JPH08105582A - Surface treatment method of steel pipe coupling made of high chromium alloy steel having excellent anti-galling property - Google Patents
Surface treatment method of steel pipe coupling made of high chromium alloy steel having excellent anti-galling propertyInfo
- Publication number
- JPH08105582A JPH08105582A JP23985194A JP23985194A JPH08105582A JP H08105582 A JPH08105582 A JP H08105582A JP 23985194 A JP23985194 A JP 23985194A JP 23985194 A JP23985194 A JP 23985194A JP H08105582 A JPH08105582 A JP H08105582A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- coating layer
- thickness
- powder
- molybdenum disulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Non-Disconnectible Joints And Screw-Threaded Joints (AREA)
- Lubricants (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、原油または天然ガス採
掘に使用される油井管相互を連結する鋼管継手の製造方
法に関し、特にＣｒ含有量１０％以上の高Ｃｒ合金鋼製
鋼管継手の表面に耐焼き付き性および耐摩耗性に優れた
皮膜を形成する表面処理方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a steel pipe joint for connecting oil country tubular goods used for crude oil or natural gas mining, and particularly to the surface of a high Cr alloy steel pipe joint having a Cr content of 10% or more. The present invention relates to a surface treatment method for forming a film having excellent seizure resistance and abrasion resistance.
【０００２】[0002]
【従来の技術】通常、油井用の鋼管は、カップリングを
介して相互に連結されているが、鋼管の端部に形成した
雄ねじにカップリングの内面に形成した雌ねじを嵌め合
わせ、これらのねじ部を締め付けることにより、気密性
および液密着性を維持して複数の鋼管が接続される。す
なわち、油井管の先端に形成されたねじ部ならびにその
基部に形成されたテーパー部分からなる継手部分と、こ
のねじ部と螺合するねじ部および先端に先細のテーパー
部分を形成したカップリング材を回転締め付けにより、
メタル−メタルシール部を形成して完全なシール性を維
持して接続されている。しかし、メタル−メタルシール
部には高面圧が作用するため、継手の締め付け（メーク
アップ）、締め戻し（ブレークアウト）時には、該メタ
ルシール部およびねじ部にスクラッチ、ゴーリングなど
の焼付きが生じ易い。すなわち、ゴーリングが生じると
シール性が損なわれるため、鋼管の繰り返し使用可能な
回数が低下する。また、継手部に腐食が発生すると十分
なシール性の確保が困難になる。2. Description of the Related Art Normally, steel pipes for oil wells are connected to each other through a coupling. However, a male screw formed on the end of the steel pipe is fitted with a female screw formed on the inner surface of the coupling, and these screws are joined together. By tightening the parts, a plurality of steel pipes are connected while maintaining airtightness and liquid adhesion. That is, a joint portion consisting of a threaded portion formed at the tip of an oil country tubular good and a taper portion formed at the base thereof, and a coupling material having a threaded portion screwed with this threaded portion and a tapered taper portion at the tip are provided. By rotating and tightening,
A metal-metal seal portion is formed to maintain a perfect seal. However, since a high surface pressure acts on the metal-metal seal portion, seizure such as scratches and galling occurs on the metal seal portion and the screw portion when the joint is tightened (make up) and unfastened (breakout). easy. That is, when the galling occurs, the sealing property is impaired, and the number of times the steel pipe can be used repeatedly decreases. Further, if corrosion occurs in the joint, it becomes difficult to secure sufficient sealing performance.
【０００３】そこで、このようなゴーリング発生の軽減
が可能な鋼管継手を得るため、従来から種々の提案が行
われている。例えば、銅、亜鉛等の電気めっき層を設け
る方法（特公平１−１２９９５号公報、特公昭６０−５
７５１９号公報）、メタル−メタルシール部の表面最大
粗さと表面処理皮膜層、特に銅、亜鉛等の電気めっき層
の厚さを規定して設ける方法（特開平６−１０１５４号
公報）、燐酸マンガン系化成処理皮膜層を形成する方法
（特公平５−４００３４号公報、特開昭６０−１２１３
８号公報、特開平５−１１７８７０号公報）およびメタ
ル−メタルシール部の表面最大厚さを規定してフッ素樹
脂粉末を分散混合した合成樹脂皮膜を形成する方法（特
開昭６１−１２４７９２号公報）あるいは二硫化モリブ
デン粉末を分散混合した合成樹脂皮膜を形成する方法
（特開昭６１−１３６０８７号公報）等が提案されてい
る。Therefore, in order to obtain a steel pipe joint capable of reducing the occurrence of such galling, various proposals have been conventionally made. For example, a method of providing an electroplating layer of copper, zinc or the like (Japanese Patent Publication No. 12995/1990, Japanese Patent Publication No. 60-5).
No. 7519), a maximum surface roughness of a metal-metal seal portion, and a method for defining the thickness of a surface treatment film layer, particularly an electroplating layer of copper, zinc or the like (JP-A-6-10154), manganese phosphate. Method of forming a system chemical conversion coating layer (Japanese Patent Publication No. 5-40034, JP-A-60-1213)
No. 8, JP-A-5-117870) and a method for forming a synthetic resin film in which fluororesin powder is dispersed and mixed by defining the maximum surface thickness of the metal-metal seal portion (JP-A-61-2124792). ) Or a method of forming a synthetic resin film in which molybdenum disulfide powder is dispersed and mixed (JP-A-61-136087).
【０００４】[0004]
【発明が解決しようとする課題】一方、近年耐蝕性を増
すために１０％以上の高Ｃｒ合金鋼、さらにこれにＮ
ｉ，Ｍｏ等を添加した高Ｃｒ合金鋼製の高耐蝕性油井管
が使用されるようになり、前記の各方法に関しては、下
記の如き問題が生じている。すなわち、 （１）高Ｃｒ合金鋼製の鋼管継手に電気めっき法による
銅、亜鉛めっき層等を設ける方法に関しては、めっき皮
膜層の均一被覆性および良好なめっき皮膜の密着性を確
保するために、煩雑な処理工程による対策を講じる必要
がある。通常、高Ｃｒ含有合金鋼からなる鋼管継手にめ
っき層を施すに際しては、強酸洗によるＣｒ鋼表面の酸
化物からなる不働態皮膜の除去、ストライクめっき法等
による活性化処理を施し、さらにめっき層とＣｒ鋼の密
着性を向上せしめるためにＮｉめっき層を設け、その上
にＣｕめっきあるいはＺｎめっき等を行う方法が採用さ
れている。すなわち、煩雑な活性化処理およびめっき工
程に鋼管継手が曝されるため、ストライクめっき浴ある
いはその他めっき浴から鋼中およびめっき層にＨ2が侵
入する機会が多く、そのため遅れ破壊が生じる危険性が
大きく、また生産性、コスト面からも極めて不利であ
る。さらに、硫化水素等が含有される腐食環境下に長期
間曝される条件下において、Ｃｕめっき等の鋼材より電
位的に貴な金属がめっき層として設けられる場合には、
めっき層欠陥部からの穿孔腐食が、また亜鉛めっき層の
場合には、Ｈ2 の発生を伴う腐食が進行して鋼中に侵
入、遅れ破壊を促進させる可能性が大きい等の問題点を
有する。On the other hand, in recent years, in order to increase the corrosion resistance, high Cr alloy steel of 10% or more, and further N
High corrosion resistant oil country tubular goods made of high Cr alloy steel to which i, Mo and the like have been added have come to be used, and the following problems occur with respect to each of the above methods. That is, (1) Regarding a method of providing a copper, zinc plating layer, etc. by electroplating on a steel pipe joint made of high Cr alloy steel, in order to ensure uniform coating property of the plating film layer and good adhesion of the plating film. It is necessary to take measures by complicated processing steps. Usually, when a plating layer is applied to a steel pipe joint made of a high Cr content alloy steel, a passivation film made of oxide on the surface of the Cr steel is removed by strong pickling, an activation treatment is performed by a strike plating method, and the plating layer is further applied. In order to improve the adhesion between Cr steel and Cr steel, a method of providing a Ni plating layer and performing Cu plating or Zn plating on it is adopted. That is, since the steel pipe joint is exposed to the complicated activation process and plating process, H 2 often enters the steel and the plating layer from the strike plating bath or other plating baths, which may cause delayed fracture. It is large and extremely disadvantageous in terms of productivity and cost. Further, when a metal, which is more noble than the steel material such as Cu plating, is provided as a plating layer under the condition of being exposed to a corrosive environment containing hydrogen sulfide and the like for a long time,
There is a problem that there is a high possibility that piercing corrosion from the defective portion of the plating layer, and in the case of the zinc plating layer, the corrosion accompanied by the generation of H 2 will progress to penetrate into the steel and promote delayed fracture. .
【０００５】（２）燐酸マンガン系化成処理皮膜層を設
ける方法については、１０％以上の高Ｃｒ合金鋼に対し
ては、鋼表面に生成されるＣｒ酸化物の影響により、密
着性に優れた皮膜を均一に生成せしめることは極めて困
難である。従って、Ｃｒを含有する鋼管継手に対して、
燐酸マンガン系化成処理皮膜層を均一に形成せしめる方
法として、該処理に先立って予め鉄めっき層を設ける方
法あるいは鋼素地表面に平均粗さ２０〜６０μｍの凹凸
加工を施す方法が提案されている。これらの方法のう
ち、１０％以上のＣｒを含有する鋼管継手に対して、鉄
めっき層を設けて燐酸マンガン系化成処理を施すことに
より、燐酸マンガン系化成処理皮膜層を均一に形成せし
めることは可能である。しかしながら、該高Ｃｒ合金鋼
製の鋼管継手は、燐酸マンガン系化成処理皮膜層が設け
られた普通鋼あるいは低合金鋼製の鋼管継手に比較し
て、材質強度の影響によるものか、あるいは皮膜層の付
着強度が不十分なことに起因するためか、その原因は特
定出来ないものの、メークアップ、ブレークアウトの繰
り返し使用に対しても比較的少ない回数で、スクラッチ
やゴーリングの発生が生じ易い欠点を有するため、殆ど
実用化されていない。また、鋼素地に凹凸加工を施して
燐酸マンガン系化成処理皮膜層を生成せしめる方法に関
しては、Ｃｒ含有量数％程度の低Ｃｒ合金鋼に対しては
燐酸マンガン系化成処理皮膜層の均一な生成に有効であ
るものの、Ｃｒ含有量１０％以上の高Ｃｒ合金鋼製鋼管
継手に対する該皮膜層の形成は極めて困難である。(2) Regarding the method of forming the manganese phosphate-based chemical conversion treatment coating layer, the adhesion is excellent for 10% or more high Cr alloy steel due to the influence of the Cr oxide formed on the steel surface. It is extremely difficult to form a film uniformly. Therefore, for steel pipe joints containing Cr,
As a method for uniformly forming the manganese phosphate-based chemical conversion treatment coating layer, a method of previously providing an iron plating layer prior to the treatment or a method of subjecting the surface of the steel substrate to unevenness having an average roughness of 20 to 60 μm has been proposed. Among these methods, it is not possible to uniformly form a manganese phosphate-based chemical conversion coating layer by providing an iron plating layer and performing manganese phosphate-based chemical conversion treatment on a steel pipe joint containing 10% or more of Cr. It is possible. However, the steel pipe joint made of the high Cr alloy steel is not affected by the material strength or the coating layer as compared with the steel pipe joint made of the manganese phosphate-based chemical conversion treatment coating layer made of the ordinary steel or the low alloy steel. Although the cause cannot be specified, perhaps due to insufficient adhesion strength of the, but the drawback that scratches and galling are likely to occur with a relatively small number of times even after repeated use of make-up and breakout. Since it has, it has hardly been put to practical use. Further, regarding the method of forming the manganese phosphate-based chemical conversion coating film layer by subjecting the steel base material to the concavo-convex process, a uniform formation of the manganese phosphate-based chemical conversion coating film layer is obtained for a low Cr alloy steel having a Cr content of several%. However, it is extremely difficult to form the coating layer on a steel pipe joint made of high Cr alloy steel having a Cr content of 10% or more.
【０００６】（３）フッ素樹脂粉末あるいは二硫化モリ
ブデン粉末を分散混合した合成樹脂皮膜、所謂固体潤滑
皮膜層を鋼管継手に形成する方法に関しては、鋼管継手
部のメタル−メタルシール部の表面粗度を規定するとと
もに、固体潤滑皮膜層の厚さを最大表面粗度以下に設定
することにより、これらの相乗効果により潤滑性能の向
上が計られている。しかしながら、これらの処理による
鋼管継手が長期間腐食環境下に曝された場合、腐食水溶
液が固体潤滑皮膜層あるいは欠陥部を通って侵入し、皮
膜下の鋼素地の腐食をもたらすため、固体潤滑皮膜層の
密着性が劣化する。そのため、固体潤滑皮膜層の経時密
着性が劣化する傾向が大きい。特に、この傾向は、メー
クアップ、ブレークアウトの繰り返しにより、固体潤滑
皮膜層の摩耗、損傷が生じると著しく促進される。ま
た、固体潤滑皮膜層自体が摩耗、損傷するため、長期間
に亘る使用に際しては、その潤滑機能を確保しうる寿命
が自ら限定される。したがって、該方法による鋼管継手
は、固体潤滑皮膜層の経時による剥離あるいは繰り返し
使用に伴う皮膜層の摩耗、損傷等に起因して耐ゴーリン
グ性が劣化するので、その繰り返し使用回数が限定され
る等の問題点を有する。 以上のように、従来法による
鋼管継手、特にＣｒ含有量が１０％以上の高Ｃｒ合金鋼
製継手にあっては、耐ゴーリング性、耐腐食性あるいは
生産性の観点から十分に満足するものが得られていな
い。特に、高Ｃｒ合金鋼製の鋼管継手を長期に亘って繰
り返し使用するのに対して、十分に優れた性能を有する
高Ｃｒ合金鋼製継手が得られていない。(3) Regarding the method for forming a so-called solid lubricant film layer, which is a synthetic resin film in which fluororesin powder or molybdenum disulfide powder is dispersed and mixed, on the steel pipe joint, the surface roughness of the metal-metal seal part of the steel pipe joint part By setting the thickness of the solid lubricating coating layer to be equal to or less than the maximum surface roughness, the synergistic effect of these effects improves the lubricating performance. However, when the steel pipe joints subjected to these treatments are exposed to a corrosive environment for a long period of time, the corrosive aqueous solution penetrates through the solid lubricating coating layer or the defective portion and causes corrosion of the steel base under the coating, so that the solid lubricating coating The adhesion of the layer deteriorates. Therefore, there is a large tendency that the solid lubricating coating layer has a deteriorated adhesiveness over time. In particular, this tendency is remarkably promoted when wear and damage of the solid lubricating coating layer occur due to repeated makeup and breakout. Further, since the solid lubricating coating layer itself is worn or damaged, the life for which the lubricating function can be secured is limited by itself during long-term use. Therefore, in the steel pipe joint according to the method, the galling resistance is deteriorated due to peeling of the solid lubricating coating layer over time or abrasion and damage of the coating layer due to repeated use, so that the number of times of repeated use is limited, etc. Has the problem of. As described above, the conventional steel pipe joints, especially the high Cr alloy steel joints having a Cr content of 10% or more, are sufficiently satisfactory from the viewpoint of galling resistance, corrosion resistance or productivity. Not obtained. In particular, while a steel pipe joint made of high Cr alloy steel is repeatedly used for a long period of time, a joint made of high Cr alloy steel having sufficiently excellent performance has not been obtained.
【０００７】[0007]
【課題を解決するための手段】本発明は、従来の１０％
以上のＣｒを含有する高Ｃｒ合金鋼製鋼管継手の前記し
た問題点、特に長期間に亘る鋼管継手の繰り返し使用に
対する継手部皮膜層の摩耗、損傷および腐食に起因する
耐ゴーリング性の劣化に関する問題点を解決して、使用
寿命の長い耐ゴーリング性、耐腐食性に優れる鋼管継手
を提供するものである。而して、本発明の要旨は、１０
％以上のＣｒを含有する高Ｃｒ合金鋼製鋼管継手部分の
ピンまたはカップリングの少なくとも一方側、特にカッ
プリング材のねじ部およびメタルシール部に対して、厚
さ１μｍ〜２０μｍの窒化処理層、厚さ０．５μｍ〜１
５μｍの鉄めっき層あるいは１０％以下のＮｉ，Ｃｏの
一種または二種を含有する鉄合金めっき層の下地処理層
と厚さ５μｍ〜２５μｍの燐酸マンガン系化成処理皮膜
層、さらに二硫化モリブデン粉末とエポキシ樹脂、フラ
ン樹脂、ポリアミドイミド樹脂の中より選定した一種を
必須成分として含有し、 0.5 ≦｛（二硫化モリブデン粉末）の含有量｝／｛（エ
ポキシ樹脂、フラン樹脂、ポリアミドイミド樹脂の中よ
り選定した一種）の含有量｝≦３．０（重量比） の組成比で構成される固体潤滑剤を塗布し、加熱処理を
施して、厚さ１０μｍ〜４５μｍの固体潤滑皮膜層から
なる三層皮膜層を形成せしめることを特徴とするもので
ある。The present invention is 10% of the conventional one.
The above-mentioned problems of the steel pipe joint made of high Cr alloy steel containing Cr as described above, in particular, the problem of deterioration of galling resistance due to wear, damage and corrosion of the coating layer of the joint portion due to repeated use of the steel pipe joint for a long period of time By solving the problems, it is possible to provide a steel pipe joint having a long service life and excellent in galling resistance and corrosion resistance. Therefore, the gist of the present invention is 10
At least one side of the pin or the coupling of the high Cr alloy steel pipe joint portion containing Cr in an amount of 1% or more, particularly for the screw portion and the metal seal portion of the coupling material, a nitriding layer having a thickness of 1 μm to 20 μm, Thickness 0.5 μm-1
A 5 μm iron plating layer or an undercoating layer of an iron alloy plating layer containing 10% or less of one or two kinds of Ni and Co, a manganese phosphate chemical conversion treatment coating layer having a thickness of 5 μm to 25 μm, and molybdenum disulfide powder. Contains one selected from epoxy resin, furan resin, polyamide-imide resin as an essential component, 0.5 ≤ {content of (molybdenum disulfide powder)} / {(epoxy resin, furan resin, polyamide-imide resin) Content of 1 type selected} ≦ 3.0 (weight ratio) A solid lubricant composed of a composition ratio is applied, and heat treatment is performed to form a three-layer solid lubricant film layer having a thickness of 10 μm to 45 μm. It is characterized in that a film layer is formed.
