CN112575280A - 一种耐海水腐蚀铁基非晶防护涂层及其制备方法 - Google Patents
一种耐海水腐蚀铁基非晶防护涂层及其制备方法 Download PDFInfo
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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Abstract
本发明属于海洋装备防腐蚀领域，具体涉及一种耐海水腐蚀铁基非晶防护涂层及其制备方法。所述方法包括如下步骤：称取一定质量的铁基非晶粉末；对待喷涂的基体进行粗化处理；采用等离子喷涂方式，在待喷涂基体表面进行喷涂，获得喷涂态铁基非晶涂层；对喷涂态铁基非晶涂层采用水溶性Al2O3或水溶性SiO2封孔剂进行封孔处理，获得低孔隙率高耐蚀性的铁基非晶涂层。本发明利用等离子喷涂和封孔方法复合处理获得低孔隙率铁基非晶防护涂层，制备工艺简单，同时水溶性纳米Al2O3或SiO2封孔剂，具有良好的耐腐蚀能力和极强的附着力，能够有效降低等离子喷涂涂层的孔隙率，抑制腐蚀性介质的渗透，提高涂层耐海水腐蚀性能，进而提高钻井隔水套管等海洋装备的使用寿命。
Description
技术领域
本发明属于海洋装备防腐蚀领域，具体涉及一种耐海水腐蚀铁基非晶防护涂层及其制备方法。
背景技术
在海上石油的勘探中，钻井隔水套管是整个钻井系统中重要而又薄弱的环节，是影响海上钻井装备安全的关键因素，因而隔水套管的长周期安全服役性能对于石油、天然气的开采起着重要的作用。海洋钻井隔水套管长期暴露在腐蚀性极强的海水介质中，海水中的氯离子会腐蚀隔水套管表面，造成隔水套管失效。因此，钻井隔水套管亟需低成本、高效的耐腐蚀防护处理技术。
非晶合金微观结构长程无序、短程有序，使之具有高强度、高硬度以及优异的耐腐蚀性能。热喷涂技术操作方便、适用范围广，是提高基体材料表面耐腐蚀性能中常用的一种方法。其中，等离子喷涂技术具有较高焰流速度，喷涂粒子在冷却变形堆积形成涂层时具有极高的冷却速度，有利于非晶涂层的制备。将非晶合金与技术相结合，制备出优异的耐磨耐腐蚀性非晶涂层。但等离子喷涂涂层中孔隙的存在严重威胁涂层的耐腐蚀性能。因此，降低涂层孔隙缺陷便成了提高涂层耐蚀性的关键问题。
为了解决该问题，人们提出了许多降低涂层孔隙率的方法，如激光重熔、封孔处理、热处理等方法。CN201110137702.0公开了一种超音速火焰喷涂铁基非晶涂层的封孔剂及其应用，该发明使用磷酸铝密封剂，密封剂渗透深度可达到50～60μm，能实现对超音速火焰喷涂涂层有效封孔深度，进而提高涂层的耐蚀性和耐磨性能。CN201610749373.8涉及一种提高超音速火焰喷涂铁基非晶涂层长期耐蚀性的封孔剂和封孔工艺，该封孔剂为无毒的无机类封孔剂，制备工艺简单，操作方便，本发明密封工艺能实现对超音速火焰喷涂铁基非晶涂层的深层有效密封，提高涂层在腐蚀环境中的长期耐蚀性及使用寿命。CN201610749222.2公开了一种热喷涂非晶合金涂层的孔隙封闭处理方法，该方法首先通过电化学处理溶解涂层孔隙周围贫铬的不耐蚀区域，从根本上消除涂层中腐蚀过程中的薄弱环节，再通过后续的环氧树脂封闭处理大幅度提高涂层耐蚀性能，该发明可消除涂层中的不耐蚀区域，从根本上提高涂层的耐蚀性能。
发明内容
本发明的目的在于提供一种耐海水腐蚀铁基非晶防护涂层及其制备方法。
