TW201615295A - Opened top for seamless pipe manufacturing - Google Patents
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本發明是關於一種藉由孟內斯曼(Mannesmann)穿孔法製作無縫管中所使用之用以製造無縫管之穿孔頂頭，尤其是關於經長壽命化之穿孔頂頭。 BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a perforated plug for use in making seamless tubes for use in seamless tubes by Mannesmann perforation, and more particularly to perforated plugs that have a long life.
油井管主要以孟內斯曼穿孔法製造。穿孔所使用之穿孔頂頭於工具中暴露於最嚴酷的使用條件下。近年來，於無縫管中使用熱作下之變形阻力較高之不鏽鋼、高合金，因此穿孔頂頭之壽命越來越短，甚至極限為1道次穿孔。 Oil well pipes are mainly manufactured by the Mennesmann perforation method. The perforated plug used for perforation is exposed to the tool under the most severe conditions of use. In recent years, stainless steel and high alloys with high deformation resistance under hot work have been used in the seamless pipe, so the life of the piercing plug is getting shorter and shorter, and even the limit is one pass perforation.
關於穿孔頂頭之延長壽命化，有人提出有PTA(Plasma Transferred Arc、電漿轉移電弧)被覆、藉由電弧噴塗之表面改質之壽命改善方法。 With regard to the prolonged life of the perforated plug, a life improvement method of PTA (Plasma Transferred Arc, plasma transfer arc) coating and surface modification by arc spraying has been proposed.
專利文獻1中揭示有一種穿孔軋延用頂頭，其藉由於母材之表面電弧噴塗以Fe為主成分之鐵線材，而形成由Fe3O4或FeO等氧化物及Fe(金屬)構成之被膜。藉由該被膜可實現優異之遮熱性及抗燒黏性，獲得長壽命之穿孔頂頭。 Patent Document 1 discloses a piercing and rolling head which is formed by an arc wire of Fe 3 O 4 or FeO and Fe (metal) by arc-spraying a surface of Fe on the surface of a base material. Membrane. By using the film, excellent heat shielding and anti-scratch resistance can be achieved, and a long-life perforated plug can be obtained.
專利文獻2主要是關於專利文獻1之素材之改良， 揭示有鑄造後、經脫氫處理之高硬度之素材。 Patent Document 2 mainly relates to improvement of the material of Patent Document 1, It reveals the high hardness material after casting and dehydrogenation treatment.
此等發明雖然成功地使穿孔頂頭長壽命化，但存在成本較高、品質不一致等問題。 Although these inventions have succeeded in prolonging the life of the perforated plug, there are problems such as high cost and inconsistent quality.
作為先前以來之延長壽命化之方法，有人提出有於表面賦予氧化皮膜之發明。 As a method for prolonging the life of the prior art, there has been proposed an invention in which an oxide film is provided on the surface.
專利文獻3揭示一種於表面形成有氧化皮膜之熱作加工用工具。氧化皮膜自外層起為赤鐵礦、磁鐵礦、方鐵礦，若磁鐵礦有40體積%以上，則使壽命延長。 Patent Document 3 discloses a hot working tool in which an oxide film is formed on the surface. The oxide film is hematite, magnetite, and galena from the outer layer, and if the magnetite is 40% by volume or more, the life is prolonged.
專利文獻4揭示一種可使工具壽命延長之熱作製管工具之製造方法。專利文獻4揭示有：模具鑄造之凝固組織與砂模相較為微細，其結果於基體表面生成之氧化皮膜因基地組織之微細化而變得緻密，耐剝離性及耐燒黏性提高。 Patent Document 4 discloses a method of manufacturing a hot pipe making tool which can extend the life of the tool. Patent Document 4 discloses that the solidified structure and the sand mold phase of the mold casting are finer, and as a result, the oxide film formed on the surface of the substrate is densified by the refinement of the base structure, and the peeling resistance and the scratch resistance are improved.
專利文獻5揭示一種即使將變形阻力較高之材料製管之情形，亦具有較高之使用壽命之熱作製管用工具。專利文獻5中藉由大量添加Mo、W而確保高溫變形性，藉由Ni、W而改善皮膜之耐剝離性、耐摩耗性。 Patent Document 5 discloses a tool for hot work pipe having a high service life even in the case of a pipe made of a material having a high deformation resistance. In Patent Document 5, high-temperature deformability is ensured by adding a large amount of Mo and W, and the peeling resistance and abrasion resistance of the film are improved by Ni and W.
