CN116273798A - 一种内壁沉积耐腐蚀涂层的无缝钢管及组合物和制备方法 - Google Patents
一种内壁沉积耐腐蚀涂层的无缝钢管及组合物和制备方法 Download PDFInfo
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Abstract
本发明公开了一种内壁沉积耐腐蚀涂层的无缝钢管及组合物和制备方法,该无缝钢管由304、316材质的母材及内壁的耐腐蚀涂层组成,钢管母材为单相奥氏体组织,内壁沉积的耐腐蚀涂层含质量比15‑20%Cr、5‑10%Al、1‑3Ni%、1‑3Si%、0.5‑1%P、其余为Fe,涂层与母材冶金结合,涂层厚度20‑40μm。本发明技术中无缝钢管内壁涂层沉积过程与无缝钢管的固溶热处理过程中同步,避免了传统涂层制备工艺需要额外加热、多次处理等问题,提高了生产效率,节约成本。同时,涂层制备原料为浆状原料,可以均匀涂覆在管内壁,克服了无缝钢管口径小、长度大的尺寸限制瓶颈,提高了涂层原料利用率,进一步提高了生产效率。
Description
技术领域
本发明属于无缝钢管制造技术领域,具体涉及一种内壁沉积耐腐蚀涂层的无缝钢管及组合物和制备方法。
背景技术
无缝钢管是由整支圆钢穿孔而成的,表面上没有焊缝的钢管,称之为无缝钢管。根据生产方法,无缝钢管可分热轧无缝钢管、冷轧无缝钢管。无缝钢管的用途非常广泛,包括结构、流体输送、低中压锅炉、高压锅炉、化肥设备、石油裂化、地质钻探、金刚石岩芯钻探、石油钻探、船舶、汽车半轴套管、柴油机等等,都会用到无缝钢管,使用无缝钢管可以避免出现渗漏等问题,保证了使用效果,提高材料利用率。
钢管腐蚀问题普遍存在于国民经济和国防建设的各个部门,既给国民经济带来了巨大的损失.也给生产和生活造成极大的困难。钢管在自然条件下(大气,天然水体、土壤)或人为条件(酸、碱、盐及其它介质)下,每时每刻都在发生腐蚀.一种自发进行的无谓的消耗。其根本原因钢质管道是因为处于热力学不稳定状态,在上述条件下它们就要恢复原来的相对稳定的状态.生成铁氧化物碳酸盐等.或转变为可溶性离子。腐蚀不仅是钢铁资源的浪费,还会因腐蚀使管道、设备使用寿命缩短更换新管道设备的造价费用远远超过金属材料本身的价格,生产成本因此而增大,降低了经济效益腐蚀造成的直接和间接经济损失是巨大的。
高温涂层技术可以显著提高管道内壁抗腐蚀能力,从而延长部件的服役寿命。但是,无缝钢管具内径小、长度大的结构特点。如何在管内壁优异的涂层成分设计、稳定的制备工艺等均未有效解决。日本在2007-2011年制定了关于涂层的ISO标准(ISO 21809系列标准),从而建立了关于涂层的世界标准。日本以该标准为基础制定了JIS G3477(聚乙烯涂层钢管)系列标准。应对这些标准,新日铁住金开发出采用高耐久性环氧底漆的3层聚乙烯涂层钢管。这种钢管已经在世界广泛使用。新日铁住金以日本水道钢管协会为中心,开发出外面底漆涂层、内面无溶剂环氧树脂涂层的组合涂层的钢管长寿化技术,采用这种技术,水道钢管的寿命可达100年,但是并不适用于高温腐蚀环境。在国内,西安热工院自主研发的“高温涂层技术”在锅炉用无缝钢管上得到应用,应用结果表明,该涂层技术可提高其抗高温蒸汽氧化能力1000倍以上,大幅降低机组全寿命期内接管座氧化皮生长、剥落和堆积的风险,为解决锅炉蒸汽流通部件的氧化皮问题开辟了新思路和途径,目前该技术还仅限于高温蒸汽环境。国电热工院早期采用了热浸渗铝技术,在锅炉管道表面形成了以FeAl为主相的合金化层,显著提高了管道抗烟气腐蚀能力,并在马头电厂得到了示范应用。但是,受热浸渗铝工艺所限,能处理的管子比较短(2~3米),大大增加了施工中的焊接量,因而未能得到推广。中国科学院金属研究所发明了一种大气条件下无保护气氛或保护层的料浆高速渗铝方法。该法将工件表面沉积渗铝料浆,在无保护气氛和保护层下直接对工件加热,可以在工件表层获得一定厚度的富铝层。但对锅炉使用的超长管内壁实施此工艺,工艺性和可行性尚待确认。
