JP2003231974A - Surface-treated steel material, manufacturing method therefor, and chemical treatment solution - Google Patents
Surface-treated steel material, manufacturing method therefor, and chemical treatment solutionInfo
- Publication number
- JP2003231974A JP2003231974A JP2002045983A JP2002045983A JP2003231974A JP 2003231974 A JP2003231974 A JP 2003231974A JP 2002045983 A JP2002045983 A JP 2002045983A JP 2002045983 A JP2002045983 A JP 2002045983A JP 2003231974 A JP2003231974 A JP 2003231974A
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- Prior art keywords
- chemical conversion
- steel material
- conversion treatment
- treatment liquid
- potassium
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Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】本発明は、Cr含有鋼材等の鋼
材の表面に化成皮膜を生成させるための化成処理液およ
びそれを用いて表面処理を行う表面処理鋼材の製造方法
に関する。TECHNICAL FIELD The present invention relates to a chemical conversion treatment liquid for forming a chemical conversion coating on the surface of a steel material such as a Cr-containing steel material and a method for producing a surface-treated steel material using the same.
【０００２】本発明はさらにそのような表面処理方法に
より得られる表面処理鋼材、特に耐焼付き性に優れた表
面処理鋼材に関する。The present invention further relates to a surface-treated steel material obtained by such a surface-treatment method, and particularly to a surface-treated steel material excellent in seizure resistance.
【０００３】[0003]
【従来の技術】化成処理は、例えば、鋼材表面と腐食性
溶液とを化学反応させて鋼材表面に、固着性のある腐食
生成物を形成する処理であって、通常、その腐食性溶液
の種類によってリン酸塩処理、クロメート処理およびシ
ュウ酸塩処理等と呼ばれる。2. Description of the Related Art Chemical conversion treatment is performed, for example, on steel surfaces and corrosiveness.
This is a treatment that chemically reacts with a solution to form a sticky corrosion product on the surface of steel materials, and is usually called phosphate treatment, chromate treatment, oxalate treatment, etc. depending on the type of the corrosive solution. .
【０００４】しかしながら、高Cr含有鋼材のような鋼材
には、そのような従来の化成処理によっても化成皮膜を
設けることができなかった。従来にあっても、例えば、
特開昭57−82478 号公報に開示されているように、アル
カリ金属リン酸塩を主成分とし、チタン化合物と塩素酸
塩を含有する化成処理液で鋼材表面に化成処理を行った
後、リン酸亜鉛を含有する化成処理液による更なる化成
処理を施す方法は公知である。しかし、この方法では、
２回の処理を必要とする。しかも、高Cr含有鋼材、例え
ば13％Cr含有鋼材には、健全なリン酸塩の化成皮膜を表
面に形成することができなかった。However, it has not been possible to form a chemical conversion coating on a steel material such as a high Cr content steel material by such a conventional chemical conversion treatment. Even in the past, for example,
As disclosed in JP-A-57-82478, after chemical conversion treatment is performed on the surface of a steel material with a chemical conversion treatment liquid containing an alkali metal phosphate as a main component and a titanium compound and a chlorate, the phosphorus is A method of performing a further chemical conversion treatment with a chemical conversion treatment liquid containing zinc acid is known. But with this method,
Requires two treatments. Moreover, it was not possible to form a sound phosphate chemical conversion coating on the surface of a high Cr content steel material, for example, a 13% Cr content steel material.
【０００５】特開平５−40034 号公報には、フッ素イオ
ンを添加した、マンガンとリン酸を含有する化成処理液
で表面処理を行う方法が開示されている。しかし、この
方法でもCr含有鋼材には依然として、化成皮膜は設ける
ことができなかった。Japanese Unexamined Patent Publication (Kokai) No. 5-40034 discloses a method of performing surface treatment with a chemical conversion treatment liquid containing manganese and phosphoric acid, to which fluorine ions are added. However, even with this method, the conversion coating could not be formed on the Cr-containing steel material.
【０００６】ところで、油井鋼管は、カップリングを介
して相互に接続される。このとき、鋼管の端部に形成し
た雄ネジにカップリングの内面に形成した雌ネジを嵌め
合わせ、これらのネジを締め付けることにより、気密性
および液密性を維持しながら複数の鋼管が接続される。
ところが、この締め付け時に各ネジに大きなトルクが働
くため、ネジ表面にゴーリングなどの欠陥が生じやすく
油井鋼管の繰り返し使用回数が低減する。また、ネジ表
面に腐食が発生すると、充分な気密性および液密性を確
保することが困難となる。By the way, the oil well steel pipes are connected to each other through a coupling. At this time, by fitting the male screw formed on the end of the steel pipe with the female screw formed on the inner surface of the coupling and tightening these screws, multiple steel pipes are connected while maintaining airtightness and liquid tightness. It
However, since a large torque acts on each screw at the time of this tightening, defects such as galling are likely to occur on the screw surface, and the number of repeated use of the oil well steel pipe is reduced. Further, if corrosion occurs on the screw surface, it becomes difficult to secure sufficient airtightness and liquid tightness.
【０００７】[0007]
【課題を解決するための手段】したがって、従来は、Cr
含有鋼から製造される油井鋼管のネジ継手のネジ表面に
はCuなどの軟質金属のめっきを施すことでゴーリングの
防止を図っていたが、かかる方法はめっき操作の工数を
要すること等から更なる改善が求められている。[Means for Solving the Problems] Therefore, conventionally, Cr
We tried to prevent galling by plating a soft metal such as Cu on the thread surface of the threaded joint of the oil well steel pipe manufactured from the containing steel, but this method requires more man-hours for plating operation, etc. Improvement is required.
【０００８】このように、従来にあっても、Cr含有鋼材
でもその表面に健全なリン酸亜鉛皮膜あるいはリン酸マ
ンガン皮膜等の化成皮膜を安定して形成できる技術が求
められていた。As described above, there has conventionally been a demand for a technique capable of stably forming a sound chemical conversion coating such as a zinc phosphate coating or a manganese phosphate coating on the surface of a Cr-containing steel material.
【０００９】本発明の目的は、例えば0.5 〜13％のCrを
含有するCr含有鋼材の表面にもリン酸塩の化成皮膜を安
定して形成できる化成処理液を提供することである。本
発明の別の目的は、上述のCr含有鋼材の表面にでもリン
酸塩の化成皮膜を安定して形成できる表面処理を行う表
面処理鋼材の製造方法を提供することである。An object of the present invention is to provide a chemical conversion treatment liquid capable of stably forming a phosphate chemical conversion coating on the surface of a Cr-containing steel material containing, for example, 0.5 to 13% Cr. Another object of the present invention is to provide a method for producing a surface-treated steel material which carries out a surface treatment capable of stably forming a phosphate chemical conversion coating even on the surface of the Cr-containing steel material.
【００１０】本発明のさらに別の目的は、そのようなリ
ン酸塩の化成皮膜を備えた表面処理鋼材を提供すること
にある。Yet another object of the present invention is to provide a surface-treated steel material provided with such a phosphate conversion coating.