【０００８】また、本発明は、高Ｃｒ合金鋼製鋼管継手
部分のねじ部およびメタルシール部に対して、厚さ１μ
ｍ〜２０μｍの窒化処理層、厚さ０．５μｍ〜１５μｍ
の鉄めっき層あるいは１０％以下のＮｉ，Ｃｏの一種ま
たは二種を含有する鉄合金めっき層の下地処理層と厚さ
５μｍ〜２５μｍの燐酸マンガン系化成処理皮膜層、さ
らに二硫化モリブデン粉末と該粉末に対して１０重量％
〜５０重量％のＣｕ、Ｚｎ粉末の一種または二種および
エポキシ樹脂、フラン樹脂、ポリアミドイミド樹脂の中
より選定した一種を必須成分として含有し、 0.5 ≦｛（二硫化モリブデン粉末とＣｕ、Ｚｎ粉末の一
種または二種）の含有量｝／｛（エポキシ樹脂、フラン
樹脂、ポリアミドイミド樹脂の中より選定した一種）の
含有量｝≦ 3.0（重量比） の組成比で構成される固体潤滑剤を塗布し、加熱処理を
施して、厚さ１０μｍ〜４５μｍの固体潤滑皮膜層から
なる三層皮膜層を設けることを特徴とする。Further, according to the present invention, the thickness of the high Cr alloy steel pipe joint portion is 1 μm with respect to the thread portion and the metal seal portion.
m-20 μm nitriding layer, thickness 0.5 μm-15 μm
Of the iron plating layer or an iron alloy plating layer containing 10% or less of one or two kinds of Ni and Co, a manganese phosphate-based chemical conversion treatment coating layer having a thickness of 5 μm to 25 μm, and a molybdenum disulfide powder. 10% by weight to powder
-50% by weight of one or two kinds of Cu, Zn powder and one selected from epoxy resin, furan resin and polyamide-imide resin as an essential component, 0.5 ≤ {(molybdenum disulfide powder and Cu, Zn powder 1) or 2))} / {(a type selected from epoxy resin, furan resin, polyamide-imide resin)} ≦ 3.0 (weight ratio) It is characterized in that a three-layer coating layer composed of a solid lubricating coating layer having a thickness of 10 μm to 45 μm is provided by coating and heat treatment.
【０００９】さらに、本発明においては、二硫化モリブ
デン粉末の粒子径がフィッシャー法による測定により
０．４５μｍ〜１０μｍの範囲、ＣｕあるいはＺｎ粉末
の粒子径が０．５μｍ〜１０μｍの範囲の一種または二
種、また分子量が２，０００〜１０，０００の範囲のエ
ポキシ樹脂、分子量が１５０〜２５０の範囲のフラン樹
脂、分子量が１０，０００〜２５，０００の範囲のポリ
アミドイミド樹脂の中より選定した一種で構成されるこ
とを特徴とする固体潤滑剤を用いて、固体潤滑皮膜層を
形成せしめることを特徴とする。Further, in the present invention, the molybdenum disulfide powder has a particle size of 0.45 μm to 10 μm as measured by the Fischer method, and a Cu or Zn powder has a particle size of 0.5 μm to 10 μm. A kind selected from epoxy resins having a molecular weight of 2,000 to 10,000, furan resins having a molecular weight of 150 to 250, and polyamide-imide resins having a molecular weight of 10,000 to 25,000. It is characterized in that a solid lubricant film layer is formed by using a solid lubricant characterized in that
【００１０】以上のように、本発明の方法は、 高面圧下で摺動が繰り返される使用条件に対応する
ため、潤滑性能に優れるとともに、摩耗および損傷が起
こりにくい固体潤滑皮膜層を鋼管継手に形成せしめる対
策を講じた。すなわち、潤滑性能に優れる二硫化モリブ
デン粉末および靱性と硬度の向上に有効な有機樹脂バイ
ンダーを選定し、これらを必須成分として含有せしめた
固体潤滑剤の適正組成の検討により、前記性能の確保が
可能な固体潤滑皮膜層が得られる方法を見出し、本発明
に適用した。さらに、本発明においては、固体潤滑剤に
適正量のＣｕ粉末およびＺｎ粉末の一種または二種を含
有せしめることにより、固体潤滑皮膜層の高面圧下にお
けるさらなる耐摩耗性の向上が可能なことを見出し、そ
の適用による対策も併せ講じた。従って、本発明の構成
による固体潤滑剤を用いて固体潤滑皮膜層を形成するこ
とにより、潤滑性および耐摩耗性、すなわち皮膜強度の
向上効果が得られる。As described above, the method of the present invention is applicable to the condition of repeated sliding under a high surface pressure, and therefore, the solid lubricating coating layer having excellent lubrication performance and less likely to be worn and damaged is applied to the steel pipe joint. We have taken measures to form it. That is, it is possible to secure the above performance by selecting molybdenum disulfide powder with excellent lubrication performance and an organic resin binder that is effective in improving toughness and hardness, and examining the proper composition of the solid lubricant containing these as essential components. A method for obtaining such a solid lubricating coating layer was found and applied to the present invention. Furthermore, in the present invention, it is possible to further improve the wear resistance of the solid lubricant film layer under high surface pressure by containing an appropriate amount of one or two kinds of Cu powder and Zn powder in the solid lubricant. The headline and measures to apply it were also taken. Therefore, by forming the solid lubricating coating layer using the solid lubricant according to the constitution of the present invention, an effect of improving lubricity and wear resistance, that is, coating strength can be obtained.
【００１１】 また、前記の固体潤滑皮膜層の処理後
および腐食環境下に長期間曝される場合の密着性、所謂
経時密着性の向上、さらには高面圧下での繰り返し摺動
により固体潤滑皮膜層に摩耗、損傷が生じた場合に対し
ても、さらなる潤滑寿命の向上を計るため、固体潤滑皮
膜層の下層に窒化処理層、鉄めっき層あるいはＮｉ，Ｃ
ｏの一種または二種を含有する鉄合金めっき層と燐酸マ
ンガン系化成処理皮膜層を生成せしめる対応策を講じ
た。すなわち、燐酸マンガン系化成処理皮膜層の均一な
生成が困難な１０％以上のＣｒを含有する高Ｃｒ合金鋼
製鋼管継手に対して、窒化処理層、鉄めっき層あるいは
鉄合金めっき層を設けることにより、燐酸マンガン系化
成処理皮膜層の均一な生成を可能ならしめ、該皮膜層と
固体潤滑皮膜層との相乗効果の活用による性能向上を計
った。すなわち、燐酸マンガン系化成処理皮膜層は生成
される結晶粒子の間に多くの空隙が生成されるため、固
体潤滑皮膜層が空隙に多量にトラップされた状態で付
着、形成される。そのため、密着性に優れた固体潤滑皮
膜層が形成され、また燐酸マンガン系化成処理皮膜層の
塗膜下腐食の抑制効果による経時密着性の向上効果が得
られる。さらに、固体潤滑皮膜層が摩耗、損傷後も、燐
酸マンガン系化成処理皮膜層と該皮膜層にトラップされ
た固体潤滑皮膜層との相乗効果による潤滑機能の長期に
亘る接続効果が可能となる。Further, after the treatment of the solid lubricating coating layer and in the case where the solid lubricating coating is exposed to a corrosive environment for a long period of time, the so-called temporal adhesiveness is improved, and further, the solid lubricating coating is repeatedly slid under a high surface pressure. Even if the layer is worn or damaged, the nitriding layer, iron plating layer or Ni, C layer under the solid lubricating coating layer should be added in order to further improve the lubricating life.
Countermeasures were taken to form an iron alloy plating layer containing one or two kinds of O and a manganese phosphate-based chemical conversion treatment coating layer. That is, a nitriding layer, an iron plating layer or an iron alloy plating layer is provided for a high Cr alloy steel pipe joint containing 10% or more of Cr, which makes it difficult to uniformly form a manganese phosphate chemical conversion coating layer. As a result, the manganese phosphate-based chemical conversion treatment coating layer can be uniformly formed, and the synergistic effect of the coating layer and the solid lubricating coating layer is utilized to improve the performance. That is, in the manganese phosphate-based chemical conversion treatment coating layer, many voids are generated between the crystal grains to be produced, so that the solid lubricating coating layer is attached and formed in a state of being trapped in a large amount in the voids. Therefore, a solid lubricating coating layer having excellent adhesiveness is formed, and the effect of improving the temporal adhesiveness due to the effect of suppressing under-coating corrosion of the manganese phosphate-based chemical conversion coating layer can be obtained. Further, even after the solid lubricating coating layer is worn or damaged, a synergistic effect between the manganese phosphate-based chemical conversion treatment coating layer and the solid lubricating coating layer trapped in the coating layer enables a long-term connection effect of the lubricating function.
【００１２】以上のように、本発明の方法は、１０％以
上のＣｒを含有する高Ｃｒ合金鋼製鋼管継手に対して、
窒化処理層、鉄めっき層あるいは鉄合金めっき層と燐酸
マンガン系化成処理皮膜層を設けるとともに、靱性、硬
度および潤滑性能に優れた固体潤滑皮膜層を生成せしめ
ることによって、密着性、皮膜強度ならびに潤滑性能に
著しく優れ、特に潤滑寿命の長期間に亘る確保が可能な
表面処理皮膜層を形成せしめたものである。そのため、
本発明の方法による高Ｃｒ合金鋼製鋼管継手は、鋼管の
長期使用、すなわちメークアップ、ブレークアウトの繰
り返し回数の増大に対して、耐焼き付き性、耐摩耗性、
耐久性に極めて優れる。すなわち、長期間に亘る繰り返
し使用に対して、従来法に比較して焼き付きとムシレの
発生を防止し得る耐ゴーリング性に極めて優れた鋼管継
手が得られる。As described above, the method of the present invention can be applied to a steel pipe joint made of a high Cr alloy steel containing 10% or more of Cr.
By providing a nitriding layer, an iron plating layer or an iron alloy plating layer and a manganese phosphate-based chemical conversion coating layer, and by producing a solid lubricating coating layer with excellent toughness, hardness and lubrication performance, adhesion, coating strength and lubrication can be obtained. A surface-treated coating layer is formed which is extremely excellent in performance and can secure a lubricating life over a long period of time. for that reason,
The steel pipe joint made of high Cr alloy steel according to the method of the present invention has seizure resistance, wear resistance, and resistance to long-term use of the steel pipe, that is, increase in the number of repetitions of make-up and breakout.
Extremely excellent in durability. That is, it is possible to obtain a steel pipe joint having extremely excellent galling resistance capable of preventing the occurrence of seizure and rustling as compared with the conventional method even after repeated use over a long period of time.
【００１３】以下に、本発明の目的を達成する高Ｃｒ合
金鋼製鋼管継手を製造するための表面処理方法について
詳述する。而して、本発明においては、１０％以上の高
Ｃｒ合金鋼からなる鋼管継手に対して、燐酸マンガン系
化成処理皮膜層を均一に形成せしめるための下地処理層
として、窒化処理層、鉄めっき層あるいはＮｉ，Ｃｏの
一種または二種を１０％以下含有する鉄合金めっき層が
設けられるが、その厚さとしては、窒化処理層の厚さは
１μｍ以上〜２０μｍ以下、鉄めっき層と鉄合金めっき
層の厚さは０．５μｍ以上〜１５μｍ以下とするのが望
ましい。すなわち、窒化処理層の厚さが１μｍ未満では
窒化処理層に欠陥部が多く、密着性の良好な燐酸マンガ
ン系化成処理皮膜層を均一に安定して得るための下地層
としての機能を有しない。また、鉄めっき層あるいは鉄
合金めっき層の厚さが０．５μｍ未満ではめっき層に欠
陥部が多く生成され、また、燐酸マンガン系化成処理浴
中で部分的な溶解が生じる等の原因により、均一な密着
性に優れる燐酸マンガン系化成処理皮膜層の生成が阻害
されるので好ましくない。The surface treatment method for producing the steel pipe joint made of high Cr alloy steel which achieves the object of the present invention will be described in detail below. Thus, in the present invention, a steel pipe joint made of 10% or more of high Cr alloy steel is treated with a nitriding layer, an iron plating layer as a base treatment layer for uniformly forming a manganese phosphate-based chemical conversion coating layer. A layer or an iron alloy plating layer containing 10% or less of one or two kinds of Ni and Co is provided. The thickness of the nitriding layer is 1 μm or more to 20 μm or less. The thickness of the plated layer is preferably 0.5 μm or more and 15 μm or less. That is, when the thickness of the nitriding layer is less than 1 μm, the nitriding layer has many defects and does not function as a base layer for uniformly and stably obtaining a manganese phosphate-based chemical conversion coating layer having good adhesion. . Further, when the thickness of the iron plating layer or the iron alloy plating layer is less than 0.5 μm, many defects are generated in the plating layer, and because of partial dissolution in the manganese phosphate-based chemical conversion treatment bath, Formation of a manganese phosphate-based chemical conversion treatment coating layer having excellent uniform adhesion is hindered, which is not preferable.
【００１４】一方、これら下地処理層に関し、窒化処理
層の厚さが２０μｍを超える場合には、下地層としての
効果が飽和すると共に、むしろ窒化層は硬度が高いた
め、その厚さが増加し過ぎると高Ｃｒ含有合金鋼の材質
劣化をもたらすので好ましくない。また、鉄めっき層あ
るいは鉄合金めっき層の厚さが１５μｍを超える場合に
は、上記と同様に燐酸マンガン系化成処理皮膜の均一な
生成に対する下地被覆層としての効果が飽和するととも
に、経済的に不利であり、さらには継手部材を高面圧下
で回転締め付けを行ってメタル−メタルシール部を形成
せしめる場合に、鉄系下地めっき層にクラックが発生し
易くなる等の問題が生じるので好ましくない。従って、
本発明においては、窒化層の厚さは１μｍ以上〜２０μ
ｍ以下の厚さ、好ましくは５μｍ以上〜１５μｍ以下の
厚さに限定され、鉄めっき層あるいは鉄合金めっき層の
厚さは０．５μｍ以上〜１５μｍ以下の厚さ、好ましく
は１μｍ以上〜５μｍ以下の厚さが適用される。On the other hand, regarding the undercoat layer, when the thickness of the nitriding layer exceeds 20 μm, the effect as the underlayer is saturated, and the hardness of the nitride layer is rather high, so that the thickness thereof increases. If it is too much, the material of the high Cr content alloy steel is deteriorated, which is not preferable. Further, when the thickness of the iron plating layer or the iron alloy plating layer exceeds 15 μm, the effect as the undercoat layer on the uniform formation of the manganese phosphate-based chemical conversion treatment film is saturated as in the above, and at the same time, economically. It is not preferable, and further, when the joint member is rotationally tightened under a high surface pressure to form the metal-metal seal portion, there is a problem that cracks easily occur in the iron-based undercoat layer, which is not preferable. Therefore,
In the present invention, the thickness of the nitride layer is 1 μm or more and 20 μm or more.
The thickness of the iron plating layer or the iron alloy plating layer is 0.5 μm or more and 15 μm or less, preferably 1 μm or more and 5 μm or less. Thickness is applied.
【００１５】また、該下地処理層として使用される鉄系
合金めっき層は、鉄に対する合金化元素１０重量％以下
のＦｅ−Ｎｉ，Ｆｅ−ＣｏあるいはＦｅ−Ｎｉ−Ｃｏ合
金めっきから構成するのが良い。この合金めっき層を下
地処理層として用いることにより、鉄めっき層を用いた
下地めっき層に比較して均一微細な燐酸マンガン系化成
処理皮膜を形成せしめる効果が得られるが、合金化元素
が１０重量％を超える場合には均一な燐酸マンガン系化
成処理皮膜の生成が阻害される場合がある。従って、本
発明において鉄系合金めっき層からなる下地処理層とし
ては、Ｎｉ，ＣｏあるいはＮｉとＣｏの含有組成分が１
０％以下、特に５％以下のＦｅ−Ｎｉ，Ｆｅ−Ｃｏ，Ｆ
ｅ−Ｎｉ−Ｃｏ合金めっき層が好適である。The iron-based alloy plating layer used as the undercoat layer is made of Fe-Ni, Fe-Co or Fe-Ni-Co alloy plating containing 10% by weight or less of an alloying element with respect to iron. good. By using this alloy plating layer as the undercoating layer, the effect of forming a uniform fine manganese phosphate-based chemical conversion coating film can be obtained as compared with the undercoating layer using the iron plating layer. If it exceeds%, the formation of a uniform manganese phosphate-based chemical conversion coating may be hindered. Therefore, in the present invention, the undercoating layer made of the iron-based alloy plating layer contains Ni, Co, or Ni and Co in a composition of 1%.
Fe-Ni, Fe-Co, F of 0% or less, especially 5% or less
An e-Ni-Co alloy plating layer is suitable.
【００１６】而して、高Ｃｒ合金鋼製の継手部分に燐酸
マンガン系化成処理皮膜層を均一に生成せしめるための
これら下地処理層、すなわち、窒化処理層、鉄めっき層
あるいは鉄合金めっき層を設ける方法については、特に
限定されるものではない。すなわち、継手部分を脱脂、
酸洗あるいは脱脂、ショットブラスト等の表面清浄化お
よび活性化処理を施した後、窒化処理については処理浴
組成として、例えば、 （Ａ） ＮａＣＮ ２５％ ＫＣＮ １０％ ＮａＣＮＯ ２５％ ＫＣＮＯ １０％ Ｎａ2 ＣＯ3 ２０％ Ｋ2 ＣＯ3 １０％ （Ｂ） ＮａＣＮＯ １０％ ＫＣＮＯ ４５％ Ｎａ2 ＣＯ3 １０％ Ｋ2 ＣＯ3 ３５％ のような窒素化合物を含有する溶融塩浴が用いられると
ともに、浴温が４００〜７００℃の条件で、目的とする
窒化処理層の厚さを得るために鋼管継手のサイズ、処理
温度などの適用される条件に対応してそれぞれ選定され
た処理時間で処理される。Thus, these undercoating layers, that is, the nitriding layer, the iron plating layer or the iron alloy plating layer, for uniformly forming the manganese phosphate chemical conversion coating layer on the joint portion made of the high Cr alloy steel, are formed. The method of providing is not particularly limited. That is, degreasing the joint part,
After surface cleaning and activation such as pickling or degreasing, shot blasting, etc., the treatment bath composition for nitriding treatment is, for example, (A) NaCN 25% KCN 10% NaCNO 25% KCNO 10% Na 2 CO. 3 with 20% K 2 CO 3 10% (B) NaCNO 10% KCNO 45% Na 2 CO 3 10% K 2 CO 3 molten salt bath containing 35% of such nitrogen compounds are used, the bath temperature 400 The treatment is performed at a temperature of up to 700 ° C. for a treatment time selected in accordance with the applicable conditions such as the size of the steel pipe joint and the treatment temperature in order to obtain the target thickness of the nitriding treatment layer.
【００１７】また、鉄めっきあるいは鉄合金めっきにつ
いては処理浴組成として、例えば、硫酸鉄−塩化鉄−塩
化アンモン系Ｆｅめっき浴、硫酸鉄−塩化ニッケル−硼
酸系Ｆｅ−Ｎｉ合金めっき浴、硫酸鉄−塩化コバルト−
硼酸系Ｆｅ−Ｃｏ合金めっき浴、硫酸鉄−塩化ニッケル
−塩化コバルト−塩化アンモン系Ｆｅ−Ｎｉ−Ｃｏ合金
めっき浴等が用いられ、電流密度１〜２０Ａ／ｄｍ2 、
浴温が室温〜６０℃の条件下で、目的とするめっき厚を
得るために設定した電解時間で電気めっきを行う。ま
た、鉄系合金めっきについては、前述の電気めっき浴に
含有されるＦｅ2+に対してＮｉ2+、Ｃｏ2+添加量と電流
密度を選定することにより、めっき組成が調整される。For iron plating or iron alloy plating, the treatment bath composition is, for example, iron sulfate-iron chloride-ammonium chloride Fe plating bath, iron sulfate-nickel chloride-boric acid Fe-Ni alloy plating bath, iron sulfate. -Cobalt chloride-
A boric acid-based Fe-Co alloy plating bath, an iron sulfate-nickel chloride-cobalt chloride-ammonium chloride Fe-Ni-Co alloy plating bath, or the like is used, and the current density is 1 to 20 A / dm 2 .
