CN113286869B - 组合物及具备由该组合物构成的润滑覆膜层的管用螺纹接头 - Google Patents
组合物及具备由该组合物构成的润滑覆膜层的管用螺纹接头 Download PDFInfo
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- CN113286869B CN113286869B CN201980087938.2A CN201980087938A CN113286869B CN 113286869 B CN113286869 B CN 113286869B CN 201980087938 A CN201980087938 A CN 201980087938A CN 113286869 B CN113286869 B CN 113286869B
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Images
Classifications
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
提供一种用于获得具有优异的耐烧结性和优异的高扭矩性能的管用螺纹接头的组合物,以及具备由该组合物形成的润滑覆膜层、具有优异的耐烧结性和优异的高扭矩性能的管用螺纹接头。本申请的组合物是用于在管用螺纹接头上形成润滑覆膜层(21)的组合物,其含有聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐。本申请的管用螺纹接头具备:公扣部(3),其具有包含公扣部侧螺纹部的公扣部侧接触表面(34);母扣部(4),其具有包含母扣部侧螺纹部的母扣部侧接触表面(44);以及润滑覆膜层(21),其以最表层的形式位于所述公扣部侧接触表面(34)上和所述母扣部侧接触表面(44)上中的至少一者上,由上述组合物构成。
Description
技术领域
本申请涉及一种组合物及具备由该组合物构成的润滑覆膜层的管用螺纹接头。
背景技术
油井管被用于油田、天然气田的开采。油井管是根据井的深度连接多根钢管而形成的。钢管的连接通过将形成于钢管端部的管用螺纹接头彼此紧螺纹而进行。
作为用于紧固油井管的典型管用螺纹接头,可列举出由被称为公扣部的部件和被称为母扣部的部件构成的公母扣部结构。公扣部包括形成于钢管端部的外周面的公扣部侧螺纹部。公扣部还可以包括公扣部侧金属密封部和公扣部侧台肩部。母扣部包括形成于钢管端部的内周面的母扣部侧螺纹部。母扣部还可以包括母扣部侧金属密封部和母扣部侧台肩部。钢管彼此间紧螺纹时,公扣部侧螺纹部与母扣部侧螺纹部接触。在管用螺纹接头包括金属密封部和台肩部的情况下,紧螺纹时,金属密封部彼此以及台肩部彼此接触。
在油井管下降作业时,由于故障等各种原因,有时会将油井管暂时从油井拉上来后,将已紧固的管用螺纹接头拧松,再次紧固后再下降。公扣部和母扣部的螺纹部、金属密封部和台肩部会在钢管紧螺纹和松螺纹时反复受到强摩擦。在这些部位,如果针对摩擦的耐久性不足,则在反复紧螺纹和松螺纹时,会发生粘扣(不能修复的烧结)。因此,管用螺纹接头要求足够的针对摩擦的耐久性,即优异的耐烧结性。
以往,为了提高管用螺纹接头的耐烧结性和气密性,使用被称为“润滑油”或“复合润滑脂”的含有重金属粉的粘稠液态润滑剂(油脂型润滑油)。复合润滑脂涂布于螺纹接头的接触表面(即螺纹部;或在管用螺纹接头具有金属密封部和台肩部的情况下是螺纹部、金属密封部和台肩部)。API标准BUL 5A2中记载有复合润滑脂的例子。
但是,复合润滑脂中所含的Pb等重金属有可能对环境造成影响。因此,作为代替复合润滑脂的新型润滑剂,提出了各种润滑覆膜。
国际公开第2009/057754号(专利文献1)和国际公开第2014/024755号(专利文献2)提出了一种用于形成耐烧结性优异的润滑覆膜层的组合物,其不含有可能对环境造成影响的重金属。
专利文献1记载的用于在管用螺纹接头上形成润滑覆膜的组合物包含松香和氟化钙中的一者或两者、金属皂、蜡、以及碱性芳香族有机酸金属盐。专利文献1记载了:该润滑覆膜形成用组合物基本不含铅等有害的重金属,对地球环境的负荷非常小。另外,由该组合物形成的润滑覆膜的防锈性也优异,可抑制管用螺纹接头在保管过程中生锈。因此,管用螺纹接头即使反复拧紧和拧松也可持续发挥润滑功能,拧紧后可确保气密性。
专利文献2记载的用于在管用螺纹接头上形成润滑覆膜的组合物含有三聚氰胺氰脲酸酯、碱性芳香族有机酸金属盐,并且含有选自松脂系物质、蜡、金属皂和润滑性粉末中的1种以上。专利文献2记载了使用该组合物形成润滑覆膜时,可抑制管用螺纹接头生锈,即使反复拧紧和拧松也可持续发挥润滑功能,拧紧后可确保气密性。
现有技术文献
专利文献
专利文献1:国际公开第2009/057754号
专利文献2:国际公开第2014/024755号
发明内容
发明要解决的问题
另一方面,在对管用螺纹接头进行紧螺纹时,紧固完成时的扭矩(以下称为紧固扭矩)不论螺纹过盈量的大小,以可获得足够的密封面压力的方式设定。在紧螺纹的最终阶段,螺纹彼此间的面压力升高。如果在面压力升高时扭矩也稳定地增加而不产生烧结,则容易调节紧固扭矩。因此,对于管用螺纹接头,要求在高面压力时扭矩也稳定地增加的性能。以下,将该性能称为高扭矩性能。
对于具有台肩的管用螺纹接头来说,将高扭矩性能定义为:在表示紧螺纹时的钢管转数与扭矩的关系的扭矩图的转数高于台肩扭矩的区域中,维持刚上肩时的扭矩增加率的性能。对于具有台肩的管用螺纹接头来说,可表示为台肩摩阻扭矩ΔT’。
在管用螺纹接头具有台肩部的情况下,紧螺纹时公扣部和母扣部的台肩部彼此接触。将此时产生的扭矩称为台肩扭矩。对管用螺纹接头进行紧螺纹时,达到台肩扭矩后,进一步进行紧螺纹直至紧固完成。由此,管用螺纹接头的气密性提升。过度进行紧螺纹时,构成公扣部和母扣部的至少一者的金属开始发生塑性变形。将此时产生的扭矩称为屈服扭矩。台肩摩阻扭矩ΔT’是指上述台肩扭矩与上述屈服扭矩之差。
在管用螺纹接头具有台肩部的情况下,台肩摩阻扭矩ΔT’越大,越容易调节紧固扭矩。即使在管用螺纹接头不具有台肩部的情况下,如果在高面压力时扭矩稳定地增加,则也容易调节紧固扭矩。
使用专利文献1和专利文献2公开的组合物,也可形成改善耐烧结性、容易调节紧固扭矩的润滑覆膜。但是,优选通过其它的组合物和润滑覆膜也可获得优异的耐烧结性和高扭矩性。
本申请的目的在于提供一种用于得到具有优异的耐烧结性和优异的高扭矩性能的管用螺纹接头的组合物、和具备由该组合物形成的润滑覆膜层、具有优异的耐烧结性和优异的高扭矩性能的管用螺纹接头。
用于解决问题的方案
本申请的组合物是用于在管用螺纹接头上形成润滑覆膜层的组合物,含有聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐。
本申请的管用螺纹接头具备:公扣部,其具有包含公扣部侧螺纹部的公扣部侧接触表面;母扣部,其具有包含母扣部侧螺纹部的母扣部侧接触表面;以及润滑覆膜层,其以位于最表层的形式位于公扣部侧接触表面上和母扣部侧接触表面上中的至少一者上,由上述组合物构成。
发明的效果
本申请的管用螺纹接头具备含有聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐的润滑覆膜层作为最表层。因此,本申请的管用螺纹接头即使反复紧固也具有优异的耐烧结性。本申请的管用螺纹接头还具有优异的高扭矩性能。
附图说明
图1为示出对具有台肩部的管用螺纹接头进行紧螺纹时的钢管转数与扭矩的关系的图。
图2为示出用实施例中的试验编号9和试验编号11的组合物进行法莱克斯试验的结果的图。
图3为示出润滑覆膜层中的聚异丁烯含量(质量%)与台肩摩阻扭矩ΔT’(相对值)的关系的图。
图4为示出润滑覆膜层中的聚异丁烯含量(质量%)与耐烧结性的关系的图。
图5为示出本实施方式的接箍型管用螺纹接头的结构的图。
图6为示出本实施方式的一体型管用螺纹接头的结构的图。
图7为管用螺纹接头的截面图。
图8为示出本实施方式的不具有金属密封部和台肩部的管用螺纹接头的结构的图。
图9为本实施方式的管用螺纹接头的截面图。