【００１１】[0011]
【発明が解決しようとする課題】本発明者らは、カリウ
ム化合物をリン酸塩系化成処理液に添加することにより
皮膜形成能が飛躍的に向上すること、さらに化成皮膜形
成が困難であったCr含有鋼材でもリン酸塩系の化成皮膜
を安定して形成できることを知った。DISCLOSURE OF THE INVENTION The present inventors have found that the addition of a potassium compound to a phosphate-based chemical conversion treatment solution dramatically improves the film forming ability, and it has been difficult to form a chemical conversion film. We have found that a phosphate-based chemical conversion coating can be stably formed even on Cr-containing steel.
【００１２】本発明者らは、そのような知見をもとに、
更に研究・開発を続け、かかるカリウム化合物、特に四
硼酸カリウムの作用効果がクロメート処理、シュウ酸塩
処理等による化成皮膜一般に見られることを知り、本発
明を完成した。Based on such knowledge, the present inventors have
Further research and development was carried out, and it was found that the action and effect of such a potassium compound, especially potassium tetraborate, was found in general chemical conversion coatings by chromate treatment, oxalate treatment, etc., and the present invention was completed.
【００１３】本発明は、広義には、鋼材とその表面の少
なくとも１つの部位に設けた化成皮膜から成り、該化成
皮膜はカリウム量が0.1 〜1000 mg/m2であり、厚みが５
〜50μｍ、好ましくは５〜35μｍであることを特徴とす
る表面処理鋼材である。In a broad sense, the present invention comprises a steel material and a chemical conversion coating formed on at least one site on the surface thereof, the chemical conversion coating having a potassium content of 0.1 to 1000 mg / m 2 and a thickness of 5
The surface-treated steel material is characterized by having a thickness of -50 μm, preferably 5-35 μm.
【００１４】本発明の好適態様にあっては、前記化成皮
膜が、リン酸塩系化成皮膜、例えばリン酸亜鉛系化成皮
膜、またはリン酸マンガン系化成皮膜である。油井鋼管
のカップリングの継手部にはリン酸マンガン系化成皮膜
を、油井鋼管の継手部にはリン酸亜鉛系化成被膜をそれ
ぞれ設けることが好ましい。In a preferred aspect of the present invention, the chemical conversion coating is a phosphate chemical conversion coating such as a zinc phosphate chemical conversion coating or a manganese phosphate chemical conversion coating. It is preferable to provide a manganese phosphate-based chemical conversion coating on the coupling portion of the oil well steel pipe and a zinc phosphate-based chemical conversion coating on the coupling portion of the oil well steel pipe, respectively.
【００１５】別の面からは、本発明は、亜鉛とリン酸、
またはマンガンとリン酸を含有し、さらにカリウムを含
有する化成処理液を用いて鋼材表面に化成処理を行うこ
とを特徴とする表面処理鋼材の製造方法である。From another aspect, the present invention provides zinc and phosphoric acid,
Alternatively, it is a method for producing a surface-treated steel material, which comprises subjecting a steel material surface to a chemical conversion treatment using a chemical conversion treatment liquid containing manganese and phosphoric acid and further containing potassium.
【００１６】このときの化成処理液は、カリウムを含む
イオンのモル濃度が６×10-4％以上、７×10-1％以下で
あることが好ましい。化成処理は、60〜100 ℃、好まし
くは70〜100 ℃の温度で少なくとも５分間鋼材を前記化
成処理液に浸漬して行う。The chemical conversion treatment liquid at this time preferably has a molar concentration of ions containing potassium of 6 × 10 -4 % or more and 7 × 10 -1 % or less. The chemical conversion treatment is performed by immersing the steel material in the chemical conversion treatment liquid at a temperature of 60 to 100 ° C, preferably 70 to 100 ° C for at least 5 minutes.
【００１７】あるいは、化成処理は、60〜100 ℃、好ま
しくは70〜100 ℃の温度で少なくとも５分間鋼材に化成
処理液を供給して行うさらに別の面からは、本発明は、
亜鉛とリン酸、またはマンガンとリン酸を含有し、さら
にカリウムを含有することを特徴とする鋼材用化成処理
液である。Alternatively, the chemical conversion treatment is performed by supplying the chemical conversion treatment liquid to the steel material at a temperature of 60 to 100 ° C., preferably 70 to 100 ° C. for at least 5 minutes.
A chemical conversion treatment liquid for steel, which contains zinc and phosphoric acid, or manganese and phosphoric acid, and further contains potassium.
【００１８】本発明のかかる態様にあっては、前記カリ
ウムを含むイオンのモル濃度が６×10-4％以上、７×10
-1％以下であることが好ましい。本発明にかかる化成処
理液において、マンガンとリン酸を含有し、さらにカリ
ウムを含有し、全酸度を30以上55未満、全酸度の遊離酸
度に対する比を３〜15に調整することが好ましい。In such an embodiment of the present invention, the ion concentration including the potassium is 6 × 10 −4 % or more and 7 × 10 4.
It is preferably -1 % or less. The chemical conversion treatment liquid according to the present invention preferably contains manganese and phosphoric acid, further contains potassium, and has a total acidity of 30 to less than 55 and a ratio of the total acidity to the free acidity of 3 to 15.
【００１９】[0019]
【発明の実施の形態】本発明をさらに具体的に説明する
が、本明細書において、「％」は特に断りがないかぎり
「質量％」を意味する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. In the present specification, "%" means "mass%" unless otherwise specified.
【００２０】本発明によれば、処理すべき鋼材の表面を
脱脂、水洗した後で、リン酸塩系、クロム酸塩系、シュ
ウ酸塩系等の化成処理を行う。特に好ましくは亜鉛とリ
ン酸あるいはマンガンとリン酸とを含有する化成処理液
で化成処理を行う。かかる化成処理液は、亜鉛−リン酸
系あるいはマンガン−リン酸系化成処理液とも称され
る。化成処理方法それ自体は、公知であり、したがっ
て、化成処理方法それ自体についての説明は割愛する。According to the present invention, the surface of the steel material to be treated is degreased, washed with water, and then subjected to chemical conversion treatment such as phosphate, chromate or oxalate. Particularly preferably, the chemical conversion treatment is performed with a chemical conversion treatment liquid containing zinc and phosphoric acid or manganese and phosphoric acid. Such a chemical conversion treatment liquid is also called a zinc-phosphoric acid-based or manganese-phosphoric acid-based chemical conversion treatment liquid. The chemical conversion treatment method itself is known, and therefore, the description of the chemical conversion treatment method itself will be omitted.
【００２１】本発明において鋼材の化学組成は、特に限
定されるものではないが、従来技術では化成処理が困難
な、Crを質量％（以下、単に％で表す）で0.5 〜13％含
有するCr含有鋼材が好ましい。In the present invention, the chemical composition of the steel material is not particularly limited, but it is difficult to carry out chemical conversion treatment in the prior art, and Cr containing 0.5 to 13% by mass% (hereinafter simply expressed as%) is contained. Containing steel is preferred.