Electroplating is performed under the condition that the bath temperature is room temperature to 60 ° C. and the electrolysis time is set to obtain a desired plating thickness. Regarding the iron-based alloy plating, the plating composition is adjusted by selecting the addition amounts of Ni 2+ and Co 2+ and the current density with respect to Fe 2+ contained in the electroplating bath.
【００１８】次いで、これらの下地被覆層が施された鋼
管継手に対して、燐酸マンガン系化成処理皮膜層が設け
られる。この燐酸マンガン系化成処理皮膜層の形成は、
従来かかる鋼管継手の耐ゴーリング性の向上のために施
されている、既に公知の燐酸マンガン系化成処理方法が
適用される。すなわち、下地被覆処理層が設けられた高
Ｃｒ含有合金鋼製継手は、脱脂、水洗後、または酸洗等
の表面清浄化と活性化処理後に直接あるいは前処理工程
を行って燐酸マンガン系化成処理が施される。前処理浴
としては、例えば、濃度が０．１〜３．０ｇ／ｌの（チ
タンコロイド−ピロリン酸ソーダ）系浴、（マンガンコ
ロイド−ピロリン酸ソーダ）系浴等が用いられるが、特
に規定されるものではない。これに続いて施される燐酸
マンガン系化成処理についても、本発明においては特に
規定されるものではなく、例えば、第一燐酸マンガンを
主成分として含有する（Ｍｎ2+−Ｎｉ2+−ＰＯ4 3-−Ｎ
Ｏ 3 - ）系化成処理浴、あるいは（Ｍｎ2+−Ｎｉ2+−Ｆ
ｅ2+−ＰＯ4 3-−ＮＯ3 -−Ｆ- ）系化成処理浴等が使
用され、温度７５〜９８℃で目標とする皮膜厚さに対応
した処理時間で皮膜層が設けられる。Next, steel coated with these undercoat layers
Manganese phosphate-based chemical conversion coating layer is provided on the pipe joint
Can be The formation of this manganese phosphate-based chemical conversion coating layer is
Conventional steel pipe joints have been applied to improve the galling resistance.
Already known manganese phosphate chemical conversion treatment method
Applied. In other words, the high
Cr-containing alloy steel joints are degreased, washed with water, or pickled.
Direct or pretreatment process after surface cleaning and activation treatment of
Then, manganese phosphate-based chemical conversion treatment is performed. Pretreatment bath
For example, a concentration of 0.1 to 3.0 g / l (
Tan colloid-sodium pyrophosphate bath, (manganese
Although a Lloyd-sodium pyrophosphate bath is used,
It is not specified in. Phosphoric acid applied subsequently
Regarding the manganese-based chemical conversion treatment, particularly in the present invention
Not specified, for example, manganese monophosphate
Contains as the main component (Mn2+-Ni2+-POFour 3--N
O 3 -) System chemical conversion treatment bath, or (Mn2+-Ni2+-F
e2+-POFour 3--NO3 --F-) A system chemical conversion bath is used
Used to meet the target film thickness at temperatures of 75-98 ℃
The coating layer is provided in the treatment time.
【００１９】この燐酸マンガン系化成処理皮膜層の厚さ
は、本発明の目的に対応するためには、５μｍ以上〜２
５μｍ以下の範囲で適用される。すなわち、燐酸マンガ
ン系化成処理皮膜層の厚さが５μｍ未満では、化成処理
皮膜層の均一被覆性が十分でなく、固体潤滑皮膜層に対
する十分な密着性向上効果、特に腐食環境に長期間曝さ
れた場合の密着性、所謂経時後の密着性向上効果が得ら
れにくく、また、固体潤滑皮膜層が消耗後の潤滑性能が
良好でなく、本発明の目的とする鋼管継手の耐久性に優
れる耐ゴーリング性の向上効果が不十分である。一方、
燐酸マンガン系化成処理皮膜層の厚さが２５μｍを超え
て生成される場合には、二次結晶が生成される傾向が著
しく、該皮膜層自体の密着性が劣化すると共に、固体潤
滑皮膜層の密着性も劣化させるので好ましくない。従っ
て、本発明においては、燐酸マンガン系化成処理皮膜層
の厚さは５μｍ以上〜２５μｍ以下の範囲、好ましくは
１０μｍ以上〜２５μｍ以下の範囲に限定される。The thickness of the manganese phosphate-based chemical conversion treatment coating layer is 5 μm or more to 2 for the purpose of the present invention.
It is applied in the range of 5 μm or less. That is, when the thickness of the manganese phosphate-based chemical conversion coating layer is less than 5 μm, the uniform coating property of the chemical conversion coating layer is not sufficient, and sufficient adhesion improving effect to the solid lubricating coating layer, especially exposure to a corrosive environment for a long period of time. In the case of contact, the so-called aging adhesion improvement effect is difficult to obtain, and the solid lubricating coating layer does not have good lubrication performance after wear, and the durability of the steel pipe joint that is the object of the present invention is excellent. The effect of improving the goring property is insufficient. on the other hand,
When the thickness of the manganese phosphate chemical conversion coating layer exceeds 25 μm, secondary crystals tend to be formed significantly, the adhesion of the coating layer itself deteriorates, and the solid lubricating coating layer Adhesion is also deteriorated, which is not preferable. Therefore, in the present invention, the thickness of the manganese phosphate-based chemical conversion coating layer is limited to the range of 5 μm to 25 μm, preferably 10 μm to 25 μm.
【００２０】さらに、本発明においては以上のように構
成された下地処理層と燐酸マンガン系化成処理皮膜層を
有する高Ｃｒ合金鋼からなる鋼管継手の焼き付きの発生
を防止する機能を一段と向上させるために、固体潤滑皮
膜層が設けられる。而して、本発明の目的を達成するた
めには、該固体潤滑皮膜層は燐酸マンガン系化成処理皮
膜層との密着性に優れると共に、高面圧下での潤滑性能
と皮膜強度に優れる皮膜層が形成されることが必要であ
る。従って、本発明においては、皮膜に対する潤滑機能
の付与を目的とした二硫化モリブデン粉末を必須成分と
して含有せしめるとともに、皮膜の密着性ならびに皮膜
強度の向上を狙いとして分子量がそれぞれ２，０００〜
１０，０００の範囲のエポキシ樹脂、１５０〜２５０の
範囲のフラン樹脂および１０，０００〜２５，０００の
範囲のポリアミドイミド樹脂の中より選定した一種をバ
インダーとして含有して構成される固体潤滑剤が用いら
れる。また、該固体潤滑剤に対して、形成される皮膜の
より一層の耐摩耗性の向上を目的として、必要に応じて
Ｃｕ粉末、Ｚｎ粉末の一種または二種が含有される。Further, in the present invention, in order to further improve the function of preventing the seizure of the steel pipe joint made of the high Cr alloy steel having the base treatment layer and the manganese phosphate-based chemical conversion treatment coating layer configured as described above. Is provided with a solid lubricating coating layer. Therefore, in order to achieve the object of the present invention, the solid lubricating coating layer has excellent adhesion to the manganese phosphate-based chemical conversion coating layer, and also has excellent lubricating performance and coating strength under high surface pressure. Need to be formed. Therefore, in the present invention, a molybdenum disulfide powder for the purpose of imparting a lubricating function to the coating is contained as an essential component, and the molecular weight is 2,000 to 2,000 respectively for the purpose of improving the adhesiveness and the coating strength of the coating.
A solid lubricant comprising a binder selected from the group consisting of an epoxy resin in the range of 10,000, a furan resin in the range of 150 to 250, and a polyamide-imide resin in the range of 10,000 to 25,000 as a binder. Used. Further, one or two kinds of Cu powder and Zn powder are contained in the solid lubricant, if necessary, for the purpose of further improving the wear resistance of the formed film.
【００２１】而して、本発明の目的を達成するために
は、被処理材に対して、フイッシャー法による測定粒径
が０．４５μｍ〜１０μｍの二硫化モリブデン粉末と上
述の有機樹脂が、 0.5 ≦｛（二硫化モリブデン粉末）の含有量｝／｛（エ
ポキシ樹脂、フラン樹脂あるいはポリアミドイミド樹脂
の中より選定した一種）の含有量｝≦ 3.0（重量比） の組成比で構成される固体潤滑剤を塗布し、１５０℃〜
３００℃の温度範囲における加熱ベーキング処理を施し
て、厚さが１０μｍ以上〜４５μｍ以下の固体潤滑皮膜
層を形成せしめることが必要である。すなわち、固体潤
滑剤に添加される二硫化モリブデン粉末のフイッシャー
法による測定粒子径が０．４５μｍ未満では、二硫化モ
リブデン粉末の本発明の目的とする耐ゴーリング性に対
する潤滑機能向上の効果が得られ難い。In order to achieve the object of the present invention, the molybdenum disulfide powder having a particle size of 0.45 μm to 10 μm measured by the Fisher method and the above-mentioned organic resin are added to the material to be treated in an amount of 0.5. Solid lubrication with a composition ratio of ≤ {(molybdenum disulfide powder) content} / {(a kind selected from epoxy resin, furan resin or polyamide-imide resin) ≤3.0 (weight ratio) Apply the agent, 150 ℃ ~
It is necessary to perform a heat baking treatment in the temperature range of 300 ° C. to form a solid lubricating coating layer having a thickness of 10 μm or more and 45 μm or less. That is, if the molybdenum disulfide powder added to the solid lubricant has a particle size of less than 0.45 μm measured by the Fisher method, the effect of improving the lubricating function on the galling resistance of the molybdenum disulfide powder, which is the object of the present invention, can be obtained. hard.
【００２２】一方、その粒子径が１０μｍを超える場合
には、皮膜に含有される二硫化モリブデン粉末の潤滑性
向上効果が飽和するとともに、目的とする固体潤滑皮膜
の厚さの調整が困難なため、好ましくない。したがっ
て、本発明において使用される二硫化モリブデン粉末
は、フイッシャー法により測定した粒子径が０．４５μ
ｍ以上〜１０μｍ以下の範囲、好ましくは２μｍ以上〜
５μｍ以下の範囲に規制される。また、該潤滑剤を構成
する有機樹脂系バインダーは、それぞれエポキシ樹脂が
分子量２，０００〜１０，０００、フラン樹脂が１５０
〜２５０、ポリアミドイミド樹脂が１０，０００〜２
５，０００に規制される。すなわち、エポキシ樹脂の分
子量が２，０００未満、フラン樹脂の分子量が１５０未
満、ポリアミドイミド樹脂の分子量が１０，０００未満
では、生成される皮膜に本発明の目的とする靱性と硬度
を付与するのが困難であり、またエポキシ樹脂の分子量
が１０，０００、フラン樹脂の分子量が２５０、ポリア
ミドイミド樹脂の分子量が２５，０００をそれぞれ超え
る場合には、生成される皮膜の靱性と硬度の向上効果が
飽和されるとともに、むしろ所定厚さに処理剤を均一に
塗布するのが困難であり、また生成される皮膜と燐酸マ
ンガン系化成処理皮膜層との密着性が劣化するので好ま
しくない。On the other hand, when the particle diameter exceeds 10 μm, the effect of improving the lubricity of the molybdenum disulfide powder contained in the coating is saturated, and it is difficult to adjust the thickness of the target solid lubricating coating. , Not preferable. Therefore, the molybdenum disulfide powder used in the present invention has a particle size of 0.45 μm measured by the Fisher method.
m or more and 10 μm or less, preferably 2 μm or more
It is regulated within the range of 5 μm or less. In addition, the organic resin-based binder that constitutes the lubricant is such that the epoxy resin has a molecular weight of 2,000 to 10,000, and the furan resin is 150.
~ 250, 10,000-2 polyamide imide resin
It is regulated to 5,000. That is, when the molecular weight of the epoxy resin is less than 2,000, the molecular weight of the furan resin is less than 150, and the molecular weight of the polyamideimide resin is less than 10,000, the toughness and hardness targeted by the present invention are imparted to the formed film. When the molecular weight of the epoxy resin is more than 10,000, the molecular weight of the furan resin is more than 250, and the molecular weight of the polyamide-imide resin is more than 25,000, it is difficult to improve the toughness and hardness of the resulting film. In addition to being saturated, it is rather difficult to apply the treatment agent uniformly to a predetermined thickness, and the adhesion between the formed film and the manganese phosphate-based chemical conversion treatment film layer deteriorates, which is not preferable.
【００２３】したがって、本発明においては、固体潤滑
皮膜層の形成に適用される潤滑剤に使用される有機樹脂
系バインダーは、分子量が２，０００〜１０，０００以
下、好ましくは３，０００〜５，０００の範囲のエポキ
シ樹脂、分子量が１５０〜２５０以下、好ましくは１７
０〜２２０の範囲のフラン樹脂、分子量が１０，０００
〜２５，０００以下、好ましくは１５，０００〜２０，
０００の範囲のポリアミドイミド樹脂に規制されるとと
もに、これら樹脂の中より選定した一種が用いられる。Therefore, in the present invention, the organic resin binder used in the lubricant applied to form the solid lubricating coating layer has a molecular weight of 2,000 to 10,000 or less, preferably 3,000 to 5. Epoxy resin having a molecular weight of 150 to 250, preferably 17
Furan resin in the range of 0-220, molecular weight 10,000
~ 25,000 or less, preferably 15,000-20,
In addition to being regulated by the polyamide-imide resin in the range of 000, one selected from these resins is used.
【００２４】而して、本発明の目的とする効果を達成す
るためには、固体潤滑皮膜層を形成するための固体潤滑
剤に関し、前記の二硫化モリブデン粉末と有機樹脂バイ
ンダーの組成比が重要であり、本発明においては、該組
成比は重量比で、 0.5 ≦｛（二硫化モリブデン粉末）の含有量｝／｛（エ
ポキシ樹脂、フラン樹脂あるいはポリアミドイミド樹脂
の中より選定した一種）の含有量｝≦ 3.0（重量比） の範囲に規制される。該組成比が０．５未満の場合に
は、形成される固体潤滑皮膜層の目的とする潤滑機能の
向上効果が得られ難く、また該組成比が３．０を超える
場合には、形成された固体潤滑皮膜層の密着性が劣化
し、特に皮膜層からの二硫化モリブデン粉末の剥離が著
しい等の欠点を生じるので好ましくない。したがって、
固体潤滑皮膜層を形成するために使用される処理剤の必
須含有成分である二硫化モリブデン粉末と有機樹脂バイ
ンダーの含有組成比は、０．５〜３．０の範囲、好まし
くは０．８〜２．０の範囲に規制される。Therefore, in order to achieve the effect of the present invention, the composition ratio of the molybdenum disulfide powder and the organic resin binder is important for the solid lubricant for forming the solid lubricating film layer. In the present invention, the composition ratio is a weight ratio of 0.5 ≦ {(content of molybdenum disulfide powder)} / {(one selected from epoxy resin, furan resin or polyamideimide resin) The amount is regulated within the range of ≦ 3.0 (weight ratio). When the composition ratio is less than 0.5, it is difficult to obtain the intended effect of improving the lubricating function of the solid lubricating coating layer formed, and when the composition ratio exceeds 3.0, it is formed. Further, the adhesion of the solid lubricating coating layer is deteriorated, and in particular, the molybdenum disulfide powder is remarkably peeled from the coating layer, which is disadvantageous. Therefore,
The content composition ratio of the molybdenum disulfide powder, which is an essential content component of the treatment agent used for forming the solid lubricating coating layer, and the organic resin binder is in the range of 0.5 to 3.0, preferably 0.8 to It is regulated within the range of 2.0.
【００２５】また、本発明においては、形成される固体
潤滑皮膜層の耐摩耗性をさらに向上させるために、処理
剤にＣｕ粉末、Ｚｎ粉末の一種または二種が必要に応じ
て添加される。これら粉末は、粒径が０．５μｍ以上〜
１０μｍ以下の範囲で使用され、処理剤に含有される二
硫化モリブデン粉末に対して１０％以上〜５０％（重量
％）以下の範囲で添加される。すなわち、粒径が０．５
μｍ未満の粒径のＣｕ粉末あるいはＺｎ粉末が固体潤滑
皮膜層に含有されても、皮膜層の耐摩耗性の向上効果が
小さく、また使用される粒径が１０μｍを超える場合に
は、固体潤滑皮膜層の所定厚さに調整することが困難な
ため、好ましくない。Further, in the present invention, in order to further improve the wear resistance of the formed solid lubricating coating layer, one or two kinds of Cu powder and Zn powder are added to the treatment agent as needed. These powders have a particle size of 0.5 μm or more
It is used in the range of 10 μm or less and is added in the range of 10% to 50% (wt%) with respect to the molybdenum disulfide powder contained in the treatment agent. That is, the particle size is 0.5
Even if Cu powder or Zn powder having a particle diameter of less than μm is contained in the solid lubricating coating layer, the effect of improving the wear resistance of the coating layer is small, and if the used particle diameter exceeds 10 μm, solid lubricating It is not preferable because it is difficult to adjust the coating layer to a predetermined thickness.
【００２６】さらに、これら粉末の添加量が二硫化モリ
ブデン粉末に対して、１０重量％未満では、目的とする
耐摩耗性の向上効果が小さく、また５０重量％を超える
場合には、生成される固体潤滑皮膜層の潤滑性能および
燐酸マンガン系化成処理皮膜層との密着性の劣化をもた
らすので好ましくない。したがって、固体潤滑剤にＣｕ
粉末あるいはＺｎ粉末が添加、使用される場合には、粒
径は０．５μｍ以上〜１０μｍ以下、好ましくは０．８
μｍ以上〜６．５μｍ以下の範囲、またその添加量は二
硫化モリブデンに対して１０重量％以上〜５０重量％以
下、好ましくは２０重量％以上〜４２．５重量％以下の
範囲にそれぞれ規制される。Further, if the addition amount of these powders is less than 10% by weight with respect to the molybdenum disulfide powder, the desired effect of improving the wear resistance is small, and if it exceeds 50% by weight, it is produced. It is not preferable because it leads to deterioration of the lubricating performance of the solid lubricating coating layer and the adhesion to the manganese phosphate-based chemical conversion coating layer. Therefore, the solid lubricant is Cu
When powder or Zn powder is added and used, the particle size is 0.5 μm or more and 10 μm or less, preferably 0.8 μm or less.
The range of μm or more to 6.5 μm or less, and the addition amount thereof are regulated to the range of 10% by weight or more to 50% by weight or less, preferably 20% by weight or more to 42.5% by weight or less, based on molybdenum disulfide. It
【００２７】而して、以上のように構成された固体潤滑
剤は、狙いとする皮膜厚さ、塗布方法等に対応して、溶
剤を用いて粘度調整を行って、前記の下地処理と燐酸マ
ンガン系化成処理を施した高Ｃｒ含有鋼管継手に塗布さ
れる。これら固体潤滑剤の粘度調整方法あるいは処理剤
の塗布方法等については、本発明において特に規定され
るものではなく、従来から行われている方法により、例
えば溶剤としてケトン系溶剤等を用いて粘度調整を行
い、スプレイ塗布方式等により塗布処理が施される。Thus, the solid lubricant having the above-described structure is adjusted in viscosity by using a solvent in accordance with the intended film thickness, coating method, etc., and the above-mentioned base treatment and phosphoric acid are applied. It is applied to a high Cr content steel pipe joint that has been subjected to manganese chemical conversion treatment. The method for adjusting the viscosity of these solid lubricants or the method for applying the treatment agent is not particularly specified in the present invention, and it is possible to adjust the viscosity by a conventional method, for example, using a ketone solvent as the solvent. Then, the coating process is performed by a spray coating method or the like.
