JP2015030871A - Steel material processing method - Google Patents
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Abstract
Description
本発明は、鋼材に硫黄を侵入させる鋼材処理方法に関する。 The present invention relates to a steel material processing method for allowing sulfur to enter a steel material.
鋼材の表面における摩擦特性および潤滑特性を改善するために、硫黄を侵入させる処理が行われている。この硫黄を侵入させる処理として、コーベット法と呼ばれる電解浸硫が知られている（非特許文献１参照）。コーベット法は、１９０℃の溶融塩浴中で、処理品を陽極とし、浴槽を陰極として１０〜２０分電解を行うことで、硫化鉄の拡散層を処理品の表面に形成する。また、無電解で硫化被膜を製造する手法も知られている（非特許文献２参照）。 In order to improve the friction characteristics and lubrication characteristics on the surface of the steel material, a treatment for intruding sulfur is performed. As a treatment for intruding sulfur, electrolytic sulfurization called a corbette method is known (see Non-Patent Document 1). In the corvette method, a diffusion layer of iron sulfide is formed on the surface of the treated product by performing electrolysis for 10 to 20 minutes using a treated product as an anode and a bath as a cathode in a molten salt bath at 190 ° C. In addition, a technique for producing a sulfide film without electrolysis is also known (see Non-Patent Document 2).
しかしながら、鋼材は製造過程において酸化被膜が形成されている。この酸化被膜は、鋼材に硫黄を侵入させる前に、除去している。この除去の方法としては、酸洗浄などがある（非特許文献３参照）。このように、従来では、鋼材に硫黄を侵入させる処理を行う場合、前処理として酸洗浄を行っており、工程が煩雑になるなどの問題があった。 However, the steel material has an oxide film formed during the manufacturing process. This oxide film is removed before sulfur enters the steel material. As this removal method, there is acid cleaning or the like (see Non-Patent Document 3). As described above, conventionally, when the treatment for intruding sulfur into the steel material is performed, the acid cleaning is performed as the pretreatment, and there is a problem that the process becomes complicated.
本発明は、以上のような問題点を解消するためになされたものであり、工程を煩雑にすることなく、鋼材に硫黄を侵入させる処理ができるようにすることを目的とする。 The present invention has been made to solve the above-described problems, and an object of the present invention is to make it possible to perform a process of intruding sulfur into a steel material without complicating the process.
本発明に係る鋼材処理方法は、チオシアン酸塩を溶解したｐＨが４〜６の範囲のいずれかの水溶液からなる処理液を用意する第１工程と、処理対象の鋼材に無電解で処理液を接触させて鋼材に硫黄を侵入させる第２工程とを備える。 The steel material treatment method according to the present invention includes a first step of preparing a treatment liquid comprising an aqueous solution having a pH of 4 to 6 in which thiocyanate is dissolved, and electroless treatment of the steel material to be treated. A second step of bringing sulfur into the steel material by bringing it into contact.
上記鋼材処理方法において、処理対象の鋼材は、表面に酸化被膜が形成されている。なお、チオシアン酸塩は、チオシアン酸アンモニウムであればよい。 In the steel material processing method, an oxide film is formed on the surface of the steel material to be processed. The thiocyanate may be ammonium thiocyanate.
以上説明したことにより、本発明によれば、工程を煩雑にすることなく、鋼材に硫黄を侵入させる処理ができるようになるという優れた効果が得られる。 As described above, according to the present invention, it is possible to obtain an excellent effect that it is possible to perform a process of intruding sulfur into a steel material without complicating the process.
以下、本発明の実施の形態について図を参照して説明する。図１は、本発明の実施の形態における鋼材処理方法を説明するフローチャートである。この処理方法は、まず、ステップＳ１０１で、チオシアン酸塩を溶解したｐＨが４〜６の範囲のいずれかの水溶液からなる処理液を用意する。例えば、濃度を２０％としたチオシアン酸アンモニウムの水溶液を作製して処理液とすればよい。チオシアン酸アンモニウムの水溶液はいわゆる弱酸性であり、作製した処理液のｐＨは、４．２程度となる。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a flowchart for explaining a steel material processing method according to an embodiment of the present invention. In this processing method, first, in step S101, a processing solution is prepared which is made of any aqueous solution having a pH of 4 to 6 in which thiocyanate is dissolved. For example, an aqueous solution of ammonium thiocyanate having a concentration of 20% may be prepared as a treatment liquid. The aqueous solution of ammonium thiocyanate is so-called weakly acidic, and the pH of the prepared treatment liquid is about 4.2.
次に、ステップＳ１０２で、処理対象の鋼材に無電解で処理液を接触させて鋼材に硫黄を侵入させる。例えば、所定の容器に上記処理液を収容し、この処理液中に、処理対象の鋼材を浸漬すればよい。ここで、鋼材は、表面に酸化被膜が形成されている状態である。 Next, in step S102, the treatment liquid is brought into contact with the steel material to be treated in an electroless manner so that sulfur enters the steel material. For example, the processing liquid may be stored in a predetermined container, and the steel material to be processed may be immersed in the processing liquid. Here, the steel material is in a state where an oxide film is formed on the surface.
