Chlorine-induced high temperature corrosion of HVAF-sprayed Ni-based alumina and chromia forming coatings

Chlorine-induced corrosion of HVAF-sprayed Ni21Cr and Ni5Al coatings was investigated in 5 vol.% O2 + 500vppm HCl + N2 with and without KCl at 600 °C up to 168 h. Both coatings were protective in the absence of KCl. With KCl, Ni21Cr degraded through a two-stage mechanism: 1) formation of K2CrO4 followed by diffusion of Cl− through the oxide grain boundaries to yield chlorine and a non-protective oxide, and 2) inward diffusion of chlorine though defects in the non-protective oxide, leading to breakaway oxidation. Cl−/Cl2 could not diffuse through the protective alumina scale formed on Ni5Al, hence the corrosion resistance increased

Ni-based coatings for high temperature corrosion protection

Biomass/waste-fired boilers severely suffer from high temperature corrosion of critical load-bearing components, e.g. water-wall and superheater tubes, due to presence of Cl-containing corrosive species. Deposition of a dense and adherent Ni-based coating by high velocity air-fuel (HVAF) thermal spray technique is a promising approach to extend the component's lifetime and, hence, increase the thermal/electrical efficiency of the boilers. In this research, high temperature corrosion of candidate Ni-based coatings –Ni21Cr, Ni21Cr7AlY, Ni5Al, Ni21Cr9Mo, Ni21Cr9Mo-SiO2 – sprayed by HVAF has been investigated through detailed laboratory studies in ambient air, moisture and HCl-laden environments. The exposures were conducted at 600 °C for up to 168 h with and without presence of KCl salt. All coatings were highly protective in all environments in the absence of KCl due to formation of corresponding protective scales of alumina or chromia on the coating surface. When KCl was introduced, chromia-forming coatings degraded through a two-stage mechanism; 1) formation of K2CrO4 and Cl- followed by diffusion of Cl- through oxide grain boundaries, leading to formation of Cl2, metal chlorides as well as a nonprotective oxide, and 2) inward diffusion of the formed Cl2 through defects in the non-protective oxide, leading to metal chloride evaporation and breakaway oxidation. The corrosion behavior of the chromia-forming Ni21Cr coating was improved by addition of alloying elements such as Al and Mo. It was also shown that adding dispersed SiO2 further increased the corrosion resistance of the coatings. The oxide scale formed in the presence of SiO2 effectively suppressed Cl- ingress and lowered the corrosion rate, since the formed oxide was continuous, adherent andrich in Cr. The performance of the coatings in the complex Cl-containing environment was ranked as (from highest to lowest corrosion resistance); Ni21Cr9Mo-SiO2 > Ni21Cr7AlY > Ni5Al > Ni21Cr9Mo > Ni21Cr, confirming the enhanced corrosion protection of chromia-forming coatings in the presence of alloying elements and dispersed SiO2

Corrosion Behavior of HVAF-Sprayed Bi-Layer Coatings

In a variety of engineering applications, components are subjected to corrosive environment. Protective coatings are essential to improve the functional performances and/or extend the lifetime of the components. Thermal sprayingas a cost-effective coating deposition technique offers high flexibility in coatings' chemistry/morphology/microstructure design. However, the inherent pores formed during spraying limit the use of coatings for corrosion protection. The recently developed supersonic spray method, High-Velocity-Air-Fuel (HVAF), brings significant advantages in terms of cost and coating properties. Although severely reduced, the pores are not completely eliminated even with the HVAF process. In view of the above gap to have a high quality coating, bi-layer coatings have been developed to improve the corrosion resistance of the coatings. In a bi-layer coating, an intermediate layer is deposited on the substrate before spraying the coating. The electrochemical behavior of each layer is important to ensure a good corrosion protection. The corrosion behavior of the layers strongly depends on coating composition and microstructure, which are affected by feedstock material and spraying process. Therefore, the objective of the researchis to explore the relationships between feedstock material, spraying process, microstructure and corrosion behavior of bi-layer coatings. A specific motivationis to understand the corrosion mechanisms of the intermediate layer which forms the basis for developing superior protective coatings. Cr3C2-NiCr top layer and intermediate layers (Fe-, Co- and Ni-based) were sprayed by different thermal spraying processes. Microstructure analysis, as well as various corrosion tests, e.g., electrochemical, salt spray and immersion tests were performed. The results showed a direct link between the corrosion potential (Ecorr) of the intermediate layer and the corrosion mechanisms. It was found that the higher corrosion resistance of Ni-based coatings than Fe- and Co-based coatings was due to higher Ecorr of the coating in the galvanic couple with top layers. Inter-lamellar boundaries and interconnected pores reduced the corrosion resistance of intermediate layers, however a sufficient reservoir of protective scale-forming elements (such as Cr or Al) improved the corrosion behavior