專利文獻6揭示一種具有穩定且較長工具壽命之無接縫鋼管穿孔軋延用工具。於專利文獻6中，將形成於基材側之皮膜層形成為與鐵氧體複雜地纏繞之網狀皮膜層，進一步使自皮膜層與基材之界面朝基材側沿深度方向500μm之範圍之組織成為以面積率計具有50%以上之肥粒鐵相之組織，抑制皮膜層之剝離或磨損，提高穿孔軋延用工具之壽命。 Patent Document 6 discloses a tool for piercing and rolling a seamless steel pipe having a stable and long tool life. In Patent Document 6, the film layer formed on the substrate side is formed into a mesh film layer which is densely wound with the ferrite, and further, the interface between the film layer and the substrate is in the range of 500 μm in the depth direction toward the substrate side. The structure is a structure having an iron particle phase of 50% or more in area ratio, suppresses peeling or abrasion of the film layer, and improves the life of the tool for piercing and rolling.
[專利文獻1]國際公開第2009/057471號 [Patent Document 1] International Publication No. 2009/057471
[專利文獻2]國際公開第2014/050975號 [Patent Document 2] International Publication No. 2014/050975
[專利文獻3]日本特開平8-193241號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 8-193241
[專利文獻4]日本特開平8-300014號公報 [Patent Document 4] Japanese Patent Laid-Open No. Hei 8-300014
[專利文獻5]日本特開平7-60314號公報 [Patent Document 5] Japanese Patent Laid-Open No. Hei 7-60314
[專利文獻6]日本特開2003-129184號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2003-129184
以穿孔頂頭之長壽命化為目的，迄今有很多的發明被完成，但依然無法獲得滿足不鏽鋼、高合金之穿孔壽命之穿孔頂頭。 In order to achieve the long life of the perforated plug, many inventions have been completed so far, but it is still impossible to obtain a perforated plug that satisfies the perforation life of stainless steel and high alloy.
穿孔頂頭之損傷是由於(1)頭部熔損及燒黏、及(2)軀體部之皺紋及剜傷。對於任一種損傷，皆會影響高溫強度及皮膜性狀(密著性、厚度)。更進一步地，作為其他損傷則有(3)縱向裂痕(割損)。對於此損傷會影響延性、韌性及耐熱龜裂性。 The damage to the perforated head is due to (1) melt damage and burnt of the head, and (2) wrinkles and bruises on the body. For any type of damage, it affects high temperature strength and film properties (adhesion, thickness). Further, as other damages, there are (3) longitudinal cracks (cuts). For this damage, it affects ductility, toughness and heat crack resistance.
若不能同時解決此等3個問題，則無法達成穿孔頂頭之長壽命化。本發明之目的是提供一種用以製造無縫管之穿孔頂頭，其藉由(1)提高高溫強度、(2)改善皮膜性狀(密著性、厚度)、(3)提高延性、韌性，改善耐熱龜裂性，從而長壽命化。 If these three problems cannot be solved at the same time, the long life of the piercing plug cannot be achieved. The object of the present invention is to provide a perforated plug for manufacturing a seamless pipe, which improves (1) high temperature strength, (2) improves film properties (adhesion, thickness), (3) improves ductility, toughness, and improves It has heat-resistant cracking properties and thus long life.
本發明者們對使穿孔頂頭長壽命化之方法專心致力於研究。其結果發現：藉由選定適當的成分組成、使淬火性提高、使頂頭之組織成為適當量之碳化物及麻田散鐵，可大幅改善高溫強度。 The present inventors focused on research on a method for prolonging the life of a perforated plug. As a result, it has been found that the high-temperature strength can be greatly improved by selecting an appropriate composition of the composition, improving the hardenability, and making the structure of the plug into an appropriate amount of carbide and 麻田散铁.
於製造穿孔頂頭之最後步驟中，為了賦予潤滑性、絕熱性而實施賦予皮膜之處理，於生成皮膜之後，為防止皮膜之剝離以冷卻速度20~50℃/小時進行爐冷。本發明者們發現：藉由以此冷卻速度使碳化物析出且選定進行麻田散鐵變態之適當成分組成，可使高溫強度提升。 In the final step of producing the perforated plug, a film is applied to impart lubricity and heat insulation, and after the film is formed, furnace cooling is performed at a cooling rate of 20 to 50 ° C / hour to prevent peeling of the film. The present inventors have found that high temperature strength can be improved by precipitating carbides at this cooling rate and selecting an appropriate component composition for metamorphizing the granulated iron.
又，本發明者們發現：皮膜之密著性與頂頭組織之晶粒粗細度有關。 Moreover, the inventors have found that the adhesion of the film is related to the grain thickness of the head tissue.