上述した方法により、鋼材に対して酸化被膜除去のためなどの前処理を行うことなく、鋼材に硫黄を侵入させることができる。ここで、処理液のｐＨが４より小さすぎると、硫黄が侵入した表面の層が溶解するなどにより、硫黄が進入した状態が得られないことが考えられるため、ｐＨは４以上とすることが重要である。なお、ここで用いるチオシアン酸塩は、常温で水溶性を有するものである。従って、処理液は、水溶性を有するチオシアン酸塩の水溶液であり、ｐＨが４〜６の範囲のいずれかとなっている水溶液である。 By the above-described method, sulfur can be introduced into the steel material without performing a pretreatment such as for removing an oxide film on the steel material. Here, if the pH of the treatment liquid is too small, it is considered that the state in which sulfur has entered cannot be obtained due to dissolution of the surface layer into which sulfur has entered, and therefore the pH should be 4 or more. is important. The thiocyanate used here is water-soluble at room temperature. Therefore, the treatment liquid is an aqueous solution of thiocyanate having water solubility, and an aqueous solution having a pH in the range of 4-6.
［実施例１］
次に、実施例を用いてより詳細に説明する。まず、処理対象として、長さ７ｃｍ、直径１．２ｃｍの円柱型で、表面に厚さ３０〜４０μｍの酸化被膜が形成されている状態の高強度鋼材を試験片として用意した。次に、処理液として、ｐＨが４．２の２０％チオシアン酸アンモニウム水溶液を用意した。次に、用意した処理液を５０℃に加熱し、試験片を所定時間浸漬した。処理液温度は２０℃程度でもよいが、５０℃に加熱することで、硫黄の侵入を促進させることができる。
[Example 1]
Next, it demonstrates in detail using an Example. First, as a treatment object, a high strength steel material having a columnar shape having a length of 7 cm and a diameter of 1.2 cm and having an oxide film having a thickness of 30 to 40 μm formed on the surface was prepared as a test piece. Next, a 20% ammonium thiocyanate aqueous solution having a pH of 4.2 was prepared as a treatment liquid. Next, the prepared treatment liquid was heated to 50 ° C., and the test piece was immersed for a predetermined time. Although the treatment liquid temperature may be about 20 ° C., the penetration of sulfur can be promoted by heating to 50 ° C.
上述した処理において、処理液のｐＨの変化を観察したところ、図２に示すように、試験片を処理液中に浸漬した直後からｐＨが急激に上昇し、１２時間経過した後から、ｐＨは６前後でほぼ一定に保たれていることが確認されている。 In the treatment described above, when the change in pH of the treatment liquid was observed, as shown in FIG. 2, the pH rapidly increased immediately after the test piece was immersed in the treatment liquid, and after 12 hours had elapsed, the pH was It has been confirmed that the value is kept almost constant at around 6.
次に、上述した処理を１日（２４ｈ）継続した後、および４日（９６ｈ）継続した後に、試験片の状態を確認した。この確認は、試験片の表面に形成されていた密着性の低い沈殿皮膜を除去してから実施した。確認方法として、試験片の断面を電子線マイクロアナライザー（ＥＰＭＡ）で分析した。分析した結果を図３に示す。 Next, after the above-described treatment was continued for 1 day (24 h) and after 4 days (96 h), the state of the test piece was confirmed. This confirmation was carried out after removing the deposited film with low adhesion formed on the surface of the test piece. As a confirmation method, the cross section of the test piece was analyzed with an electron beam microanalyzer (EPMA). The analysis results are shown in FIG.
図３において、（ａ−０），（ａ−１），（ａ−２）は、走査型電子顕微鏡像を示している。また、（ｂ−０），（ｂ−１），（ｂ−２）は、ＥＰＭＡにより分析された酸素の分布を示し、（ｃ−１），（ｃ−２）は、ＥＰＭＡにより分析された硫黄の分布を示している。ＥＰＭＡの分析結果においては、色が薄い箇所ほど濃度が高いことを示している。 In FIG. 3, (a-0), (a-1), and (a-2) show scanning electron microscope images. In addition, (b-0), (b-1), and (b-2) show the distribution of oxygen analyzed by EPMA, and (c-1) and (c-2) were analyzed by EPMA. It shows the distribution of sulfur. The EPMA analysis results show that the lighter the color, the higher the density.
また、（ａ−０），（ｂ−０）は、処理前の状態を示している。また、（ａ−１），（ｂ−１），（ｃ−１）は、処理を１日（２４ｈ）継続した後の状態を示している。また、（ａ−２），（ｂ−２），（ｃ−２）は、処理を４日（９６ｈ）継続した後の状態を示している。 Further, (a-0) and (b-0) indicate the state before processing. Further, (a-1), (b-1), and (c-1) show states after the processing is continued for one day (24h). Further, (a-2), (b-2), and (c-2) show states after the processing is continued for 4 days (96h).