实现本发明目的的技术解决方案为：一种耐海水腐蚀铁基非晶防护涂层的制备方法，包括如下步骤：
步骤(1)：称取粒径范围为38～54μm的铁基非晶粉末，所述铁基非晶粉末包含铁、铬、碳、硼和钼，其中Fe、Cr、C、B、Mo原子比为37.5:27.5:10～14:15～11:10，然后干燥备用；
步骤(2)：对待喷涂的基体进行粗化处理；
步骤(3)：采用等离子喷涂方式，在待喷涂基体表面进行喷涂，获得喷涂态铁基非晶涂层；
步骤(4)：对喷涂态铁基非晶涂层采用水溶性Al2O3或水溶性SiO2封孔剂进行封孔处理，获得低孔隙率高耐蚀的铁基非晶涂层。
进一步的，所述步骤(1)中的干燥具体为：80±2℃烘箱中干燥1-3h备用。
进一步的，所述步骤(2)中“对待喷涂的基体进行粗化处理”具体为：对待喷涂的基体进行清洗、干燥，采用棕刚玉喷砂粗化处理，粗化处理后的表面粗糙度为Ra 8.0-10.0。
进一步的，所述步骤(3)中等离子喷涂的参数为：电流为500～530A，电压为50～65V，氩气流量为40～65L/min，氢气流量为2～8L/min，喷涂距离为110～130mm，送粉速度为10～30g/min。
进一步的，所述步骤(4)中封孔处理包括如下步骤：
步骤(4-1)涂层预处理：对喷涂态铁基非晶涂层进行预处理；
步骤(4-2)涂层封孔处理：采用浸渍法，超声法或刷涂法进行封孔处理；
步骤(4-3)热处理：对封孔处理后的涂层进行热处理。
进一步的，所述步骤(4-2)中采用浸渍法封孔具体是将喷涂态铁基非晶涂层浸泡在封孔剂中0.5～3h；
采用超声法封孔具体是在持续超声搅拌下将喷涂态铁基非晶涂层浸入封孔剂中0.5～3h，然后再静置半小时让封孔剂进入到涂层的微小孔隙中；
采用刷涂法封孔具体是利用刷子蘸取封孔剂涂刷在喷涂态铁基非晶涂层表面，直至封孔剂在喷涂态铁基非晶涂层表面未出现气泡停止刷涂。
进一步的，所述步骤(4-3)的热处理具体为：先将封孔处理后的铁基非晶涂层在空气中晾干直至去除表面残留水分，然后在烘干箱中80℃保温1～3小时。
一种采用上述的方法制备的铁基非晶防护涂层，所述涂层的厚度为150～400μm。
一种上述的涂层用于海洋装备耐海水腐蚀的用途。
进一步的，所述涂层用于钻井隔水套管。
本发明与现有技术相比，其显著优点在于：
(1)本发明中封孔剂为水溶性Al2O3或水溶性SiO2封孔剂，不含甲醛、苯、重金属等有害物质，干燥后变为透明光亮膜层，具有良好的耐腐蚀能力和极强的附着力，且来源广泛，成本低廉。
(2)本发明所涉及的等离子喷涂和封孔方法工艺简单，制备的低孔隙率铁基非晶涂层可以有效隔绝海水介质与钻井隔水套管等海洋装备，有效提高钻井隔水套管等海洋装备耐海水腐蚀性能，大大延长海洋装备服役寿命。
附图说明
图1为实施例1APS3(H2流量为3L/min的涂层)涂层采用Al2O3封孔剂封孔前后涂层的动极化曲线图。
图2为实施例2APS5(H2流量为5L/min的涂层)涂层采用Al2O3封孔剂封孔前后涂层的动极化曲线图。
具体实施方式
下面结合附图对本发明作进一步详细描述。
实施例1：
一种耐海水腐蚀铁基非晶防护涂层的制备方法，包括如下步骤：
1.称取一定质量的粒径范围为38～54μm的铁基非晶粉末，铁基非晶粉末包含铁铬碳硼钼，其中Fe、Cr、C、B、Mo原子比为37.5:27.5:12:13:10。然后放于80℃烘箱中干燥2h备用；