发明内容
本发明的目的在于克服上述现有技术的缺点,提供了一种内壁沉积耐腐蚀涂层的无缝钢管及组合物和制备方法,该方法可以实现内壁含有冶金结合耐蚀涂层的无缝钢管制备。
为达到上述目的,本发明采用以下技术方案:
一种内壁沉积耐腐蚀涂层的无缝钢管的制备方法,其特征在于,包括如下工艺步骤:
步骤一:对固溶热处理前的无缝钢管进行酸洗,直至裸露金属表面,并采用碱溶液或脂溶性溶剂除油;
步骤二:按照质量百分比计,称取5~8%醋酸纤维素酯,5~10%的磷酸,2~5%铬酐、10~30%的铬粉、5~10%的铝粉、2~5%的硅粉、5~10%的氧化硅、其余为乙酰丙酮溶液;将上述物质混合搅拌均匀后,使用球磨机氩气保护球磨24小时,得到浆状原料;
步骤三:将浆状原料均匀涂覆在步骤一处理后的钢管内壁,涂覆厚度为100-150μm,烘干后进行无缝钢管固溶热处理工艺。
所述的制备方法,无缝钢管固溶热处理在氩气保护下进行,加热温度1100-1200℃、保温时间不少于15min,水冷淬火。
所述的制备方法,无缝钢管的制备流程适用于冷拔或热挤压的制备工艺。
根据任一所述制备方法获得的无缝钢管,内壁沉积的耐腐蚀涂层含质量比15-20%Cr、5-10%Al、1-3Ni%、1-3Si%、0.5-1%P、其余为Fe,涂层与母材冶金结合,涂层厚度20-40μm。
所述的无缝钢管,该无缝钢管由304、316材质的母材及内壁的耐腐蚀涂层组成,钢管母材为单相奥氏体组织。
一种用于在无缝钢管内壁沉积耐腐蚀涂层的组合物,其组分为:5~8%醋酸纤维素酯,5~10%的磷酸,2~5%铬酐、10~30%的铬粉、5~10%的铝粉、2~5%的硅粉、5~10%的氧化硅、其余为乙酰丙酮溶液。
本发明具有以下有益效果:
本发明所述的一种内壁沉积耐腐蚀涂层的无缝钢管及其制备方法,管内壁涂层沉积过程与无缝钢管的固溶热处理过程中同步,避免了传统涂层制备工艺需要额外加热、多次处理等问题,提高了生产效率,节约成本。同时,涂层制备原料为浆状原料,金属粉末起到渗剂作用,有机醋酸纤维素酯与无机磷酸溶液共同形成高粘度粘结剂,保障涂覆的料浆快速干燥、高粘合力且无开裂。本发明浆状原料可以均匀涂覆在管内壁,克服了无缝钢管口径小、长度大的尺寸限制瓶颈,提高了涂层原料利用率,进一步提高了生产效率。
附图说明
图1为本发明的实施例一中处理后的无缝钢管截面组织形貌;(a)为母材组织形貌,(b)为涂层组织形貌;
图2本发明的实施例二中处理后的无缝钢管截面组织形貌;(a)母材组织形貌;(b)涂层组织形貌;
具体实施方式
以下结合具体实施例,对本发明进行详细说明。
以制备内壁沉积耐腐蚀涂层的304无缝钢管为例,304无缝钢管的传统制备流程制备包含炼钢、铸造、坯料热成形、退火、热挤压制管、固溶热处理,淬火,矫直,加工清理等诸多工序,具体执行标准可参考《GB/T14976-2002)用于输送流体的不锈钢制成的热轧(挤、扩)和冷拔(轧)无缝钢管》规范执行。
实施例一
在304无缝钢管内壁沉积耐腐蚀涂层:
步骤一:对固溶热处理前的304无缝钢管进行酸洗,直至裸露金属表面,并采用碱溶液或脂溶性溶剂除油;
步骤二:按照质量百分比计,称取8%醋酸纤维素酯,5%的磷酸,5%铬酐、30%的铬粉、5%的铝粉、5%的硅粉、5%的氧化硅、其余为乙酰丙酮溶液;将上述物质混合搅拌均匀后,使用球磨机氩气保护球磨24小时,得到浆状原料;