图10为与图9不同的其它实施方式的管用螺纹接头的截面图。
图11为与图9和图10不同的其它实施方式的管用螺纹接头的截面图。
图12为用于说明实施例中的台肩摩阻扭矩ΔT’的图。
具体实施方式
以下,参照附图对本实施方式进行详细说明。图中对相同或相当部分标以相同的附图标记,不再重复其说明。
本发明人等对用于形成管用螺纹接头的润滑覆膜层的组合物与管用螺纹接头的耐烧结性和高扭矩性能的关系进行了各种研究。其结果,获得以下认知。
钢管彼此紧螺纹时,事先已确定完成紧螺纹的最佳扭矩。图1为示出对具有台肩部的管用螺纹接头进行紧螺纹时的钢管转数与扭矩的关系的图。图1也称为扭矩图。参照图1,如果对管用螺纹接头进行紧螺纹,则一开始,扭矩与转数成比例地上升。此时的扭矩的上升率低。如果进一步紧螺纹,则台肩部彼此接触。将此时的扭矩称为台肩扭矩。达到台肩扭矩后,如果进一步紧螺纹,则扭矩会再次与转数成比例地上升。此时的扭矩的上升率比达到台肩扭矩前更高。扭矩达到规定数值(紧固扭矩)的时刻,紧螺纹完成。
紧螺纹时的扭矩达到紧固扭矩时,金属密封部彼此以合适的面压力过盈配合。在这种情况下,管用螺纹接头的气密性提升。另外,在油井中,螺纹接头承受高压缩应力或高弯曲应力。为了在这样的应力下管用螺纹接头的紧固也不会松弛,管用螺纹接头需要以足够高的扭矩(合适的紧固扭矩)紧固。
如果在达到紧固扭矩后进一步实施紧螺纹,则扭矩变得过高。如果扭矩变得过高,则公扣部和母扣部的一部分会发生塑性变形。将此时的扭矩称为屈服扭矩。如果台肩扭矩与屈服扭矩之差、即台肩摩阻扭矩ΔT’大,则紧固扭矩的范围可以有富余。其结果,容易调节紧固扭矩。因此,台肩摩阻扭矩ΔT’优选较大。
为了增大台肩摩阻扭矩ΔT’,降低台肩扭矩、或提高屈服扭矩是有效的。但是,如果只是单纯地改变润滑覆膜层的组成使得摩擦系数增大或减低,则台肩扭矩和屈服扭矩通常仍以同样的方式表现。例如,润滑覆膜层的摩擦系数升高时,屈服扭矩升高,但台肩扭矩也升高(高上肩)。其结果,有时即使已达到规定的拧紧扭矩,台肩面也不接触,未完成拧紧(无上肩)。相反,润滑覆膜层的摩擦系数低时,台肩扭矩降低,但屈服扭矩也降低。其结果,有时台肩部或密封部以低的拧紧扭矩屈服,无法实现高拧紧扭矩下的紧固。
本发明人等进行了深入研究,结果获得了以往未曾被知晓的以下认知:通过使润滑覆膜层中含有聚异丁烯,可以一边将台肩扭矩保持在与以往相同的水平,一边提高屈服扭矩,使台肩摩阻扭矩ΔT’增大。对于这一点,用图进行详细说明。
图2为示出用实施例中的试验编号9和试验编号11所示的组合物进行法莱克斯试验的结果的图。法莱克斯试验是指将旋转的轴颈销夹在两个V形块之间,测定施加在块上的载荷和通过施加载荷所产生的摩擦扭矩的试验。通过法莱克斯试验测定烧结载荷的方法在例如ASTM D 3233中有规定。图2为示出在轴颈销的表面涂布试验编号9或试验编号11的组合物并使轴颈销旋转后,对施加在块上的载荷、旋转的轴颈销和V形块之间产生的摩擦扭矩进行测定的结果的曲线图。图2的纵轴表示摩擦扭矩。图2的横轴表示施加在块上的载荷。
参照图2,从低载荷状态至某一程度的范围为止,使用试验编号9的组合物的情况与使用试验编号11的组合物的情况同样地扭矩上升。但是,在使用不含聚异丁烯的试验编号11的组合物的情况下,载荷升高一定水平以上时,扭矩的上升率减少。这说明在图1的紧螺纹的最终阶段,金属密封部和台肩部承受的载荷(面压力)快速上升时,如果是不含聚异丁烯的组合物,则扭矩的上升变缓。即,在如图1所示的扭矩图的转数高于台肩扭矩的区域中,无法维持刚上肩时的扭矩增加率。在这种情况下,无法提高屈服扭矩。但是,在使用含有聚异丁烯的试验编号9的组合物的情况下,载荷升高一定水平以上后,扭矩的上升率未减少。这说明在图1的紧螺纹的最终阶段,载荷(面压力)快速上升时扭矩也可继续上升。即,在如图1所示的扭矩图的转数高于台肩扭矩的区域中,可维持刚上肩时的扭矩增加率。在这种情况下,可提高屈服扭矩。
通过一边保持低台肩扭矩一边提高屈服扭矩,可使台肩摩阻扭矩ΔT’增大。图3为示出润滑覆膜层中的聚异丁烯含量(质量%)与台肩摩阻扭矩ΔT’(相对值)的关系的图。图3是由后述的实施例得到的。图3的纵轴表示台肩摩阻扭矩ΔT’(相对值)。图3的横轴表示润滑覆膜层中的聚异丁烯含量(质量%)。需要说明的是,台肩摩阻扭矩ΔT’(相对值)的各数值是以使用API标准润滑油代替润滑覆膜层时的台肩摩阻扭矩ΔT’的数值为基准(100)而以相对值的形式求出的数值。图3中的白圆符号(○)表示形成有润滑覆膜层的实施例的台肩摩阻扭矩ΔT’(相对值)。图3中的三角符号(△)表示使用API标准润滑油代替润滑覆膜层时的台肩摩阻扭矩ΔT’(基准值,即100)。
参照图3,不含聚异丁烯的试验编号11的台肩摩阻扭矩ΔT’(相对值)为60。而含有聚异丁烯的试验编号9的台肩摩阻扭矩ΔT’(相对值)为115。具备由含有聚异丁烯的组合物构成的润滑覆膜层的管用螺纹接头在紧螺纹的最终阶段的高面压力下,扭矩也稳定地上升而不会提高台肩扭矩。因此,屈服扭矩提高。其结果,台肩摩阻扭矩ΔT’(相对值)大于100。
参照图3可知,润滑覆膜层含有聚异丁烯时,在其它实施例中,台肩摩阻扭矩ΔT’(相对值)也大于100。即,润滑覆膜层含有聚异丁烯时,可获得优异的高扭矩性能。
本发明人等还发现,在润滑覆膜层含有聚异丁烯的情况下,可获得与以往的API润滑油同等的耐烧结性或在以往的API润滑油以上的高耐烧结性。
图4为示出润滑覆膜层中的聚异丁烯含量(质量%)与耐烧结性的关系的图。图4是由后述的实施例得到的。图4的纵轴表示在螺纹部未产生不可恢复的烧结且在金属密封部未产生烧结而完成紧固的次数(次)。图4的横轴表示润滑覆膜层中的聚异丁烯含量(质量%)。
参照图4,润滑覆膜层含有聚异丁烯时,能够不产生烧结而反复完成紧螺纹的次数为与以往的API润滑油同等的10次或其以上。即,润滑覆膜层含有聚异丁烯时,不仅可获得优异的高扭矩性能,还可获得优异的耐烧结性。
综上,润滑覆膜层含有聚异丁烯时,不仅可获得优异的高扭矩性能,还可获得优异的耐烧结性。通过润滑覆膜层含有聚异丁烯而可提高管用螺纹接头的高扭矩性能和耐烧结性的详细机制尚未明确。但是,本发明人等是如下认为的。
聚异丁烯是在常温(约25℃)下半固体状的聚合物,推测其易溶于润滑覆膜层所含的蜡。聚异丁烯还有可能在管用螺纹接头滑动时,即使温度升高,也能够抑制蜡的粘度下降。推测其结果是能够获得管用螺纹接头的高扭矩性能。有可能在这种情况下,进一步由于润滑覆膜层中的蜡的粘度也得以保持,因此可保持润滑覆膜层的厚度。推测其结果可能使得耐烧结性提高。
基于以上认知完成的本实施方式的组合物是用于在管用螺纹接头上形成润滑覆膜层的组合物,含有聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐。
本实施方式的组合物含有聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐。因此,具备由该组合物构成的润滑覆膜层的管用螺纹接头具有优异的耐烧结性和优异的高扭矩性能。
优选为在将组合物中的不挥发性成分的总量设为100质量%时,上述组合物含有聚异丁烯:5~30质量%、金属皂:2~30质量%、蜡:2~30质量%、和碱性芳香族有机酸金属盐:10~70质量%。
在这种情况下,管用螺纹接头的耐烧结性和高扭矩性能进一步提高。
优选上述组合物进一步含有润滑性粉末。
在这种情况下,管用螺纹接头的润滑性提升。
优选在将上述组合物中的不挥发性成分的总量设为100质量%时,上述组合物含有润滑性粉末:0.5~20质量%。
优选上述润滑性粉末为选自由石墨和聚四氟乙烯组成的组中的1种或2种。
上述组合物可进一步含有挥发性有机溶剂。
本实施方式的管用螺纹接头具备:公扣部,其具有包含公扣部侧螺纹部的公扣部侧接触表面;母扣部,其具有包含母扣部侧螺纹部的母扣部侧接触表面;以及润滑覆膜层,其以最表层的形式位于公扣部侧接触表面上和母扣部侧接触表面上中的至少一者上,由上述组合物构成。
管用螺纹接头具备以最表层的形式位于公扣部侧接触表面上和母扣部侧接触表面上中的至少一者上,由含有聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐的组合物构成的润滑覆膜层时,管用螺纹接头的耐烧结性和高扭矩性能提升。