【００２８】次いで、処理剤が塗布処理された高Ｃｒ含
有鋼管継手に加熱ベーキング処理を施して、本発明の目
的とする固体潤滑皮膜層が形成せしめられる本発明にお
いては、該加熱ベーキング処理の方法あるいは条件につ
いては、特に規定されるものではなく、固体潤滑剤に使
用される有機樹脂系バインダーの性状に対応して加熱温
度は任意に設定されるとともに、また加熱方法について
も、従来からの公知の方法が採用される。例えば、熱風
乾燥、ガスもしくは電気加熱、赤外線法等が用いられ、
加熱温度１５０℃〜３００℃、好ましくは１８０℃〜２
７０℃の温度範囲で加熱ベーキング処理が施される。な
お、加熱処理時間は、鋼管継手のサイズ、形状等に対応
して任意に設定すればよく、また加熱処理時間の短縮お
よび固体潤滑剤の塗布後、加熱ベーキング処理の間にお
けるたれ現象を防止するため、鋼管継手を固体潤滑剤の
塗布処理に先立って予め予熱処理を行う等の対策を講じ
ても良い。Next, in the present invention in which the high Cr content steel pipe joint coated with the treating agent is subjected to a heating baking treatment to form a solid lubricating coating layer, which is the object of the present invention, the heating baking treatment method is used. Alternatively, the conditions are not particularly specified, and the heating temperature is arbitrarily set according to the properties of the organic resin binder used for the solid lubricant, and the heating method is also known from the related art. Method is adopted. For example, hot air drying, gas or electric heating, infrared method, etc. are used,
Heating temperature 150 ° C to 300 ° C, preferably 180 ° C to 2
The heating and baking treatment is performed in the temperature range of 70 ° C. The heat treatment time may be arbitrarily set according to the size, shape, etc. of the steel pipe joint, and also shortens the heat treatment time and prevents the sagging phenomenon during the heating baking treatment after the application of the solid lubricant. Therefore, it is possible to take measures such as pre-heating the steel pipe joint in advance before applying the solid lubricant.
【００２９】これらの方法により、高Ｃｒ含有鋼からな
る鋼管継手に形成される固体潤滑皮膜層の皮膜厚さは１
０μｍ以上〜４５μｍ以下の範囲に限定される。この皮
膜厚さが１０μｍ未満の場合には、本発明の目的とする
潤滑性能向上の効果が少なく、特に鋼管継手のメークア
ップとブレークアウトの繰り返し使用回数が減少する等
の問題を生じるので好ましくない。一方、該皮膜層の厚
さが４５μｍを超える場合には、潤滑機能向上効果が飽
和するとともに、経済的に不利である。むしろ、固体潤
滑皮膜層の密着性が劣化する傾向が増加し、該皮膜層の
剥離によるムシレの発生する原因になるので好ましくな
い。したがって、固体潤滑皮膜層は、本発明の方法にお
いては、その厚さが１０μｍ以上〜４５μｍ以下、好ま
しくは１５μｍ以上〜３０μｍ以下の範囲に限定され
る。By these methods, the coating thickness of the solid lubricating coating layer formed on the steel pipe joint made of high Cr content steel is 1
It is limited to the range of 0 μm to 45 μm. If the coating thickness is less than 10 μm, the effect of improving the lubrication performance, which is the object of the present invention, is small, and problems such as a decrease in the number of times of repeated make-up and breakout of steel pipe joints occur, which is not preferable. . On the other hand, when the thickness of the coating layer exceeds 45 μm, the lubricating function improving effect is saturated and it is economically disadvantageous. On the contrary, it is not preferable because the tendency of the solid lubricating coating layer to deteriorate in adhesion tends to increase and cause peeling of the coating layer to cause rusting. Therefore, in the method of the present invention, the thickness of the solid lubricating coating layer is limited to a range of 10 μm to 45 μm, preferably 15 μm to 30 μm.
【００３０】而して、前記のように構成された固体潤滑
剤を用いて燐酸マンガン系化成処理皮膜層に固体潤滑皮
膜層を形成することにより、該固体潤滑皮膜は燐酸マン
ガン系化成処理皮膜層との相互作用によって密着性に非
常に優れるとともに、皮膜の靱性と硬度、すなわち皮膜
強度および潤滑性能に極めて優れる。特に、本発明の目
的とする用途に対しては、前記の各固体潤滑剤のうち、
二硫化モリブデン粉末−ポリアミドイミド樹脂およびそ
れにＣｕ粉末あるいはＺｎ粉末を添加した固体潤滑剤を
用いて形成される固体潤滑皮膜層が、他の樹脂系に比較
してその靱性と硬度に優れ、またＣｕ粉末等の添加効果
によってさらに耐摩耗性が向上するため、より優れた効
果が得られる。すなわち、形成される固体潤滑皮膜層の
強度に特に優れるため、高面圧下での摺動を繰り返し受
ける使用条件下での皮膜寿命の向上効果により、長期間
に亘るメークアップとブレークアウトの繰り返し使用に
対して極めて有効である。By forming a solid lubricant film layer on the manganese phosphate-based chemical conversion coating film layer using the solid lubricant having the above-mentioned structure, the solid lubricant film is converted into a manganese phosphate-based chemical conversion film layer. It has excellent adhesion due to the interaction with and also has excellent toughness and hardness of the coating, that is, coating strength and lubricating performance. Particularly, for the intended use of the present invention, among the above solid lubricants,
A solid lubricating coating layer formed by using a solid lubricant containing molybdenum disulfide powder-polyamideimide resin and Cu powder or Zn powder has excellent toughness and hardness as compared with other resin systems, and Cu Since the wear resistance is further improved by the effect of adding powder or the like, a more excellent effect can be obtained. That is, since the strength of the formed solid lubricating coating layer is particularly excellent, repeated use of make-up and breakout over a long period of time is possible due to the effect of improving the coating life under operating conditions where it is repeatedly subjected to sliding under high surface pressure. Is extremely effective against
【００３１】以上のように、本発明においては、１０重
量％以上のＣｒを含有する高Ｃｒ含有鋼製鋼管の継手部
分に、窒化処理層、鉄めっき層あるいは鉄合金めっき層
からなる下地処理層と燐酸マンガン系化成処理皮膜層お
よびこれら皮膜層を介して密着性ならびに皮膜強度と潤
滑性能に極めて優れる固体潤滑皮膜層からなる三層皮膜
層が形成されるため、これら各皮膜層の相乗効果により
長期間に亘る使用条件において耐ゴーリング性に極めて
優れる鋼管の継手を得ることが出来る。すなわち、本発
明の方法による三層皮膜層を有する鋼管継手は、ねじ部
あるいはメタル−メタルシール部にコンパウンドグリー
スを塗布してメークアップ、ブレークアウトが行われる
通常の作業条件下においては勿論のこと、さらにコンパ
ウンドグリースが十分に塗布されていないような条件
下、あるいは意識的にコンパウンドグリースを塗布しな
い使用条件下においても、皮膜の焼き付き、ムシレの発
生が起こりにくく、耐ゴーリング性に極めて優れる。As described above, in the present invention, the undercoating layer consisting of the nitriding layer, the iron plating layer or the iron alloy plating layer is formed on the joint portion of the steel pipe for high Cr content steel containing 10% by weight or more of Cr. And a manganese phosphate-based chemical conversion coating layer and a three-layer coating layer consisting of a solid lubricating coating layer having extremely excellent adhesion, coating strength and lubrication performance are formed through these coating layers, so the synergistic effect of each of these coating layers It is possible to obtain a steel pipe joint having excellent galling resistance under long-term use conditions. That is, the steel pipe joint having the three-layer coating layer according to the method of the present invention is, of course, under normal working conditions in which the compound grease is applied to the thread portion or the metal-metal seal portion to make up and break out. Further, even under conditions where the compound grease is not sufficiently applied, or even under use conditions in which the compound grease is not intentionally applied, seizure of the film and crease hardly occur, and the galling resistance is extremely excellent.
【００３２】また、本発明の処理は、油井管の連結に用
いられる継手部分、すなわち油井管の先端に形成された
ねじ部とその基部に形成されたテーパ部分からなるピン
およびこのねじ部と螺合するねじ部と先端に先細のテー
パ部分を形成したカップリングの両方に施しても良く、
またどちらかの片方、特にカップリングにのみ施しても
良い。本発明は特に油井管ねじ継手の皮膜構造について
言及したものであり、皮膜と継手形状の組み合せについ
て特定するものではない。Further, according to the process of the present invention, a joint portion used for connecting oil country tubular goods, that is, a pin formed of a threaded portion formed at the tip of the oil country tubular goods and a taper portion formed at the base thereof, and the threaded portion It may be applied to both the mating screw part and the coupling with a tapered part at the tip.
Also, it may be applied to either one, especially to the coupling. The present invention particularly refers to the coating structure of the oil well pipe threaded joint, and does not specify the combination of the coating and the joint shape.
【００３３】[0033]
【作用】１０％以上のＣｒを含有するＣｒ含有鋼、さら
にこれにＮｉ，Ｍｏ等を添加した高Ｃｒ含有鋼から製造
された鋼管継手に対して、下地処理層として窒化処理
層、鉄めっき層あるいは鉄合金めっき層を設けることに
より、高Ｃｒ含有鋼に、従来その形成が困難とされてい
る燐酸マンガン系化成処理皮膜層の均一な生成を可能な
らしめるため、さらにこれら皮膜層を介して密着性が極
めて向上すると共に、靱性、硬度および潤滑性能に著し
く優れる固体潤滑皮膜層が形成せしめられる。その結
果、本発明の方法により、高面圧下での摺動を繰り返し
受ける使用条件、すなわちメークアップとブレークアウ
トが繰り返し行われる条件下において、皮膜強度と潤滑
性能に優れる固体潤滑皮膜層、ならびに燐酸マンガン系
化成処理皮膜層との相乗効果によって、鋼管継手部のメ
タル同士の接触によるシール部およびねじ部の焼き付き
の発生防止、特に繰り返し使用回数の増加に対する耐久
性に著しく優れる高Ｃｒ合金鋼製鋼管継手が得られる。[Function] For a steel pipe joint manufactured from a Cr-containing steel containing 10% or more of Cr, and a high Cr-containing steel in which Ni, Mo, etc. are added to the steel pipe joint, a nitriding layer and an iron plating layer are used as an undercoating layer. Alternatively, by providing an iron alloy plating layer, it is possible to uniformly form a manganese phosphate-based chemical conversion treatment coating layer, which has been difficult to form, on steel containing a high amount of Cr. In addition to the extremely improved properties, a solid lubricating coating layer having excellent toughness, hardness and lubricating performance can be formed. As a result, according to the method of the present invention, a solid lubricating coating layer excellent in coating strength and lubricating performance, and a phosphoric acid layer, are used under conditions of repeated sliding under high surface pressure, that is, under conditions where makeup and breakout are repeated. A synergistic effect with the manganese-based chemical conversion coating layer prevents the occurrence of seizure in the seal part and the screw part due to the contact between the metal parts of the steel pipe joint part, and in particular, it is a high Cr alloy steel pipe that has outstanding durability against repeated use. A joint is obtained.
【００３４】[0034]
【実施例】表１にそれぞれの組成を示すＣｒ含有量１０
％以上の高Ｃｒ含有合金鋼から製造された鋼管の継手部
分、すなわち図１に示すカップリング（継手部材）１と
ピン２（鋼管先端継手部）について、それぞれの継手部
分を構成するねじ部３およびメタルーメタルシール部４
に対して、カップリング１のみ、あるいはカップリング
１とピン２に本発明の方法による窒化処理、鉄めっきあ
るいは鉄合金めっきによる下地処理層、燐酸マンガン系
化成処理皮膜層および固体潤滑皮膜層を設けた鋼管継手
を作成し、評価試験に供した。なお、評価試験および性
能は、以下の方法により実施した。すなわち、本発明の
処理を施した評価材を図２に示すように、カップリング
１とピン２を嵌合させた。次いで、締め付け機により、
試験条件に応じて所定のトルク値でメークアップし、図
２のカップリング１およびピン２のそれぞれのねじ部
３、メタル−メタルシール部４に高面圧を付与しつつ摺
動させた。かかる後に、締め付け機によりカップリング
１およびピン２をメークアップと逆の方向に回転させブ
レークアウトした。ブレークアウトした後に、カップリ
ング１、ピン２のねじ部３およびメタル−メタルシール
部４を観察し、表面処理皮膜の剥離状況ならびにゴーリ
ングの発生状況を調査した。調査の結果、皮膜の剥離、
ゴーリングが生じていない場合、あるいは軽度の場合に
は、さらにカップリング１とピン２を嵌合させ、前述の
締め付け機により同一の条件でメークアップを行った。
以上のように、評価材について皮膜の剥離、ゴーリング
が発生するまでメークアップ、ブレークアウトを繰り返
し、最大１５回まで調査し、評価を行った。なお、メー
クアップ、ブレークアウトに際しては、カップリングに
対してピンを１〜３ｒｐｍの速度で回転させて評価試験
を行った。[Example] Cr content of each composition shown in Table 1 is 10
% Or more of a high Cr content alloy steel, the joint portion of the steel pipe, that is, the coupling (joint member) 1 and the pin 2 (steel pipe tip joint portion) shown in FIG. And metal-metal seal part 4
On the other hand, only the coupling 1 or the coupling 1 and the pin 2 are provided with a nitriding treatment by the method of the present invention, an undercoating layer by iron plating or iron alloy plating, a manganese phosphate-based chemical conversion coating layer and a solid lubricating coating layer. A steel pipe joint was prepared and subjected to an evaluation test. The evaluation test and performance were carried out by the following methods. That is, as shown in FIG. 2, the evaluation material treated according to the present invention was fitted with the coupling 1 and the pin 2. Then, by the tightening machine,
Makeup was performed at a predetermined torque value according to the test conditions, and the coupling 1 and the pin 2 of FIG. 2 were slid while applying high surface pressure to the respective threaded portions 3 and metal-metal seal portions 4. After this, the coupling 1 and the pin 2 were rotated in the direction opposite to the make-up by the tightening machine to break out. After the breakout, the coupling 1, the screw portion 3 of the pin 2 and the metal-metal seal portion 4 were observed to investigate the peeling state of the surface treatment film and the occurrence state of galling. As a result of the investigation, peeling of the film,
When no galling occurred or when it was mild, the coupling 1 and the pin 2 were further fitted, and makeup was performed under the same conditions by the above-mentioned tightening machine.
As described above, the evaluation materials were repeatedly made up and broken out until peeling of the coating and galling occurred, and the evaluation was conducted up to 15 times for evaluation. In addition, at the time of make-up and break-out, the pin was rotated at a speed of 1 to 3 rpm with respect to the coupling to perform an evaluation test.
【００３５】[0035]
【表１】 [Table 1]
【００３６】実施例１ 供試鋼Ａを用いて作成した内径５．５インチのカップリ
ング１およびこれに対応したサイズのピン２の先端部を
溶剤脱脂後、（２０％ＮａＣＮ−１５％ＫＣＮ−１７．
５％ＮａＣＮＯ−１７．５％ＫＣＮＯ−１０％Ｎａ2 Ｃ
Ｏ3 −２０％Ｋ 2 ＣＯ3 ）からなる溶融塩浴中で、４５
０℃、３０分間の加熱窒化処理を行い、オイルバス中で
冷却した。該窒化処理材を溶剤脱脂して、５％Ｈ2 ＳＯ
4 水溶液中で室温、５秒の酸洗、水洗後、０．８ｇ／ｌ
の（チタンコロイド−ピロリン酸ソーダ）系前処理浴に
よる室温で２分間の前処理を行ってから、（８．７g/l
Ｍｎ2+−０．２g/l Ｎｉ2+−０．６g/l Ｆｅ2+−３２．
３g/l ＰＯ4 3- −５．７g/l ＮＯ3 - −０．６g/l
Ｆ- ）系浴からなる燐酸マンガン系化成処理浴を用い
て、９０℃、１０分間の処理により燐酸マンガン系化成
処理皮膜層を設けた。次いで、平均粒子径２．５μｍの
二硫化モリブデン粉末と平均分子量４，２００のエポキ
シ樹脂を主要成分として含有するとともに、 ｛（平均粒子径２．５μｍの二硫化モリブデン粉末）の
含有量｝／｛（平均分子量４，２００のエポキシ樹脂）
の含有量｝＝１．３（重量比） の組成比で構成される固体潤滑剤を塗布し、１８０℃で
２０分間の加熱ベーキング処理を施して、固体潤滑皮膜
層を設けた。すなわち、本発明の処理によりカップリン
グ１とピン２のねじ部３ならびにメタルシール部４にそ
れぞれ窒化処理層６．４μｍ、燐酸マンガン系化成処理
皮膜層１３μｍおよび固体潤滑皮膜層１６．５μｍから
なる三層皮膜層を評価材に形成せしめた。カップリング
１およびピン２のねじ部３とメタルシール部４にＡＰＩ
ＢＵ１５Ａ２ Ｓｅｃｔ２相当のコンパウンドグリース
を塗布し、シール部４に３，０００ｋｇ／ｃｍ2 の面圧
を付与しつつ、継手部に対してメークアップ、ブレーク
アウトの繰り返しテストを行った。該テストの１０回目
までは焼き付きとムシレの発生が殆ど生じなかったが、
１１回目のテストにおいて焼き付きとムシレがかなり生
じた。Example 1 A coupling having an inner diameter of 5.5 inches prepared using the test steel A.
The tip of the ring 1 and the corresponding size pin 2
After solvent degreasing, (20% NaCN-15% KCN-17.
5% NaCNO-17.5% KCNO-10% Na2C
O3-20% K 2CO345) in a molten salt bath consisting of
Heat nitriding treatment at 0 ° C for 30 minutes, and in an oil bath
Cooled. Solvent degreasing the nitriding material to 5% H2SO
Four0.8 g / l after pickling and rinsing at room temperature for 5 seconds in aqueous solution
(Titanium colloid-sodium pyrophosphate) system pretreatment bath
After pretreatment at room temperature for 2 minutes, (8.7g / l
Mn2+-0.2g / l Ni2+-0.6g / l Fe2+-32.
3g / l POFour 3--5.7g / l NO3 --0.6 g / l
F-) Manganese phosphate chemical conversion treatment bath consisting of
By treatment at 90 ° C for 10 minutes
A treatment film layer was provided. Then, the average particle diameter of 2.5 μm
Molybdenum disulfide powder and epoxide with average molecular weight of 4,200
In addition to containing a resin as a main component, {(molybdenum disulfide powder with an average particle diameter of 2.5 μm)
Content} / {(epoxy resin having an average molecular weight of 4,200)
Content of the solid} = 1.3 (weight ratio)
A solid lubricating film is formed by heating for 20 minutes.
Layers were provided. That is, by the treatment of the present invention
The threaded portion 3 of the plug 1 and pin 2 and the metal seal portion 4
Nitrided layer 6.4 μm each, manganese phosphate-based chemical conversion treatment
From coating layer 13 μm and solid lubricating coating layer 16.5 μm
The following three-layer coating layer was formed on the evaluation material. Coupling
1 and the threaded portion 3 of the pin 2 and the metal seal portion 4 API
Compound grease equivalent to BU15A2 Sect2
And apply 3,000 kg / cm to the seal part 4.2 Surface pressure
While giving up, make up and break the joint
Repeated out test. 10th of the test
Until then, there was almost no occurrence of burn-in and muscular,
In the 11th test, burn-in and mussels were considerably produced.