【００２２】その鋼材の形態についても特に制限され
ず、例えば油井鋼管またはカップリングとして用いられ
る継目なし鋼管の継手部、特にネジ継手部であってもよ
い。あるいはそれ以外の管材、棒材、板材等であっても
よい。しかし、その経済効果を考えた場合、Cr含有鋼か
らなる油井鋼管などの継目なし鋼管のネジ継手部に本発
明を適用することが好ましい。The form of the steel material is not particularly limited, and may be, for example, a joint portion of an oil well steel pipe or a seamless steel pipe used as a coupling, particularly a screw joint portion. Alternatively, it may be a pipe material, a rod material, a plate material, or the like other than the above. However, in consideration of its economic effect, it is preferable to apply the present invention to a threaded joint portion of a seamless steel pipe such as an oil well steel pipe made of Cr-containing steel.
【００２３】鋼材の処理すべき表面部位の表面粗さをRm
ax 0.1〜60μｍに調整することが好ましい。ここに、
「化成皮膜」は、溶液と鋼材表面との化学反応で生じた
生成物が鋼材表面に密着して皮膜状に生成したものを言
い、溶液の種類によってリン酸塩系、クロム酸塩系、シ
ュウ酸塩系などの化成皮膜がある。本発明の場合、カリ
ウムが化成皮膜中に含まれる限り特に制限ない。しか
し、本発明を油井鋼管のような継目なし鋼管の継手部に
適用する場合、リン酸塩系化成皮膜が好ましい。その理
由は、リン酸塩系、特にリン酸−マンガン系あるいはリ
ン酸−亜鉛系の化成皮膜は鋼材表面への密着性に優れる
とともに防錆性と耐ゴーリング性に優れるからである。
より好ましくはリン酸−マンガン系化成皮膜である。The surface roughness of the surface portion of the steel material to be treated is Rm
It is preferable to adjust ax to 0.1 to 60 μm. here,
"Chemical conversion film" refers to a product formed by a chemical reaction between a solution and the surface of a steel product that adheres to the surface of the steel product to form a film. Depending on the type of solution, phosphate-based, chromate-based, and shu-shu There is a chemical conversion coating such as an acid salt system. In the case of the present invention, there is no particular limitation as long as potassium is contained in the chemical conversion film. However, when the present invention is applied to a joint portion of a seamless steel pipe such as an oil well steel pipe, a phosphate chemical conversion coating is preferable. The reason is that a phosphate-based, particularly phosphoric acid-manganese-based or phosphoric acid-zinc-based chemical conversion coating has excellent adhesion to the surface of the steel material as well as excellent rust prevention and galling resistance.
More preferably, it is a phosphoric acid-manganese-based chemical conversion coating.
【００２４】「化成処理液」は、そのような化成皮膜を
形成させるための処理液である。これについても、リン
酸塩系、クロム酸塩系、シュウ酸塩系等がある。本発明
の場合、このような化成処理液にカリウム化合物が含有
されるが、その目的は化成皮膜の生成を促進させると共
に生成した化成皮膜の均質性を向上させ、スケムラ（金
属露出) を防止することである。ただし、化成処理液に
ＦイオンおよびAlイオンが共に存在すると、同時に存在
するFeイオンおよびZnイオンとの作用により、場合によ
り K2Al(Fe、Zn)F6 のスラッジが生成・沈殿してしま
い、カリウム化合物の添加による効果が得られないこと
がある。したがって、好ましくは、フッ素イオンの不存
在下で化成処理を行う。The "chemical conversion treatment liquid" is a treatment liquid for forming such a chemical conversion film. Again, there are phosphate-based, chromate-based, oxalate-based, and the like. In the case of the present invention, a potassium compound is contained in such a chemical conversion treatment liquid, the purpose of which is to promote the formation of the chemical conversion film and improve the homogeneity of the formed chemical conversion film, and prevent squela (metal exposure). That is. However, if both F ions and Al ions are present in the chemical conversion treatment liquid, the sludge of K 2 Al (Fe, Zn) F 6 may be generated and precipitated due to the action of Fe ions and Zn ions that are present at the same time. However, the effect of adding a potassium compound may not be obtained. Therefore, the chemical conversion treatment is preferably performed in the absence of fluorine ions.
【００２５】本発明において使用できるカリウム化合物
としては、硼酸塩（例えば、四硼酸カリウム）、水酸化
物（例えば、水酸化カリウム）、弗化物（例えば、弗化
カリウム）、硝酸塩（例えば、硝酸カリウム）、塩化物
（例えば、塩化カリウム）、硫酸塩（例えば、硫酸カリ
ウム）等がある。これらのカリウム化合物を１種、もし
くは２種以上を混合して使用してもよい。好ましくは硼
酸塩、より好ましくは四硼酸カリウムである。このカリ
ウム化合物を亜鉛あるいはマンガンを含有する化成処理
液中に添加して使用する。The potassium compound which can be used in the present invention includes borate salts (eg potassium tetraborate), hydroxides (eg potassium hydroxide), fluorides (eg potassium fluoride), nitrates (eg potassium nitrate). , Chloride (eg potassium chloride), sulfate (eg potassium sulfate) and the like. You may use these potassium compounds 1 type or in mixture of 2 or more types. Borate is preferable, and potassium tetraborate is more preferable. This potassium compound is used by adding it to a chemical conversion treatment liquid containing zinc or manganese.
【００２６】化成皮膜の形成に及ぼすカリウムの作用機
構は、リン酸塩系化成処理液の場合、次のように考える
ことができる。化成処理液中にカリウム化合物を添加す
ることにより、液中の亜鉛あるいはマンガンとリン酸の
平衡状態が崩れ、可溶性のリン酸カリウムとなり液中に
溶解する。このとき、余剰の亜鉛あるいはマンガンは、
羽毛状突起を有する不溶性のゲル状の浮遊物質を生成す
る。この浮遊物が鋼材表面に速やかに吸着して鋼材表面
にリン酸塩の皮膜形成を促進させる核となり、スケムラ
（金属露出）の少ない健全なリン酸塩皮膜を形成するも
のと推定される。The mechanism of action of potassium on the formation of the chemical conversion film can be considered as follows in the case of the phosphate chemical conversion treatment liquid. By adding a potassium compound to the chemical conversion treatment liquid, the equilibrium state of zinc or manganese and phosphoric acid in the liquid is broken, and soluble potassium phosphate is dissolved in the liquid. At this time, excess zinc or manganese is
This produces an insoluble, gel-like floating material with feathery processes. It is presumed that these suspended solids are rapidly adsorbed on the surface of the steel material and serve as nuclei for promoting the formation of a phosphate film on the surface of the steel material, and form a healthy phosphate film with less unevenness (metal exposure).