Ni-based coatings for high temperature corrosion protection

Biomass/waste-fired boilers severely suffer from high temperature corrosion of critical load-bearing components, e.g. water-wall and superheater tubes, due to presence of Cl-containing corrosive species. Deposition of a dense and adherent Ni-based coating by high velocity air-fuel (HVAF) thermal spray technique is a promising approach to extend the component's lifetime and, hence, increase the thermal/electrical efficiency of the boilers. In this research, high temperature corrosion of candidate Ni-based coatings –Ni21Cr, Ni21Cr7AlY, Ni5Al, Ni21Cr9Mo, Ni21Cr9Mo-SiO2 – sprayed by HVAF has been investigated through detailed laboratory studies in ambient air, moisture and HCl-laden environments. The exposures were conducted at 600 °C for up to 168 h with and without presence of KCl salt. All coatings were highly protective in all environments in the absence of KCl due to formation of corresponding protective scales of alumina or chromia on the coating surface. When KCl was introduced, chromia-forming coatings degraded through a two-stage mechanism; 1) formation of K2CrO4 and Cl- followed by diffusion of Cl- through oxide grain boundaries, leading to formation of Cl2, metal chlorides as well as a nonprotective oxide, and 2) inward diffusion of the formed Cl2 through defects in the non-protective oxide, leading to metal chloride evaporation and breakaway oxidation. The corrosion behavior of the chromia-forming Ni21Cr coating was improved by addition of alloying elements such as Al and Mo. It was also shown that adding dispersed SiO2 further increased the corrosion resistance of the coatings. The oxide scale formed in the presence of SiO2 effectively suppressed Cl- ingress and lowered the corrosion rate, since the formed oxide was continuous, adherent andrich in Cr. The performance of the coatings in the complex Cl-containing environment was ranked as (from highest to lowest corrosion resistance); Ni21Cr9Mo-SiO2 > Ni21Cr7AlY > Ni5Al > Ni21Cr9Mo > Ni21Cr, confirming the enhanced corrosion protection of chromia-forming coatings in the presence of alloying elements and dispersed SiO2

Electrochemical Behavior of Bilayer Thermal-Spray Coatings in Low-Temperature Corrosion Protection

