion plating apparatus for 1 hour, and the surface of the steel material is made of titanium nitride having a thickness of 3 μm A nitride layer was formed.

The steel material having the titanium nitride layer formed on the surface in this manner was further brushed with a coating agent solution containing 8% concentration of ammonium zirconium carbonate (Daiichi Rare Element Chemical Co., Ltd.) and yttrium oxide, and then 150 ° C. And dried. When the adhesion amount of Zr and Y was measured with a fluorescent X-ray analyzer, Zr was 600 mg / m ² and Y was 35 mg / m ² .

  In this way, with respect to the steel material on which the titanium nitride layer formed with the inorganic compound layer made of oxide containing zirconium and yttrium was formed, a high frequency of 800 ° C. × 5 seconds was applied using the same induction hardening apparatus as in Example 1. Immediately cooled with water and quenched.

<Example 8>
Using a SCM440 tempered material having a diameter of 8 mm and a length of 12 mm as a base material, this surface was degreased and cleaned, and then treated with an ion plating apparatus for 2 hours, and a hard nitride made of chromium nitride having a thickness of 5 μm on the steel surface. A layer was formed.

The steel material with the chromium nitride layer formed on the surface is then dip coated with a 4% concentration titanium oxide neutral water dispersion sol (Pal Titanium 5603: Anatase + Amorphous Sol, manufactured by Nihon Parkerizing Co., Ltd.). After removing, it was dried at 180 ° C. The amount of Ti deposited was measured with a fluorescent X-ray analyzer and found to be 180 mg / m ² .

  In this way, the steel material on which the chromium nitride layer formed with the inorganic compound layer containing titanium oxide is further heated at a rate of about 150 ° C./sec using an induction hardening device to generate a high frequency of 850 ° C. × 3 seconds. In addition, it was immediately cooled with water and quenched.

<Example 9>
Using a SCM440 tempered material with a diameter of 8 mm and a length of 12 mm as a base material, this surface was degreased and cleaned, and then treated with a plasma CVD apparatus for 3 hours, and a hard nitride layer made of boron nitride having a thickness of 3 μm on the steel surface Formed.

The steel material with the boron nitride layer formed on the surface in this way is dip coated with a 4% concentration titanium oxide neutral water dispersion sol (Pal Titanium 5603: Anatase + Amorphous Sol, manufactured by Nihon Parkerizing Co., Ltd.). After removing, it was dried at 180 ° C. The amount of Ti deposited was measured with a fluorescent X-ray analyzer and found to be 160 mg / m ² .

  The steel material on which the boron nitride layer on which the inorganic compound layer containing titanium oxide has been formed in this way is further heated at a rate of about 150 ° C./sec using an induction hardening device to generate a high frequency of 850 ° C. × 3 seconds. In addition, it was immediately cooled with water and quenched.

<Example 10>
A tempered material (SCM440) having a diameter of 20 mm and a length of 40 mm is used as a base material. After this surface is degreased and cleaned, it is treated with an ion plating apparatus for 2 hours to form a zirconium nitride layer having a thickness of 3 μm on the steel surface. did.

The steel material having the hard nitride layer formed on the surface was further dip coated with a sol solution of 2% tantalum hydroxide and 0.3% niobium hydroxide, and then dried. The amount of tantalum deposited was measured with a fluorescent X-ray analyzer and found to be 70 mg / m ² .

  Thus, about the steel material which formed the zirconium nitride layer in which the inorganic compound layer containing a tantalum and niobium was formed, using the same induction hardening apparatus as Example 1, the high frequency of 850 degreeC * 3 second was added, and water cooling was carried out immediately. And quenching.

<Example 11>
Using a SCM440 tempered material with a diameter of 8 mm and a length of 12 mm as a base material, this surface was degreased and washed, and then softened in a molten salt bath at 570 ° C. for 2 hours (tuftride treatment: manufactured by Nihon Parkerizing Co., Ltd.) ) To form a 12 μm thick iron nitride layer on the steel surface.

The steel material having the iron nitride layer formed on the surface in this manner was further dip-coated with a coating solution containing 2% hafnium oxalate and then dried at 250 ° C. When the adhesion amount of Hf was measured with a fluorescent X-ray analyzer, Hf was 120 mg / m ² .

  In this way, the steel material on which the iron nitride layer formed with the inorganic compound layer composed of the oxide containing Hf was further applied with a high frequency of 800 ° C. × 5 seconds using the same induction hardening apparatus as in Example 1. Immediately cooled with water and quenched.

<Comparative Example 1>
The same carbon steel material as in Example 1 was used as a base material, this surface was degreased and washed, and then soft nitriding treatment (tuftride treatment: manufactured by Nihon Parkerizing Co., Ltd.) at 570 ° C. for 1 hour in a molten salt bath. After forming an iron nitride layer having a thickness of 12 μm, the same induction hardening apparatus as in Example 1 was used to apply a high frequency of 850 ° C. × 3 seconds, followed by quenching immediately by water cooling.

<Comparative example 2>
The same carbon steel material as in Example 1 was used as a base material, this surface was degreased and washed, and then soft nitriding treatment (tuftride treatment: manufactured by Nihon Parkerizing Co., Ltd.) at 570 ° C. for 1 hour in a molten salt bath. An iron nitride layer having a thickness of about 5 μm was formed.

The steel material having the iron nitride layer formed on the surface in this manner was further dip-coated with a carburizing inhibitor solution containing silicon oxide as a component, and the excess liquid was removed, followed by drying. The amount of Si deposited was measured with a fluorescent X-ray analyzer and found to be 350 mg / m ² .