I started.
【００３７】比較例１ 供試鋼Ａを用いて作成した内径５．５インチのカップリ
ング１とピン２の先端部を溶剤脱脂後、グリットブラス
トを用いて、カップリング１とピン２のねじ部３および
メタルシール部４の表面最大粗さを３５μｍに調整し
た。該処理後、水洗し、０．８ｇ／ｌの（チタンコロイ
ド−ピロリン酸ソーダ）系前処理を行い、（８．７g/l
Ｍｎ2+−０．２g/l Ｎｉ2+−０．６g/l Ｆｅ2+−３２．
３g/l ＰＯ 4 3- −５．７g/l ＮＯ3 - −０．６g/l
Ｆ- ）系浴からなる燐酸マンガン系化成処理浴を用いて
９０℃、１０分間の処理を施して比較例とした。しかし
ながら、該比較材には殆ど燐酸マンガン系化成処理皮膜
層が生成されず、実施例１と同一条件で評価試験を行っ
た結果、繰り返しテスト２回目のテストにおいて焼き付
きとムシレが著しく、評価試験を中断した。Comparative Example 1 A coupling having an inner diameter of 5.5 inches prepared using the test steel A.
After degreasing the tips of the ring 1 and pin 2 with solvent, grit brass
And the threaded portion 3 of the coupling 1 and the pin 2 and
Adjust the maximum surface roughness of the metal seal part 4 to 35 μm
Was. After the treatment, it is washed with water to give 0.8 g / l (titanium colloid
Do-sodium pyrophosphate) pretreatment was performed (8.7 g / l
Mn2+-0.2g / l Ni2+-0.6g / l Fe2+-32.
3g / l PO Four 3--5.7g / l NO3 --0.6 g / l
F-) Using a manganese phosphate chemical conversion treatment bath consisting of
It was treated at 90 ° C. for 10 minutes as a comparative example. However
However, most of the comparative materials are manganese phosphate-based chemical conversion coatings.
An evaluation test was conducted under the same conditions as in Example 1 without forming a layer.
As a result, repeated tests burned in the second test
The sharpness was remarkable and the evaluation test was interrupted.
【００３８】実施例２ 供試鋼Ｃを用いて作成した内径７インチのカップリング
１を水系脱脂剤を用いて脱脂を行い、（１０％ＨＮＯ3
＋１％ＨＦ）系水溶液により室温、３０秒の酸洗、水洗
後、（２５０ｇ／ｌＦｅＳＯ4 ・７Ｈ2 Ｏ−４２ｇ／ｌ
ＦｅＣｌ2 ・４Ｈ2 Ｏ−２０ｇ／ｌＮＨ4 Ｃｌ）系組成
の電気めっき浴を用いて電流密度１０Ａ／ｄｍ2 で６０
秒間の電解処理により、鉄めっき層を設けた。次いで、
水洗後直ちに（９．５g/l Ｍｎ2+−０．１５g/l Ｎｉ2+
−１．０g/l Ｆｅ2+−３６g/l ＰＯ4 3- −６．１g/l Ｎ
Ｏ3 - −０．３g/l Ｆ- ）系浴からなる燐酸マンガン系
化成処理浴を用いて、９５℃、１０分間の処理により燐
酸マンガン系化成処理皮膜層を設けた。さらに、平均粒
子径２．８μｍの二硫化モリブデン粉末と平均分子量１
８５のフラン樹脂を主要成分として含有するとともに、 ｛（平均粒子径２．８μｍの二硫化モリブデン粉末）の
含有量｝／｛（平均分子量１８５のフラン樹脂）の含有
量｝＝１．８（重量比） の組成比で構成される固体潤滑剤を塗布し、２００℃で
３０分間の加熱ベーキング処理を施して、固体潤滑皮膜
層を設けた。すなわち、本発明の処理によりカップリン
グ１のねじ部３ならびにメタルシール部４にそれぞれ鉄
めっき層１．５μｍ、燐酸マンガン系化成処理皮膜層１
８μｍおよび固体潤滑皮膜層１５μｍからなる三層皮膜
層を評価材に形成せしめた。実施例１と同様に、コンパ
ウンドグリースを塗布し、シール部４に４，０００ｋｇ
／ｃｍ2 の面圧を付与しつつ、継手部に対してメークア
ップ、ブレークアウトの繰り返しテストを行った。該テ
ストの１１回目まではシール部の焼き付きとムシレは殆
ど発生しなかったが、１２回目のテストにおいて焼き付
きとムシレがかなり生じた。Example 2 Coupling 1 having an inner diameter of 7 inches made of test steel C was degreased with an aqueous degreasing agent to obtain (10% HNO 3
+ 1% HF) aqueous solution at room temperature for 30 seconds after pickling and water washing, then (250 g / l FeSO 4 .7H 2 O-42 g / l
FeCl 2 .4H 2 O-20 g / l NH 4 Cl) -based composition electroplating bath at a current density of 10 A / dm 2
An iron plating layer was provided by electrolytic treatment for 2 seconds. Then
Immediately after washing with water (9.5 g / l Mn 2+ -0.15 g / l Ni 2+
-1.0g / l Fe 2+ -36g / l PO 4 3- -6.1g / l N
A manganese phosphate chemical conversion treatment coating layer was formed by treatment at 95 ° C. for 10 minutes using a manganese phosphate chemical conversion treatment bath consisting of an O 3 − −0.3 g / l F − ) -based bath. Further, molybdenum disulfide powder having an average particle diameter of 2.8 μm and an average molecular weight of 1
In addition to containing 85 furan resin as a main component, {(content of molybdenum disulfide powder having an average particle diameter of 2.8 μm)} / {content of (furan resin having an average molecular weight of 185)} = 1.8 (weight The solid lubricant having a composition ratio of (4) was applied and heat baking treatment was performed at 200 ° C. for 30 minutes to form a solid lubricating coating layer. That is, by the treatment of the present invention, the threaded portion 3 and the metal seal portion 4 of the coupling 1 have an iron plating layer of 1.5 μm and a manganese phosphate-based chemical conversion coating layer 1 respectively.
A three-layer coating layer composed of 8 μm and a solid lubricating coating layer of 15 μm was formed on the evaluation material. Compound grease was applied in the same manner as in Example 1, and 4,000 kg was applied to the seal portion 4.
While applying a surface pressure of / cm 2 , the joint part was repeatedly tested for make-up and breakout. Up to the 11th test, seizure and swelling of the seal hardly occurred, but in the 12th test, seizure and swelling occurred considerably.
【００３９】比較例２ 供試鋼Ｃを用いて作成した内径７インチのカップリング
１を実施例２と同一の前処理を行った後、同一条件で
１．５μｍの鉄めっき層と１８μｍの燐酸マンガン系化
成処理層を設けた。さらに、実施例２と同一組成の固体
潤滑剤を塗布し、２００℃で３０分間の加熱ベーキング
処理を施し、実施例２と同一組成で構成される厚さ５μ
ｍの固体潤滑皮膜層を形成せしめて、比較例とした。該
比較材を実施例２と同一条件で評価試験を行った結果、
繰り返しテスト８回目において焼き付きとムシレの発生
が著しく、評価試験を中断した。Comparative Example 2 A coupling 1 having an inner diameter of 7 inches prepared by using a test steel C was subjected to the same pretreatment as in Example 2, and then under the same conditions, a 1.5 μm iron plating layer and 18 μm phosphoric acid were used. A manganese-based chemical conversion treatment layer was provided. Further, a solid lubricant having the same composition as that of Example 2 was applied, and a heating baking treatment was performed at 200 ° C. for 30 minutes to form a film having the same composition as Example 2 and a thickness of 5 μm.
As a comparative example, a solid lubricating coating layer of m was formed. As a result of performing an evaluation test on the comparative material under the same conditions as in Example 2,
In the eighth repeat test, the occurrence of burn-in and swelling was remarkable, and the evaluation test was interrupted.
【００４０】実施例３ 供試鋼Ｂを用いて作成した内径７インチのカップリング
１を水系脱脂剤を用いて脱脂を行い、ガラスビーズショ
ット（粒子径♯１００、圧力５ｋｇｆ／ｃｍ2、６０
秒）による前処理後、（２５％ＮａＣＮ−１０％ＫＣＮ
−２５％ＮａＣＮＯ−１０％ＫＣＮＯ−２０％Ｎａ2 Ｃ
Ｏ3 −１０％Ｋ2 ＣＯ3 ）系溶融塩浴中で、５７０℃、
２０分間の加熱窒化処理を施し、オイルバス中で冷却し
た。該窒化処理材を水系脱脂剤による脱脂、１０％Ｈ2
ＳＯ4 水溶液中での室温、１０秒間の酸洗、水洗後、
０．５ｇ／ｌの（マンガンコロイド−ピロリン酸ソー
ダ）系前処理浴を用いて室温で２０秒間の前処理を行っ
てから、（８g/l Ｍｎ2+−０．３g/l Ｎｉ2+−０．２g/
l Ｆｅ2+−２９．５g/l ＰＯ4 3- −５．４g/l ＮＯ 3 -
−０．３g/l Ｆ- ）系浴からなる燐酸マンガン系化成処
理浴を用いて、８５℃、１３分間の処理により燐酸マン
ガン系化成処理皮膜層を設けた。次いで、平均粒子径
３．０μｍの二硫化モリブデン粉末と平均分子量２０，
０００のポリアミドイミド樹脂を主要成分として含有す
るとともに、 ｛（平均粒子径３．０μｍの二硫化モリブデン粉末）の
含有量｝／｛（平均分子量２０，０００のポリアミドイ
ミド樹脂）の含有量｝＝０．８（重量比） の組成比で構成される固体潤滑剤を塗布し、２５０℃で
３０分間の加熱ベーキング処理を施して、固体潤滑皮膜
層を設けた。すなわち、本発明の処理によりカップリン
グ１のねじ部３ならびにメタルシール部４にそれぞれ窒
化処理層１０μｍ、燐酸マンガン系化成処理皮膜層１２
μｍおよび固体潤滑皮膜層１５μｍからなる三層皮膜層
を評価材に形成せしめた。実施例１と同様に、コンパウ
ンドグリースを塗布し、シール部４に４，０００ｋｇ／
ｃｍ2 の面圧を付与しつつ、継手部に対してメークアッ
プ、ブレークアウトの繰り返しテストを行った。該テス
トの１３回目までは焼き付きとムシレの発生が殆ど生じ
なかったが、１４回目のテストにおいて焼き付きとムシ
レがかなり生じた。Example 3 Coupling 1 having an inner diameter of 7 inches prepared from test steel B was degreased with an aqueous degreasing agent, and shot with glass beads (particle diameter # 100, pressure 5 kgf / cm 2 , 60).
Second), after pretreatment with (25% NaCN-10% KCN
-25% NaCNO-10% KCNO- 20% Na 2 C
O 3 at -10% K 2 CO 3) based molten salt bath, 570 ° C.,
It was subjected to a heating nitriding treatment for 20 minutes and cooled in an oil bath. The nitriding material is degreased with an aqueous degreasing agent, 10% H 2
At room temperature in SO 4 aqueous solution for 10 seconds after pickling and water washing,
After pretreatment for 20 seconds at room temperature using a 0.5 g / l (manganese colloid-sodium pyrophosphate) pretreatment bath, (8 g / l Mn 2+ −0.3 g / l Ni 2+ − 0.2 g /
l Fe 2+ −29.5 g / l PO 4 3 − −5.4 g / l NO 3 −
A manganese phosphate chemical conversion treatment coating layer was formed by treatment at 85 ° C. for 13 minutes using a manganese phosphate chemical conversion treatment bath consisting of −0.3 g / l F − ) -based bath. Then, molybdenum disulfide powder having an average particle diameter of 3.0 μm and an average molecular weight of 20,
000 polyamide imide resin as a main component, and {(content of molybdenum disulfide powder having an average particle diameter of 3.0 μm)} / {content of (polyamide imide resin having an average molecular weight of 20,000)} = 0 A solid lubricant having a composition ratio of 0.8 (weight ratio) was applied, and heat baking treatment was performed at 250 ° C. for 30 minutes to form a solid lubricating coating layer. That is, by the treatment of the present invention, the threaded portion 3 and the metal seal portion 4 of the coupling 1 each have a nitriding treatment layer of 10 μm and a manganese phosphate-based chemical conversion treatment coating layer 12 respectively.
The evaluation material was formed with a three-layered coating layer consisting of a coating layer of .mu.m and a solid lubricating coating layer of 15 .mu.m. Compound grease was applied in the same manner as in Example 1, and 4,000 kg /
While applying a surface pressure of cm 2 , the joint part was repeatedly tested for make-up and breakout. Up to the 13th test, seizure and swelling were hardly generated, but in the 14th test, seizure and swelling were considerably generated.
【００４１】比較例３ 供試鋼Ｂを用いて作成した内径７インチのカップリング
１に対して、実施例３と同一方法によりねじ部３および
メタルシール部４に窒化処理層１０μｍと燐酸マンガン
系化成処理皮膜層１２μｍを設けた。次いで、平均粒子
径３．０μｍの二硫化モリブデン粉末と平均分子量２
０，０００のポリアミドイミド樹脂を主要成分として含
有するとともに、 ｛（平均粒子径３．０μｍの二硫化モリブデン粉末）の
含有量｝／｛（平均分子量２０，０００のポリアミドイ
ミド樹脂）の含有量｝＝４．０（重量比） の組成比で構成される固体潤滑剤を塗布し、２００℃で
３０分間の加熱ベーキング処理を施して、厚さ１５μｍ
の固体潤滑皮膜層を形成せしめて比較例とした。該比較
材に、実施例３と同様にコンパウンドグリースを塗布
し、シール部４に４，０００ｋｇ／ｃｍ2 の面圧を付与
しつつ、継手部に対してメークアップ、ブレークアウト
の繰り返しテストを行った。その結果、固体潤滑皮膜層
の剥離が著しく、繰り返しテスト５回目のテストにおい
て評価試験を中断した。Comparative Example 3 With respect to the coupling 1 having an inner diameter of 7 inches prepared by using the test steel B, the nitriding layer of 10 μm and the manganese phosphate-based material were formed on the screw part 3 and the metal seal part 4 in the same manner as in Example 3. A chemical conversion treatment coating layer 12 μm was provided. Next, molybdenum disulfide powder having an average particle diameter of 3.0 μm and an average molecular weight of 2
In addition to containing 50,000 polyamide-imide resins as main components, {(content of molybdenum disulfide powder having an average particle diameter of 3.0 μm)} / {content of (polyamide-imide resin having an average molecular weight of 20,000)} = 4.0 (weight ratio), a solid lubricant composed of a composition ratio is applied, and heat baking is performed at 200 ° C. for 30 minutes to obtain a thickness of 15 μm.
The solid lubricating coating layer of 1 was formed as a comparative example. Compound grease was applied to the comparative material in the same manner as in Example 3, and the joint portion was repeatedly subjected to make-up and breakout tests while applying a surface pressure of 4,000 kg / cm 2 to the seal portion 4. It was As a result, the solid lubricant film layer was significantly peeled off, and the evaluation test was interrupted in the fifth repeat test.
【００４２】実施例４ 供試鋼Ｂを用いて作成した内径７インチのカップリング
１を水系脱脂剤を用いて脱脂を行い、（１０％ＨＮＯ3
＋１％ＨＦ）系水溶液により室温で４５秒の酸洗後、
（３３０ｇ／ｌＦｅＳＯ4 ・７Ｈ2 Ｏ−１０ｇ／ｌＮｉ
Ｃｌ2 ・６Ｈ2 Ｏ−１０ｇ／ｌＣｏＣｌ2 ・６Ｈ2 Ｏ−
２０ｇ／ｌＮＨ4 Ｃｌ）系めっき浴中で７．５Ａ／ｄｍ
2 −１３０秒間の電解処理により、Ｆｅ−１％Ｎｉ−１
％Ｃｏ系合金めっき層を設けた。次いで、水洗、１０％
Ｈ2 ＳＯ4 浴による１０秒の酸洗、水洗を行って、直ち
に（８g/l Ｍｎ2+−０．３g/l Ｎｉ2+−０．７g/l Ｆｅ
2+−２９．５g/l ＰＯ4 3- −５．４g/l ＮＯ 3 - −０．
５g/l Ｆ- ）系浴からなる燐酸マンガン系化成処理浴を
用いて、９２℃、１５分間の処理により燐酸マンガン系
化成処理皮膜層を設けた。次いで、平均粒子径３．５μ
ｍの二硫化モリブデン粉末と平均分子量１８，０００の
ポリアミドイミド樹脂を主要成分として含有するととも
に、 ｛（平均粒子径３．５μｍの二硫化モリブデン粉末）の
含有量｝／｛（平均分子量１８，０００のポリアミドイ
ミド樹脂）の含有量｝＝１．８（重量比） の組成比で構成される固体潤滑剤を塗布し、２６０℃で
２５分間の加熱ベーキング処理を施して、固体潤滑皮膜
層を設けた。すなわち、本発明の処理によりカップリン
グ１のねじ部３ならびにメタルシール部４にそれぞれＦ
ｅ−１％Ｎｉ−１％Ｃｏ系合金めっき層２．５μｍ、燐
酸マンガン系化成処理皮膜層１７μｍおよび固体潤滑皮
膜層１２μｍからなる三層皮膜層を評価材に形成せしめ
た。実施例１と同様に、コンパウンドグリースを塗布
し、シール部４に４，０００ｋｇ／ｃｍ2 の面圧を付与
しつつ、継手部に対してメークアップ、ブレークアウト
の繰り返しテストを行った。該テストの１２回目までは
焼き付きとムシレの発生を生じなかったが、１３回目の
テストにおいて焼き付きとムシレがかなり生じた。Example 4 Coupling 1 having an inner diameter of 7 inches prepared from test steel B was degreased with an aqueous degreasing agent (10% HNO 3
+ 1% HF) -based aqueous solution, after pickling for 45 seconds at room temperature,
(330g / lFeSO 4 · 7H 2 O-10g / lNi
Cl 2 · 6H 2 O-10g / lCoCl 2 · 6H 2 O-
20 g / l NH 4 Cl) -based plating bath 7.5 A / dm
By electrolytic treatment for 2 to 130 seconds, Fe-1% Ni-1
% Co-based alloy plating layer was provided. Then, wash with water, 10%
Immediately (8 g / l Mn 2+ -0.3 g / l Ni 2+ -0.7 g / l Fe was performed after pickling with H 2 SO 4 bath for 10 seconds and washing with water.
2+ -29.5g / l PO 4 3- -5.4g / l NO 3 - -0.
Using a manganese phosphate-based chemical conversion treatment bath consisting of a 5 g / l F − ) - based bath, a manganese phosphate-based chemical conversion treatment coating layer was provided by treatment at 92 ° C. for 15 minutes. Next, average particle size 3.5μ
m molybdenum disulfide powder and a polyamideimide resin having an average molecular weight of 18,000 as main components, and {(content of molybdenum disulfide powder having an average particle diameter of 3.5 μm)} / {(average molecular weight 18,000) Content of polyamidoimide resin} = 1.8 (weight ratio), a solid lubricant composed of a composition ratio is applied, and heating baking treatment is performed at 260 ° C. for 25 minutes to form a solid lubricating film layer. It was That is, the threaded portion 3 and the metal seal portion 4 of the coupling 1 are each subjected to F by the treatment of the present invention.