管用螺纹接头可在公扣部侧接触表面上具备上述润滑覆膜层。
优选管用螺纹接头进一步在公扣部侧接触表面与润滑覆膜层之间具备镀层。
在这种情况下,管用螺纹接头的耐烧结性和耐腐蚀性提升。
优选管用螺纹接头进一步在润滑覆膜层与镀层之间具备化学转化处理覆膜。
在这种情况下,润滑覆膜层的密合性提升。
优选为,在管用螺纹接头不具备镀层的情况下,公扣部侧接触表面为经过选自由喷砂处理和酸洗组成的组中的1种或2种处理的面;在管用螺纹接头具备镀层的情况下,镀层表面为经过选自由喷砂处理和酸洗组成的组中的1种或2种处理的面。
管用螺纹接头可在母扣部侧接触表面上具备上述润滑覆膜层。
优选管用螺纹接头进一步在母扣部侧接触表面与润滑覆膜层之间具备镀层。
在这种情况下,管用螺纹接头的耐烧结性和耐腐蚀性提升。
优选管用螺纹接头进一步在润滑覆膜层与镀层之间具备化学转化处理覆膜。
在这种情况下,润滑覆膜层的密合性提升。
优选在管用螺纹接头不具备镀层的情况下,母扣部侧接触表面为经过选自由喷砂处理和酸洗组成的组中的1种或2种处理的面;在管用螺纹接头具备镀层的情况下,镀层表面为经过选自由喷砂处理和酸洗组成的组中的1种或2种处理的面。
优选管用螺纹接头的公扣部侧接触表面进一步包含公扣部侧金属密封部和公扣部侧台肩部,母扣部侧接触表面进一步包含母扣部侧金属密封部和母扣部侧台肩部。
以下,对本实施方式的组合物和具备由该组合物形成的润滑覆膜层的管用螺纹接头进行详述。
[管用螺纹接头]
管用螺纹接头具备公扣部和母扣部。图5为示出本实施方式的接箍型管用螺纹接头的结构的图。参照图5,管用螺纹接头具备钢管1和接箍2。在钢管1的两端形成公扣部3,公扣部3在外表面具有公扣部侧螺纹部。在接箍2的两端形成母扣部4,母扣部4在内表面具有母扣部侧螺纹部。通过对公扣部3和母扣部4进行紧螺纹,接箍2被安装至钢管1的端部。虽然未图示,但有时在未安装配合部件的钢管1的公扣部3和接箍2的母扣部4上,为了保护各自的螺纹部而安装有保护件。
另一方面,也可以不使用接箍2,而采用钢管1的一端为公扣部3、另一端为母扣部4的一体型管用螺纹接头。图6为本实施方式的一体型管用螺纹接头的结构的图。参照图6,管用螺纹接头具备钢管1。在钢管1的一端形成公扣部3,公扣部3在外表面具有公扣部侧螺纹部。在钢管1的另一端形成母扣部4,母扣部4在内表面具有母扣部侧螺纹部。通过对公扣部3和母扣部4进行紧螺纹,可使钢管1彼此连接。本实施方式的管用螺纹接头可使用接箍型和一体型这两种管用螺纹接头。
图7为管用螺纹接头的截面图。图7中,公扣部3具备公扣部侧螺纹部31、公扣部侧金属密封部32和公扣部侧台肩部33。图7中,母扣部4具备母扣部侧螺纹部41、母扣部侧金属密封部42和母扣部侧台肩部43。将对公扣部3和母扣部4进行紧螺纹时接触的部分称为接触表面34和44。具体而言,对公扣部3和母扣部4进行紧螺纹时,螺纹部彼此(公扣部侧螺纹部31和母扣部侧螺纹部41)、金属密封部彼此(公扣部侧金属密封部32和母扣部侧金属密封部42)、以及台肩部彼此(公扣部侧台肩部33和母扣部侧台肩部43)相互接触。图7中,公扣部侧接触表面34包括公扣部侧螺纹部31、公扣部侧金属密封部32和公扣部侧台肩部33。图7中,母扣部侧接触表面44包括母扣部侧螺纹部41、母扣部侧金属密封部42和母扣部侧台肩部43。
图7中,在公扣部3上,从钢管1的端部起,依次设置公扣部侧台肩部33、公扣部侧金属密封部32和公扣部侧螺纹部31。另外,在母扣部4上,从钢管1或接箍2的端部起,依次设置母扣部侧螺纹部41、母扣部侧金属密封部42和母扣部侧台肩部43。但是,公扣部侧螺纹部31和母扣部侧螺纹部41、公扣部侧金属密封部32和母扣部侧金属密封部42、以及公扣部侧台肩部33和母扣部侧台肩部43的设置不限于图7的设置,可适当改变。例如,如图6所示,也可以在公扣部3上,从钢管1的端部起,依次设置公扣部侧金属密封部32、公扣部侧螺纹部31、公扣部侧金属密封部32、公扣部侧台肩部33、公扣部侧金属密封部32和公扣部侧螺纹部31。也可以在母扣部4上,从钢管1或接箍2的端部起,依次设置母扣部侧金属密封部42、母扣部侧螺纹部41、母扣部侧金属密封部42、母扣部侧台肩部43、母扣部侧金属密封部42和母扣部侧螺纹部41。
图5和图6中,图示了具备金属密封部(公扣部侧金属密封部32和母扣部侧金属密封部42)和台肩部(公扣部侧台肩部33和母扣部侧台肩部43)的所谓的高级接头。但是,也可以没有金属密封部(公扣部侧金属密封部32和母扣部侧金属密封部42)和台肩部(公扣部侧台肩部33和母扣部侧台肩部43)。图8中给出了没有金属密封部32,42和台肩部33,43的管用螺纹接头的示例。本实施方式的润滑覆膜层也可有利地适用于没有金属密封部32,42和台肩部33,43的管用螺纹接头。没有金属密封部32,42和台肩部33,43的情况下,公扣部侧接触表面34包括公扣部侧螺纹部31。在没有金属密封部32,42和台肩部33,43的情况下,母扣部侧接触表面44包括母扣部侧螺纹部41。
[润滑覆膜层]
管用螺纹接头在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上具备润滑覆膜层。图9为本实施方式的管用螺纹接头的截面图。润滑覆膜层21通过如后述的制造方法那样,将用于形成润滑覆膜层21的组合物涂布于公扣部侧接触表面34上和母扣部侧接触表面44上的至少一者上后,使其干燥而形成。
[用于形成润滑覆膜层21的组合物]
用于形成润滑覆膜层21的组合物含有聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐。因此,润滑覆膜层21也含有聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐。组合物可以是无溶剂型组合物(即,仅含有上述成分),也可以是溶解在溶剂中的溶剂型组合物。是溶剂型组合物的情况下,各成分的质量%是指将组合物的不挥发性成分的总量(组合物中所含的溶剂以外的全部成分的总质量)设为100%时的质量%。即,组合物中的各成分的含量与润滑覆膜层21中的各成分的含量相同。以下,也将用于形成润滑覆膜层21的组合物简称为“组合物”。
以下,对组合物中的各成分进行详述。只要没有特别说明,涉及各成分的“%”表示基于组合物的不挥发性成分总量的质量%。本实施方式中不挥发性成分是指组合物中所含的溶剂以外的全部成分。不挥发性成分是指例如聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐。
[聚异丁烯]
聚异丁烯为如通式-(-C(CH3)2-CH2-)n-所表示的异丁烯的聚合物。聚异丁烯由于在分子中没有不饱和键,因此具有化学惰性,对臭氧、酸、碱等的抵抗性强。聚异丁烯为粘性高的半固体状聚合物。聚异丁烯的粘着性和粘性高。推测在组合物含有聚异丁烯的情况下,即使在高温下发生滑动,也可以抑制组合物的粘度下降。其结果,推测在组合物含有聚异丁烯的情况下,在紧螺纹的最终阶段的高面压力下,润滑覆膜层21的摩擦界面上的摩擦阻力急剧增加,高扭矩性能提升。
如上所述,组合物含有聚异丁烯时,管用螺纹接头的高扭矩性能提升。进而,组合物含有聚异丁烯时,管用螺纹接头的耐烧结性也与以往的API润滑油为同等程度或提高至其以上。
聚异丁烯含量优选为5~30%。聚异丁烯含量为5%以上时,可稳定地获得足够的高扭矩性能。因此,聚异丁烯含量的下限优选为5%,更优选为8%,进一步优选为10%。另一方面,聚异丁烯含量为30%以下时,可抑制润滑覆膜层21的强度下降。聚异丁烯含量为25%以下时,还可抑制摩擦增加,维持高耐烧结性。因此,润滑覆膜层21中的聚异丁烯含量的上限优选为30%,更优选为25%。
聚异丁烯的平均分子量(Mv)优选为30000以上。因此,聚异丁烯的平均分子量的下限优选为30000,更优选为50000。另一方面,聚异丁烯的平均分子量为100000以下时,组合物的粘度可控制在合适的范围,生产率提升。因此,聚异丁烯的平均分子量的上限优选为100000,更优选为90000,进一步优选为70000。
