防垢耐蚀耐磨涂层的制备与性能研究
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摘要
为了改善油田设备的结垢腐蚀磨损现象,本文以Al2O3-13％TiO2和Cr3C2-NiCr为原料,La2O3为添加剂,在原材料中分别加入3wt%、6wt%及9wt%的La2O3设计了两类复合喷涂粉末,并采用等离子喷涂技术制备Al2O3-13％TiO2基和Cr3C2-NiCr基涂层,研究了涂层的组织与性能。采用ANSYS软件对涂层界面应力进行了计算,结果表明：单层结构的Al2O3-13％TiO2与NiCr-Cr3C2涂层内的残余应力分布规律相同,喷涂粒子到达涂层的冲击速度对基体及陶瓷涂层内的残余应力分布均有较大的影响。双层结构的Al2O3-13％TiO2涂层由于添加了过渡层有效缓解了界面应力突变,但对于物性参数与基体相差不大的双层结构的Cr3C2-NiCr涂层,过渡层的添加对应力的缓解效果并不明显。
涂层的组织与性能研究结果表明：在本试验条件下,NiCr-Cr3C2涂层的组织致密性、显微硬度、结合强度、接触角、耐蚀性及冲蚀磨损性较Al2O3-13％TiO2涂层更高。NiCr-Cr3C2涂层因表面能较低,导致垢的诱导期增长及附着力较小,成垢总量明显减少,其防垢性能也优于Al2O3-13％TiO2涂层。在本试验条件下,在Al2O3-13％TiO2和Cr3C2-NiCr涂层中加入稀土后,当稀土含量低于6%时,两类涂层的致密性、显微硬度、结合强度、接触角均随稀土含量的增加而增大,表面能、腐蚀电流、结垢增重及冲蚀失重则随稀土含量的增加而降低；当稀土含量高于6%时,两类涂层组织恶化,显微硬度、结合强度、接触角出现下降的趋势,而表面能、腐蚀电流、结垢增重及冲蚀失重呈现增大的趋势。当稀土氧化物为6%时,明显改善了喷涂层不致密、晶粒粗大和不均匀的缺陷,涂层防垢、耐蚀及冲蚀性能最优。涂层结垢机理是当采出水浓度达到过饱和状态,则溶液中存在的离子或分子的团簇就生成品核,晶核长大形成晶体析出形成垢物。涂层腐蚀破坏过程均为沿颗粒边界产生腐蚀裂纹,逐渐向涂层内部和沿着颗粒边界扩展,最终导致涂层呈块状脱落。冲蚀失效机制为熔融颗粒之间和层间弱结合面处失效导致的层状剥落。
In order to solve scaling and corrosion phenomena of oilfield equipment, the experiment choose Al2O3-13%TiO2 and Cr3C2-NiCr powder,La2O3 as additive.La2O3 were added to raw materials as two kinds of composite powder, the percentage of which is 3wt%,6wt% and 9wt%.The Al2O3-13%TiO2 and Cr3C2-NiCr ceramic coatings are prepared by plasma spraying equipment, micro structure and properties of coatings are studied. Interface stress of coatings is calculated with ANSYS software Results of calculation indicate that Al2O3-13%TiO2 and Cr3C2-NiCr coatings of single structure have the same rule of residual stress distribution. Speed of spraying particle arriving at surface of coatings and substrate affects the impact of residual stress distribution.Transition layer addition of Al2O3-13%TiO2 coating can significantly reduce its interface stress. But when parameter of substrate and Cr3C2-NiCr coating is not different, influence of transition layer is not obvious.
Research results of micro structure and properties of coatings show that in the condition of the experiment, micro structure density, micro-hardness, binding strength, contact angle, anti-corrosion and anti-wear of Cr3C2-NiCr coating is greater than which of Al2O3-13%TiO2 coating. Low surface energy of NiCr-Cr3C2 coating causes induction growth and adhesion reduction of scale, its anti-scaling performance is superior to Al2O3-13%TiO2 coating. In the condition of the experiment, rare earth mixed into Al2O3-13%TiO2 and Cr3C2-NiCr coating, when addition of rare earth is less than 6%, microstructure density, micro-hardness, binding strength and contact angle of two kinds of coatings increases with addition of rare earth increasing, surface energy, corrosion current, scale weight increment, erosion weight loss reduce with addition of rare earth increasing; when addition of rare earth is more than 6%, microstructure of two kinds of coatings deteriorate, micro-hardness, binding strength and contact angle present the trend of reducing, surface energy, corrosion current, scale weight increment and erosion weight loss present the trend of increasing. When addition of rare earth is 6%, undense defects, coarse grains, asymmetric defects are improved, anti-scale and anti-corrosion and anti-wear of coatings are optimalizing. Scaling mechanism of coating is that when the concentration of produced water is saturated, MPCs of ion or molecule of solution generates crystal nucleus, alternative grows to crystals, which separate out and form to scale. Initiation and propagation of cracks and delamination spallings is the main corrosion failure mechanism. Erosion mechanism is layer strip resulted from interlaminar and particles weak bonding zones.