於穿孔頂頭中使用模具或砂模鑄造而成之鑄鋼品。鑄造後之晶粒達數百μm~數十mm之粗大。於經肥粒鐵-波來鐵變態之穿孔頂頭中，為了賦予皮膜之熱處理(沃斯田鐵變態)所致之粗大的晶粒將變得微細。然而，經麻田散鐵變態之穿孔頂頭，即使為賦予皮膜而進行沃斯田鐵變態，仍會因所謂的”記憶效應”而使晶粒保持粗大，與先前之穿孔頂頭相比，皮膜之密著性下降。 A cast steel product cast in a perforated plug using a mold or a sand mold. The grain after casting is as large as several hundred μm to several tens of mm. In the perforated plug of the ferrite-ferrite metamorphosis, the coarse grains due to the heat treatment of the coating (Worthfield iron metamorphosis) will become fine. However, the perforated plug of the metamorphic iron of the smectite iron, even if the Worthite iron metamorphosis is imparted to the film, the grain remains thick due to the so-called "memory effect", and the film is dense compared with the previous piercing head. The decline in sex.
僅反覆進行退火(annealing)時，具有本發明之成分組成之合金只會重複沃斯田鐵→麻田散鐵→沃斯田鐵→麻田散鐵變態，晶粒仍然保持鑄造之數百μm~數十mm之粗大晶粒。 When annealing is repeated only, the alloy having the composition of the present invention will only repeat the Vostian iron→Mada loose iron→Worthian iron→Mada iron metamorphosis, and the crystal grains remain hundreds of μm of casting. Large grain of ten mm.
於圖1、圖2分別顯示藉由賦予皮膜之加熱、爐冷 處理而經肥粒鐵-波來鐵變態之穿孔頂頭與經麻田散鐵變態之穿孔頂頭之晶粒照片。肥粒鐵-波來鐵組織之頂頭之晶粒達20μm之微細，但經麻田散鐵變態之頂頭之晶粒則達約500μm之粗大。其結果，麻田散鐵組織頂頭之皮膜交界面積如圖2所示明顯較肥粒鐵+波來鐵組織頂頭來得小，使用各頂頭進行13Cr不鏽鋼穿孔試驗，其結果頂頭壽命亦自6道次下減半至3道次。即，僅單純地使穿孔頂頭之組織成為麻田散鐵，雖然可使高溫強度提高，但不能獲得充分之皮膜密著性。 Figure 1 and Figure 2 show the heating by the film, the furnace is cooled. A photograph of the grain of the perforated head of the fermented iron-wave-iron metamorphic state and the perforated head of the metamorphic iron of the field. The grain of the top of the ferrite-iron-iron structure is as fine as 20 μm, but the grain of the head of the metamorphic iron of the granulated iron is about 500 μm. As a result, the junction area of the membrane of the head of the Ma Tian loose iron structure is obviously smaller than that of the ferrite iron + the Borne iron structure head as shown in Fig. 2, and the 13Cr stainless steel perforation test is performed using each head, and the result of the head life is also from 6 passes. Halve to 3 passes. In other words, simply by making the structure of the perforated plug into the granulated iron, the high-temperature strength can be improved, but sufficient film adhesion cannot be obtained.
於賦予皮膜中，基質與皮膜之交界面積越大者，皮膜之密著性越優異。相較於基質之晶粒內，皮膜選擇性地去氧化晶界，故頂頭之晶粒越微細，基質與皮膜之交界面積越增加，其結果皮膜之密著性提高。 In the film imparted to the film, the greater the interface area between the substrate and the film, the more excellent the adhesion of the film. Compared with the grain of the matrix, the film selectively deoxidizes the grain boundary, so the finer the crystal grains of the plug, the more the interface area between the matrix and the film increases, and the adhesion of the film is improved.
因此，本發明者們專心致力於研究：在賦予皮膜時使麻田散鐵變態此種頂頭之賦予皮膜的情況下，使晶粒微細化之方法。其結果發現：藉由於賦予皮膜之前使碳化物粗大凝集，可使頂頭組織之平均晶粒變得微細。 Therefore, the inventors of the present invention have devoted themselves to research on a method of refining crystal grains in the case where the film is imparted to the film by the mascara when the film is imparted. As a result, it was found that the average crystal grains of the plug structure can be made fine by coarsely agglomerating the carbides before the film is applied.
又，關於延性、韌性、耐熱龜裂性，一般而言認為經麻田散鐵變態之穿孔頂頭之延性、韌性、耐熱龜裂性會低於先前之經肥粒鐵-波來鐵變態之穿孔頂頭。然而，本發明者們發現：藉由使C量與碳化物量最佳化，相較於迄今之穿孔頂頭，反倒可使延性、韌性、耐熱龜裂性提高。 In addition, regarding ductility, toughness, and heat crack resistance, it is generally considered that the ductility, toughness, and heat crack resistance of the perforated plug which is metamorphosed by the granulated iron in the field are lower than that of the previous perforated head of the ferrite-wave-iron metamorphosis. . However, the inventors have found that by optimizing the amount of C and the amount of carbide, the ductility, toughness, and heat crack resistance can be improved as compared with the perforated plugs hitherto.