【００２７】ところで、その原因は必ずしも明確ではな
いが、カリウム化合物に代えてナトリウム化合物(Na2B4
O7・10H2O)を添加した化成処理液を使用すると、厚さ10
μmの化成皮膜値が得られたがスケムラが大きく、実用
的とは云えない。したがって、上述のようなすぐれた効
果はカリウム化合物特有のものと考えられる。By the way, although the cause is not always clear, a sodium compound (Na 2 B 4
(O 7・ 10H 2 O) is added, the chemical treatment solution
A chemical conversion coating value of μm was obtained, but the unevenness of the surface was large and it was not practical. Therefore, the excellent effects as described above are considered to be peculiar to potassium compounds.
【００２８】このようなカリウム化合物の化成処理液へ
の添加は、粉末の状態であるいは水溶液にしてから行う
ことができる。その添加時期は、最初に化成処理液を調
製するときに添加してもよいが、化成処理を行う直前に
あるいは化成処理中に添加してもよい。The addition of such a potassium compound to the chemical conversion treatment liquid can be carried out in the form of powder or in the form of an aqueous solution. The addition time may be added when the chemical conversion treatment liquid is first prepared, or may be added immediately before the chemical conversion treatment or during the chemical conversion treatment.
【００２９】本発明の好適態様にあっては、上記化成処
理液は、カリウム化合物を含有するリン酸マンガン系化
成処理液であって、全酸度を30以上、55未満、全酸度の
遊離酸度に対する比を3 〜15に調整したリン酸マンガン
系化成処理液である。In a preferred embodiment of the present invention, the above chemical conversion treatment liquid is a manganese phosphate chemical conversion treatment liquid containing a potassium compound and having a total acidity of 30 or more and less than 55 and a free acidity of the total acidity. It is a manganese phosphate-based chemical conversion treatment liquid with the ratio adjusted to 3 to 15.
【００３０】ここに、「全酸度」は、被検体液10mlをフ
ェノールフタレインを指示薬として0.1ml/l の濃度の水
酸化ナトリウム液で中和滴定したときの滴定値(ml 数)
である。「遊離酸度」とは、被検体液10mlをブロムフェ
ノールを指示薬として中和滴定したときの滴定値(ml
数) である。「全酸度の遊離酸度に対する比」とは、全
酸度/ 遊離酸度であり、酸比とも称する。Here, the "total acidity" is a titration value (number of ml) when 10 ml of the test liquid is neutralized and titrated with a sodium hydroxide solution having a concentration of 0.1 ml / l using phenolphthalein as an indicator.
Is. "Free acidity" is the titration value (ml) when 10 ml of the test liquid was neutralized and titrated using bromphenol as an indicator.
Number). The “ratio of total acidity to free acidity” is total acidity / free acidity and is also referred to as acid ratio.
【００３１】全酸度が30未満では、被処理鋼材に形成さ
れるリン酸マンガン系皮膜が十分に均質でなく、スケム
ラが発生する場合があり、たとえ均質な化成皮膜が形成
されたとしても、皮膜形成に要する処理時間が極端に長
くなり経済的に好ましくない。また、全酸度が55以上と
なると、被処理鋼材表面に形成されるリン酸マンガン系
結晶が極端に粗大化し、そのためスケムラが生じたり、
被処理鋼材との密着性が劣化し、耐ゴーリング性を損な
うことから好ましくない。より好ましくは35〜53であ
る。When the total acidity is less than 30, the manganese phosphate-based coating formed on the steel to be treated is not sufficiently homogeneous and may cause unevenness in the coating. Even if a uniform chemical conversion coating is formed, the coating is formed. The processing time required for formation is extremely long, which is not economically preferable. Further, when the total acidity is 55 or more, the manganese phosphate-based crystal formed on the surface of the steel to be treated is extremely coarsened, which may cause unevenness in the surface,
It is not preferable because the adhesion with the steel material to be treated is deteriorated and the galling resistance is impaired. It is more preferably 35 to 53.
【００３２】同様に、全酸度の遊離酸度に対する比は、
3 〜15、より好ましくは、6 〜11であり、その理由は、
全酸度の限定理由と同じである。化成処理液中のカリウ
ム化合物の濃度は、質量％で、0.01〜10％を含有するこ
とが好ましい。カリウム化合物の濃度が0.01％未満で
は、皮膜厚みが不足する。一方、カリウム化合物の濃度
が10％を超えると、皮膜形成のための効果が飽和する。
皮膜厚みを均一にするという観点からは、より好ましく
は0.1 〜10％とする。さらに好ましくは0.1 〜１％とす
る。これはカリウムを含むイオンのモル濃度で、ほぼ６
×10-4％以上、７×10-1％以下に相当する。より好まし
い範囲は、同じくカリウムを含むイオンのモル濃度で、
ほぼ６×10-3％以上、７×10-1％以下、さらに好ましい
範囲は、ほぼ６×10-3％以上、７×10-2％以下である。Similarly, the ratio of total acidity to free acidity is
3 to 15, more preferably 6 to 11, for the reason
This is the same as the reason for limiting the total acidity. The concentration of the potassium compound in the chemical conversion treatment liquid is preferably 0.01 to 10% by mass. If the concentration of the potassium compound is less than 0.01%, the film thickness will be insufficient. On the other hand, when the concentration of the potassium compound exceeds 10%, the effect for forming the film is saturated.
From the viewpoint of making the film thickness uniform, it is more preferably 0.1 to 10%. It is more preferably 0.1 to 1%. This is the molar concentration of ions including potassium, which is approximately 6
This corresponds to x10 -4 % or more and 7x10 -1 % or less. A more preferable range is the molar concentration of ions also containing potassium,
It is approximately 6 × 10 -3 % or more and 7 × 10 -1 % or less, and a more preferable range is approximately 6 × 10 -3 % or more and 7 × 10 -2 % or less.
【００３３】化成処理液と鋼材表面とを反応させると
き、具体的には、浸漬時、スプレー塗布時等のいずれに
あっても、化成処理液の温度を60〜100 ℃、好ましくは
70〜100 ℃に調整する。When the chemical conversion treatment liquid and the surface of the steel material are reacted with each other, specifically at the time of dipping, spray coating, etc., the temperature of the chemical conversion treatment liquid is 60 to 100 ° C., preferably
Adjust to 70-100 ° C.