本说明书中,聚异丁烯的平均分子量(Mv)是指粘均分子量。粘均分子量通过以下方法测定。用毛细管粘度计对聚异丁烯的稀释用液的流下时间进行测定,求出特性粘度[η]。用得到的特性粘度[η]、Mark-Houwink的公式([η]=KMa),计算出粘均分子量(Mv)。
聚异丁烯可使用例如JXTG能源株式会社(JXTG Nippon Oil&EnergyCorporation)制造的TETRAX(注册商标)(3T~6T级)、HIMOL(商品名称)(4H~6H级)等。
[金属皂]
金属皂是脂肪酸的除钠和钾以外的所有金属盐的总称。组合物含有金属皂时,管用螺纹接头的耐烧结性和防锈性提升。
脂肪酸是饱和或不饱和的链状单羧酸的总称。脂肪酸为选自由例如月桂酸、十三烷酸、肉豆蔻酸、棕榈酸、羊毛棕榈酸、硬脂酸、异硬脂酸、12-羟基硬脂酸、油酸、反油酸、花生酸、山萮酸、芥酸、木蜡酸、羊毛蜡酸、蓖麻油酸、褐煤酸、亚油酸、亚麻酸、蓖麻酸、辛酸和癸二酸组成的组中的1种或2种以上。从润滑性、防锈性的角度出发,金属皂的脂肪酸优选为碳数12~30的脂肪酸。碳数12~30的脂肪酸为选自由例如月桂酸、十三烷酸、肉豆蔻酸、棕榈酸、羊毛棕榈酸、硬脂酸、异硬脂酸、12-羟基硬脂酸、油酸、反油酸、花生酸、山萮酸、芥酸、木蜡酸、羊毛蜡酸、蓖麻油酸、褐煤酸、亚油酸、亚麻酸和蓖麻酸组成的组中的1种或2种以上。
金属皂的金属为选自由例如钙、碱土金属、锌、铝和锂组成的组中的1种或2种以上。金属优选为钙。盐可为中性盐和碱性盐的任意一者。
组合物中的金属皂的含量优选为2~30%。金属皂的含量为2%以上时,可充分提高润滑覆膜层21的耐烧结性和防锈性。含量为30%以下时,润滑覆膜层21的密合性、强度进一步稳定地提高。金属皂的含量的下限更优选为4%,进一步优选为10%。金属皂的含量的上限更优选为19%,进一步优选为17%。
[蜡]
蜡是常温下为固体、加热则变为液体的有机物的总称。蜡为选自由动物性、植物性、矿物性和合成蜡组成的组中的1种或2种以上。动物性的蜡为选自由例如蜜蜡和鲸蜡组成的组中的1种或2种。植物性的蜡为选自由例如木蜡、巴西棕榈蜡、小烛树蜡和米糠蜡组成的组中的1种或2种以上。矿物性的蜡为选自由例如石蜡、微晶蜡、矿脂、褐煤蜡、地蜡和精制地蜡组成的组中的1种或2种以上。合成蜡为选自由例如氧化蜡、聚乙烯蜡、费托蜡、酰胺蜡和固化蓖麻油(蓖麻蜡)组成的组中的1种或2种以上。作为一例,蜡的分子量为1000以下。蜡优选为分子量150~500的石蜡。
蜡可降低润滑覆膜层21的摩擦,提高耐烧结性。蜡还降低可润滑覆膜层21的流动性,提高润滑覆膜层21的强度。
组合物中的蜡的含量优选为2~30%。蜡的含量为2%以上时,可充分获得上述效果。含量为30%以下时,润滑覆膜层21的密合性、强度进一步稳定地提高。蜡的含量的下限更优选为5%,进一步优选为10%。蜡的含量的上限更优选为20%,进一步优选为15%。
[碱性芳香族有机酸金属盐]
碱性芳香族有机酸金属盐为由芳香族有机酸和过量的碱(碱金属或碱土金属)构成的盐。碱性芳香族有机酸金属盐为例如在常温下呈油脂状或半固体的物质。
组合物中含有碱性芳香族有机酸金属盐时,润滑覆膜层21的防腐蚀性显著提高。组合物中含有碱性芳香族有机酸金属盐时,管用螺纹接头的耐烧结性也提升。该效果是由于:通过碱性芳香族有机酸金属盐以胶体状微粒状态存在于润滑覆膜层21中,过量的金属盐被物理吸附、或被有机酸基化学吸附。
芳香族有机酸为选自由例如磺酸盐、酚盐、水杨酸盐和羧酸盐组成的组中的1种或2种以上。
构成碱性芳香族有机酸金属盐的阳离子部分的碱为选自由碱金属和碱土金属组成的组中的1种或2种。优选碱为选自由碱土金属组成的组中的1种或2种。进一步优选碱为选自由钙、钡和镁组成的组中的1种或2种。
碱性芳香族有机酸金属盐其碱值越高,作为固体润滑剂发挥功能的微粒金属盐的量越升高。其结果,润滑覆膜层21的耐烧结性提升。另外,如果碱值高达某一程度以上,则具有将酸成分中和的作用。其结果,润滑覆膜层21的防锈性也提高。因此,碱性芳香族有机酸金属盐的碱值(JIS K2501(2003))(需要说明的是,在使用2种以上的情况下,为考虑了量在内的碱值的加权平均值)优选为50~500mgKOH/g。碱值为50mgKOH/g以上时,可充分获得上述效果。碱值为500mgKOH/g以下时,可降低亲水性,可获得足够的防锈性。碱性芳香族有机酸金属盐的碱值的下限更优选为100mgKOH/g,进一步优选为200mgKOH/g,最优选为250mgKOH/g。碱性芳香族有机酸金属盐的碱值的上限更优选为450mgKOH/g。碱性芳香族有机酸金属盐的碱值通过基于JIS K2501(2003)的方法来测定。
碱性芳香族有机酸金属盐的含量优选为10~70%。如上所述,碱性芳香族有机酸金属盐为油脂状或半固体的物质,还能够发挥润滑覆膜层21的基剂的作用。因此,可以大量含有至组合物的70%。因此,碱性芳香族有机酸金属盐的含量的上限优选为70%,更优选为60%,进一步优选为55%。碱性芳香族有机酸金属盐的含量的下限优选为10%,更优选为20%,进一步优选为40%。
[润滑性粉末]
为了进一步提高润滑覆膜层21的润滑性,优选组合物含有润滑性粉末。润滑性粉末是具有润滑性的固体粉末的总称。润滑性粉末可以使用公知的物质。
润滑性粉末大致分为例如以下4种。润滑性粉末含有选自由以下的(1)~(4)组成的组中的1种或2种以上。
(1)通过具有易滑动的特定的晶体结构、例如六方晶层状晶体结构而表现出润滑性的物质(例如,石墨、土状石墨、氧化锌、氮化硼和滑石);
(2)通过在晶体结构的基础上还具有反应性元素而表现出润滑性的物质(例如,二硫化钼、二硫化钨、氟化石墨、硫化锡、硫化铋和有机钼);
(3)通过化学反应性而表现出润滑性的物质(例如,硫代硫酸盐化合物);
(4)通过摩擦应力下的塑性或粘塑性行为而表现出润滑性的物质(例如,聚四氟乙烯(PTFE)、聚酰胺、铜(Cu)和氰尿酸三聚氰胺(MCA))。
优选润滑性粉末含有选自由上述(1)~(4)组成的组中的1种或2种以上。即,润滑性粉末优选为选自由石墨、土状石墨、氧化锌、氮化硼、滑石、二硫化钼、二硫化钨、氟化石墨、硫化锡、硫化铋、有机钼、硫代硫酸盐化合物、聚四氟乙烯(PTFE)、聚酰胺、铜(Cu)和氰尿酸三聚氰胺(MCA)组成的组中的1种或2种以上。润滑性粉末更优选为选自由二硫化钼、石墨、聚四氟乙烯(PTFE)和氟化石墨组成的组中的1种或2种以上。润滑性粉末进一步优选为选自由石墨和聚四氟乙烯(PTFE)组成的组中的1种或2种。作为润滑性粉末,从润滑覆膜层21的密合性和防锈性的角度出发优选为石墨,从成膜性的角度出发优选为土状石墨。从润滑性的角度出发,润滑性粉末优选为聚四氟乙烯(PTFE)。
组合物中的润滑性粉末的含量优选为0.5~20%。润滑性粉末的含量为0.5%以上时,管用螺纹接头的耐烧结性进一步提高。因此,能够不产生烧结地进行紧螺纹和松螺纹的次数增加。另一方面,润滑性粉末的含量为20%以下时,润滑覆膜层21的强度进一步提高。因此,可抑制润滑覆膜层21的损耗。因此,润滑性粉末的含量的上限优选为20%,更优选为15%,进一步优选为10%。润滑性粉末的含量的下限优选为0.5%,更优选为3%,进一步优选为5%。
[挥发性有机溶剂]
组合物可以含有挥发性有机溶剂。在常温下进行涂布的情况下,向润滑覆膜层21的成分的混合物中添加挥发性有机溶剂,制备组合物。挥发性有机溶剂与组合物所含的物质不同,在润滑覆膜层形成工序中蒸发。因此,挥发性有机溶剂通常实质上不残留于润滑覆膜层21中。但是,由于本实施方式的润滑覆膜层21可以是粘稠液体或半固体,因此有时残留有例如1%以下的挥发性有机溶剂。“挥发性”是指在覆膜形态下,在室温至150℃的温度下表现出蒸发的趋势。
挥发性有机溶剂的种类没有特别限制。挥发性有机溶剂为例如石油系溶剂。石油系溶剂是指例如选自由与JIS K2201(2006)规定的工业用汽油相当的溶剂、矿物油精、芳香族石油石脑油、二甲苯和溶纤剂组成的组中的1种或2种以上。
挥发性有机溶剂优选闪点为30℃以上且初馏温度为150℃以上、终点为210℃以下的溶剂。在这种情况下,挥发性有机溶剂操作较容易、而且蒸发快、干燥时间短。