A three-layer coating layer consisting of e-1% Ni-1% Co alloy plating layer 2.5 μm, manganese phosphate-based chemical conversion coating layer 17 μm, and solid lubricating coating layer 12 μm was formed as the evaluation material. In the same manner as in Example 1, compound grease was applied, and while applying a surface pressure of 4,000 kg / cm 2 to the seal portion 4, repeated tests of make-up and breakout were performed on the joint portion. No seizure or swelling occurred until the 12th test of the test, but seizure and swelling occurred considerably in the 13th test.
【００４３】比較例４ 供試鋼Ｂを用いて作成した内径７インチのカップリング
１に対して、実施例３と同一方法によりねじ部３および
メタルシール部４にＦｅ−１％Ｎｉ−１％Ｃｏ系合金め
っき層２．５μｍと燐酸マンガン系化成処理皮膜層１７
μｍを設けた。次いで、平均粒子径３．５μｍの二硫化
モリブデン粉末と平均分子量１８，０００のポリアミド
イミド樹脂を主要成分として含有するとともに、 ｛（平均粒子径３．５μｍの二硫化モリブデン粉末）の
含有量｝／｛（平均分子量１８，０００のポリアミドイ
ミド樹脂）の含有量｝＝０．２（重量比） の組成比で構成される固体潤滑剤を塗布し、２５０℃で
３０分間の加熱ベーキング処理を施して、厚さ１２μｍ
の固体潤滑皮膜層を形成せしめて、比較例とした。該比
較材に実施例４と同様にコンパウンドグリースを塗布
し、シール部４に４，０００ｋｇ／ｃｍ2 の面圧を付与
しつつ、継手部に対してメークアップ、ブレークアウト
の繰り返しテストを行った。その結果、固体潤滑皮膜層
の潤滑性能の向上効果が不十分なため、繰り返しテスト
７回目のテストにおいて、焼き付きとムシレの発生が著
しく、評価試験を中断した。Comparative Example 4 With respect to the coupling 1 having an inner diameter of 7 inches prepared by using the test steel B, the screw portion 3 and the metal seal portion 4 were Fe-1% Ni-1% in the same manner as in Example 3. Co-based alloy plating layer 2.5 μm and manganese phosphate-based chemical conversion treatment coating layer 17
μm was provided. Next, while containing a molybdenum disulfide powder having an average particle diameter of 3.5 μm and a polyamideimide resin having an average molecular weight of 18,000 as main components, {(content of molybdenum disulfide powder having an average particle diameter of 3.5 μm)} / {(Content of polyamide-imide resin having an average molecular weight of 18,000) = 0.2 (weight ratio) A solid lubricant having a composition ratio of: was applied, and heat baking treatment was performed at 250 ° C. for 30 minutes. , Thickness 12 μm
The solid lubricating film layer of was formed as a comparative example. Compound grease was applied to the comparative material in the same manner as in Example 4, and the joint portion was repeatedly subjected to make-up and break-out tests while applying a surface pressure of 4,000 kg / cm 2 to the seal portion 4. . As a result, the effect of improving the lubricating performance of the solid lubricating coating layer was insufficient, so that in the seventh test of the repeated test, the occurrence of seizure and rusting was remarkable, and the evaluation test was interrupted.
【００４４】実施例５ 供試鋼Ａを用いて作成した内径７インチのカップリング
１を水系脱脂剤を用いて脱脂、ガラスビーズショット
（粒子径♯１００、圧力５ｋｇｆ／ｃｍ2 、９０秒）に
よる前処理後、（２５％ＮａＣＮ−１０％ＫＣＮ−２０
％ＮａＣＮＯ−１５％ＫＣＮＯ−２０％Ｎａ2 ＣＯ3 −
１０％Ｋ2 ＣＯ3 ）系溶融塩浴中で、５８０℃、１５分
間の加熱窒化処理を施し、オイルバス中で冷却した。該
窒化処理材を水系脱脂剤による脱脂、１０％Ｈ2 ＳＯ4
水溶液中での室温、５秒の酸洗、水洗後、０．５ｇ／ｌ
の（チタンコロイド−ピロリン酸ソーダ）系前処理浴に
よる室温で２分間の前処理工程を行ってから、（９．０
g/l Ｍｎ2+−０．２g/l Ｎｉ 2+−０．６g/l Ｆｅ2+−３
３．５g/l ＰＯ4 3- −５．７g/l ＮＯ 3 - −０．６g/l
Ｆ- ）系浴からなる燐酸マンガン系化成処理浴を用い
て、９０℃、１０分間の処理により燐酸マンガン系化成
処理皮膜層を設けた。次いで、カップリング１を１７５
℃で１５分間予熱加熱を行った後、平均粒子径３．０μ
ｍの二硫化モリブデン粉末と平均分子量２０，０００の
ポリアミドイミド樹脂を主要成分として含有するととも
に、 ｛（平均粒子径３．０μｍの二硫化モリブデン粉末）の
含有量｝／｛（平均分子量２０，０００のポリアミドイ
ミド樹脂）の含有量｝＝１．０（重量比） の組成比で構成される固体潤滑剤を塗布し、２４０℃で
３０分間の加熱ベーキング処理を施して、固体潤滑皮膜
層を設けた。すなわち、本発明の処理によりカップリン
グ１のねじ部３ならびにメタルシール部４にそれぞれ窒
化処理層１１．５μｍ、燐酸マンガン系化成処理皮膜層
１３．５μｍおよび固体潤滑皮膜層１８．５μｍからな
る三層皮膜層を評価材に形成せしめた。該評価材を対象
に、カップリング１およびピン２のねじ部３とメタル−
メタルシール部４にコンパウンドグリースを塗布しない
条件下で、シール部４に３，５００ｋｇ／ｃｍ2の面圧
を付与しつつ、継手部に対してメークアップ、ブレーク
アウトの繰り返しテストを行った。該テストを１０回繰
り返し行った結果は、シール部の焼き付き、ムシレの発
生が殆ど生じなかったが、１１回目のテストにおいて焼
き付きとムシレがかなり生じた。Example 5 Coupling with an inner diameter of 7 inches prepared by using the test steel A
Degreasing 1 using an aqueous degreasing agent, glass bead shot
(Particle size # 100, pressure 5 kgf / cm2 , 90 seconds)
After pretreatment with (25% NaCN-10% KCN-20
% NaCNO-15% KCNO-20% Na2CO3−
10% K2CO3) System molten salt bath, 580 ℃, 15 minutes
A heating nitriding treatment was performed between them, and they were cooled in an oil bath. The
Degreasing the nitriding material with an aqueous degreasing agent, 10% H2SOFour
After washing at room temperature for 5 seconds in an aqueous solution for 5 seconds and then washing with water, 0.5 g / l
(Titanium colloid-sodium pyrophosphate) system pretreatment bath
After performing a pretreatment step for 2 minutes at room temperature according to
g / l Mn2+-0.2g / l Ni 2+-0.6g / l Fe2+-3
3.5g / l POFour 3--5.7g / l NO3 --0.6 g / l
F-) Manganese phosphate chemical conversion treatment bath consisting of
By treatment at 90 ° C for 10 minutes
A treatment film layer was provided. Then coupling 1 175
After preheating for 15 minutes at ℃, average particle size 3.0μ
m molybdenum disulfide powder with an average molecular weight of 20,000
It also contains polyamide-imide resin as a main component
Of {(molybdenum disulfide powder with an average particle size of 3.0 μm)
Content} / {(polyamide having an average molecular weight of 20,000)
(Solid resin) content = 1.0 (weight ratio) A solid lubricant composed of a composition ratio of
A solid lubricating film is formed by heating for 30 minutes.
Layers were provided. That is, by the treatment of the present invention
The thread 3 and metal seal 4 of
Chemical treatment layer 11.5 μm, manganese phosphate-based chemical conversion treatment coating layer
13.5 μm and solid lubricating coating layer 18.5 μm
A three-layer coating layer was formed on the evaluation material. Target the evaluation material
In addition, the threaded portion 3 of the coupling 1 and the pin 2 and the metal-
Do not apply compound grease to the metal seal part 4.
Under the conditions, the seal part 4 is 3,500 kg / cm2Surface pressure
While giving up, make up and break the joint
Repeated out test. Repeat the test 10 times
The result of re-doing is that the seal part is seized and squeezed.
Almost no raw, but in the 11th test
A lot of tightness and mussels occurred.
【００４５】比較例５ 供試鋼Ａを用いて作成した内径７インチのカップリング
１を水系脱脂剤を用いて脱脂を行い、グリットブラスト
を用いてカップリング１のねじ部３およびメタルシール
部４の表面最大粗さを２０μｍに調整した。次いで、１
７５℃で１５分間予熱加熱を行った後、実施例４と同様
の方法により厚さ１８．５μｍの固体潤滑皮膜層を形成
せしめて、比較例とした。該比較材に、実施例４と同様
にコンパウンドグリースを塗布することなく、シール部
４に３，５００ｋｇ／ｃｍ2 の面圧を付与しつつ、継手
部に対してメークアップ、ブレークアウトの繰り返しテ
ストを行った。その結果、繰り返しテスト４回目に固体
潤滑皮膜層の摩耗、損傷に起因する焼き付きとムシレの
発生が著しく、評価試験を中断した。COMPARATIVE EXAMPLE 5 A coupling 1 having an inner diameter of 7 inches made of a test steel A was degreased with an aqueous degreasing agent, and a screw portion 3 and a metal seal portion 4 of the coupling 1 were subjected to grit blasting. The maximum surface roughness of was adjusted to 20 μm. Then 1
After preheating at 75 ° C. for 15 minutes, a solid lubricating coating layer having a thickness of 18.5 μm was formed in the same manner as in Example 4 to give a comparative example. Similar to Example 4, the comparative material was subjected to repeated test of make-up and breakout on the joint portion while applying a surface pressure of 3,500 kg / cm 2 to the seal portion 4 without applying compound grease. I went. As a result, the seizure and rusting caused by abrasion and damage of the solid lubricating coating layer were remarkable at the fourth repeat test, and the evaluation test was interrupted.
【００４６】実施例６ 供試鋼Ｃを用いて作成した内径７インチのカップリング
１を水系脱脂剤を用いて脱脂を行い、（１０％ＨＮＯ3
＋１％ＨＦ）系水溶液により室温、６０秒の酸洗後、
（３００ｇ／ｌＦｅＳＯ4 ・７Ｈ2 Ｏ−３５ｇ／ｌＮｉ
Ｃｌ2 ・６Ｈ2 Ｏ−３０ｇ／ｌＨ3 ＢＯ3 ）系組成の電
気めっき浴を用いて電流密度１５Ａ／ｄｍ 2 で８２．５
秒間の電解処理により、Ｎｉ含有量３．５％のＦｅ−Ｎ
ｉ系合金めっき層を設けた。次いで、水洗、３％Ｈ2 Ｓ
Ｏ4 浴で室温、３秒の酸洗、水洗後、直ちに（８．７g/
l Ｍｎ2+−０．２g/l Ｎｉ2+−０．６g/l Ｆｅ2+−３
２．３g/l ＰＯ4 3- −５．７g/l ＮＯ 3 - −０．５g/l
Ｆ- ）系浴からなる燐酸マンガン系化成処理浴を用い
て、９５℃、１０分間の処理により燐酸マンガン系化成
処理皮膜層を生成せしめた。次いで、平均粒子径４．０
μｍと１．０μｍの二硫化モリブデン粉末および平均分
子量１６，０００のポリアミドイミド樹脂を主要成分と
して含有するとともに、 〔｛（平均粒子径４．０μｍの二硫化モリブデン粉末）
の７５重量％と（平均粒子径１．０μｍの二硫化モリブ
デン粉末）の２５重量％からなる二硫化モリブデン粉
末｝の含有量〕 ／｛（平均分子量１６，０００のポリ
アミドイミド樹脂）の含有量｝＝１．１ （重量比） の組成比で構成される固体潤滑剤を塗布し、２６０℃で
２５分間の加熱ベーキング処理を施して、固体潤滑皮膜
層を設けた。すなわち、本発明の処理によりカップリン
グ１のねじ部３ならびにメタルシール部４にそれぞれＦ
ｅ−Ｎｉ系合金めっき層３．０μｍ、燐酸マンガン系化
成処理皮膜層１５μｍおよび固体潤滑皮膜層１６μｍか
らなる三層皮膜層を評価材に形成せしめた。実施例１と
同様に、コンパウンドグリースを塗布し、シール部４に
４，０００ｋｇ／ｃｍ2 の面圧を付与しつつ、継手部に
対してメークアップ、ブレークアウトの繰り返しテスト
を行った。該テストの１３回目までは焼き付きとムシレ
の発生を生じなかったが、１４回目のテストにおいて焼
き付きとムシレがかなり生じた。Example 6 A coupling having an inner diameter of 7 inches, which was prepared using the test steel C.
1 was degreased with a water-based degreasing agent (10% HNO3
+ 1% HF) aqueous solution at room temperature for 60 seconds after pickling,
(300g / lFeSOFour・ 7H2O-35g / lNi
Cl2・ 6H2O-30g / lH3BO3) System composition
Current density of 15 A / dm using air plating bath 2At 82.5
Fe-N with a Ni content of 3.5% by electrolytic treatment for 2 seconds
An i-based alloy plating layer was provided. Then, wash with water, 3% H2S
OFourImmediately after washing with water at room temperature for 3 seconds with acid and water (8.7 g /
l Mn2+-0.2g / l Ni2+-0.6g / l Fe2+-3
2.3g / l POFour 3--5.7g / l NO3 --0.5 g / l
F-) Manganese phosphate chemical conversion treatment bath consisting of
By treatment at 95 ° C for 10 minutes
A treated coating layer was generated. Then, the average particle diameter is 4.0.
μm and 1.0 μm molybdenum disulfide powder and average content
Polyamide-imide resin with a molecular weight of 16,000 as the main component
In addition to containing [{(molybdenum disulfide powder having an average particle diameter of 4.0 μm)
Of 75% by weight (of molybdenum disulfide having an average particle diameter of 1.0 μm)
Den powder) 25% by weight of molybdenum disulfide powder
End} content] / {(polyethylene having an average molecular weight of 16,000)
Content of amido-imide resin} = 1.1 (weight ratio)
A solid lubricating film after a 25 minute heat baking process
Layers were provided. That is, by the treatment of the present invention
F on the thread part 3 and the metal seal part 4 of the plug 1 respectively.
e-Ni alloy plating layer 3.0 μm, manganese phosphate based
15 μm of chemical treatment coating layer and 16 μm of solid lubricating coating layer
A three-layer coating layer composed of the above was formed on the evaluation material. Example 1 and
Similarly, apply compound grease to the seal part 4.
4,000 kg / cm2 While applying the surface pressure of
Repeated make-up and break-out tests
Was done. Burn-in and smashing up to the 13th test
Was not generated, but it was burned in the 14th test.
A lot of tightness and mussels occurred.
【００４７】比較例６ 供試鋼Ｃを用いて作成した内径７インチのカップリング
１に対して、実施例４と同一方法によりねじ部３および
メタルシート部４にＦｅ−３．５％Ｎｉ系合金めっき層
３．０μｍを設けた。次いで、実施例６と同一の固体潤
滑剤を塗布、同一の処理により厚さ１６μｍの固体潤滑
皮膜層を形成せしめて、比較例とした。該比較材を実施
例６と同様にコンパウンドグリースを塗布し、シール部
４に４，０００ｋｇ／ｃｍ2 の面圧を付与しつつ、継手
部に対してメークアップ、ブレークアウトの繰り返しテ
ストを行った。その結果、繰り返しテスト７回目に固体
潤滑皮膜層の摩耗、部分的な剥離に起因する焼き付きと
ムシレの発生が著しく、評価試験を中断した。Comparative Example 6 With respect to the coupling 1 having an inner diameter of 7 inches prepared by using the test steel C, the screw portion 3 and the metal sheet portion 4 were made of Fe-3.5% Ni system by the same method as in Example 4. An alloy plating layer 3.0 μm was provided. Then, the same solid lubricant as in Example 6 was applied, and a solid lubricating film layer having a thickness of 16 μm was formed by the same treatment to make a comparative example. Compound grease was applied to the comparative material in the same manner as in Example 6, and a repeated test of make-up and breakout was performed on the joint portion while applying a surface pressure of 4,000 kg / cm 2 to the seal portion 4. . As a result, the evaluation of the solid lubricant film layer was interrupted at the seventh time of the repeated test because of the remarkable abrasion and partial peeling of the solid lubricating coating layer.
【００４８】実施例７ 供試鋼Ａを用いて作成した内径７インチのカップリング
１を水系脱脂剤を用いて脱脂を行い、１０％ＨＣｌ水溶
液により５０℃で３０秒の酸洗を行った後、（１５％Ｎ
ａＣＮ−２０％ＫＣＮ−１５％ＮａＣＮＯ−１０％ＫＣ
ＮＯ−２０％Ｎａ2 ＣＯ3 −１０％Ｋ2 ＣＯ3 ）系溶融
塩浴中で、５９０℃、１０分間の加熱窒化処理を施し、
オイルバス中で冷却した。該窒化処理材を水系脱脂剤に
よる脱脂、５％Ｈ2 ＳＯ4 水溶液中での室温、１秒の酸
洗、水洗後、直ちに（９．５g/lＭｎ2+−０．１５g/l
Ｎｉ2+−０．４g/l Ｆｅ2+−３６g/l ＰＯ4 3- −６．１
g/l ＮＯ 3 - −０．３g/l Ｆ- ）系浴からなる燐酸マン
ガン系化成処理浴を用いて、９０℃、２０分間の処理に
より窒化処理層表面に燐酸マンガン系化成処理皮膜層を
生成せしめた。次いで、カップリング１を１８０℃で１
５分間予熱加熱を行った後、平均粒子径４．３μｍの二
硫化モリブデン粉末と平均粒子径１．０μｍのＣｕ粉末
および平均分子量２０，０００のポリアミドイミド樹脂
を主要成分として含有するとともに、 〔｛（平均粒子径４．３μｍの二硫化モリブデン粉末）
の７１重量％と（平均粒子径１．０μｍのＣｕ粉末）の
２９重量％からなる混合物＊｝の含有量〕／｛（平均分
子量２０，０００のポリアミドイミド樹脂）の含有量｝
＝１．０（重量比） （＊二硫化モリブデン粉末に対するＣｕ粉末の添加量；
約４１重量％） の組成比で構成される固体潤滑剤を塗布し、２７０℃で
２０分間の加熱処理を施して、固体潤滑皮膜層を設け
た。すなわち、本発明の処理によりカップリング１のね
じ部３ならびにメタルシール部４にそれぞれ窒化処理層
７．５μｍ、燐酸マンガン系化成処理皮膜層１６μｍお
よび固体潤滑皮膜層１５μｍからなる三層皮膜層を評価
材に形成せしめた。実施例１と同様にコンパウンドグリ
ースを塗布し、シール部４に４，０００ｋｇ／ｃｍ2 の
面圧を付与しつつ、継手部に対してメークアップ、ブレ
ークアウトの繰り返しテストを行った。該テストを１５
回繰り返し行った結果は、シール部の焼き付き、ムシレ
の発生が極めて少なく、非常に良好であった。Example 7 The coupling 1 having an inner diameter of 7 inches prepared from the test steel A was degreased with an aqueous degreasing agent, and pickled with a 10% HCl aqueous solution at 50 ° C. for 30 seconds. , (15% N
aCN-20% KCN-15% NaCNO-10% KC
NO-20% Na 2 CO 3 -10% K 2 CO 3 ) -based molten salt bath was subjected to a heat nitriding treatment at 590 ° C. for 10 minutes,
Cooled in an oil bath. The nitriding material was degreased with a water-based degreasing agent at room temperature in an aqueous 5% H 2 SO 4 solution for 1 second, followed by immediate pickling (9.5 g / l Mn 2+ -0.15 g / l).