  About the steel material on which the iron nitride layer in which the inorganic compound layer containing titanium oxide was formed in this manner was further heated using the same induction hardening apparatus as in Example 1 at 850 ° C. × 3 seconds, Immediately cooled with water and quenched.

<Comparative Example 3>
The same carbon steel material as in Example 1 was used as a base material, and this surface was degreased and washed, and then treated with an ion plating apparatus for 1 hour to form a hard nitride layer made of titanium nitride having a thickness of 3 μm on the steel material surface. . Further, using the same induction hardening apparatus as in Example 1, a high frequency of 850 ° C. × 3 seconds was applied, and immediately quenched with water.

<Comparative example 4>
The same carbon steel material as in Example 1 was used as a base material, this surface was degreased and cleaned, and then treated with an ion plating apparatus for 1 hour, and a hard nitride layer made of chromium nitride having a thickness of 5 μm on the steel material surface. Formed. Further, using the same induction hardening apparatus as in Example 1, a high frequency of 850 ° C. × 3 seconds was applied, and immediately quenched with water.

<Comparative Example 5>
The same carbon steel material as in Example 1 was used as a substrate, and this surface was degreased and cleaned, and then treated with a plasma CVD apparatus for 3 hours to form a hard nitride layer made of boron nitride having a thickness of 3 μm on the steel material surface. Further, using the same induction hardening apparatus as in Example 1, a high frequency of 850 ° C. × 3 seconds was added, and immediately quenched with water.

(Evaluation test)
The steel material subjected to these treatments was cut with a microcutter, the remaining state of the nitride layer was confirmed with a metal microscope, and the hardness of a cross section of 0.1 mm from the outermost surface and the surface was measured with a micro Vickers hardness meter. Table 1 shows a list of evaluation test results. 1 to 3 show cross-sectional metal micrographs in Example 1, Comparative Example 1, and Comparative Example 2. FIG. In addition, the white part of the center of FIGS. 1-3 is an inorganic compound layer containing iron nitride, and the lower part is a steel base part.

From the table, in Examples 1 to 11 of the present invention, the nitride layer on the surface remains without being damaged even after quenching, and the surface hardness and the hardness of the cross section from the surface to a certain depth are sufficiently high. Recognize. On the other hand, in Comparative Example 1 in which the protective layer was not coated, the oxidative decomposition of the compound layer made of iron nitride progressed, and the nitride changed to an oxide, resulting in a decrease in surface hardness. On the other hand, even in Comparative Example 2 in which the protective layer was formed of Si oxide, the compound layer was damaged and partly lost, and a sufficient quenching effect was obtained because the thermal conductivity of the SiO ₂ film was poor. This is not preferable because a decrease in cross-sectional hardness is observed.

  Hardening method of steel member, hardened steel member, manufacturing method of hardened steel member and quenching surface protective agent of the present invention are parts such as gears, shafts, cams, etc., tools, molds for machines, automobiles, industrial machines, machine tools, etc. It can be applied to all steel members that require hardness, wear resistance and fatigue strength, such as bearings. In addition, by selecting the composition of the inorganic compound layer, it is possible to impart corrosion resistance, adhesion / adhesion, and antistatic properties at the same time. Wide range is possible.

It is a compound layer cross-sectional photograph after hardening of the steel materials of Example 1. It is a compound layer cross-sectional photograph after hardening of the steel materials of the comparative example 1. It is a compound layer cross-sectional photograph after hardening of the steel material of the comparative example 2.

Claims (12)

  It is a steel member before quenching treatment, and a hard nitride layer is formed on the surface of the steel member by a nitrogen diffusion treatment, and further on the hard nitride layer, Ti, Zr, Hf, V, Nb, A steel member in which a ceramic precursor layer is formed by applying a ceramic precursor containing at least one element selected from the group consisting of Ta, Cr, W, Mo and Al .   The steel member according to claim 1, wherein the ceramic precursor layer further contains at least one selected from Ca, Mg, Y, Sc and Ba. The ceramic precursor layer contains at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo, and Al in a total of 1 to 2000 mg in terms of the metal. The steel member according to claim 1 or 2, which is contained in a range of / m ² .   The steel according to any one of claims 1 to 3, wherein the hard nitrided layer is formed by a process selected from salt bath nitriding, gas soft nitriding, ion nitriding, and plasma nitriding. Element.   (I) At least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo, and Al for a steel material having a hard nitride layer on the surface. The method of any one of Claims 1-4 manufactured by the method of including the process of applying the liquid containing the ceramic precursor to contain, and the process of removing the solvent of the liquid containing the said ceramic precursor (ii). Steel member according to item.   The steel member according to claim 5, wherein the liquid containing the ceramic precursor further contains at least one selected from Ca, Mg, Y, Sc, and Ba.   The steel member according to claim 5 or 6, wherein the solvent of the liquid containing the ceramic precursor is neutral to alkaline.   A hard nitrided steel member obtained by quenching the steel member according to any one of claims 1 to 7, and formed on the surface of the steel member by nitrogen diffusion treatment Steel members with physical layers.   The steel member according to claim 8, which is a mechanical structural component used in a high surface pressure region.   The steel member according to claim 9, which is a shaft, a gear, a piston, a shaft, or a cam.   The steel member according to any one of claims 8 to 10, wherein the quenching process is performed at 800 to 850 ° C.   The steel member according to any one of claims 8 to 11, wherein the quenching treatment is induction hardening.