对于挥发性有机溶剂的含量,可根据组合物的涂布方法适当调节,使得组合物调节至合适的粘度即可。将不挥发性成分的总量设为100g时,挥发性有机溶剂的含量为例如20~50g。
[其它成分]
组合物还可以含有其它公知的防锈添加剂、防腐剂、着色颜料等。
[防锈添加剂]
润滑覆膜层21优选具有到实际使用为止的长期的防锈性。因此,组合物可以含有防锈添加剂。防锈添加剂是具有耐腐蚀性的添加剂的总称。防锈添加剂为选自由例如三聚磷酸铝、亚磷酸铝和钙离子交换二氧化硅组成的组中的1种或2种以上。防锈添加剂优选含有选自由钙离子交换二氧化硅和亚磷酸铝组成的组中的1种或2种。作为防锈添加剂,除此之外还可以使用市售的反应拒水剂等。
[防腐剂]
润滑覆膜层21可以进一步含有防腐剂。防腐剂也是具有耐腐蚀性的添加剂的总称。
组合物中的其它成分(防锈添加剂、防腐剂和着色颜料等)的总含量优选为2~10质量%。其它成分的总含量为2%以上时,润滑覆膜层21的防锈性进一步稳定地提高。其它成分的总含量为10质量%以下时,润滑覆膜层21的润滑性稳定地提高。
通过将上述聚异丁烯、金属皂、蜡、碱性芳香族有机酸金属盐和其它成分混合,可以制造用于形成润滑覆膜层21的组合物。通过在管用螺纹接头的公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上涂布组合物后使其干燥,可以制造具有润滑覆膜层21的本实施方式的管用螺纹接头。
[润滑覆膜层的厚度]
润滑覆膜层21的厚度优选为10~40μm。润滑覆膜层21的厚度为10μm以上时,可稳定地获得高润滑性。另一方面,润滑覆膜层21的厚度为40μm以下时,润滑覆膜层21的密合性稳定。进而,润滑覆膜层21的厚度为40μm以下时,由于滑动面的螺纹公差(间隙)变大,因此滑动时的面压力降低。因此,可抑制紧固扭矩变得过高。因此,润滑覆膜层21的厚度优选为10~40μm。
润滑覆膜层21的厚度通过以下方法测定。用浸了乙醇的脱脂棉擦拭管用螺纹接头的公扣部侧接触表面34或母扣部侧接触表面44的任意测定部位(面积:5mm×20mm)。由擦拭前的脱脂棉的重量与擦拭后的脱脂棉的重量的差,计算出润滑覆膜层21的重量。由擦拭的润滑覆膜层21的重量、润滑覆膜层21的密度和测定部位的面积,计算出润滑覆膜层21的平均膜厚。
[润滑覆膜层的设置]
润滑覆膜层21以最表层的形式设置在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上。如图9所示,润滑覆膜层21可以仅设置于公扣部侧接触表面34上。如图10所示,润滑覆膜层21也可以仅设置于母扣部侧接触表面44上。如图11所示,润滑覆膜层21还可以在公扣部侧接触表面34上和母扣部侧接触表面44上均设置。
另外,润滑覆膜层21可以设置于公扣部侧接触表面34上和母扣部侧接触表面44上的至少一者的整体,也可以仅设置于局部。在管用螺纹接头具有金属密封部(公扣部侧金属密封部32和母扣部侧金属密封部42)和台肩部(公扣部侧台肩部33和母扣部侧台肩部43)的情况下,金属密封部32,42、台肩部33,43尤其在紧螺纹的最终阶段,面压力升高。因此,在具有金属密封部(公扣部侧金属密封部32和母扣部侧金属密封部42)和台肩部(公扣部侧台肩部33和母扣部侧台肩部43)的公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上局部地设置润滑覆膜层21的情况下,可以在公扣部侧金属密封部32、母扣部侧金属密封部42、公扣部侧台肩部33和母扣部侧台肩部43中的至少一处上设置润滑覆膜层21。另一方面,如果在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者的整体上设置润滑覆膜层21,则管用螺纹接头的生产效率提升。
润滑覆膜层21可以是单层,也可以是多层。多层是指从接触表面34或44侧起层叠了2层以上的润滑覆膜层21的状态。通过反复进行组合物的涂布和干燥,可以形成2层以上的润滑覆膜层21。润滑覆膜层21只要以最表层的形式设置在公扣部侧接触表面34上或母扣部侧接触表面44上中的至少一者上,既可以直接设置在公扣部侧接触表面34上或母扣部侧接触表面44上中的至少一者上,也可以在形成了后述的镀层或/和化学转化处理覆膜的基础上设置。
[镀层]
优选本实施方式的管用螺纹接头进一步在公扣部侧接触表面34与润滑覆膜层21之间、或/和母扣部侧接触表面44与润滑覆膜层21之间具备镀层。镀层为例如基于Cu、Sn或Ni金属的单层镀层、或基于Cu-Sn合金的单层镀覆、基于Zn-Co合金的单层镀覆、基于Zn-Ni合金的单层镀覆、或基于Cu-Sn-Zn合金镀覆的单层镀覆、Cu层和Sn层的双层镀层、和基于Ni层、Cu层以及Sn层的三层镀层。
镀层的硬度优选以显微维氏硬度计为300以上。镀层的硬度为300以上时,管用螺纹接头的耐腐蚀性进一步稳定地提高。
镀层的硬度如下测定。在管用螺纹接头的镀层中,选择5处任意区域。在所选择的各区域中,依据JIS Z2244(2009)测定维氏硬度(HV)。试验条件为:试验温度设为常温(25℃)、试验力设为2.94N(300gf)。将所得到的值(共5个)的平均值定义为镀层的硬度。
如果是如上述Cu层和Sn层的双层镀层、或基于Ni层、Cu层以及Sn层的三层镀层这种多层镀层,优选最下层的镀层的膜厚小于1μm。镀层的膜厚(多层镀覆时为总膜厚)优选为5~15μm。
镀层的厚度如下测定。使基于ISO(International Organization forStandardization)21968(2005)的涡流相位式膜厚测量仪的探针接触镀层的表面。测定探针输入侧的高频磁场与其激发的镀层上的涡流之间的相位差。将该相位差转换成镀层的厚度。
[化学转化处理覆膜]
优选本实施方式的管用螺纹接头进一步在润滑覆膜层21与镀层之间具备化学转化处理覆膜。在管用螺纹接头仅在公扣部侧接触表面34上具备镀层的情况下,化学转化处理覆膜设置于公扣部侧接触表面34上的镀层与润滑覆膜层21之间。在管用螺纹接头仅在母扣部侧接触表面44上具备镀层的情况下,化学转化处理覆膜设置于母扣部侧接触表面44上的镀层与润滑覆膜层21之间。在管用螺纹接头在公扣部侧接触表面34上和母扣部侧接触表面44上均具备镀层的情况下,化学转化处理覆膜在公扣部侧接触表面34上的镀层与润滑覆膜层21之间以及母扣部侧接触表面44上的镀层与润滑覆膜层21之间中的至少一者设置。
化学转化处理覆膜为例如磷酸盐化学转化处理覆膜、草酸盐化学转化处理覆膜和硼酸盐化学转化处理覆膜。化学转化处理覆膜是多孔的。因此,在化学转化处理覆膜上形成有润滑覆膜层21时,由于所谓的“锚固效应”,润滑覆膜层21的密合性进一步提高。化学转化处理覆膜的优选的厚度为5~40μm。化学转化处理覆膜的厚度为5μm以上时,可确保足够的耐腐蚀性。化学转化处理覆膜的厚度为40μm以下时,润滑覆膜层21的密合性稳定地提高。
化学转化处理覆膜的厚度通过以下方法求出。将形成有化学转化处理覆膜的管用螺纹接头沿化学转化处理覆膜的厚度方向(与管用螺纹接头的轴向垂直的方向)裁断。使用光学显微镜以500倍的倍率观察化学转化处理覆膜的截面,测定化学转化处理覆膜的厚度。由上述测定方法所测定的化学转化处理覆膜的厚度为10μm以下时,重新裁断,再次测定。在这种情况下,沿从与管用螺纹接头的轴向垂直的方向起倾斜60°的方向裁断管用螺纹接头。使用光学显微镜以500倍的倍率观察所得到的化学转化处理覆膜的截面,测定化学转化处理覆膜的厚度。对化学转化处理覆膜的厚度进行再次测定的情况下,将再次测定的厚度作为化学转化处理覆膜的厚度。
[喷砂处理或酸洗]
本实施方式的管用螺纹接头中,与润滑覆膜层21接触的润滑覆膜层21之下的表面可以是经喷砂处理或酸洗的表面。“与润滑覆膜层21接触的润滑覆膜层21之下的表面”,在管用螺纹接头在公扣部侧接触表面34上不具备镀层的情况下(即,在公扣部侧接触表面34上直接形成了润滑覆膜层21的情况下),指的是公扣部侧接触表面34;在管用螺纹接头在公扣部侧接触表面34上具备镀层的情况下,指的是镀层表面。“与润滑覆膜层21接触的润滑覆膜层21之下的表面”,在管用螺纹接头在母扣部侧接触表面44上不具备镀层的情况下(即,在母扣部侧接触表面44上直接形成了润滑覆膜层21的情况)下,指的是母扣部侧接触表面44;在管用螺纹接头在母扣部侧接触表面44上具备镀层的情况下,指的是镀层表面。