Ni 2+ -0.4g / l Fe 2+ -36g / l PO 4 3- -6.1
A manganese phosphate-based chemical conversion coating layer was formed on the surface of the nitriding layer by treatment at 90 ° C. for 20 minutes using a manganese phosphate-based chemical conversion treatment bath consisting of a g / l NO 3 − −0.3 g / l F − ) -based bath. I generated it. Then coupling 1 at 180 ° C for 1
After preheating for 5 minutes, molybdenum disulfide powder having an average particle diameter of 4.3 μm, Cu powder having an average particle diameter of 1.0 μm, and a polyamideimide resin having an average molecular weight of 20,000 are contained as main components, and [{ (Molybdenum disulfide powder having an average particle diameter of 4.3 μm)
Content of a mixture *} of 71% by weight of and (29% by weight of Cu powder having an average particle diameter of 1.0 μm)] / {content of (polyamideimide resin having an average molecular weight of 20,000)}
= 1.0 (weight ratio) (* Cu powder addition amount to molybdenum disulfide powder;
A solid lubricant having a composition ratio of about 41% by weight) was applied and heat treatment was performed at 270 ° C. for 20 minutes to form a solid lubricating coating layer. That is, a three-layer coating layer consisting of a nitriding treatment layer of 7.5 μm, a manganese phosphate-based chemical conversion treatment coating layer of 16 μm and a solid lubricating coating layer of 15 μm was evaluated on the screw portion 3 and the metal seal portion 4 of the coupling 1 by the treatment of the present invention. Formed on wood. Compound grease was applied in the same manner as in Example 1, and a repeated test of make-up and breakout was performed on the joint portion while applying a surface pressure of 4,000 kg / cm 2 to the seal portion 4. 15 tests
As a result of repeating the process twice, the occurrence of seizure and rustle in the seal portion was extremely small, and the result was very good.
【００４９】比較例７ 供試鋼Ａを用いて作成した内径７インチのカップリング
１に対して、実施例７と同一方法によりねじ部３とメタ
ルシール部４に窒化処理層７．５μｍを設けた。次い
で、その表面を水系脱脂剤を用いて脱脂、水洗後に、実
施例５と同一の固体潤滑剤を塗布、同一の処理により厚
さ１５μｍの固体潤滑皮膜層を形成せしめて、比較例と
した。該比較材を実施例５と同様にコンパウンドグリー
スを塗布し、シール部４に４，０００ｋｇ／ｃｍ2 の面
圧を付与しつつ、継手部に対してメークアップ、ブレー
クアウトの繰り返しテストを行った。その結果、繰り返
しテスト８回目に固体潤滑皮膜層の摩耗、部分的な剥離
が著しく、評価試験を中断した。Comparative Example 7 With respect to the coupling 1 having an inner diameter of 7 inches prepared by using the test steel A, a nitriding layer of 7.5 μm was provided on the screw part 3 and the metal seal part 4 by the same method as in Example 7. It was Then, after degreasing the surface with an aqueous degreasing agent and washing with water, the same solid lubricant as in Example 5 was applied, and a solid lubricating coating layer having a thickness of 15 μm was formed by the same treatment to make a comparative example. Compound grease was applied to the comparative material in the same manner as in Example 5, and a repeated test of make-up and breakout was performed on the joint portion while applying a surface pressure of 4,000 kg / cm 2 to the seal portion 4. . As a result, wear and partial peeling of the solid lubricating coating layer were remarkable on the eighth repeat test, and the evaluation test was interrupted.
【００５０】実施例８ 供試鋼Ｂを用いて作成した内径７インチのカップリング
１を溶剤脱脂剤を用いて脱脂を行い、（１０％ＨＮＯ3
＋１％ＨＦ）系水溶液により室温で６０秒の酸洗、水洗
後、（２５０ｇ／ｌＦｅＳＯ4 ・７Ｈ2 Ｏ−４２ｇ／ｌ
ＦｅＣｌ2 ・４Ｈ2 Ｏ−２０ｇ／ｌＮＨ4 Ｃｌ）系組成
の電気めっき浴を用いて電流密度８Ａ／ｄｍ2 で５０秒
間の電解処理により、鉄めっき層を設けた。次いで、水
洗後直ちに、（９．５g/l Ｍｎ2+−０．１５g/l Ｎｉ2+
−０．４g/l Ｆｅ2+−３６g/l ＰＯ4 3- −６．１g/l Ｎ
Ｏ 3 - −０．３g/l Ｆ- ）系浴からなる燐酸マンガン系
化成処理浴を用いて、９０℃、１５分間の処理により窒
化処理層表面に燐酸マンガン系化成処理皮膜層を生成せ
しめた。次いで、カップリング１を１８０℃で１５分間
予熱加熱を行った後、平均粒子径４．３μｍの二硫化モ
リブデン粉末と平均粒子径２．５μｍのＣｕ粉末および
平均分子量１８，０００のポリアミドイミド樹脂を主要
成分として含有するとともに、 〔｛（平均粒子径４．３μｍの二硫化モリブデン粉末）
の８０重量％と（平均粒子径２．５μｍのＣｕ粉末）の
２０重量％からなる混合物＊｝の含有量〕／｛（平均分
子量１８ ，０００のポリアミドイミド樹脂）の含有
量｝＝１．０（重量比） （＊二硫化モリブデン粉末に対するＣｕ粉末の添加量；
約２５重量％） の組成比で構成される固体潤滑剤を塗布し、２７０℃で
２０分間の加熱処理を施して、固体潤滑皮膜層を設け
た。すなわち、本発明の処理によりカップリング１のね
じ部３ならびにメタルシール部４にそれぞれ鉄めっき層
１μｍ、燐酸マンガン系化成処理皮膜層２０μｍおよび
固体潤滑皮膜層２５μｍからなる三層皮膜層を評価材に
形成せしめた。実施例５と同様に、カップリング１およ
びピン２のねじ部３とメタルシール部４にコンパウンド
グリースを塗布しない条件で、シール部４に４，０００
ｋｇ／ｃｍ2 の面圧を付与しつつ、継手部に対してメー
クアップ、ブレークアウトの繰り返しテストを行った。
該テストを１１回繰り返し行った結果は、シール部の焼
き付き、ムシレの発生が殆ど生じなかったが、１２回目
のテストにおいて焼き付きとムシレがかなり生じた。Example 8 Coupling 1 having an inner diameter of 7 inches prepared from test steel B was degreased with a solvent degreasing agent (10% HNO 3
+ 1% HF) aqueous solution at room temperature for 60 seconds after pickling and water washing, then (250 g / l FeSO 4 .7H 2 O-42 g / l
An iron plating layer was provided by electrolytic treatment for 50 seconds at a current density of 8 A / dm 2 using an electroplating bath of FeCl 2 .4H 2 O-20 g / l NH 4 Cl) -based composition. Then, immediately after washing with water (9.5 g / l Mn 2+ -0.15 g / l Ni 2+
-0.4g / l Fe 2+ -36g / l PO 4 3- -6.1g / l N
A manganese phosphate-based chemical conversion coating layer was formed on the surface of the nitriding layer by treatment at 90 ° C. for 15 minutes using a manganese phosphate-based chemical conversion treatment bath consisting of O 3 − −0.3 g / l F − ) -based bath. . Next, after preheating the coupling 1 at 180 ° C. for 15 minutes, molybdenum disulfide powder having an average particle diameter of 4.3 μm, Cu powder having an average particle diameter of 2.5 μm, and a polyamideimide resin having an average molecular weight of 18,000 are used. In addition to containing it as a main component, [{(molybdenum disulfide powder with an average particle size of 4.3 μm)]
Content of a mixture *} of 80% by weight of 20% by weight of (Cu powder having an average particle diameter of 2.5 μm)] / {content of (polyamideimide resin having an average molecular weight of 18,000)} = 1.0 (Weight ratio) (* Addition amount of Cu powder to molybdenum disulfide powder;
A solid lubricant having a composition ratio of about 25% by weight) was applied and heat treatment was performed at 270 ° C. for 20 minutes to form a solid lubricating coating layer. That is, by the treatment of the present invention, a three-layer coating layer consisting of an iron plating layer of 1 μm, a manganese phosphate-based chemical conversion coating layer of 20 μm and a solid lubricating coating layer of 25 μm was used as an evaluation material on the screw portion 3 and the metal seal portion 4 of the coupling 1, respectively. Formed. As in the case of Example 5, the seal portion 4 was 4,000 under the condition that the compound grease was not applied to the screw portion 3 of the coupling 1 and the pin 2 and the metal seal portion 4.
While applying a surface pressure of kg / cm 2 , repeated tests of make-up and breakout were performed on the joint.
As a result of repeating the test 11 times, seizure of the seal portion and generation of swelling hardly occurred, but seizure and swelling occurred considerably in the 12th test.
【００５１】比較例８ 供試鋼Ｂを用いて作成した内径７インチのカップリング
１に対して、実施例８と同一の方法によりねじ部３とメ
タルシール部４に鉄めっき層１μｍを設けた。次いで、
実施例７と同一の固体潤滑剤を用いると共に、同一の処
理により厚さ２５μｍの固体潤滑皮膜層を形成せしめ
て、比較例とした。該比較材を実施例７と同様に、コン
パウンドグリースを塗布することなく、シール部４に
４，０００ｋｇ／ｃｍ2 の面圧を付与しつつ、継手部に
対してメークアップ、ブレークアウトの繰り返しテスト
を行った。その結果、繰り返しテスト４回目に固体潤滑
皮膜層の摩耗、剥離がかなり生じるとともに、焼き付き
とムシレの発生が著しく、評価試験を中断した。Comparative Example 8 With respect to the coupling 1 having an inner diameter of 7 inches prepared by using the sample steel B, the threaded portion 3 and the metal seal portion 4 were provided with an iron plating layer of 1 μm by the same method as in Example 8. . Then
The same solid lubricant as in Example 7 was used, and a solid lubricant film layer having a thickness of 25 μm was formed by the same treatment, and this was made a comparative example. Similar to Example 7, the comparative material was subjected to repeated make-up and break-out tests on the joint portion while applying a surface pressure of 4,000 kg / cm 2 to the seal portion 4 without applying compound grease. I went. As a result, abrasion and peeling of the solid lubricating coating layer were considerably generated at the fourth time of the repeated test, and seizure and rust were remarkably generated, so that the evaluation test was interrupted.
【００５２】実施例９ 供試鋼Ｂを用いて作成した内径７インチのカップリング
１を溶剤脱脂を行い、（１０％ＨＮＯ3 ＋１％ＨＦ）系
水溶液により室温で６０秒の酸洗、水洗後、（３３０ｇ
／ｌＦｅＳＯ4 ・７Ｈ2 Ｏ−１２ｇ／ｌＣｏＣｌ2 ・６
Ｈ2 Ｏ−１５ｇ／ｌＨ3 ＢＯ3 ）系めっき浴中で電流密
度２０Ａ／ｄｍ2 、４０秒間の電解処理により、Ｆｅ−
１．２％Ｃｏ系合金めっき層を設けた。次いで、水洗、
５％Ｈ2ＳＯ4 浴による１０秒の酸洗、水洗を行って、
濃度０．３ｇ／ｌの（マンガンコロイド−ピロリン酸ソ
ーダ）系前処理による室温で１分間の前処理を行い、
（９．５g/l Ｍｎ2+−０．１５g/l Ｎｉ2+−０．９g/l
Ｆｅ2+−３６g/l ＰＯ4 3- −６．１g/l ＮＯ 3 - −１．
０g/l Ｆ- ）系浴からなる燐酸マンガン系化成処理浴を
用いて、９０℃、１２．５分間の処理により燐酸マンガ
ン系化成処理皮膜層を設けた。さらに、カップリング１
を１６０℃で２０分間予熱加熱を行った後、平均粒子径
３．５μｍの二硫化モリブデン粉末、平均粒子径０．８
μｍのＣｕ粉末、平均粒子径５．０μｍのＺｎ粉末およ
び平均分子量１８，０００のポリアミドイミド樹脂を主
要成分として含有するとともに、 〔｛（平均粒子径３．５μｍの二硫化モリブデン粉末）
の７６重量％と（平均粒子径０．８μｍのＣｕ粉末）の
１２重量％と（平均粒子径５．０μｍのＺｎ粉末）の１
２重量％からなる混合物＊｝の含有量〕／｛（平均分子
量１８，０００のポリアミドイミド樹脂）の含有量｝＝
１．２（重量比） （＊二硫化モリブデン粉末に対するＣｕ，Ｚｎ粉末の添
加量；Ｃｕ粉末約１５．８重量％、Ｚｎ粉末約１５．８
重量％） の組成比で構成される固体潤滑剤を塗布し、２５０℃で
２５分間の加熱処理を施して、固体潤滑皮膜層を設け
た。すなわち、本発明の処理によりカップリング１のね
じ部３ならびにメタルシール部４にそれぞれＦｅ−１．
２％Ｃｏ系合金層２．０μｍ、燐酸マンガン系化成処理
皮膜層１０μｍおよび固体潤滑皮膜層２１μｍからなる
三層皮膜層を評価材に形成せしめた。実施例１と同様の
コンパウンドグリースをピン２のねじ部３とメタルシー
ル部４に塗布し、シール部４に４，０００ｋｇ／ｃｍ2
の面圧を付与しつつ、継手部に対してメークアップ、ブ
レークアウトの繰り返しテストを行った。該テストを１
５回繰り返し行った結果は、シール部の焼き付き、ムシ
レの発生が極めて少なく、非常に良好であった。Example 9 Coupling 1 having an inner diameter of 7 inches prepared from test steel B was degreased with a solvent, and then pickled with a (10% HNO 3 + 1% HF) system aqueous solution at room temperature for 60 seconds and then washed with water. , (330g
/ LFeSO 4 · 7H 2 O- 12g / lCoCl 2 · 6
H 2 O-15 g / lH 3 BO 3 ) -based plating bath was subjected to electrolytic treatment at a current density of 20 A / dm 2 for 40 seconds to produce Fe-
A 1.2% Co-based alloy plating layer was provided. Then wash with water,
After pickling for 10 seconds and washing with water in a 5% H 2 SO 4 bath,
Pretreatment with a concentration of 0.3 g / l (manganese colloid-sodium pyrophosphate) pretreatment at room temperature for 1 minute,
(9.5 g / l Mn 2+ -0.15 g / l Ni 2+ -0.9 g / l
Fe 2+ -36g / l PO 4 3- -6.1g / l NO 3 - -1.
A manganese phosphate-based chemical conversion coating layer was provided by treatment at 90 ° C. for 12.5 minutes using a manganese phosphate-based chemical conversion treatment bath consisting of a 0 g / l F − ) -based bath. Furthermore, coupling 1
Was preheated at 160 ° C. for 20 minutes, and then molybdenum disulfide powder having an average particle diameter of 3.5 μm and an average particle diameter of 0.8
In addition to containing Cu powder of μm, Zn powder of average particle size 5.0 μm and polyamideimide resin of average molecular weight 18,000 as main components, [{(molybdenum disulfide powder of average particle size 3.5 μm)]
76% by weight, 12% by weight (Cu powder having an average particle diameter of 0.8 μm) and 1% (Zn powder having an average particle diameter of 5.0 μm)
2% by weight mixture *} content] / {(polyamideimide resin having an average molecular weight of 18,000) content} =
1.2 (weight ratio) (* Amount of Cu, Zn powder added to molybdenum disulfide powder; Cu powder about 15.8 wt%, Zn powder about 15.8)
% By weight), and a solid lubricant film layer was formed by applying a solid lubricant having a composition ratio of 50% by weight to a heat treatment at 250 ° C. for 25 minutes. That is, according to the processing of the present invention, the screw portion 3 and the metal seal portion 4 of the coupling 1 are respectively made of Fe-1.
A three-layer coating layer consisting of a 2% Co-based alloy layer 2.0 µm, a manganese phosphate-based chemical conversion coating layer 10 µm, and a solid lubricating coating layer 21 µm was formed on the evaluation material. The same compound grease as in Example 1 was applied to the screw portion 3 and the metal seal portion 4 of the pin 2 and the seal portion 4 was 4,000 kg / cm 2.
Repeated tests of make-up and breakout were performed on the joint while applying the surface pressure of. The test 1
As a result of repeating 5 times, the seizure of the seal portion and the generation of rustle were extremely small, and the result was very good.
【００５３】比較例９ 供試鋼Ｂを用いて作成した内径７インチのカップリング
１に対して、実施例６と同一の方法による脱脂、酸洗処
理後に、（１５０ｇ／ｌＦｅＳＯ4 ・７Ｈ2 Ｏ−１００
ｇ／ｌＣｏＣｌ2 ・６Ｈ2 Ｏ−２０ｇ／ｌＨ3 ＢＯ3 ）
系めっき浴中で電流密度２０Ａ／ｄｍ2 、４０秒間の電
解処理により、Ｆｅ−１５％Ｃｏ系合金めっき層を設け
た。次いで、実施例９と同一の方法による燐酸マンガン
系化成処理皮膜層および固体潤滑皮膜層の形成処理を実
施し、比較例とした。すなわち、上記処理により、比較
材のねじ部３とメタルシール部４には、Ｆｅ−１５％Ｃ
ｏ系合金めっき層２０μｍ、不均一、まばらに生成され
た燐酸マンガン系化成処理皮膜層および実施例９と同一
組成で構成される厚さ２１μｍの固体潤滑皮膜層が形成
された。該比較材を実施例９と同様にコンパウンドグリ
ースを塗布し、シール部４に４，０００ｋｇ／ｃｍ2 の
面圧を付与しつつ、継手部に対してメークアップ、ブレ
ークアウトの繰り返しテストを行った。その結果、繰り
返しテスト７回目のテストにおいて、皮膜層の剥離が著
しく、評価試験を中断した。以上の通り、本発明の窒化
処理層、鉄めっき層あるいは鉄合金めっき層からなる下
地被覆層、燐酸マンガン系化成処理皮膜層および固体潤
滑皮膜層の三層皮膜層で構成された高Ｃｒ合金鋼製の鋼
管継手は、皮膜の密着性、皮膜強度ならびに潤滑性能な
らびに耐久性に著しく優れる。そのため、メークアッ
プ、ブレークアウトの繰り返し回数の増大に対して、皮
膜の焼き付きおよびムシレの発生が起こり難く、長期間
に亘る使用条件下での耐ゴーリング性に著しく優れるこ
とが判かる。Comparative Example 9 Coupling 1 having an inner diameter of 7 inches prepared using test steel B was subjected to degreasing and pickling treatment in the same manner as in Example 6 and then (150 g / l FeSO 4 .7H 2 O -100
g / lCoCl 2 · 6H 2 O -20g / lH 3 BO 3)
A Fe-15% Co-based alloy plating layer was provided by electrolytic treatment for 40 seconds at a current density of 20 A / dm 2 in a system-based plating bath. Then, the manganese phosphate-based chemical conversion treatment coating layer and the solid lubricating coating layer were formed by the same method as in Example 9 to give a comparative example. That is, by the above treatment, Fe-15% C was added to the screw portion 3 and the metal seal portion 4 of the comparative material.