涂层的组织与性能研究结果表明：在本试验条件下,NiCr-Cr3C2涂层的组织致密性、显微硬度、结合强度、接触角、耐蚀性及冲蚀磨损性较Al2O3-13％TiO2涂层更高。NiCr-Cr3C2涂层因表面能较低,导致垢的诱导期增长及附着力较小,成垢总量明显减少,其防垢性能也优于Al2O3-13％TiO2涂层。在本试验条件下,在Al2O3-13％TiO2和Cr3C2-NiCr涂层中加入稀土后,当稀土含量低于6%时,两类涂层的致密性、显微硬度、结合强度、接触角均随稀土含量的增加而增大,表面能、腐蚀电流、结垢增重及冲蚀失重则随稀土含量的增加而降低；当稀土含量高于6%时,两类涂层组织恶化,显微硬度、结合强度、接触角出现下降的趋势,而表面能、腐蚀电流、结垢增重及冲蚀失重呈现增大的趋势。当稀土氧化物为6%时,明显改善了喷涂层不致密、晶粒粗大和不均匀的缺陷,涂层防垢、耐蚀及冲蚀性能最优。涂层结垢机理是当采出水浓度达到过饱和状态,则溶液中存在的离子或分子的团簇就生成品核,晶核长大形成晶体析出形成垢物。涂层腐蚀破坏过程均为沿颗粒边界产生腐蚀裂纹,逐渐向涂层内部和沿着颗粒边界扩展,最终导致涂层呈块状脱落。冲蚀失效机制为熔融颗粒之间和层间弱结合面处失效导致的层状剥落。
In order to solve scaling and corrosion phenomena of oilfield equipment, the experiment choose Al2O3-13%TiO2 and Cr3C2-NiCr powder,La2O3 as additive.La2O3 were added to raw materials as two kinds of composite powder, the percentage of which is 3wt%,6wt% and 9wt%.The Al2O3-13%TiO2 and Cr3C2-NiCr ceramic coatings are prepared by plasma spraying equipment, micro structure and properties of coatings are studied. Interface stress of coatings is calculated with ANSYS software Results of calculation indicate that Al2O3-13%TiO2 and Cr3C2-NiCr coatings of single structure have the same rule of residual stress distribution. Speed of spraying particle arriving at surface of coatings and substrate affects the impact of residual stress distribution.Transition layer addition of Al2O3-13%TiO2 coating can significantly reduce its interface stress. But when parameter of substrate and Cr3C2-NiCr coating is not different, influence of transition layer is not obvious.
Research results of micro structure and properties of coatings show that in the condition of the experiment, micro structure density, micro-hardness, binding strength, contact angle, anti-corrosion and anti-wear of Cr3C2-NiCr coating is greater than which of Al2O3-13%TiO2 coating. Low surface energy of NiCr-Cr3C2 coating causes induction growth and adhesion reduction of scale, its anti-scaling performance is superior to Al2O3-13%TiO2 coating. In the condition of the experiment, rare earth mixed into Al2O3-13%TiO2 and Cr3C2-NiCr coating, when addition of rare earth is less than 6%, microstructure density, micro-hardness, binding strength and contact angle of two kinds of coatings increases with addition of rare earth increasing, surface energy, corrosion current, scale weight increment, erosion weight loss reduce with addition of rare earth increasing; when addition of rare earth is more than 6%, microstructure of two kinds of coatings deteriorate, micro-hardness, binding strength and contact angle present the trend of reducing, surface energy, corrosion current, scale weight increment and erosion weight loss present the trend of increasing. When addition of rare earth is 6%, undense defects, coarse grains, asymmetric defects are improved, anti-scale and anti-corrosion and anti-wear of coatings are optimalizing. Scaling mechanism of coating is that when the concentration of produced water is saturated, MPCs of ion or molecule of solution generates crystal nucleus, alternative grows to crystals, which separate out and form to scale. Initiation and propagation of cracks and delamination spallings is the main corrosion failure mechanism. Erosion mechanism is layer strip resulted from interlaminar and particles weak bonding zones.
引文
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