经喷砂处理或酸洗的表面的表面粗糙度提升。更具体而言,在公扣部侧接触表面34、母扣部侧接触表面44和镀层表面经喷砂处理或酸洗的情况下,公扣部侧接触表面34、母扣部侧接触表面44和镀层表面的表面粗糙度高。在这种情况下,其上形成的润滑覆膜层21的密合性进一步提高。表面粗糙度优选以算术平均偏差Ra计为1.0~8.0μm。算术平均偏差Ra越大,润滑覆膜层21的接触面积越大。因此,基于锚固效应,与润滑覆膜层21的密合性提升。如果润滑覆膜层21的密合性提高,则管用螺纹接头的耐烧结性进一步提高。算术平均偏差Ra为1.0μm以上时,润滑覆膜层21的密合性进一步提高。算术平均偏差Ra为8.0μm以下时,可抑制摩擦,可抑制润滑覆膜层21的损伤和剥离。
本说明书中所提到的算术平均偏差Ra根据JIS B 0601(2001)进行测定。使用SIINanoTechnology Inc.制造的扫描型探针显微镜SPI3800N进行测定。测定条件为:在样品的2μm×2μm的区域,采集数据数为1024×1024。基准长度为2.5mm。
[润滑覆膜层、镀层和化学转化处理覆膜的设置]
只要在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上设置润滑覆膜层21,镀层和化学转化处理覆膜的设置并不特别限定。将仅具备润滑覆膜层21的情况作为方式1。将具备润滑覆膜层21、且在其下具备镀层的情况作为方式2。将具备润滑覆膜层21、且在其下具备化学转化处理覆膜的情况作为方式3。将具备润滑覆膜层21、且在其下具备化学转化处理覆膜和镀层的情况作为方式4。将不具备润滑覆膜层21的情况作为方式5。只要满足上述条件,公扣部侧接触表面34和母扣部侧接触表面44有可能出现方式1~5的任意一种情况。具体而言,公扣部侧接触表面34为方式1~方式4时,母扣部侧接触表面44可以是方式1~方式5的任意一者。另外,公扣部侧接触表面34为方式5时,母扣部侧接触表面44为方式1~方式4的任意一者。相反地,母扣部侧接触表面44为方式1~方式4时,公扣部侧接触表面34可以是方式1~方式5的任意一者。另外,母扣部侧接触表面44为方式5时,公扣部侧接触表面34为方式1~方式4的任意一者。任意一种方式中,公扣部侧接触表面34、母扣部侧接触表面44和镀层表面均可以是适当实施了喷砂处理或酸洗的表面。
[管用螺纹接头的母材]
管用螺纹接头的母材的组成并不特别限定。母材为例如碳钢、不锈钢和合金钢等。在合金钢之中,含有Cr、Ni和Mo等合金元素的双相不锈钢和Ni合金等高合金钢的耐腐蚀性高。因此,如果母材使用这些高合金钢,则在含有硫化氢、二氧化碳等的腐蚀环境中,可获得优异的耐腐蚀性。
[制造方法]
以下,对本实施方式的管用螺纹接头的制造方法进行说明。
本实施方式的管用螺纹接头的制造方法具备润滑覆膜层形成工序:在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上,使用本实施方式的组合物形成润滑覆膜层21。
[润滑覆膜层形成工序]
在润滑覆膜层形成工序中,通过添加溶剂和/或加热,使上述组合物的构成成分的混合物液化,并涂布在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上。根据需要,使涂布在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上的组合物干燥,形成润滑覆膜层21。润滑覆膜层21的性状不限。润滑覆膜层21的性状为例如固体、粘稠液体或半固体。
首先,制造组合物。无溶剂型组合物可通过例如将聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐的混合物加热形成熔融状态并混炼来制造。也可以将全部成分以粉末状的形式混合而得到的粉末混合物作为组合物。
溶剂型组合物可通过例如在挥发性有机溶剂中溶解或分散聚异丁烯、金属皂、蜡和碱性芳香族有机酸金属盐并混合来制造。
如果是无溶剂型组合物,则可以使用热熔法涂布组合物。热熔法中,加热组合物使其熔融,形成低粘度的流动状态。通过由具有保温功能的喷枪喷雾流动状态的组合物来进行。组合物在具备合适的搅拌装置的罐内加热而熔融,通过压缩机经由计量泵供给至喷枪的喷头(保持在规定温度),进行喷雾。加热温度为例如90~130℃。罐内和喷头的保持温度根据组合物的构成成分的熔点来调节。对于涂布方法,可以用毛刷涂布和浸渍等代替喷雾涂布。组合物的加热温度优选为比组合物的熔点高10~50℃的温度。涂布组合物时,优选将待涂布组合物的公扣部侧接触表面34上和母扣部侧接触表面44上的至少一者预先加热至比基剂的熔点高的温度。由此能够得到良好的被覆性。
如果是溶剂型组合物,则通过喷雾涂布等将处于溶液状态的组合物涂布在接触表面上。在这种情况下,优选将组合物的粘度调节为可在常温和常压的环境下进行喷雾涂布。
如果是无溶剂型组合物,则通过使涂布在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上的组合物冷却,而使得熔融状态的组合物干燥,形成润滑覆膜层21。冷却方法可以按公知的方法实施。冷却方法为例如大气自然冷却和空气冷却。
如果是溶剂型组合物,则通过使涂布在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上的组合物干燥,形成润滑覆膜层21。干燥方法可以按公知的方法实施。干燥方法为例如自然干燥、低温鼓风干燥和真空干燥。
冷却可以通过氮气和二氧化碳气体冷却系统等的快速冷却来实施。在实施快速冷却的情况下,从已涂布组合物的公扣部侧接触表面34或/和母扣部侧接触表面44的反面(对于母扣部4来说是钢管1或接箍2的外表面,对于公扣部3来说是钢管1的内表面)进行间接冷却。由此,能够抑制由润滑覆膜层21的快速冷却导致的劣化。
本实施方式的制造方法可以在润滑覆膜层形成工序之前包括以下工序。
[镀层形成工序]
本实施方式的管用螺纹接头的制造方法可以在润滑覆膜层形成工序之前具备镀层形成工序。镀层可以通过例如电镀处理或冲击镀覆处理来形成。
[电镀处理]
电镀处理为通过例如电镀来形成镀层的处理。在形成镀层的情况下,在电镀处理中,可以在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上,通过电镀处理形成Zn合金镀层。或者在电镀处理中,可以在使公扣部侧接触表面34和母扣部侧接触表面44的至少一者经喷砂处理或酸洗变得粗糙后,通过电镀处理形成Zn合金镀层。
如果实施电镀处理,则管用螺纹接头的耐烧结性和耐腐蚀性提升。在形成镀层的情况下,电镀处理工序为例如基于Cu、Sn或Ni金属的单层镀覆处理、基于Cu-Sn合金的单层镀覆处理、基于Zn-Co合金的单层镀覆处理、基于Zn-Ni合金的单层镀覆处理、或基于Cu-Sn-Zn合金镀覆的单层镀覆处理、Cu层和Sn层的双层镀覆处理、以及基于Ni层、Cu层和Sn层的三层镀覆处理。对于由Cr含量为5%以上的钢形成的钢管1,优选Cu-Sn合金镀覆处理、镀Cu-镀Sn的双层镀覆处理、和镀Ni-镀Cu-镀Sn的三层镀覆处理。
电镀处理可以按公知的方法实施。例如,准备含有镀层中包含的金属元素的离子的镀浴。接着,将公扣部侧接触表面34上和母扣部侧接触表面44上的至少一者浸渍于镀浴。通过对浸渍的公扣部侧接触表面34或/和母扣部侧接触表面44通电,在公扣部侧接触表面34上和母扣部侧接触表面44上中的至少一者上形成镀层。镀浴的温度和镀覆时间等条件可以适当设定。
更详细而言,例如,在形成Cu-Sn-Zn合金镀层的情况下,镀浴含有铜离子、锡离子和锌离子。镀浴的组成优选为Cu:1~50g/L、Sn:1~50g/L和Zn:1~50g/L。电镀的条件为例如镀浴pH:1~10、镀浴温度:60℃、电流密度:1~100A/dm2以及处理时间:0.1~30分钟。
