International Journal of Advanced Mechatronics and Robotics (IJAMR) Vol. 3, No. 2, July-December 2011; pp.

85-95; International Science Press, ISSN: 0975-6108

Hot-corrosion Resistance of Alloy and Composite Coatings: A Review

Harkulvinder Singh1*, Sukhpal Singh Chatha1, Hazoor Singh Sidhu1 & Kovid Sharma1

Yadavindra College of Engineering, Punjabi University Guru Kashi Campus, * Talwandi Sabo, Punjab, India-151302, ( Corresponding Author: harkulvinder84@gmail.com ) (E-mail: Sukhpal_chatha@yahoo.com), (hazoors@yahoo.com), (kovids@yahoo.com)

ABSTRACT
Hot corrosion is a serious problem in boilers, gas turbines, internal combustion engines, and industrial waste incinerators. It consumes the materials at an unpredictably rapid rate. Alloys used at high temperature should possess good mechanical properties, corrosion and oxidation resistance. Thermal spray technology encompasses a group of coating processes that provide functional surfaces to protect or improve the performance of a substrate or component. Many types and forms of materials can be thermal sprayed, Which provide protection from corrosion, wear, and abrasion and for a variety of other applications. The use of protective coatings has been an answer to remedy the lack of high temperature surface stability of metals and alloys in harsh environments. This study is done with the aim of putting together the performance capabilities and applications of alloy and composite coatings. Keywords: Hot corrosion, Alloys, Composites, Coating.

1. INTRODUCTION Coatings and surface modification technologies allow the engineer to improve the performance, extend the life, and enhance the appearance of materials used for engineering components. These technologies have been developed because the interactions of manufactured components with other components, liquid, and/or gaseous environments can result in component degradation and failure (Davis J. R., 2004). Metals and alloys sometimes experience accelerated oxidation when their surfaces are covered with a thin film of fused salt in an oxidizing gas atmosphere at elevated temperatures. This is known as high temperature or hot corrosion where a porous nonprotective oxide scale is formed at the surfaces and sulphides in the substrate (Singh H et al, 2007). Hot corrosion is an accelerated form of oxidation that occurs at higher temperature in the presence of salt contaminants such as Na2SO4, NaCl,V2O5 that combine to form molten deposits, which damage the protective oxide layer (N. eliaz et al, 2002). Hot corrosion is a serious problem in boilers, gas turbines, internal combustion engines, and industrial waste

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incinerators. As a consequence the load-carrying abilities of the components are reduced (Sidhu T. S. et al, 2006). In combustion products of fuel oil, sulfur is typically present as Na2SO4, which occurs when the metals are heated in the temperature range of 700-900C, in the presence of sulfate deposits. Vanadium as an impurity in fuel oil causes serious corrosion problems because of the formation of V2O5 (Ismail and Anees, 2004). Protective coatings on superalloys encounter two types of high temperature corrosion degradation i.e High temperature hot corrosion (HTHC) and Low temperature hot corrosion (LTHC). High temperature hot corrosion (HTHC) also designated as Type 1, occurs at temperatures in the 800 to 950C range. It is caused by molten salt deposition on the coating surface. The primarily active constituent of this salt is sodium sulphate Na2SO4. Low temperature hot corrosion (LTHC), also known as Type 2, occurs in the 650-750C range. The low temperature hot corrosion mechanism involves acidic fluxing of protective oxides by sulphur trioxide (SO3) dissolved in molten sulphates (Bala N. et al, 2010). 1.1. Coating Hot components of gas turbines and energy systems operating in aggressive environments are subjected to a number of modes of attacks which include oxidation, sulphidising, carburizing, chlorination, erosion and hot corrosion induced by molten salts. The use of protective coatings has been an answer to remedy the lack of high temperature surface stability of metals and alloys in harsh environments (Bhatia R. et al, 2010). Thermal spray coatings can be applied to overcome the steam oxidation problem since it alters the surface without affecting the bulk material properties. Thermal spray coating of FeAl, FeCrAl and NiAl powders on 9Cr-1Mo steel was attempted to improve the steam oxidation resistance for boiler applications (Sundararajan T. et al, 2003). Most high temperature alloys are iron, nickel or cobalt-base because these elements have high melting point. Unfortunately, their oxides are not protective enough in the combustion environment of a fossil-fuel power plant at temperatures above 550C. Nevertheless, addition of other elements to establish more protective oxides such as Cr2O3, Al2O3, or SiO2 has improved their corrosion resistance (Calderon J. P. et al, 1997). Overlay coatings include a family of corrosion resistant alloys specially designed for high temperature surface protection. They referred to as M-Cr-Al-Y coatings, where m is alloy base metal (Ni, Co or combination of two). The high resistance of high chromium, Nickle chromium alloys to high temperature oxidation and corrosion makes them widely used as thermally sprayed coating in fossil fuel-fired boilers, waste incineration boilers and electric furnaces (Parkash S., et al, 2005). Cr and Al are added in Fe and Ni-based superalloys to enhance the oxidation resistance (Chawla V., et al, 2009). Cr3C2-NiCr and NiCrBSi coatings obtained by thermal spraying show good tribological properties in severe working conditions such as at high temperatures or in aggressive environment applications. These coatings maintain their high wear and corrosion resistance up to 1253 K and are used to improve the performance life of the components working at elevated temperatures (Sidhu T. S. et al, 2007). The corrosion resistance of the Ni-based coating founded higher than that of the