【００３４】例えば、リン酸マンガン系化成処理液の温
度は、60〜100 ℃が好ましい。リン酸−亜鉛系の化成処
理液の温度は、70〜100 ℃である。70〜90℃が好まし
い。それぞれ60℃未満、70℃未満では、皮膜形成反応速
度が極端に低下するおそれがあるからである。リン酸マ
ンガン系化成処理液では、85℃以上、好ましくは95〜98
℃である。沸騰した化成処理液では水分の蒸発が激しく
なり、化成処理液の濃度が高くなってしまうためであ
る。特にリン酸亜鉛系化成処理液の場合、90℃を超える
と初期反応段階において下地鉄面に対するエッチング作
用が激しくなり、多量の水素ガスが発生し、油井管継手
のような鋼管の底部にはガス溜まりができるため皮膜形
成を阻害し、均質で健全な皮膜が形成できないおそれが
あるためである。このような温度での浸漬時間あるいは
スプレー塗布の場合の化成処理液との接触時間は５分以
上である。For example, the temperature of the manganese phosphate-based chemical conversion treatment liquid is preferably 60 to 100 ° C. The temperature of the phosphoric acid-zinc-based chemical conversion treatment liquid is 70 to 100 ° C. 70 to 90 ° C is preferable. If the temperature is less than 60 ° C. and less than 70 ° C., respectively, the film formation reaction rate may be extremely reduced. In the manganese phosphate-based chemical conversion treatment liquid, 85 ℃ or more, preferably 95 ~ 98
℃. This is because in the boiling chemical conversion treatment liquid, the evaporation of water becomes more intense and the concentration of the chemical conversion treatment liquid becomes higher. In particular, in the case of zinc phosphate chemical conversion treatment liquid, when it exceeds 90 ° C, the etching action on the underlying iron surface becomes severe in the initial reaction stage, a large amount of hydrogen gas is generated, and gas is generated at the bottom of the steel pipe such as the oil well pipe joint. This is because there is a possibility that the formation of a film will be hindered by the accumulation and that a uniform and sound film cannot be formed. The immersion time at such temperature or the contact time with the chemical conversion treatment solution in the case of spray coating is 5 minutes or more.
【００３５】カリウムを含有する処理液を鋼材表面に適
用することで皮膜形成処理を行う方法は特に限定される
ものではなく、予め脱脂・水洗等の予備処理を行ってか
ら、カリウムを含有する処理液に浸漬する方法や、カリ
ウムを含有する処理液をスプレー等により鋼材表面に供
給する方法が適用できる。The method for forming a film by applying a treatment liquid containing potassium to the surface of a steel material is not particularly limited, and a treatment containing potassium after a preliminary treatment such as degreasing or washing with water is performed in advance. A method of immersing in a liquid or a method of supplying a treatment liquid containing potassium to the surface of the steel material by spraying or the like can be applied.
【００３６】一般に、リン酸マンガン系の化成処理で
は、被処理鋼材を予め脱脂、水洗、酸洗、水洗等の予備
処理を行った後、リン酸マンガンとピロリン酸ナトリウ
ムとの混合水溶液等による表面調整処理が必要とされて
いるが、本発明におけるリン酸マンガン系化成処理の場
合には、そのような表面調整処理を必要としない。In general, in the manganese phosphate-based chemical conversion treatment, the steel material to be treated is preliminarily subjected to pretreatments such as degreasing, washing with water, pickling, washing with water and the like, and then the surface is treated with a mixed aqueous solution of manganese phosphate and sodium pyrophosphate. Although a conditioning treatment is required, such surface conditioning treatment is not required in the case of the manganese phosphate-based chemical conversion treatment of the present invention.
【００３７】本発明にかかる化成処理液を用いて形成さ
れた化成皮膜は鋼材表面を均質に被覆することができ
る。このような化成皮膜のカリウム含有量は、0.1 〜10
00 mg/m2となり、その際、厚さを５〜50μm 、好ましく
は５〜35μm とすることで、その効果を十分に発揮でき
る。さらに、結晶粒が微細で緻密なために結晶間にグリ
スや固体潤滑剤などの潤滑剤を保持する性質に優れ、良
好な潤滑性を呈するのであって、特に油井管の継手部、
特にネジ部に設けることで、優れた特性を発揮できる。The chemical conversion film formed by using the chemical conversion treatment liquid according to the present invention can uniformly coat the surface of the steel material. The potassium content of such a conversion coating is 0.1-10.
It becomes 00 mg / m 2 , and at that time, the effect can be sufficiently exhibited by setting the thickness to 5 to 50 μm, preferably 5 to 35 μm. Furthermore, since the crystal grains are fine and dense, they are excellent in the property of holding a lubricant such as grease or a solid lubricant between the crystals, and exhibit good lubricity, particularly the joint portion of the oil well pipe,
Particularly, by providing the screw portion, excellent characteristics can be exhibited.
【００３８】カリウム含有量が0.1mg/m2以上で化成皮膜
の均一性が向上し、スケムラが減少する。また1000 mg/
m2を超えても皮膜性状は変わらないので、経済性を考慮
すれば1000 mg/m2以下とすることが好ましい。When the potassium content is 0.1 mg / m 2 or more, the uniformity of the chemical conversion coating is improved and the unevenness of the coating is reduced. 1000 mg /
Since the film properties do not change even if it exceeds m 2 , it is preferably 1000 mg / m 2 or less in consideration of economical efficiency.
【００３９】化成皮膜は、厚さが５μm 未満では耐食性
などの化成皮膜としての十分な特性を発揮できない。一
方、50μm を超える厚みの皮膜を形成した場合には、当
然のことながら化成液中のリン酸や亜鉛やマンガンの消
費量が多く液寿命も短くなる。経済性を考慮すれば35μ
m 以下が好ましい。If the thickness of the chemical conversion film is less than 5 μm, sufficient properties as a chemical conversion film such as corrosion resistance cannot be exhibited. On the other hand, when a film with a thickness of more than 50 μm is formed, the amount of phosphoric acid, zinc and manganese in the chemical conversion solution is naturally large and the solution life is shortened. 35μ considering economic efficiency
m or less is preferable.
【００４０】化成処理液中のカリウム化合物の含有量と
化成皮膜のカリウム化合物の含有量とは必ずしも同一で
はなく、鋼材の種類によっても、その他の化成処理条件
によっても変わる。特に、Cr含有鋼材の場合、20〜30℃
という低い温度あるいは化成時間が５分以内では十分な
量のカリウムが化成皮膜中に含有されず、スケムラの多
い皮膜となり、耐ゴーリング性に劣る。The content of the potassium compound in the chemical conversion treatment solution and the content of the potassium compound in the chemical conversion coating are not necessarily the same, and vary depending on the type of steel material and other chemical conversion treatment conditions. Especially in the case of Cr-containing steel, 20-30 ° C
If the temperature is low or the chemical conversion time is within 5 minutes, a sufficient amount of potassium is not contained in the chemical conversion film, resulting in a film with a large amount of unevenness of scatter and poor galling resistance.
【００４１】次に、実施例に関連させて本発明の作用効
果を具体的に説明する。Next, the function and effect of the present invention will be specifically described with reference to the embodiments.
【００４２】[0042]
【実施例】[実施例１]本例では、Cr：１％、３％、13％
の各Cr含有鋼材 (Ｃ：0.25％) を使用してリン酸塩化成
処理を行った。[Example] [Example 1] In this example, Cr: 1%, 3%, 13%
Each of the Cr-containing steels (C: 0.25%) was used for phosphate chemical conversion treatment.