在形成Zn-Ni合金镀层的情况下,镀浴含有锌离子和镍离子。镀浴的组成优选为Zn:1~100g/L和Ni:1~50g/L。电镀的条件为例如镀浴pH:1~10、镀浴温度:60℃、电流密度:1~100A/dm2以及处理时间:0.1~30分钟。
[冲击镀覆处理]
冲击镀覆处理为可以通过使颗粒和被镀物在转筒内碰撞的机械镀、使用喷砂装置使颗粒碰撞被镀物的投射镀来实施的处理。
本实施方式的管用螺纹接头的制造方法可以对与润滑覆膜层21接触的表面进行喷砂处理或酸洗。通过喷砂处理或酸洗,可以形成表面粗糙度。“与润滑覆膜层21接触的表面”,在公扣部侧接触表面34不具备镀层的情况下,指的是公扣部侧接触表面34;在公扣部侧接触表面34具备镀层的情况下,指的是镀层。“与润滑覆膜层21接触的表面”,在母扣部侧接触表面44不具备镀层的情况下,指的是母扣部侧接触表面44;在母扣部侧接触表面44具备镀层的情况下,指的是镀层。
[喷砂处理]
喷砂处理为例如使用喷砂装置使颗粒碰撞被镀物的处理。喷砂处理为例如喷砂处理。喷砂处理为将喷砂材料(研磨剂)与压缩空气混合并投射至接触表面34,44的处理。喷砂材料为例如球状的球粒材料和角状的砂粒材料。通过喷砂处理,可以增大公扣部侧接触表面34、母扣部侧接触表面44或镀层的表面粗糙度。喷砂处理可以通过公知的方法实施。例如用压缩机压缩空气,将压缩空气与喷砂材料混合。喷砂材料的材质为例如不锈钢、铝、陶瓷和氧化铝等。喷砂处理的投射速度等条件可以适当设定。
[酸洗处理]
酸洗处理为将公扣部侧接触表面34或母扣部侧接触表面44的至少一者浸渍于硫酸、盐酸、硝酸或氢氟酸等强酸液中,使接触表面34或44粗糙化的处理。由此,可以增大接触表面34或44的表面粗糙度。
[化学转化处理]
本实施方式的管用螺纹接头的制造方法可以在润滑覆膜层形成工序之前具备化学转化处理工序。化学转化处理为形成表面粗糙度大的多孔的化学转化处理覆膜的处理。化学转化处理为例如磷酸盐化学转化处理、草酸盐化学转化处理和硼酸盐化学转化处理。从润滑覆膜层21的密合性的角度出发,优选磷酸盐化学转化处理。磷酸盐化学转化处理为使用例如磷酸锰、磷酸锌、磷酸铁锰或磷酸锌钙的磷酸盐化学转化处理。
化学转化处理可以按公知的方法实施。作为处理液,可以使用常规镀锌材料用的酸性磷酸盐化学转化处理液。例如,可列举出含有磷酸根离子1~150g/L、锌离子3~70g/L、硝酸根离子1~100g/L、镍离子0~30g/L的磷酸锌系化学转化处理。也可以使用管用螺纹接头所惯用的磷酸锰系化学转化处理液。液温为例如常温至100℃。处理时间可以根据期望的膜厚来适当设定,例如为15分钟。为了促进化学转化处理覆膜的形成,可以在化学转化处理前进行表面调整。表面调整为浸渍于含有胶态钛的表面调整用水溶液的处理。化学转化处理后,优选先进行水洗或热水洗涤再干燥。
以上的润滑覆膜层形成前的处理可以仅实施1种,也可以将多种处理组合。
对于润滑覆膜层形成前的处理,可以对公扣部3和母扣部4实施相同的处理,也可以对公扣部3和母扣部4实施不同的处理。
实施例
以下,对本发明的实施例进行说明。其中,本发明并不受实施例的限制。实施例中,将公扣部侧接触表面称为公扣部表面,将母扣部侧接触表面称为母扣部表面。另外,实施例中的%在没有特别指定的情况下,表示质量%。
本实施例中,管状螺纹接头使用日本制铁株式会社制造的VAM21(注册商标)。VAM21(注册商标)是外径:177.80mm(7英寸)、壁厚11.506mm(0.453英寸)的管用螺纹接头。钢种为碳钢。碳钢的组成为C:0.24%,Si:0.23%,Mn:0.7%,P:0.02%,S:0.01%,Cu:0.04%,Ni:0.05%,Cr:0.95%,Mo:0.15%,余量:Fe和杂质。
如表1所示,对各试验编号的公扣部表面和母扣部表面实施基底处理。表1的“基底处理”一栏的数字表示进行基底处理的顺序。例如,如果是“1.精磨、2.磷酸Zn”,就表示在进行精磨之后,实施磷酸锌化学转化处理。喷砂加工中使用磨粒Mesh100形成表面粗糙度。各试验编号的算术平均偏差Ra如表1所示。算术平均偏差Ra根据JIS-B0601(2013)进行测定。算术平均偏差Ra的测定使用SII NanoTechnology Inc.制造的扫描型探针显微镜SPI3800N。测定条件为:作为采集数据数的单位,在样品的2μm×2μm的区域,采集数据数为1024×1024。Zn-Ni合金的膜厚通过上述的测定方法测定。
[表1]
表1
然后,使用具有如表2所示的组成的组合物,形成润滑覆膜层,准备各试验编号的公扣部和母扣部。表2中,“组合物的不挥发性成分组成”一栏的括号内显示的是基于组合物的不挥发性成分总量的以质量%计的含量。聚异丁烯使用JXTG能源株式会社制造的TETRAX(注册商标)的3T级(平均分子量30000)、TETRAX(注册商标)的4T级(平均分子量40000)、TETRAX(注册商标)的5T级(平均分子量50000)、TETRAX(注册商标)的6T级(平均分子量60000)。金属皂使用大日本油墨化学工业株式会社制造的Ca-STEARATE(商品名称)。蜡使用日本精蜡株式会社制造的石蜡(商品名称)。碱性芳香族有机酸金属盐使用CHEMTURA公司制造的Calcinate(商品名称)C400CLR(碱值400mgKOH/g)作为碱性磺酸Ca盐。润滑性粉末如果是石墨,使用日本石墨工业株式会社制造的石墨粉末:青P(商品名称)(灰分3.79%,结晶度96.9%,平均粒径7μm)。润滑性粉末如果是PTFE,使用大金工业株式会社制造的产品名LUBRON(注册商标)L-5F。挥发性有机溶剂使用Exxon Mobil Corporation的产品名Exxsol(商品名称)D40。表2中显示为有机溶剂。需要说明的是,在试验编号12中,使用API标准BUL5A2规定的复合润滑脂代替组合物。将使用复合润滑脂的例子作为后述的高扭矩性能的基准。
[表2]
表2
[试验编号1]
试验编号1中,对公扣部表面和母扣部表面进行机械精磨。然后,在常温(约25℃)下,对公扣部表面和母扣部表面均喷雾涂布用于形成润滑覆膜层的组合物,形成润滑覆膜层。基于规定的喷雾压力和距对象面的距离,用每单位面积和单位时间所涂布的组合物的重量及其比重,计算出目标平均膜厚,以该值在120~150μm的范围的方式,涂布形成润滑覆膜层的膜厚。
[试验编号2~试验编号4和试验编号8~试验编号10]
试验编号2~试验编号4和试验编号8~试验编号10中,对公扣部表面和母扣部表面进行机械精磨。对于公扣部,在75~85℃的磷酸锌用化学转化处理液中浸渍10分钟,形成厚度10μm的磷酸锌覆膜。对于母扣部,在80~95℃的磷酸锰用化学转化处理液中浸渍10分钟,形成厚度12μm的磷酸锰覆膜。然后,在常温(约20℃)下,对公扣部表面和母扣部表面均喷雾涂布用于形成润滑覆膜层的组合物,形成润滑覆膜层。基于规定的喷雾压力和距对象面的距离,用每单位面积和单位时间所涂布的组合物的重量及其比重,计算出目标平均膜厚,以该值在120~150μm的范围的方式,涂布形成润滑覆膜层的膜厚。
[试验编号5]
试验编号5中,对公扣部表面进行机械精磨。在75~85℃的磷酸锌用化学转化处理液中浸渍10分钟,形成厚度10μm的磷酸锌覆膜。在常温(约25℃)下,向其上喷雾涂布用于形成润滑覆膜层的组合物,形成润滑覆膜层。基于规定的喷雾压力和距对象面的距离,用每单位面积和单位时间所涂布的组合物的重量及其比重,计算出目标平均膜厚,以该值在120~150μm的范围的方式,涂布形成润滑覆膜层的膜厚。
对母扣部表面进行机械精磨。在其上通过电镀实施Zn-Ni合金镀覆,形成Zn-Ni合金镀层。Zn-Ni合金镀浴使用大和化成株式会社制造的商品名称DAIN Zinalloy N-PL。电镀的条件为镀浴pH:6.5、镀浴温度:25℃、电流密度:2A/dm2以及处理时间:18分钟。Zn-Ni合金镀层的组成为Zn:85%和Ni:15%。向其上加热(约110℃)并喷雾涂布用于形成润滑覆膜层的组合物,缓慢冷却,形成润滑覆膜层。基于规定的喷雾压力和距对象面的距离,用每单位面积和单位时间所涂布的组合物的重量及其比重,计算出目标平均膜厚,以该值在120~150μm的范围的方式,涂布形成润滑覆膜层的膜厚。