即，本發明提供一種藉由(1)即使爐冷，進行麻田散鐵變態之淬火性也仍非常高之成分組成之設計、(2)使 晶粒微細化、(3)對淬火性與碳化物量較佳之碳量之最佳化，而長壽命化之穿孔頂頭，其要旨如下所述。 That is, the present invention provides a design of a component composition in which the quenching property of the metamorphic iron in the field is still very high, even if the furnace is cooled, and (2) The purpose of miniaturization of crystal grains, (3) optimization of the amount of carbon which is preferable for the hardenability and the amount of carbides, and the perforated plug which has a long life is as follows.
(1)一種用以製造無縫管之穿孔頂頭，其特徵在於：其是於表面形成有氧化皮膜之無縫管製造用穿孔頂頭，且除上述氧化皮膜外之頂頭之成分組成包含以質量%計：C：0.10~0.25%、Si：0.05~0.80%、Mn：0.20~1.00%、Ni：2.5~3.5%、Cr：1.0~2.0%、Mo：2.5~3.5%、W：2.5~3.5%、Nb：0.07~0.40%、及Ti：0.03~0.40%，剩餘部分為Fe及不可避免之雜質；除上述氧化皮膜外之頂頭之組織構成是由1~10%之碳化物及麻田散鐵組織所構成。 (1) A perforated plug for manufacturing a seamless tube, characterized in that it is a perforated plug for seamless tube manufacturing in which an oxide film is formed on the surface, and the composition of the plug other than the above oxide film contains mass% Calculated: C: 0.10~0.25%, Si: 0.05~0.80%, Mn: 0.20~1.00%, Ni: 2.5~3.5%, Cr: 1.0~2.0%, Mo: 2.5~3.5%, W: 2.5~3.5% Nb: 0.07~0.40%, and Ti: 0.03~0.40%, the remainder is Fe and unavoidable impurities; the microstructure of the plug except the above oxide film is composed of 1~10% carbide and 麻田散铁Composition.
(2)如前述(1)之用以製造無縫管之穿孔頂頭，其特徵在於：前述麻田散鐵組織之平均粒徑為50μm以下。 (2) The perforated plug for manufacturing a seamless pipe according to the above (1), wherein the granulated iron structure has an average particle diameter of 50 μm or less.
(3)如前述(1)或(2)之用以製造無縫管之穿孔頂頭，其特徵在於：前述穿孔頂頭之成分組成進一步包含下述以質量%計之一種或二種以上：Mg：0.001~0.100%、REM：0.01~0.50%、Ca：0.0005~0.0500%、Al：0.005~0.200%、及B：0.0001~0.0050%。 (3) The perforated plug for manufacturing a seamless pipe according to the above (1) or (2), wherein the component of the perforated plug further comprises one or more of the following mass%: Mg: 0.001~0.100%, REM: 0.01~0.50%, Ca: 0.0005~0.0500%, Al: 0.005~0.200%, and B: 0.0001~0.0050%.
根據本發明可提供一種長壽命之用以製造無縫管之穿孔頂頭，其高溫強度與皮膜性狀(密著性、厚度)相較先前之穿孔頂頭顯著提升，並改善延性、韌性、耐熱龜裂性。 According to the present invention, it is possible to provide a long-life perforated plug for manufacturing a seamless tube, which has a high temperature strength and a film property (adhesion, thickness) which is significantly improved compared with the previous perforated plug, and which improves ductility, toughness, and heat crack resistance. Sex.
圖1顯示經肥粒鐵-波來鐵變態之穿孔頂頭之組織圖，(a)是穿孔頂頭內部之組織，(b)是皮膜界面之組織。 Figure 1 shows a histogram of the perforated plug of the ferrite-ferrite metamorphosis, (a) the tissue inside the perforated plug, and (b) the tissue at the interface of the membrane.
圖2顯示經麻田散鐵變態之穿孔頂頭之組織圖，(a)是穿孔頂頭內部之組織，(b)是皮膜界面之組織。 Figure 2 shows the tissue diagram of the perforated plug through the metamorphic iron of the Ma Tian, (a) is the tissue inside the perforated head, and (b) is the tissue of the membrane interface.
圖3(a)顯示以掃描式電子顯微鏡(SEM)觀察經賦予皮膜之穿孔頂頭之碳化物組織圖，(b)是將碳化物黑白單色化之圖。 Fig. 3(a) is a view showing a carbide structure of a perforated plug to which a film is applied by a scanning electron microscope (SEM), and (b) is a view of monochrome blackening of a carbide.