【００４３】それぞれの試験材は、上記Cr含有鋼を真空
溶解炉で溶製後、25kg角インゴットにしてから、厚み８
mmにまで熱間圧延後、機械加工により、厚み５mm、幅25
mm、長さ：30mm、表面粗さ Rmax5μｍに調整したものを
使用した。Each test material had a thickness of 8 after being made into a 25 kg square ingot after the Cr-containing steel was melted in a vacuum melting furnace.
After hot rolling to mm, by machining, thickness 5 mm, width 25
mm, length: 30 mm, surface roughness Rmax adjusted to 5 μm was used.
【００４４】本発明において用いるカリウム化合物に
は、四硼酸カリウムを使用し、リン酸亜鉛化成処理液は
市販の化成処理液を使用した。四硼酸カリウムは、上記
リン酸亜鉛液に０〜10％の濃度で添加して化成処理液を
調製し、化成処理液の温度75℃で 500ml容量の容器に収
容し、これに脱脂・水洗等の予備処理を行った試験材を
５分間浸漬した後、引き上げて水洗、乾燥した。As the potassium compound used in the present invention, potassium tetraborate was used, and as the zinc phosphate chemical conversion treatment solution, a commercially available chemical conversion treatment solution was used. Potassium tetraborate is added to the above zinc phosphate solution at a concentration of 0 to 10% to prepare a chemical conversion treatment solution, which is stored in a 500 ml capacity container at a chemical conversion treatment temperature of 75 ° C, and degreased, washed with water, etc. The test material that had been subjected to the pretreatment of 1. was immersed for 5 minutes, then pulled up, washed with water and dried.
【００４５】試験材の鋼材表面に形成された皮膜の厚み
は、電磁膜厚計により測定した。皮膜の均質性は、走査
型電子顕微鏡(SEM) および画像解析装置により評価し
た。カリウム含有量は、化成処理後の試験材を５％クロ
ム酸の75℃水溶液に浸漬して化成皮膜のみを溶解した
後、原子吸光分析法により溶液分析を行いカリウム含有
量を決定した。The thickness of the film formed on the steel surface of the test material was measured by an electromagnetic film thickness meter. The homogeneity of the film was evaluated by a scanning electron microscope (SEM) and an image analyzer. The potassium content was determined by immersing the test material after the chemical conversion treatment in an aqueous solution of 5% chromic acid at 75 ° C. to dissolve only the chemical conversion film, and then performing solution analysis by atomic absorption spectrometry to determine the potassium content.
【００４６】表１に試験結果を示す。Table 1 shows the test results.
【００４７】[0047]
【表１】 [Table 1]
【００４８】表中の皮膜厚みは５μｍ未満に× (不可)
を、厚さ５μｍ以上に○ (良好) をそれぞれ付けた。ま
た、皮膜の均質性は鋼材表面に形成した皮膜中のスケム
ラ（金属露出）が、面積率で５％以下を○ (良好) 、５
％超20％以下を△ (普通) 、20％超の試験結果に× (不
可) をそれぞれつけた。全体評価では、皮膜厚み、皮膜
の均質性評価がいずれも○の試験結果に○ (合格) を、
いずれかが△あるいは×の試験結果に× (不合格) をそ
れぞれつけた。The film thickness in the table is less than 5 μm × (impossible)
Was evaluated as “good” with a thickness of 5 μm or more. In addition, the uniformity of the coating is ◯ (good) when the unevenness (metal exposure) in the coating formed on the steel surface is 5% or less in area ratio (good), 5
% (More than 20%) was marked as △ (normal), and more than 20% was marked as × (not possible). In the overall evaluation, the film thickness and film homogeneity evaluation are both ○ (pass) for the test result of ○,
The test results of either △ or × were marked with x (fail).
【００４９】[実施例２]本例において使用した試験材は
下記鋼組成の鋼材であった。
(1)炭素鋼：Ｃ：0.25％、
(2)Cr−Mo鋼：Ｃ：0.25％、Cr：1.0 ％、Mo：0.5 ％、
(3)Cr鋼：Ｃ：0.25％、Cr：３％、５％、13％、22％
化成処理液として市販のリン酸マンガン化成処理液を使
用した点を除いて、実施例１を繰り返した。Example 2 The test material used in this example was a steel material having the following steel composition. (1) Carbon steel: C: 0.25%, (2) Cr-Mo steel: C: 0.25%, Cr: 1.0%, Mo: 0.5%, (3) Cr steel: C: 0.25%, Cr: 3%, Example 1 was repeated except that a commercially available manganese phosphate chemical conversion solution was used as the 5%, 13%, 22% chemical conversion solution.
【００５０】四硼酸カリウムは、０〜10％の濃度で上記
リン酸マンガン化成処理液に添加し、得られた化成処理
液を、化成処理液の温度85℃で500ml 容量の容器に収容
し、これに脱脂・水洗等の予備処理を行った上記試験材
を10分間浸漬した後、引き上げて水洗、乾燥した。Potassium tetraborate was added to the above manganese phosphate chemical conversion treatment solution at a concentration of 0 to 10%, and the obtained chemical conversion treatment solution was placed in a 500 ml capacity container at a chemical conversion treatment temperature of 85 ° C. The test material, which had been pretreated by degreasing, washing with water, etc., was immersed in it for 10 minutes, then pulled up, washed with water and dried.
【００５１】得られた化成皮膜は、実施例１と同様にし
て評価した。本発明例の試験材には、炭素鋼、１Cr−0.
5Mo 鋼、３Cr鋼、５Cr鋼、13Cr鋼を使用し、比較例の試
験材には、22Cr鋼を使用した。The chemical conversion film obtained was evaluated in the same manner as in Example 1. The test materials of the examples of the present invention were carbon steel, 1Cr-0.
5Mo steel, 3Cr steel, 5Cr steel, and 13Cr steel were used, and 22Cr steel was used for the test material of the comparative example.
【００５２】表２、表３に試験結果を示す。Tables 2 and 3 show the test results.
【００５３】[0053]
【表２】 [Table 2]
【００５４】[0054]
【表３】 [Table 3]
【００５５】表中の皮膜厚みは５μｍ未満に× (不可)
を、厚さ５μｍ以上に○ (良好) をそれぞれ付けた。ま
た、皮膜の均質性は鋼材表面に形成した皮膜中のスケム
ラ（金属肌の露出）占有率が、面積率で５％以下を○
(良好) 、５％超20％以下を△(普通) 、20％超の試験結
果に× (不可) をそれぞれつけた。全体評価では、皮膜
厚み、皮膜の均質性評価がいずれも○の試験結果に○
(合格) を、いずれかが△あるいは×の試験結果に×
(不合格) をそれぞれつけた。The film thickness in the table is less than 5 μm × (impossible)
Was evaluated as “good” with a thickness of 5 μm or more. In addition, the homogeneity of the film is that the occupancy rate of the unevenness (exposed metal skin) in the film formed on the surface of the steel is 5% or less in area ratio.