Cr3C2-NiCr coatings are greatly used to protect critical components in corrosive environments and to extend their lifetime and/or improve functional performance. However, the pores formed during spraying restrict the coating’s applicability area for many corrosion protection applications. To overcome this technical challenge, bilayer coatings have been developed, in which an additional layer (the so-called intermediate layer) is deposited on the substrate before spraying the Cr3C2-NiCr coating (the so-called top layer). The corrosion behavior of the bilayer coating depends on the composition and microstructure of each layer. In the present work, different single-layer coatings (i.e., Cr3C2-NiCr, Fe- and Ni-based coatings) were initially sprayed by a high-velocity air fuel (HVAF) process. Microstructure analysis, as well as electrochemical tests, for example, open-circuit potential (OCP) and polarization tests, were performed. The potential difference (Delta E) had a great influence on galvanic corrosion between the top and intermediate layers, and thus, the coatings were ranked based on the OCP values (from high to low) as follows: NiCoCrAlY &gt; NiCr &gt; Cr3C2-NiCr &gt; NiAl &gt; Fe-based coatings (alloyed with Cr) &gt; pure Ni. The Ni-based coatings were chosen to be further used as intermediate layers with the Cr3C2-NiCr top layer due to their capabilities to show high OCP. The corrosion resistance (R-p) of the bilayer coatings was ranked (from high to low) as follows: NiCoCrAlY/Cr3C2-NiCr &gt; NiCr/Cr3C2-NiCr &gt; NiAl/Cr3C2-NiCr &gt; Ni/Cr3C2-NiCr. It was shown that splat boundaries and interconnected pores are detrimental for corrosion resistance, however, a sufficient reservoir of protective scale-forming elements (such as Cr or/and Al) in the intermediate layer can significantly improve the corrosion resistance.Projekt PROSAM</p

A Comparative Study of Corrosion Resistance for HVAF-Sprayed Fe- and Co-Based Coatings

There is an increasing demand to replace Co-based coatings with cheap and environmentally friendly Fe-based coatings in corrosive environments. The main objective of this work was to evaluate whether Fe-based coatings could present a better corrosion performance than Co-based coatings. Therefore, two types of Fe-based and one type of Co-based coatings with chemical compositions (in wt %) of Fe-28Cr-16Ni-1.85C (FeNiCrC), Fe-17Cr-12Ni (FeNiCr), andCo-28Cr-1C (CoCrC) were produced by High Velocity Air Fuel (HVAF) spraying. The corrosion behavior of the coatings was studied comparatively by electrochemical tests in 3.5 wt % NaCl solutionat 25 C. The polarization test results showed that the FeCrNiC coating protected the underlying substrate better than the CoCrC coating, while the FeCrNi coating failed to hinder the penetration of corrosive ions. Electrochemical impedance spectroscopy (EIS) measurements revealed that thesolution penetrated into the coating through defects, however the corrosion process slowed down due to clogging of the interconnected defects by corrosion products. Increasing the in-flight average particle temperature from 1400 C to 1500 C led to a denser coating with fewer defects which seemed to improve the corrosion resistance of the FeCrNiC coating. The high-alloyed Fe-based coatings had the best corrosion protection performance and can thus be recommended as a potential alternative toCo-based coatings

KCl-Induced High Temperature Corrosion Behavior of HVAF-Sprayed Ni-Based Coatings in Ambient Air

KCl-induced high temperature corrosion behavior of four HVAF-sprayed Ni-based coatings (Ni21Cr, Ni5Al, Ni21Cr7Al1Y, and Ni21Cr9Mo) under KCl deposit has been investigated in ambient air at 600°C up to 168h. The coatings were deposited onto 16Mo3 steel - a widely used boiler tube material.Uncoated substrate, 304L and Sanicro25 were used as reference materials in the test environment.SEM/EDS and XRD techniques were utilized to characterize the as-sprayed and exposed samples.The results showed that the small addition of KCl significantly accelerated degradation to the coatings. All coatings provided better corrosion resistance compared to the reference materials. The alumina-forming Ni5Al coating under KCl deposit was capable of forming a more protective oxide scale compared to the chromia-forming coatings as penetration of Cl through diffusion paths was hindered. Both active corrosion and chromate formation mechanisms were found to be responsible for Page 1 of 23ASM the corrosion damages. The corrosion resistance of the coatings based on the microstructure analysis and kinetics had the following ranking (from the best to worst): Ni5Al &gt;Ni21Cr&gt; Ni21Cr7Al1Y&gt;Ni21Cr9Mo.This article is an invited paper selected from presentations at the 2017 International Thermal Spray Conference, held June 7–9, 2017, in Düsseldorf, Germany, that has been expanded from the original presentation.</p