[试验编号6和试验编号7]
试验编号6和试验编号7中,对公扣部表面和母扣部表面进行机械精磨。然后,通过喷砂加工形成表面粗糙度。然后,在常温(约20℃)下,对公扣部表面和母扣部表面均喷雾涂布用于形成润滑覆膜层的组合物,形成润滑覆膜层。基于规定的喷雾压力和距对象面的距离,用每单位面积和单位时间所涂布的组合物的重量及其比重,计算出目标平均膜厚,以该值在120~150μm的范围的方式,涂布形成润滑覆膜层的膜厚。
[试验编号11]
试验编号11中,对公扣部表面和母扣部表面进行机械精磨。对于公扣部表面,在75~85℃的磷酸锌用化学转化处理液中浸渍10分钟,形成厚度10μm的磷酸锌覆膜。对于母扣部表面,在80~95℃的磷酸锰用化学转化处理液中浸渍10分钟,形成厚度12μm的磷酸锰覆膜。然后,在常温(约25℃)下,对公扣部表面和母扣部表面均喷雾涂布用于形成润滑覆膜层的组合物,形成润滑覆膜层。基于规定的喷雾压力和距对象面的距离,用每单位面积和单位时间所涂布的组合物的重量及其比重,计算出目标平均膜厚,以该值在120~150μm的范围的方式,涂布形成润滑覆膜层的膜厚。试验编号11的组合物中不含聚异丁烯。
[试验编号12]
试验编号12中,对公扣部表面和母扣部表面进行机械精磨和磷酸盐化学转化处理。在其上用毛刷涂布API标准润滑油。API标准润滑油是指依据API Bul 5A2制造的油井管用螺纹用复合润滑脂。API标准润滑油的组成规定以油脂为基材,含有石墨粉:18±1.0%、铅粉:30.5±0.6%和铜片:3.3±0.3%。需要说明的是,应理解在该成分范围内油井管用螺纹用复合润滑脂具有同等的性能。
[耐烧结性评价试验]
耐烧结性评价通过反复紧固试验来进行。使用试验编号1~试验编号12的公扣部和母扣部,在室温(约25℃)下反复紧螺纹和松螺纹,评价耐烧结性。紧固扭矩设为24350N·m。每进行一次紧螺纹和松螺纹,通过目视观察公扣部表面和母扣部表面。通过目视观察确认螺纹部和金属密封部中产生烧结的情况。金属密封部产生烧结便结束试验。在螺纹部的烧结轻微、可通过锉等维修来修复的情况下,修补烧结缺陷继续试验。最大反复紧固次数设为15次。耐烧结性的评价指标采用在螺纹部未产生不可恢复的烧结且在金属密封部未产生烧结的最大紧固次数。结果示于表3的“耐烧结性(在螺纹部未产生不可恢复的烧结且在金属密封部未产生烧结而完成紧固的次数(次))”一栏。
需要说明的是,试验编号12中,每进行一次紧螺纹和松螺纹,都需要重新涂抹API润滑油。这是由于通常API润滑油在使用时都是每进行一次紧螺纹和松螺纹就重新涂抹的。另外,对于API润滑油,只能设想这样的使用方法。另一方面,试验编号1~试验编号11中,持续试验而不重新形成润滑覆膜层,直至试验结束。
[表3]
表3
[高扭矩性能评价试验]
使用试验编号1~试验编号12的公扣部和母扣部,测定台肩摩阻扭矩ΔT’。具体而言,以拧紧速度10rpm、拧紧扭矩42.8kN·m进行紧螺纹。在紧螺纹时测定扭矩,绘制如图12所示的扭矩图。图12中的Ts表示台肩扭矩。图12中的MTV表示线段L与扭矩图相交的扭矩值。线段L为具有与上肩后的扭矩图中的线性区域的斜率相同的斜率、转数比该线性区域多0.2%的直线。通常,测定台肩摩阻扭矩ΔT’时,使用Ty(屈服扭矩)。但是,本实施例中,屈服扭矩(上肩后的扭矩图中的线性区域与非线性区域的边界)不明确。因此,使用线段L规定MTV。将MTV与Ts的差值作为本实施例的台肩摩阻扭矩ΔT’。以试验编号12中使用API标准润滑油代替润滑覆膜层时的台肩摩阻扭矩ΔT’的数值为基准(100),以本实施例的台肩摩阻扭矩ΔT’的相对值的形式求出高扭矩性能。结果示于表3。
[评价结果]
参照表1~表3,试验编号1~试验编号10的管用螺纹接头的形成润滑覆膜层的组合物含有聚异丁烯。因此,即使反复进行10次紧螺纹和松螺纹,也未产生烧结,表现出优异的耐烧结性。此外,高扭矩性能大于100,表现出优异的高扭矩性能。
试验编号1~试验编号5和试验编号8~试验编号10的管用螺纹接头的聚异丁烯含量为5~30%。因此,与试验编号6(聚异丁烯含量小于5%)的管用螺纹接头相比,高扭矩性能进一步改善。此外,与试验编号7(聚异丁烯含量大于30%)的管用螺纹接头相比,未烧结地完成紧固的次数更多,表现出更优异的耐烧结性。
另一方面,试验编号11的管用螺纹接头的形成润滑覆膜层的组合物不含聚异丁烯。因此,未烧结地完成紧固的次数、高扭矩性能低。
以上,对本申请的实施方式进行了说明。但是,上述实施方式仅是用于实施本申请的示例。因此,本申请不限于上述实施方式,可以在不脱离其主旨的范围内对上述实施方式进行适当变更而实施。
附图标记说明
1 钢管
2 接箍
3 公扣部
4 母扣部
21 润滑覆膜层
31 公扣部侧螺纹部
32 公扣部侧金属密封部
33 公扣部侧台肩部
34 公扣部侧接触表面
41 母扣部侧螺纹部
42 母扣部侧金属密封部
43 母扣部侧台肩部
44 母扣部侧接触表面。
Claims (18)
1.一种组合物,其用于在管用螺纹接头上形成粘稠或半固体状态的润滑覆膜层,
将所述组合物中的不挥发性成分的总量设为100质量%时,所述组合物含有
聚异丁烯:5~30质量%、
金属皂:2~19质量%、
蜡:2~20质量%、和
碱性芳香族有机酸金属盐:10~60质量%,
所述聚异丁烯的平均分子量Mv为30000~70000。
2.根据权利要求1所述的组合物,
其进一步含有润滑性粉末。
3.根据权利要求2所述的组合物,其中,
将所述组合物中的不挥发性成分的总量设为100质量%时,所述组合物含有
润滑性粉末:0.5~20质量%。
4.根据权利要求2所述的组合物,其中,
所述润滑性粉末为选自由石墨和聚四氟乙烯组成的组中的1种或2种。
5.根据权利要求3所述的组合物,其中,
所述润滑性粉末为选自由石墨和聚四氟乙烯组成的组中的1种或2种。
6.根据权利要求1~权利要求5中任一项所述的组合物,
其进一步含有挥发性有机溶剂。
7.一种管用螺纹接头,其具备:
公扣部,其具有包含公扣部侧螺纹部的公扣部侧接触表面;
母扣部,其具有包含母扣部侧螺纹部的母扣部侧接触表面;以及
粘稠或半固体状态的润滑覆膜层,其以最表层的形式位于所述公扣部侧接触表面上和所述母扣部侧接触表面上中的至少一者上,由权利要求1~权利要求6中任一项所述的组合物构成。
8.根据权利要求7所述的管用螺纹接头,
其在所述公扣部侧接触表面上具备所述润滑覆膜层。
9.根据权利要求8所述的管用螺纹接头,
其在所述公扣部侧接触表面与所述润滑覆膜层之间进一步具备镀层。
10.根据权利要求9所述的管用螺纹接头,
其在所述润滑覆膜层与所述镀层之间进一步具备化学转化处理覆膜。
11.根据权利要求8所述的管用螺纹接头,其中,
在所述公扣部侧接触表面与所述润滑覆膜层之间不具备镀层,所述公扣部侧接触表面为经过选自由喷砂处理和酸洗组成的组中的1种或2种处理的面。
12.根据权利要求9所述的管用螺纹接头,其中,
所述镀层表面为经过选自由喷砂处理和酸洗组成的组中的1种或2种处理的面。
13.根据权利要求7所述的管用螺纹接头,
其在所述母扣部侧接触表面上具备所述润滑覆膜层。
14.根据权利要求13所述的管用螺纹接头,
其在所述母扣部侧接触表面与所述润滑覆膜层之间进一步具备镀层。
15.根据权利要求14所述的管用螺纹接头,
其在所述润滑覆膜层与所述镀层之间进一步具备化学转化处理覆膜。
16.根据权利要求13所述的管用螺纹接头,其中,
在所述母扣部侧接触表面与所述润滑覆膜层之间不具备镀层,所述母扣部侧接触表面为经过选自由喷砂处理和酸洗组成的组中的1种或2种处理的面。
17.根据权利要求14所述的管用螺纹接头,其中,
所述镀层表面为经过选自由喷砂处理和酸洗组成的组中的1种或2种处理的面。
18.根据权利要求7~权利要求17中任一项所述的管用螺纹接头,其中,
所述公扣部侧接触表面进一步包含公扣部侧金属密封部和公扣部侧台肩部,
所述母扣部侧接触表面进一步包含母扣部侧金属密封部和母扣部侧台肩部。
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