(Good), 5% or more and 20% or less was evaluated as Δ (normal), and test results of 20% or more were evaluated as x (impossible). In the overall evaluation, both the film thickness and the film homogeneity evaluation were evaluated as ○.
(Pass) to the test result of either △ or ×
(Failure) is attached respectively.
【００５６】[実施例３]本例では、Cr：１％、３％、13
％の各Cr含有鋼から製造された継目なし鋼管である油井
鋼管 (Ｃ：0.25％) を使用した。Example 3 In this example, Cr: 1%, 3%, 13
% Oil-well steel pipe (C: 0.25%), which is a seamless steel pipe manufactured from each Cr-containing steel, was used.
【００５７】それぞれの試験材は、外表面が表面粗さ R
max5μｍに調整された、上記の各Cr含有鋼管より、厚み
５mm、幅25mm、長さ30mm、のものを切り出し使用した。
本例においては、市販のリン酸亜鉛化成処理液に四硼酸
カリウムを０〜10％の濃度で添加して化成処理液を調製
した。The outer surface of each test material has a surface roughness R
From each of the above Cr-containing steel pipes adjusted to max 5 μm, a pipe having a thickness of 5 mm, a width of 25 mm and a length of 30 mm was cut out and used.
In this example, a chemical conversion treatment solution was prepared by adding potassium tetraborate at a concentration of 0 to 10% to a commercially available zinc phosphate chemical conversion treatment solution.
【００５８】図１は本例の滴下方式の試験方法を示す概
略図である。図示のように、化成処理液１の温度80℃で
500ml容量の容器に収容し、これに脱脂・水洗等の予備
処理を行った試験材２の外表面側に滴下装置３から化成
処理液１を５分間滴下した後、水洗、乾燥した。なお、
化成処理液１は、加熱用温水５により加熱されており、
循環ポンプ４により再循環利用される。FIG. 1 is a schematic view showing a dropping type test method of this example. As shown in the figure, at a temperature of chemical conversion treatment liquid 1 of 80 ° C
The chemical conversion treatment liquid 1 was dropped from the dropping device 3 for 5 minutes on the outer surface side of the test material 2 which had been stored in a container of 500 ml capacity and which had been pretreated by degreasing, washing with water, etc., and then washed with water and dried. In addition,
The chemical conversion treatment liquid 1 is heated by the warm water 5 for heating,
It is recycled by the circulation pump 4.
【００５９】得られた化成皮膜は、実施例１と同様にし
て評価した。表４に試験結果を示す。The obtained chemical conversion film was evaluated in the same manner as in Example 1. Table 4 shows the test results.
【００６０】[0060]
【表４】 [Table 4]
【００６１】表中の皮膜厚みは５μｍ未満に× (不可)
を、厚さ５μｍ以上に○ (良好) をそれぞれ付けた。ま
た、皮膜の均質性は鋼管材料表面に形成した皮膜中のス
ケムラ（金属肌の露出）占有率が、面積率で５％以下を
○ (良好) 、５％超20％以下を△ (普通) 、20％超の試
験結果に× (不可) をそれぞれつけた。全体評価では、
皮膜厚み、皮膜の均質性評価がいずれも○の試験結果に
○ (合格) を、いずれかが△あるいは×の試験結果に×
(不合格) をそれぞれつけた。The film thickness in the table is less than 5 μm × (impossible)
Was evaluated as “good” with a thickness of 5 μm or more. Also, the homogeneity of the coating is that the occupancy ratio of the unevenness (exposed metal skin) in the coating formed on the surface of the steel pipe material is 5% or less in area rate (good), and 5% or more and 20% or less is △ (normal). , X (impossible) was added to the test results of more than 20%. In the overall evaluation,
The film thickness and film homogeneity evaluation are both ○ (pass) for the test result of ○ and × for the test result of either △ or ×.
(Failure) is attached respectively.
【００６２】[実施例４］本例では、Cr：１％、３％、1
3％の各Cr含有鋼 (Ｃ：0.25％) から製造した油井鋼管
を用意した。Example 4 In this example, Cr: 1%, 3%, 1
An oil well steel pipe manufactured from 3% of each Cr-containing steel (C: 0.25%) was prepared.
【００６３】それぞれの試験材は、外表面を表面粗さRm
ax 5μｍに調整した上記鋼管より切り出し、その寸法は
厚み５mm、幅25mm、長さ30mmであった。本例において
は、市販のリン酸マンガン化成処理液に四硼酸カリウム
を0.1 〜1.0 ％の濃度で添加した後、全酸度を30以上55
未満、全酸度の遊離酸度に対する比を8.2 〜9.0 に調整
した。この化成処理液を温度95℃で1000ml容量の容器に
収容し、これに脱脂・水洗等の予備処理を行った試験材
を前記化成処理液に20分間浸漬した後、水洗、乾燥し
た。The outer surface of each test material was Rm.
Cut out from the above steel pipe adjusted to ax 5 μm, the dimensions were 5 mm in thickness, 25 mm in width, and 30 mm in length. In this example, after adding potassium tetraborate to a commercially available manganese phosphate chemical conversion treatment solution at a concentration of 0.1 to 1.0%, the total acidity was 30 or more.
The ratio of total acidity to free acidity was adjusted to 8.2 to 9.0. The chemical conversion treatment liquid was stored in a container having a capacity of 1000 ml at a temperature of 95 ° C., and a test material which had been pretreated by degreasing and washing with water was immersed in the chemical conversion treatment liquid for 20 minutes, washed with water and dried.
【００６４】試験材の鋼材表面に形成された化成皮膜の
評価は、実施例１と同様にして行った。The conversion coating formed on the surface of the steel material of the test material was evaluated in the same manner as in Example 1.
【００６５】表中の皮膜の均質性はスケムラ（金属肌の
露出）占有率が、面積率で１％以下を◎ (優秀) 、１％
超５％以下を○ (良好) とした。全体評価では、皮膜の
均質性評価が◎または○の試験結果に○ (合格) をつけ
た。表５に試験結果を示す。As for the homogeneity of the film in the table, the Schemura (exposed metal skin) occupancy rate is 1% or less in area ratio ◎ (excellent), 1%
A value of more than 5% was rated as ◯ (good). In the overall evaluation, ○ (pass) was given to the test result of the film homogeneity evaluation being ◎ or ○. Table 5 shows the test results.
【００６６】[0066]
【表５】 [Table 5]
【００６７】[0067]
【発明の効果】本発明により、カリウム化合物を0.01〜
10％添加した亜鉛とリン酸またはマンガンとリン酸を含
有する化成処理液により、Crを0.5 〜13％含有する鋼材
の表面に、均質で密着性に優れた健全なリン酸塩の化成
皮膜を容易に安定して形成することができる。また、炭
素鋼についても、本発明を用いれば従来以上に密着性に
優れた厚い化成皮膜を容易に安定して形成することが可
能である。INDUSTRIAL APPLICABILITY According to the present invention, potassium compounds of 0.01 to
With a chemical conversion treatment solution containing 10% added zinc and phosphoric acid or manganese and phosphoric acid, a stable phosphate chemical conversion coating film with excellent adhesion is formed on the surface of steel containing 0.5 to 13% Cr. It can be easily and stably formed. Further, also with respect to carbon steel, by using the present invention, it is possible to easily and stably form a thick chemical conversion film having better adhesion than ever before.