An o-based alloy plating layer of 20 μm, a nonuniform, sparsely formed manganese phosphate-based chemical conversion coating layer, and a solid lubricating coating layer of 21 μm in thickness having the same composition as in Example 9 were formed. Compound grease was applied to the comparative material in the same manner as in Example 9, and the joint portion was repeatedly subjected to make-up and break-out tests while applying a surface pressure of 4,000 kg / cm 2 to the seal portion 4. . As a result, the peeling of the coating layer was remarkable in the seventh test of the repeated test, and the evaluation test was interrupted. As described above, the high Cr alloy steel composed of the nitriding layer of the present invention, the undercoating layer formed of the iron plating layer or the iron alloy plating layer, the manganese phosphate-based chemical conversion coating layer and the solid lubricating coating layer The steel pipe joint made of steel is remarkably excellent in coating adhesion, coating strength, lubrication performance and durability. Therefore, it can be seen that even if the number of repetitions of make-up and break-out is increased, it is difficult for the film to be seized and rustle to occur, and the galling resistance under a long-term use condition is remarkably excellent.
【００５４】[0054]
【発明の効果】以上のように、本発明の高Ｃｒ合金鋼製
の鋼管継手は、１０％以上のＣｒを含有する高Ｃｒ合金
鋼に対して皮膜の生成が困難な燐酸マンガン系化成処理
皮膜層の下地窒化処理層、下地鉄めっき層あるいは鉄合
金めっき層による均一な生成と必須条件として二硫化モ
リブデン粉末、あるいはこれにＣｕ、Ｚｎ粉末の一種ま
たは二種およびエポキシ樹脂、フラン樹脂、ポリアミド
イミド樹脂の中より選定した一種の有機樹脂を含有して
構成される靱性、硬度ならびに潤滑性能に優れる固体潤
滑皮膜層の形成により、三層皮膜層が設けられる。その
ため、本発明の方法により、高Ｃｒ合金鋼製鋼管継手に
設けられた表面処理皮膜層は、各皮膜層の相乗効果によ
り密着性、皮膜強度、潤滑性および耐久性に著しく優れ
る。従って、本発明の方法による鋼管継手は、高面圧下
での摺動が繰り返し受ける使用条件、すなわちメークア
ップ、ブレークアウトが繰り返し行われる条件下におい
て、鋼管継手部のメタル同士の接触によるシール部およ
びねじ部の焼き付きとムシレの発生防止、特に繰り返し
回数の増加に対する耐久性に著しく優れる。すなわち、
本発明の方法により、長期間に亘る使用に対応可能な耐
ゴーリング性に極めて優れる高Ｃｒ合金鋼製鋼管継手が
得られる。As described above, in the steel pipe joint made of the high Cr alloy steel of the present invention, it is difficult to form a film on the high Cr alloy steel containing 10% or more of Cr. Layer, nitriding layer, iron plating layer or iron alloy plating layer for uniform formation and as essential condition molybdenum disulfide powder, or one or two of Cu and Zn powder and epoxy resin, furan resin, polyamideimide A three-layer coating layer is formed by forming a solid lubricating coating layer that is excellent in toughness, hardness, and lubricating performance and is composed of one type of organic resin selected from the resins. Therefore, the surface treatment coating layer provided on the steel pipe joint made of high Cr alloy steel by the method of the present invention is remarkably excellent in adhesion, coating strength, lubricity and durability due to the synergistic effect of each coating layer. Therefore, the steel pipe joint according to the method of the present invention has a seal portion and a seal portion due to contact between metals of the steel pipe joint portion under a use condition in which sliding under high surface pressure is repeatedly received, that is, a condition where makeup and breakout are repeatedly performed. Prevents the seizure of the screw part and the occurrence of rustling, and is particularly excellent in durability against an increase in the number of repetitions. That is,
The method of the present invention makes it possible to obtain a steel pipe joint made of high Cr alloy steel which is extremely excellent in galling resistance and can be used for a long period of time.
【図１】本発明を適用した継手構成部材を示す図、FIG. 1 is a view showing a joint component member to which the present invention is applied,
【図２】各継手構成部材の組立構成を示す図である。FIG. 2 is a diagram showing an assembly configuration of each joint component member.
１ カップリング ２ ピン ３ ねじ部 ４ メタル−メタルシール部 1 Coupling 2 Pin 3 Screw part 4 Metal-metal seal part
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１０Ｎ 50:08 (72)発明者 岡 正春 福岡県北九州市戸畑区飛幡町１番１号 新 日本製鐵株式会社八幡製鐵所内 (72)発明者 永吉 治之 福岡県北九州市戸畑区飛幡町１番１号 新 日本製鐵株式会社八幡製鐵所内 (72)発明者 中島 晃 福岡県北九州市戸畑区飛幡町１番１号 新 日本製鐵株式会社八幡製鐵所内 (72)発明者 樋口 征順 福岡県北九州市戸畑区沢見一丁目７−５− 208 (72)発明者 井上 隆介 福岡県北九州市小倉北区熊谷２−28−12 (72)発明者 秋山 寿雄 栃木県下都賀郡野木町野渡953 (72)発明者 相良 和美 茨城県猿島郡境町長井戸1686−25─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Internal reference number FI Technical display location C10N 50:08 (72) Inventor Masaharu Oka 1-1 No. 1 Hibatacho, Tobata-ku, Kitakyushu, Fukuoka Japan Inside the Yawata Steel Works Co., Ltd. (72) Haruyuki Nagayoshi, Inventor Haruyuki Nagayoshi 1-1 Hibahata-cho, Tobata-ku, Kitakyushu City, Fukuoka Prefecture (72) Inside the Yawata Works (72) Inventor Akira Nakajima Tobata-ku, Kitakyushu City, Fukuoka Prefecture No. 1 Tobamachi, Hachiman Works, Nippon Steel Co., Ltd. (72) Inventor Seijun Higuchi, 7-5-208, Sawami, Tobata-ku, Kitakyushu, Kitakyushu, Fukuoka (72) Ryusuke Inoue, Kokura, Kitakyushu, Fukuoka 2-28-12 Kumagaya, Kita-ku (72) Inventor Toshio Akiyama 953 Noto, Nogi-cho, Shimotsuga-gun, Tochigi Prefecture (72) Inventor Kasumi Sagara Nagaido, Sakai-cho, Sarushima-gun, Ibaraki Prefecture 1686-25
Claims (4)
有量の合金鋼からなる油井管の継手部分のねじ部および
メタルシール部に、厚さ１μｍ〜２０μｍの窒化処理
層、厚さ０．５μｍ〜１５μｍの鉄めっき層あるいは１
０％以下のＮｉ，Ｃｏの一種または二種を含有する鉄合
金めっき層の下地処理層と厚さ５μｍ〜２５μｍの燐酸
マンガン系化成処理皮膜層、さらに二硫化モリブデン粉
末とエポキシ樹脂、フラン樹脂、ポリアミドイミド樹脂
の中より選定した一種を必須成分として含有し、 0.5 ≦｛（二硫化モリブデン粉末）の含有量｝／｛（エ
ポキシ樹脂、フラン樹脂、ポリアミドイミド樹脂の中よ
り選定した一種）の含有量｝≦３．０（重量比） の組成比で構成される固体潤滑剤を塗布し、加熱処理を
施して、厚さ１０μｍ〜４５μｍの固体潤滑皮膜層から
なる三層皮膜層を設けることを特徴とする耐ゴーリング
性に優れた高Ｃｒ合金鋼製鋼管継手の表面処理方法。1. A nitriding layer having a thickness of 1 μm to 20 μm and a thickness of 0 at a thread portion and a metal seal portion of a joint portion of an oil country tubular good made of an alloy steel having a high Cr content of 10 wt% or more. Iron plating layer of 1 to 5 μm to 15 μm or 1
A base treatment layer of an iron alloy plating layer containing 0% or less of one or two kinds of Ni and Co, a manganese phosphate-based chemical conversion treatment coating layer having a thickness of 5 μm to 25 μm, molybdenum disulfide powder and an epoxy resin, a furan resin, Contains one selected from polyamide-imide resins as an essential component, and contains 0.5 ≤ {content of (molybdenum disulfide powder)} / {(one selected from epoxy resin, furan resin, polyamide-imide resin) Amount of solid lubricant having a composition ratio of ≦ 3.0 (weight ratio) is applied and heat treatment is performed to form a three-layer coating layer consisting of a solid lubricating coating layer having a thickness of 10 μm to 45 μm. A surface treatment method for a steel pipe joint made of a high Cr alloy steel, which is excellent in galling resistance.
有量の合金鋼からなる油井管の継手部分のねじ部および
メタルシール部に、厚さ１μｍ〜２０μｍの窒化処理
層、厚さ０．５μｍ〜１５μｍの鉄めっき層あるいは１
０％以下のＮｉ，Ｃｏの一種または二種を含有する鉄合
金めっき層の下地処理層と厚さ５μｍ〜２５μｍの燐酸
マンガン系化成処理皮膜層、さらに二硫化モリブデン粉
末と該粉末に対して１０重量％〜５０重量％のＣｕ、Ｚ
ｎ粉末の一種または二種およびエポキシ樹脂、フラン樹
脂、ポリアミドイミド樹脂の中より選定した一種を必須
成分として含有し、 0.5 ≦｛（二硫化モリブデン粉末とＣｕ、Ｚｎ粉末の一
種または二種）の含有量｝／｛（エポキシ樹脂、フラン
樹脂、ポリアミドイミド樹脂の中より選定した一種）の
含有量｝≦ 3.0（重量比） の組成比で構成される固体潤滑剤を塗布し、加熱処理を
施して、厚さ１０μｍ〜４５μｍの固体潤滑皮膜層から
なる三層皮膜層を設けることを特徴とする耐ゴーリング
性に優れた高Ｃｒ合金鋼製鋼管継手の表面処理方法。2. A nitriding layer having a thickness of 1 μm to 20 μm and a thickness of 0 at a thread portion and a metal seal portion of a joint portion of an oil country tubular good made of an alloy steel having a high Cr content of 10 wt% or more. Iron plating layer of 1 to 5 μm to 15 μm or 1
A base treatment layer of an iron alloy plating layer containing 0% or less of Ni or Co, a manganese phosphate-based chemical conversion treatment coating layer having a thickness of 5 μm to 25 μm, and molybdenum disulfide powder and 10 to the powder. Wt% to 50 wt% Cu, Z
One or two kinds of n powder and one selected from epoxy resin, furan resin and polyamide-imide resin are contained as an essential component, and 0.5 ≦ {(one or two kinds of molybdenum disulfide powder and Cu, Zn powder) Content solid} / {(content selected from epoxy resin, furan resin, polyamide-imide resin)} ≦ 3.0 (weight ratio) is applied to the solid lubricant, and heat treatment is applied. And a surface treatment method for a steel pipe joint made of high Cr alloy steel excellent in galling resistance, which is characterized in that a three-layer coating layer composed of a solid lubricating coating layer having a thickness of 10 μm to 45 μm is provided.
せしめる固体潤滑剤の必須成分である二硫化モリブデン
粉末の粒子径がフィッシャー法による測定により０．４
５μｍ〜１０μｍの範囲、また分子量が２，０００〜１
０，０００の範囲のエポキシ樹脂、分子量が１５０〜２
５０の範囲のフラン樹脂、分子量が１０，０００〜２
５，０００の範囲のポリアミドイミド樹脂の中より選定
した一種で構成されることを特徴とする請求項１に記載
の方法による耐ゴーリング性に優れた高Ｃｒ合金鋼製鋼
管継手の表面処理方法。3. The particle size of the molybdenum disulfide powder, which is an essential component of the solid lubricant for forming the solid lubricating coating layer according to claim 1, is 0.4 as measured by the Fischer method.
Range of 5 μm to 10 μm, and molecular weight of 2,000 to 1
Epoxy resin in the range of 10,000, molecular weight 150-2
Furan resin in the range of 50, molecular weight 10,000 to 2
The surface treatment method for a steel pipe joint made of high Cr alloy steel excellent in galling resistance according to the method according to claim 1, wherein the surface treatment method is constituted by one selected from polyamide-imide resins in the range of 5,000.
せしめる固体潤滑剤の必須成分である二硫化モリブデン
粉末の粒子径がフィッシャー法による測定により０．４
５μｍ〜１０μｍの範囲、ＣｕあるいはＺｎ粉末の粒子
径が０．５μｍ〜１０μｍの範囲の一種または二種、ま
た分子量が２，０００〜１０，０００の範囲のエポキシ
樹脂、分子量が１５０〜２５０の範囲のフラン樹脂、分
子量が１０，０００〜２５，０００の範囲のポリアミド
イミド樹脂の中より選定した一種で構成されることを特
徴とする請求項２に記載の方法による耐ゴーリング性に
優れた高Ｃｒ合金鋼製鋼管継手の表面処理方法。4. The molybdenum disulfide powder, which is an essential component of the solid lubricant for forming the solid lubricating coating layer according to claim 2, has a particle size of 0.4 by a Fischer method.
5 to 10 μm range, one or two kinds of particles of Cu or Zn powder having a particle size range of 0.5 to 10 μm, epoxy resin having a molecular weight of 2,000 to 10,000, and molecular weight of 150 to 250 3. The high Cr excellent in galling resistance by the method according to claim 2, wherein the furan resin is a kind selected from among polyamideimide resins having a molecular weight of 10,000 to 25,000. Surface treatment method for alloy steel pipe fittings.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23985194A JPH08105582A (en) | 1994-10-04 | 1994-10-04 | Surface treatment method of steel pipe coupling made of high chromium alloy steel having excellent anti-galling property |
| US08/809,344 US6027145A (en) | 1994-10-04 | 1995-10-04 | Joint for steel pipe having high galling resistance and surface treatment method thereof |
| EP95933616A EP0786616B9 (en) | 1994-10-04 | 1995-10-04 | Steel pipe joint having high galling resistance and surface treatment method thereof |
| CN95195507A CN1159851A (en) | 1994-10-04 | 1995-10-04 | Steel pipe joint having high galling resistance and surface treatment method thereof |
| PCT/JP1995/002034 WO1996010710A1 (en) | 1994-10-04 | 1995-10-04 | Steel pipe joint having high galling resistance and surface treatment method thereof |
| DE1995627635 DE69527635T4 (en) | 1994-10-04 | 1995-10-04 | STEEL TUBE CLUTCH WITH INCREASED ABRASION SAFETY AND METHOD FOR SURFACE TREATMENT |
| NO19971523A NO328656B1 (en) | 1994-10-04 | 1997-04-03 | Stalror compound with high demolition resistance, as well as method of surface treatment thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23985194A JPH08105582A (en) | 1994-10-04 | 1994-10-04 | Surface treatment method of steel pipe coupling made of high chromium alloy steel having excellent anti-galling property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08105582A true JPH08105582A (en) | 1996-04-23 |
Family
ID=17050823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23985194A Pending JPH08105582A (en) | 1994-10-04 | 1994-10-04 | Surface treatment method of steel pipe coupling made of high chromium alloy steel having excellent anti-galling property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08105582A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000186797A (en) * | 1998-12-22 | 2000-07-04 | Daihatsu Motor Co Ltd | Plug |
| WO2003102457A1 (en) * | 2002-05-31 | 2003-12-11 | Sumitomo Metal Industries, Ltd. | Screw joint for steel pipe |
| US6679526B2 (en) | 1999-08-27 | 2004-01-20 | Sumitomo Metal Industries, Ltd. | Threaded joint for an oil well pipe |
| US6746057B2 (en) | 2001-01-25 | 2004-06-08 | Sumitomo Metal Industries, Ltd. | Threaded joint for steel pipes having improved galling resistance and rust-preventing properties |
| WO2005098300A1 (en) | 2004-04-06 | 2005-10-20 | Sumitomo Metal Industries, Ltd. | Threaded joint for steel pipe and process for producing the same |
| JP2006515394A (en) * | 2003-02-13 | 2006-05-25 | テナリス コネクションズ アクチェンゲゼルシャフト | Threaded fittings for pipes |
| US7666266B2 (en) | 2003-12-04 | 2010-02-23 | Sumitomo Metal Industries, Ltd. | Surface conditioning prior to chemical conversion treatment of a steel member |
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-
1994
- 1994-10-04 JP JP23985194A patent/JPH08105582A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000186797A (en) * | 1998-12-22 | 2000-07-04 | Daihatsu Motor Co Ltd | Plug |
| US6679526B2 (en) | 1999-08-27 | 2004-01-20 | Sumitomo Metal Industries, Ltd. | Threaded joint for an oil well pipe |
| US6746057B2 (en) | 2001-01-25 | 2004-06-08 | Sumitomo Metal Industries, Ltd. | Threaded joint for steel pipes having improved galling resistance and rust-preventing properties |
| US7360798B2 (en) | 2002-05-31 | 2008-04-22 | Sumitomo Metal Industries, Ltd. | Threaded joint for steel pipes |
| WO2003102457A1 (en) * | 2002-05-31 | 2003-12-11 | Sumitomo Metal Industries, Ltd. | Screw joint for steel pipe |
| JP2006515394A (en) * | 2003-02-13 | 2006-05-25 | テナリス コネクションズ アクチェンゲゼルシャフト | Threaded fittings for pipes |
| US7666266B2 (en) | 2003-12-04 | 2010-02-23 | Sumitomo Metal Industries, Ltd. | Surface conditioning prior to chemical conversion treatment of a steel member |
| WO2005098300A1 (en) | 2004-04-06 | 2005-10-20 | Sumitomo Metal Industries, Ltd. | Threaded joint for steel pipe and process for producing the same |
| JP2005299693A (en) * | 2004-04-06 | 2005-10-27 | Sumitomo Metal Ind Ltd | Screw joint for steel pipe and its manufacturing method |
| JP4599874B2 (en) * | 2004-04-06 | 2010-12-15 | 住友金属工業株式会社 | Threaded joint for oil well pipe and method for manufacturing the same |
| US7866706B2 (en) | 2004-04-06 | 2011-01-11 | Sumitomo Metal Industries, Ltd. | Threaded joint for steel pipe |
| US8857857B2 (en) | 2006-09-14 | 2014-10-14 | Nippon Steel & Sumitomo Metal Corporation | Threaded joint for steel pipes |
| WO2017110685A1 (en) * | 2015-12-25 | 2017-06-29 | 新日鐵住金株式会社 | Threaded joint for pipe, and manufacturing method of threaded joint for pipe |
| JPWO2017110685A1 (en) * | 2015-12-25 | 2018-08-09 | 新日鐵住金株式会社 | Threaded joint for pipe and method for manufacturing threaded joint for pipe |
| CN108474502A (en) * | 2015-12-25 | 2018-08-31 | 新日铁住金株式会社 | The manufacturing method of pipe screw joint and pipe screw joint |
| US10359133B2 (en) | 2015-12-25 | 2019-07-23 | Nippon Steel & Sumitomo Metal Corporation | Threaded connection for pipe or tube and method of producing the threaded connection for pipe or tube |
| EA034137B1 (en) * | 2015-12-25 | 2020-01-09 | Ниппон Стил Корпорейшн | Threaded connection for pipe or tube and method of producing the threaded connection for pipe or tube |
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