圖4(a)顯示碳化物凝集處理後，經賦予皮膜之穿孔頂頭之組織圖，(b)顯示不實施碳化物凝集處理，經賦予皮膜之穿孔頂頭之組織圖。 Fig. 4(a) is a view showing the structure of the perforated plug to which the film is applied after the carbide agglutination treatment, and (b) showing the structure of the perforated plug to which the film is applied without performing the carbide agglutination treatment.
以下就本發明進行詳細地說明。首先就本發明之穿孔頂頭之成分組成進行說明。以下，關於成分組成之「%」之表示是指「質量%」。 The invention will be described in detail below. First, the composition of the perforated plug of the present invention will be described. Hereinafter, the expression "%" of the component composition means "% by mass".
C是大為影響淬火性之元素。又，與Mo、W、Nb、Cr生成碳化物。C之含量未達0.10%時，淬火性降低，於賦予皮膜之處理後之冷卻中變得無法獲得麻田散鐵。若C之含量超過0.25%，則碳化物量變多，韌性及耐熱龜裂性降低。 C is an element that greatly affects hardenability. Further, carbides are formed with Mo, W, Nb, and Cr. When the content of C is less than 0.10%, the hardenability is lowered, and the granulated iron is not obtained in the cooling after the treatment for imparting the film. When the content of C exceeds 0.25%, the amount of carbide increases, and the toughness and heat crack resistance are lowered.
Si是脫氧元素。Si之含量未達0.05%時，氧量變高，延性下降。若Si之含量超過0.80%，則耐氧化性上升，氧化皮膜之膜厚變薄。 Si is a deoxidizing element. When the content of Si is less than 0.05%, the amount of oxygen becomes high and the ductility decreases. When the content of Si exceeds 0.80%, the oxidation resistance increases and the film thickness of the oxide film becomes thin.
Mn是脫氧元素。於提高淬火性上與C、Cr共同為必要元素。為獲得作為脫氧元素之效果，Mn之含量必須為 0.20%以上。若Mn之含量超過1.00%則韌性降低。 Mn is a deoxidizing element. It is an essential element together with C and Cr for improving the hardenability. In order to obtain the effect as a deoxidizing element, the content of Mn must be 0.20% or more. If the content of Mn exceeds 1.00%, the toughness is lowered.
Ni為生成密著性較高之氧化皮膜上之必要元素。Ni之含量未達2.5%時，皮膜與基質界面之凹凸減少。若Ni之含量超過3.5%，則即使進行碳化物凝集處理，晶粒亦不能變微細。 Ni is an essential element for generating an oxide film having high adhesion. When the content of Ni is less than 2.5%, the unevenness of the interface between the film and the substrate is reduced. When the content of Ni exceeds 3.5%, the crystal grains cannot be made fine even if the carbide agglomeration treatment is performed.
Cr與C、Mn同樣為淬火性提高元素。Cr之含量未達1.0時，無法獲得充分之淬火性。若Cr之含量超過2.0%，則抑制氧化皮膜之生成，皮膜厚度不足。 Cr is a quenching improving element similarly to C and Mn. When the content of Cr is less than 1.0, sufficient hardenability cannot be obtained. When the content of Cr exceeds 2.0%, the formation of an oxide film is suppressed, and the film thickness is insufficient.
Mo固溶於基質而提高高溫強度。又，藉由生成作為複碳化物之M6C(M為金屬元素。以下相同)，亦提高高溫強度。進一步地，與C、Cr、Mn同樣為淬火性提高元素。Mo之含量未達2.5%時，無法獲得充分之淬火性改善效果，高溫強度亦下降。若Mo之含量超過3.5%，則晶界碳化物增加，延性、韌性下降。 Mo is solidified in the matrix to increase the high temperature strength. Further, by generating M 6 C as a complex carbide (M is a metal element, the same applies hereinafter), the high-temperature strength is also improved. Further, it is a hardenability improving element similarly to C, Cr, and Mn. When the content of Mo is less than 2.5%, a sufficient effect of improving the hardenability cannot be obtained, and the high-temperature strength is also lowered. When the content of Mo exceeds 3.5%, grain boundary carbides increase, and ductility and toughness decrease.
W與Mo同時固溶於基質而提高高溫強度。又，生成M6C型之碳化物而提高高溫強度。又，W生成低熔點皮膜。W之含量未達2.5%時，無法獲得充分之固溶強化。若Mo之含量超過3.5%，則晶界碳化物增加，延性、韌性下降。 W and Mo are simultaneously dissolved in the matrix to increase the high temperature strength. Further, a carbide of M 6 C type is formed to increase the high temperature strength. Further, W forms a low melting point film. When the content of W is less than 2.5%, sufficient solid solution strengthening cannot be obtained. When the content of Mo exceeds 3.5%, grain boundary carbides increase, and ductility and toughness decrease.