步骤三:将浆状原料均匀涂覆在步骤一处理后的钢管内壁,涂覆厚度为150μm,烘干后进行无缝钢管固溶热处理工艺。
无缝钢管固溶热处理在氩气保护下进行,加热温度1160℃、保温时间为15min,水冷淬火。
经检测,如图1所示,图中(a)为母材组织形貌,(b)为涂层组织形貌,实施例制备的内壁沉积耐蚀涂层304无缝钢管,钢管母材组织为单相奥氏体组织,耐蚀涂层与母材基体冶金结合,厚度约为25μm,涂层成分由质量比为18%Cr、6%Al、2.5%Ni、1.2%Si、1.1%P、其余为Fe组成。
实施二
在316无缝钢管内壁沉积耐腐蚀涂层:
步骤一:对固溶热处理前的无缝钢管进行酸洗,直至裸露金属表面,并采用碱溶液或脂溶性溶剂除油;
步骤二:按照质量百分比计,称取5%醋酸纤维素酯,10%的磷酸,2%铬酐、10%的铬粉、10%的铝粉、2%的硅粉、10%的氧化硅、其余为乙酰丙酮溶液;将上述物质混合搅拌均匀后,使用球磨机氩气保护球磨24小时,得到浆状原料;
步骤三:将浆状原料均匀涂覆在步骤一处理后的钢管内壁,涂覆厚度为120μm,烘干后进行无缝钢管固溶热处理工艺。
无缝钢管固溶热处理在氩气保护下进行,加热温度1200℃、保温时间为15min,水冷淬火。
经检测实施例制备的内壁沉积耐蚀涂层304无缝钢管,钢管母材组织为单相奥氏体组织,耐蚀涂层与母材基体冶金结合,厚度约为35μm,涂层成分由质量比为17%Cr、8%Al、1.8%Ni、1.6%Si、0.8%P、其余为Fe组成。涂层样品与基体在900℃高温氧化100h后的表面氧化膜截面形貌见图2,其中涂层氧化层厚度(图2b)仅为304母材的约1/20(图2a)。
应当理解的是,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,而所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (6)
1.一种内壁沉积耐腐蚀涂层的无缝钢管的制备方法,其特征在于,包括如下工艺步骤:
步骤一:对固溶热处理前的无缝钢管进行酸洗,直至裸露金属表面,并采用碱溶液或脂溶性溶剂除油;
步骤二:按照质量百分比计,称取5~8%醋酸纤维素酯,5~10%的磷酸,2~5%铬酐、10~30%的铬粉、5~10%的铝粉、2~5%的硅粉、5~10%的氧化硅、其余为乙酰丙酮溶液;将上述物质混合搅拌均匀后,使用球磨机氩气保护球磨24小时,得到浆状原料;
步骤三:将浆状原料均匀涂覆在步骤一处理后的钢管内壁,涂覆厚度为100-150μm,烘干后进行无缝钢管固溶热处理工艺。
2.根据权利要求1所述的制备方法,其特征在于,无缝钢管固溶热处理在氩气保护下进行,加热温度1100-1200℃、保温时间不少于15min,水冷淬火。
3.根据权利要求1所述的制备方法,其特征在于,无缝钢管的制备流程适用于冷拔或热挤压的制备工艺。
4.根据权利要求1-3任一所述制备方法获得的无缝钢管,其特征在于,内壁沉积的耐腐蚀涂层含质量比15-20%Cr、5-10%Al、1-3Ni%、1-3Si%、0.5-1%P、其余为Fe,涂层与母材冶金结合,涂层厚度20-40μm。
5.根据权利要求4所述的无缝钢管,该无缝钢管由304、316材质的母材及内壁的耐腐蚀涂层组成,钢管母材为单相奥氏体组织。
6.一种用于在无缝钢管内壁沉积耐腐蚀涂层的组合物,其特征在于,其组分为:5~8%醋酸纤维素酯,5~10%的磷酸,2~5%铬酐、10~30%的铬粉、5~10%的铝粉、2~5%的硅粉、5~10%的氧化硅、其余为乙酰丙酮溶液。
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