【図１】本発明の実施例で用いる滴下方式の試験方法を
示す概略図である。FIG. 1 is a schematic view showing a dropping type test method used in Examples of the present invention.
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Claims (15)
に設けた化成皮膜から成り、該化成皮膜はカリウム量が
0.1 〜1000 mg/m2であり、厚みが５〜50μｍであること
を特徴とする表面処理鋼材。1. A steel material and a chemical conversion coating formed on at least one portion of the surface of the steel, the chemical conversion coating having a potassium content of
A surface-treated steel material having a thickness of 0.1 to 1000 mg / m 2 and a thickness of 5 to 50 μm.
る請求項１記載の表面処理鋼材。2. The surface-treated steel material according to claim 1, wherein the chemical conversion coating is a phosphate chemical conversion coating.
ン酸マンガン系化成皮膜である請求項２記載の表面処理
鋼材。3. The surface-treated steel material according to claim 2, wherein the chemical conversion coating is a zinc phosphate-based or manganese phosphate-based chemical conversion coating.
鋼組成を有することを特徴とする請求項１ないし３のい
ずれかに記載の表面処理鋼材。4. The surface-treated steel material according to claim 1, wherein the steel material has a steel composition containing 0.5 to 13 mass% of Cr.
化成皮膜を設けた表面部位がネジ継手部であることを特
徴とする請求項４記載の表面処理鋼材。5. The surface-treated steel material according to claim 4, wherein the steel material is a seamless steel pipe, and the surface portion provided with the chemical conversion film is a threaded joint portion.
求項５記載の表面処理鋼材。6. The surface-treated steel material according to claim 5, wherein the steel pipe is an oil well pipe provided with a screw.
プリングである請求項５記載の表面処理鋼材。7. The surface-treated steel material according to claim 5, wherein the steel pipe is a coupling provided with a screw for an oil country tubular good.
含有し、さらにカリウムを含有する化成処理液を用いて
鋼材に化成処理を行うことを特徴とする表面処理鋼材の
製造方法。8. A method for producing a surface-treated steel material, which comprises subjecting a steel material to a chemical conversion treatment using a chemical conversion treatment liquid containing zinc and phosphoric acid or manganese and phosphoric acid, and further containing potassium.
イオンのモル濃度が６×10-4％以上、７×10-1％以下で
あることを特徴とする請求項８記載の表面処理鋼材の製
造方法。9. The production of a surface-treated steel material according to claim 8, wherein the molar concentration of ions containing potassium in the chemical conversion treatment liquid is 6 × 10 −4 % or more and 7 × 10 −1 % or less. Method.
なくとも５分間前記鋼材の表面を前記化成処理液に浸漬
して行うことを特徴とする請求項８記載の表面処理鋼材
の製造方法。10. The method for producing a surface-treated steel material according to claim 8, wherein the chemical conversion treatment is performed by immersing the surface of the steel material in the chemical conversion treatment liquid at a temperature of 60 to 100 ° C. for at least 5 minutes.
なくとも５分間前記鋼材の表面に前記化成処理液を供給
して行うことを特徴とする請求項８記載の表面処理鋼材
の製造方法。11. The method for producing a surface-treated steel material according to claim 8, wherein the chemical conversion treatment is performed by supplying the chemical conversion treatment liquid to the surface of the steel material at a temperature of 60 to 100 ° C. for at least 5 minutes.
理を行うことを特徴とする請求項８ないし１１のいずれ
かに記載の表面処理鋼材の製造方法。12. The method for producing a surface-treated steel material according to claim 8, wherein the chemical conversion treatment is carried out in the absence of fluorine ions.
を含有し、さらにカリウムを含有することを特徴とする
鋼材用化成処理液。13. A chemical conversion treatment solution for steel, containing zinc and phosphoric acid or manganese and phosphoric acid, and further containing potassium.
が６×10-4％以上、７×10-1％以下であることを特徴と
する請求項13記載の鋼材用化成処理液。14. The chemical conversion treatment liquid for steel according to claim 13, wherein the molar concentration of the ion containing potassium is 6 × 10 −4 % or more and 7 × 10 −1 % or less.
リウムを含有する、全酸度が30以上55未満、全酸度の遊
離酸度に対する比が3 〜15である請求項13または14に記
載の鋼材用化成処理液。15. The steel product according to claim 13 or 14, which contains manganese and phosphoric acid, and further contains potassium. The total acidity is 30 or more and less than 55, and the ratio of the total acidity to the free acidity is 3 to 15. Chemical conversion treatment liquid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005054541A1 (en) * | 2003-12-04 | 2005-06-16 | Sumitomo Metal Industries, Ltd. | Surface adjustment treatment prior to chemical treatment of steel product |
| JP2009280845A (en) * | 2008-05-20 | 2009-12-03 | Nissan Motor Co Ltd | Treatment method for metal surface, and sliding component having metal surface by the treatment method |
| CN111108376A (en) * | 2017-10-05 | 2020-05-05 | 株式会社岛津制作所 | Supercritical fluid chromatograph and supercritical fluid chromatographic analysis method |
| JP2020070479A (en) * | 2018-11-01 | 2020-05-07 | 日本製鉄株式会社 | Surface treatment apparatus for cylindrical metal component and method for manufacturing cylindrical metal component |
-
2002
- 2002-02-22 JP JP2002045983A patent/JP4075404B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005054541A1 (en) * | 2003-12-04 | 2005-06-16 | Sumitomo Metal Industries, Ltd. | Surface adjustment treatment prior to chemical treatment of steel product |
| US7666266B2 (en) | 2003-12-04 | 2010-02-23 | Sumitomo Metal Industries, Ltd. | Surface conditioning prior to chemical conversion treatment of a steel member |
| NO341188B1 (en) * | 2003-12-04 | 2017-09-04 | Sumitomo Metal Ind | Surface conditioning prior to chemical treatment of steel product |
| JP2009280845A (en) * | 2008-05-20 | 2009-12-03 | Nissan Motor Co Ltd | Treatment method for metal surface, and sliding component having metal surface by the treatment method |
| CN111108376A (en) * | 2017-10-05 | 2020-05-05 | 株式会社岛津制作所 | Supercritical fluid chromatograph and supercritical fluid chromatographic analysis method |
| JP2020070479A (en) * | 2018-11-01 | 2020-05-07 | 日本製鉄株式会社 | Surface treatment apparatus for cylindrical metal component and method for manufacturing cylindrical metal component |
| JP7172453B2 (en) | 2018-11-01 | 2022-11-16 | 日本製鉄株式会社 | Surface treatment apparatus for cylindrical metal parts and method for manufacturing cylindrical metal parts |
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