Nb在生成MC型之碳化物之同時，將碳化物固溶於基質而提高高溫強度。Nb之含量未達0.07%時，無法獲得充分之強化，若Nb之含量超過0.40%，則結晶出粗大的碳化物，韌性、延性下降。 Nb dissolves carbides in the matrix while generating MC type carbides to increase high temperature strength. When the content of Nb is less than 0.07%, sufficient strengthening cannot be obtained. When the content of Nb exceeds 0.40%, coarse carbides are crystallized, and toughness and ductility are lowered.
Ti生成TiN之同時，固溶於基質而提高高溫強度。Ti之含量未達0.03%時，無法獲得充分之強化，若Ti之含量 超過0.40%，則結晶出粗大的氮化物，韌性、延性下降。 When Ti forms TiN, it dissolves in the matrix and increases the high temperature strength. When the content of Ti is less than 0.03%, sufficient strengthening cannot be obtained, if the content of Ti When it exceeds 0.40%, coarse nitride crystallizes, and toughness and ductility fall.
Mg、REM及Ca為任意之添加元素，並非必要元素，但若於特定範圍內添加，則可謀求皮膜之密著性之更進一步改善。REM為稀土類元素。 Mg, REM, and Ca are optional elements, and are not essential elements. However, if they are added in a specific range, the adhesion of the film can be further improved. REM is a rare earth element.
Mg之含量未達0.001%時，無法看見皮膜密著性之改善效果，若含量超過0.100%，則效果飽和。 When the content of Mg is less than 0.001%, the effect of improving the adhesion of the film cannot be seen, and if the content exceeds 0.100%, the effect is saturated.
REM之含量未達0.01%時，無法看見皮膜密著性之改善效果，若含量超過0.50%，則皮膜厚度變薄。 When the content of REM is less than 0.01%, the effect of improving the adhesion of the film is not observed, and if the content exceeds 0.50%, the film thickness is reduced.
Ca之含量未達0.0005%時，無法看見皮膜密著性之改善效果，若含量超過0.0500%，則效果飽和。 When the content of Ca is less than 0.0005%, the effect of improving the adhesion of the film cannot be seen, and if the content exceeds 0.0500%, the effect is saturated.
其他，作為脫氧劑，亦可於0.005~0.200%之範圍內添加Al。添加量為0.005%~0.200%。 Others, as a deoxidizer, Al may be added in the range of 0.005 to 0.200%. The amount added is 0.005% to 0.200%.
又，為提高淬火性，亦可於0.0001~0.0050%之範圍內添加B。 Further, in order to improve the hardenability, B may be added in the range of 0.0001 to 0.0050%.
成分組成之剩餘部分為Fe及不可避免之雜質。所謂不可避免之雜質是指原本就包含於原料中、或於製造過程中混入等，因而包含於本發明中之成分，並非意圖放入之成分。 The remainder of the composition of the composition is Fe and unavoidable impurities. The unavoidable impurities are those which are originally contained in the raw material or are mixed in the production process, and thus are included in the present invention, and are not intended to be contained.
由延性、韌性、耐熱龜裂性之觀點，不可避免之雜質中P及S較低為佳，較佳為0.02%以下。 From the viewpoints of ductility, toughness, and heat crack resistance, P and S are preferably lower in the unavoidable impurities, and preferably 0.02% or less.
藉由成為上述之成分組成，淬火性顯著變高，即使直接鑄造亦大部分進行麻田散鐵變態。 By becoming the above-mentioned component composition, the hardenability is remarkably high, and even in direct casting, most of the granules are metamorphosed.
以下就基質之組織與皮膜進行說明。 The structure and film of the matrix will be described below.
頂頭之組織構成為1~10%之碳化物與基質是麻 田散鐵組織。碳化物與麻田散鐵組織提高高溫強度，同時亦改善延性、韌性、耐熱龜裂性。若為本發明之成分組成，於950~1100℃下之賦予皮膜後，以20~50℃/小時之爐冷，組織進行麻田散鐵變態。 The structure of the head is 1~10% of the carbide and the matrix is hemp. Tian scattered iron organization. Carbide and mascot loose iron structure improve high temperature strength, and also improve ductility, toughness and heat crack resistance. According to the composition of the present invention, after the film is applied at 950 to 1100 ° C, the furnace is cooled at 20 to 50 ° C / hour, and the structure is metamorphosed in the field.
本發明之頂頭之情形，由於在麻田散鐵變態之前析出碳化物，故藉由光學顯微鏡或硬度測定不易辨別麻田散鐵與下部變韌鐵，在稱為麻田散鐵之組織中亦存在包含下部變韌鐵之情形。 In the case of the plug of the present invention, since the carbide is precipitated before the metamorphic iron of the granules, the granulated iron and the lower toughened iron are not easily distinguished by optical microscopy or hardness measurement, and the lower portion is also present in the structure called the granulated iron. The case of toughening iron.