2.对待喷涂不锈钢基体表面进行清洗、干燥，采用棕刚玉喷砂粗化处理，粗化处理后的表面粗糙度为Ra 8.0-10.0。
3.采用等离子喷涂方式，在待喷涂基体表面进行喷涂铁基非晶粉末，获得铁基非晶涂层。具体等离子喷涂的参数为：电流为515A，电压为57V，Ar流量为55L/min，H2流量3L/min，喷涂距离120mm，送粉量为13.67g/min。
4.对喷涂态铁基非晶涂层采用水溶性Al2O3封孔剂，并通过封孔处理获得低孔隙率的铁基非晶涂层。封孔处理工艺具体为：首先对喷涂态铁基非晶涂层进行预处理；然后采用浸渍法，超声法或刷涂法进行封孔处理，其中，采用浸渍法封孔具体是将喷涂态铁基非晶涂层浸泡在封孔剂中1h。采用超声法封孔具体是在持续超声搅拌下将喷涂态铁基非晶涂层浸入封孔剂中1h，然后再静置半小时让封孔剂进入到涂层的微小孔隙中。采用刷涂法封孔具体是利用刷子蘸取封孔剂涂刷在喷涂态铁基非晶涂层表面，直至封孔剂在喷涂态铁基非晶涂层表面未出现气泡停止刷涂；最后将封孔处理后的铁基非晶涂层在空气中晾干直至去除表面残留水分，然后在烘干箱中80℃保温3小时。
5.电化学腐蚀试验结果表明，封孔后涂层自腐蚀电位开始慢慢正移，自腐蚀电流密度明显下降，表明经过封孔处理后铁基非晶涂层的耐蚀性能显著提高。其中，刷涂封孔在提高涂层耐腐蚀性能方面效果最佳，如图1所示。
实施例2：
一种耐海水腐蚀铁基非晶防护涂层的制备方法，包括如下步骤：
1.称取一定质量的粒径范围为38～54μm的铁基非晶粉末，铁基非晶粉末包含铁铬碳硼钼，其中Fe、Cr、C、B、Mo原子比为37.5:27.5:12:13:10。然后放于80℃烘箱中干燥2h备用；
2.对待喷涂不锈钢基体表面进行清洗、干燥，采用棕刚玉喷砂粗化处理，粗化处理后的表面粗糙度为Ra 8.0-10.0。
3.采用等离子喷涂方式，在待喷涂基体表面进行喷涂铁基非晶粉末，获得铁基非晶涂层。具体等离子喷涂的参数为：电流为515A，电压为57V，Ar流量为55L/min，H2流量5L/min，喷涂距离120mm，送粉量为13.67g/min。
4.对喷涂态铁基非晶涂层采用水溶性Al2O3封孔剂，并通过封孔处理获得低孔隙率的铁基非晶涂层。封孔处理工艺具体为：首先对喷涂态铁基非晶涂层进行预处理；然后采用浸渍法，超声法或刷涂法进行封孔处理，其中，采用浸渍法封孔具体是将喷涂态铁基非晶涂层浸泡在封孔剂中1h。采用超声法封孔具体是在持续超声搅拌下将喷涂态铁基非晶涂层浸入封孔剂中1h，然后再静置半小时让封孔剂进入到涂层的微小孔隙中。采用刷涂法封孔具体是利用刷子蘸取封孔剂涂刷在喷涂态铁基非晶涂层表面，直至封孔剂在喷涂态铁基非晶涂层表面未出现气泡停止刷涂；最后将封孔处理后的铁基非晶涂层在空气中晾干直至去除表面残留水分，然后在烘干箱中80℃保温3小时。
5.电化学腐蚀试验结果表明，封孔后涂层的自腐蚀电位正移，自腐蚀电流密度降低，表明经过封孔处理后铁基非晶涂层的耐蚀性明显提高。其中，刷涂封孔在提高涂层耐腐蚀性能方面效果最佳，如图2所示。
Claims (10)
1.一种耐海水腐蚀铁基非晶防护涂层的制备方法，其特征在于，包括如下步骤：
步骤(1)：称取粒径范围为38～54μm的铁基非晶粉末，所述铁基非晶粉末包含铁、铬、碳、硼和钼，其中Fe、Cr、C、B、Mo原子比为37.5:27.5:10～14:15～11:10，然后干燥备用；
步骤(2)：对待喷涂的基体进行粗化处理；