図３の（ａ−０）に示すように、表面には内側とは異なる状態の層が形成され、この部分は、図３の（ｂ−０）に示すように、酸素が多く分布している領域であることから分かるように、処理前（０ｈ）には、酸化被膜が試験片表面に存在していることが確認される。 As shown in (a-0) of FIG. 3, a layer having a different state from the inside is formed on the surface, and in this portion, as shown in (b-0) of FIG. 3, a large amount of oxygen is distributed. As can be seen from this area, it is confirmed that the oxide film is present on the surface of the test piece before the treatment (0 h).
これに対し、２４ｈ後では、図３の（ａ−１），（ｂ−１）に示すように、酸化被膜が消失し、図３の（ｃ−１）に示すように、表面に硫黄が侵入していることが分かる。さらに、９６ｈ後には、図３の（ｃ−２）に示すように、試験片の表面より深さ５〜１０μｍの内部にまで、硫黄が侵入し、また、比較的均一に分布していることが分かる。 On the other hand, after 24 hours, as shown in (a-1) and (b-1) of FIG. 3, the oxide film disappeared, and as shown in (c-1) of FIG. You can see that it is invading. Further, after 96 hours, as shown in FIG. 3 (c-2), sulfur penetrates from the surface of the test piece to the inside of a depth of 5 to 10 μm, and is distributed relatively uniformly. I understand.
次に、試験片の表面を観察した結果を図４に示す。図４は、試験片の表面をカメラで撮影した写真である。浸漬前（０ｈ）では観察されない金属光沢が、１日（２４ｈ）浸漬後および２日（４８ｈ）浸漬後では一部で見られ、これらの段階では、表面の酸化被膜が除去され、新たに硫黄が侵入した膜が形成される途中であることが分かる。 Next, the result of observing the surface of the test piece is shown in FIG. FIG. 4 is a photograph of the surface of the test piece taken with a camera. Metal luster that is not observed before immersion (0 h) is partially observed after immersion for 1 day (24 h) and after 2 days (48 h). At these stages, the oxide film on the surface is removed and sulfur is newly added. It can be seen that the film invading is in the process of being formed.
以上のことより、チオシアン酸塩の水溶液を用いた処理により鋼材表面に均一に硫黄を侵入させるためには、４日程度の時間が必要であることが分かる。 From the above, it can be seen that it takes about 4 days to allow sulfur to penetrate uniformly into the steel surface by treatment with an aqueous solution of thiocyanate.
以上に説明したように、本発明によれば、チオシアン酸塩の水溶液を鋼材に作用させるようにしたので、工程を煩雑にすることなく、鋼材に硫黄を侵入させる処理ができるようになる。また、この処理では、製造過程で鋼材表面に生成する酸化被膜を除去する前処理をすることなく、鋼材に硫黄を侵入させることができ、例えば、鋼材表面に硫化鉄の膜を形成することができる。 As described above, according to the present invention, the aqueous solution of thiocyanate is allowed to act on the steel material, so that it is possible to perform the process of intruding sulfur into the steel material without complicating the process. Further, in this treatment, sulfur can be intruded into the steel material without performing a pretreatment for removing the oxide film formed on the steel material surface during the manufacturing process. For example, an iron sulfide film can be formed on the steel material surface. it can.
なお、本発明は以上に説明した実施の形態に限定されるものではなく、本発明の技術的思想内で、当分野において通常の知識を有する者により、多くの変形および組み合わせが実施可能であることは明白である。 The present invention is not limited to the embodiment described above, and many modifications and combinations can be implemented by those having ordinary knowledge in the art within the technical idea of the present invention. It is obvious.
Claims (3)
処理対象の鋼材に無電解で前記処理液を接触させて前記鋼材に硫黄を侵入させる第２工程と
を備えることを特徴とする鋼材処理方法。 A first step of preparing a treatment liquid comprising an aqueous solution having a pH of 4 to 6 in which thiocyanate is dissolved;
And a second step of bringing sulfur into the steel material by bringing the treatment liquid into contact with the steel material to be treated in an electroless manner.
処理対象の前記鋼材は、表面に酸化被膜が形成されていることを特徴とする鋼材処理方法。 The steel material processing method according to claim 1,
A steel material processing method, wherein the steel material to be treated has an oxide film formed on a surface thereof.
前記チオシアン酸塩は、チオシアン酸アンモニウムであることを特徴とする鋼材処理方法。 In the steel material processing method according to claim 1 or 2,
The method for treating steel materials, wherein the thiocyanate is ammonium thiocyanate.
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| JP2014012876A (en) * | 2012-07-05 | 2014-01-23 | Nippon Telegr & Teleph Corp <Ntt> | Method for suppressing hydrogen generation on steel material surface |
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| JPS5030749A (en) * | 1973-07-23 | 1975-03-27 | ||
| JPS5822388A (en) * | 1981-07-30 | 1983-02-09 | Kawasaki Heavy Ind Ltd | Surface treatment of metallic mold |
| JPH10204611A (en) * | 1997-01-13 | 1998-08-04 | Dowa Mining Co Ltd | Sulfurization treatment of ferrous articles |
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