碳化物之量使用掃描式電子顯微鏡(SEM)以3000倍觀察5視域，求得其面積率。本合金之情形，存在NbC般之結晶碳化物、與M6C般於冷卻中析出之碳化物。結晶碳化物無助於高溫強度，故自面積率之測定中除外，求出析出碳化物之面積率。圖3顯示一例。(a)顯示以掃描式電子顯微鏡(SEM)觀察經賦予皮膜之穿孔頂頭之碳化物組織圖，(b)是將碳化物黑白單色化之圖。 The amount of carbide was observed by scanning electron microscopy (SEM) at 3000 times, and the area ratio was determined. In the case of the present alloy, there are NbC-like crystalline carbides and carbides precipitated in the same manner as M 6 C in cooling. Since the crystalline carbide does not contribute to the high-temperature strength, it is excluded from the measurement of the area ratio, and the area ratio of the precipitated carbide is determined. Figure 3 shows an example. (a) shows a carbide structure diagram of a perforated plug to which a film is applied by a scanning electron microscope (SEM), and (b) is a figure which monopolizes a black and white of a carbide.
碳化物量未達1%時，高溫強度之改善不足，若超過10%則韌性、延性降低變明顯。 When the amount of carbide is less than 1%, the improvement in high-temperature strength is insufficient, and if it exceeds 10%, the decrease in toughness and ductility is remarkable.
表面皮膜之密著性依存於皮膜組成與其凹凸。若頂頭之組織之晶粒為微細，則可生成密著性較高之皮膜。 The adhesion of the surface film depends on the composition of the film and its unevenness. If the crystal grains of the structure of the plug are fine, a film having a high adhesion can be produced.
於本發明中，藉由於賦予皮膜之前實施以下處理，使碳化物粗大凝集，可使頂頭之晶粒微細化至最佳50μm以下。 In the present invention, by performing the following treatment before the film is applied, the carbides are coarsely aggregated, and the crystal grains of the plug can be made fine to an optimum of 50 μm or less.
具體而言，將經麻田散鐵變態之頂頭於AC1變態點下之700~750℃下加熱，使M6C、M23C6等碳化物凝集， 使麻田散鐵成為肥粒鐵+碳化物組織後，實施賦予皮膜。藉此，麻田散鐵記憶效應消失，可得到微細的沃斯田鐵晶粒。更具體而言，只要於AC1點-30~AC1點-150℃之溫度範圍內加熱3~20小時即可。若加熱溫度較低，碳化物無法充分凝集，若加熱溫度較高，有於實際作業時超過AC1變態點之虞。若加熱時間較短，碳化物無法充分凝集，若加熱時間較長，則效果飽和。 Specifically, the head of the metamorphic state of the granulated iron is heated at 700 to 750 ° C under the AC 1 metamorphic point to agglomerate carbides such as M 6 C and M 23 C 6 , so that the granulated iron becomes fertile iron + carbonized. After the tissue is organized, the film is applied. Thereby, the memory effect of the Ma Tian loose iron disappears, and the fine Worthite iron crystal grains can be obtained. More specifically, it can be heated for 3 to 20 hours in the temperature range of AC 1 point -30~AC 1 point -150 °C. If the heating temperature is low, the carbide cannot be sufficiently aggregated. If the heating temperature is high, it may exceed the AC 1 metamorphic point during actual operation. If the heating time is short, the carbide cannot be sufficiently aggregated, and if the heating time is long, the effect is saturated.
於圖4中，將作為藉由碳化物凝集處理之晶粒之一例，於750℃處理5小時後進行賦予皮膜處理之頂頭之照片與未處理品一起顯示。未處理之情形之平均粒徑為87μm，但藉由碳化物凝集處理，平均粒徑成為12μm之微細。 In Fig. 4, a photograph of a plug which is subjected to a film treatment after being treated at 750 ° C for 5 hours as an example of crystal grains subjected to carbide agglomeration treatment is displayed together with an untreated product. The average particle diameter in the case of no treatment was 87 μm, but the average particle diameter was 12 μm by the carbide agglutination treatment.
該凝集碳化物於進行賦予皮膜處理時，一部分固溶，一部分殘存。因為殘存碳化物與賦予皮膜冷卻時之析出碳化物於SEM觀察下難以辨別，故全部作為析出碳化物測定其面積。 When the agglomerated carbide is subjected to a film treatment, a part of it is solid-solved and a part remains. Since the residual carbide and the precipitated carbide when the film was cooled were difficult to distinguish by SEM observation, the area was measured as the precipitated carbide.