步骤(3)：采用等离子喷涂方式，在待喷涂基体表面进行喷涂，获得喷涂态铁基非晶涂层；
步骤(4)：对喷涂态铁基非晶涂层采用水溶性Al2O3或水溶性SiO2封孔剂进行封孔处理，获得低孔隙率高耐蚀的铁基非晶涂层。
2.根据权利要求1所述的方法，其特征在于，所述步骤(1)中的干燥具体为：80±2℃烘箱中干燥1-3h备用。
3.根据权利要求1所述的方法，其特征在于，所述步骤(2)中“对待喷涂的基体进行粗化处理”具体为：对待喷涂的基体进行清洗、干燥，采用棕刚玉喷砂粗化处理，粗化处理后的表面粗糙度为Ra 8.0-10.0。
4.根据权利要求1所述的方法，其特征在于，所述步骤(3)中等离子喷涂的参数为：电流为500～530A，电压为50～65V，氩气流量为40～65L/min，氢气流量为2～8L/min，喷涂距离为110～130mm，送粉速度为10～30g/min。
5.根据权利要求1所述的方法，其特征在于，所述步骤(4)中封孔处理包括如下步骤：
步骤(4-1)涂层预处理：对喷涂态铁基非晶涂层进行预处理；
步骤(4-2)涂层封孔处理：采用浸渍法，超声法或刷涂法进行封孔处理；
步骤(4-3)热处理：对封孔处理后的涂层进行热处理。
6.根据权利要求5所述的方法，其特征在于，所述步骤(4-2)中采用浸渍法封孔具体是将喷涂态铁基非晶涂层浸泡在封孔剂中0.5～3h；
采用超声法封孔具体是在持续超声搅拌下将喷涂态铁基非晶涂层浸入封孔剂中0.5～3h，然后再静置半小时让封孔剂进入到涂层的微小孔隙中；
采用刷涂法封孔具体是利用刷子蘸取封孔剂涂刷在喷涂态铁基非晶涂层表面，直至封孔剂在喷涂态铁基非晶涂层表面未出现气泡停止刷涂。
7.根据权利要求5所述的方法，其特征在于，所述步骤(4-3)的热处理具体为：先将封孔处理后的铁基非晶涂层在空气中晾干直至去除表面残留水分，然后在烘干箱中80℃保温1～3小时。
8.一种采用权利要求1-7任一项所述的方法制备的铁基非晶防护涂层，其特征在于，所述涂层的厚度为150～400μm。
9.一种权利要求8所述的涂层用于海洋装备耐海水腐蚀的用途。
10.根据权利要求9所述的用途，其特征在于，所述涂层用于钻井隔水套管。
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| CN102796983A (zh) * | 2011-05-26 | 2012-11-28 | 中国科学院金属研究所 | 一种超音速火焰喷涂铁基非晶涂层的封孔剂及其应用 |
| CN102816990A (zh) * | 2011-06-09 | 2012-12-12 | 中国钢铁股份有限公司 | 喷涂涂层的封孔剂与封孔处理方法 |
| CN103320739A (zh) * | 2013-05-30 | 2013-09-25 | 中国船舶重工集团公司第七二五研究所 | 一种海洋环境防腐镍基涂层的制备方法 |
| CN107794488A (zh) * | 2016-08-29 | 2018-03-13 | 中国科学院金属研究所 | 一种提高超音速火焰喷涂铁基非晶涂层长期耐蚀性的封孔剂和封孔工艺 |
| CN111778471A (zh) * | 2020-07-03 | 2020-10-16 | 扬州大学 | 一种耐磨减摩铁基非晶复合涂层及其制备方法 |
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