接續上述處理，實施皮膜處理。賦予皮膜處理如下進行，即：於爐內之CO濃度為1~8%之燃燒氣體氛圍下，於950~1100℃加熱3~10小時，之後以20~50℃/小時進行爐冷。若CO濃度較低，脫碳層變得比2mm深，若較高則皮膜厚度變薄。若處理溫度較低，皮膜厚度較薄，若較高，則成為包含很多細孔(氣孔)之密著性下降之皮膜。若處理時間較短，皮膜較薄，若較長則厚度飽和。若為本發明之成分組成，藉由該加熱、爐冷，組織構成成為1~10%碳化物與剩餘部分為麻田散鐵。 The above treatment is continued to carry out the film treatment. The film treatment is carried out by heating at 950 to 1100 ° C for 3 to 10 hours in a combustion gas atmosphere having a CO concentration of 1 to 8% in the furnace, followed by furnace cooling at 20 to 50 ° C / hour. If the CO concentration is low, the decarburized layer becomes deeper than 2 mm, and if it is higher, the film thickness becomes thinner. When the treatment temperature is low, the film thickness is thin, and if it is high, it becomes a film containing a lot of fine pores (pores) with a decrease in adhesion. If the treatment time is short, the film is thin, and if it is long, the thickness is saturated. According to the composition of the present invention, the structure is 1 to 10% of carbides and the remainder is 麻田散铁 by the heating and furnace cooling.
於賦予皮膜處理後，若將麻田散鐵於500~650℃回火處理，可更加改善延性、韌性、耐熱龜裂性。 After the treatment of the film, if the granulated iron is tempered at 500 to 650 ° C, the ductility, toughness and heat crack resistance can be further improved.
[實施例1] [Example 1]
鑄造具有表1所示之成分組成之外徑185mm之穿孔頂頭後，實施以電爐於700~750℃加熱5小時之碳化物凝集處理。於一部分之比較例中未實施碳化物凝集處理。之後，於爐內之CO濃度為1%之燃燒氣體氛圍下，於1000℃持溫4小時後，爐冷、進行賦予皮膜處理。 After casting a perforated plug having an outer diameter of 185 mm having the composition shown in Table 1, a carbide agglomeration treatment was carried out by heating in an electric furnace at 700 to 750 ° C for 5 hours. Carbide agglutination treatment was not carried out in a part of the comparative examples. Thereafter, the temperature was maintained at 1000 ° C for 4 hours in a combustion gas atmosphere having a CO concentration of 1% in the furnace, and then the furnace was cooled and subjected to a film treatment.
使用所獲得之於表面形成有氧化皮膜之穿孔頂頭，製管13Cr不鏽鋼，評價壽命。將結果表示於表2。比較例之穿孔頂頭之損傷為頭部熔損、割損、軀體部之皺紋，壽命亦較短，但本發明之穿孔頂頭之損傷僅為頭部熔損，壽命亦大幅延長。 The 13Cr stainless steel was fabricated using the obtained perforated plug having an oxide film formed on the surface thereof, and the life was evaluated. The results are shown in Table 2. The damage of the perforated plug of the comparative example is the head melting loss, the cut, the wrinkles of the body part, and the life is also short, but the damage of the piercing plug of the present invention is only the head melting loss, and the life is also greatly extended.
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| US9340847B2 (en) * | 2012-04-10 | 2016-05-17 | Tenaris Connections Limited | Methods of manufacturing steel tubes for drilling rods with improved mechanical properties, and rods made by the same |
| EP2902522B1 (en) * | 2012-09-28 | 2018-06-27 | Nippon Steel & Sumitomo Metal Corporation | Piercer plug material for producing seamless steel tube, and method for producing said material |
| CN103451551B (en) * | 2013-08-30 | 2015-07-01 | 北京工业大学 | Preparation method of cast steel perforator top tip with high-temperature resistance and corrosion resistance |
| CN103789685A (en) * | 2014-02-17 | 2014-05-14 | 上海海隆石油管材研究所 | High-strength high-toughness petroleum drill pipe and production method thereof |
-
2014
- 2014-08-19 JP JP2014166591A patent/JP6385195B2/en active Active
-
2015
- 2015-08-11 KR KR1020150113305A patent/KR102320752B1/en active IP Right Grant
- 2015-08-14 TW TW104126574A patent/TWI648108B/en active
- 2015-08-18 CN CN201510509250.2A patent/CN105369151B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016041844A (en) | 2016-03-31 |
| TWI648108B (en) | 2019-01-21 |
| JP6385195B2 (en) | 2018-09-05 |
| CN105369151A (en) | 2016-03-02 |
| KR20160022258A (en) | 2016-02-29 |
| KR102320752B1 (en) | 2021-11-02 |
| CN105369151B (en) | 2020-04-03 |
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