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stainless steel substrate material due to the passive film forming effect of Cr. The hot corrosion behavior of NiCrBSi coatings resistance imparted by NiCrBSi coatings may be attributed to the formation of oxides of silicon, chromium, nickel and spinels of nickel and chromium in the molten salt environment at high temperature. (Karagz M. et al, 2011). 1.2. Thermal Spray Process Thermal spraying is a group of processes in which metallic materials are deposited in a molten or semi molten conditions to form a coating (Lal et al., 2010). Thermal spraying gun produced heat using combustion of gases or electric arc. As the material is heated they change to plastic or semi-molten state and accelerated towards the substrate. A confined stream of particles strikes on substrate, flattens and forms thin splats that conform and adhere to irregularities of prepared surface and to each other. As the sprayed particles impinge upon substrate they cooled down and produce lamellar microstructure as shown in Figure 1 (AWS, 1997).

Figure 1: Basic Principle of Thermal Spray Coating & Coating Microstructure (Steffens H.D and Davis J.R, 1996, 2004).

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Alloy and composite Coatings can be deposited by electric arc spray, physical vapour deposition, detonation spraying, flame spray, vacuum plasma spray, low pressure plasma spray, high velocity oxy fuel by sputtering or by evaporation. Coatings serve more than one functions For high temperature oxidation resistance, a coating should (a) resist oxygen and metal ion diffusion, (b) have a low vapour pressure at the operating temperature, (c) have a melting point above the operating temperature, (d) have low reactivity with the substrate, and (e) have low reactivity with the high temperature environment (Datta S et al, 2005). 2. STUDIES ON COATINGS Villafane et al, 1997 observed that when the specimens of SA213 grade T-22, SA213 austenitic grade TP347H were coated with actual ash collected from the super heater of a power plant and passed through a simulated flue gas (oxygen and 0.25 v/o SO2+ 3.6 v/o O2, balance N2). The results of x rays diffraction shows the corrosiveness of the deposits varied with the atmosphere. It is also observed that the TP347H austenitic stainless steel had the best performance, as expected, and the T22 ferritic steel had the worst when coated with silicon or chromium. Caldern F. A. et al, 2011. deposited metallic coating ( NiCrFeNbMoTiAl) on SA 213-T22 alloy steel substrates with thermal projection with non-transferred arc plasma (APS) process. These coated test pieces were subject to corrosive attack in saline mixtures of 80wt. %V2O5 20wt. % Na2SO4 and 80wt.% V2O5 20wt. % K2SO4 at a temperature of 700C. The results of linear polarization resistance (LPR), electrochemical techniques, and electrochemical impedance spectroscopy (EIS) reveals that corrosive attack became more severe when exposed to corrosion by molten salts in a mixture composed by 80%V2O5 20%Na2SO4 decreasing the thickness of the sprayed layer in a larger proportion than when exposed to 80% V2O5 20% K2SO4. Calderon J. P. et al, 1997 used plain carbon steel with bond coat of Ni20Cr and uncoated 304 stainless steel as substrates and Fe75Si alloy coating deposited on bond coat . The substrates were installed in the high-temperature, fireside, corrosion zone of a steam generator for 13 months. Boiler burned heavy fuel oil with high contents of vanadium. The results of SEM/EDAX shows that the uncoated 304 stainless steel were destroyed almost completely by corrosion, whereas the carbon steel coated did not suffer a significant attack, showing that the performance of the thermal spray coating was outstanding and that the coating was not attacked by vanadium salts of the molten slag. Cr3C2-NiCr coating was deposited on SAE-347H boiler steel by HVOF spray process and investigated at 700C for 50 cycles in Na 2SO4-Fe2(SO4) molten salt, as well as air environments by Kaur M et al, 2009. The results of HVOF spray Cr3C2-NiCr coating was found to be successful in maintaining its adherence in both the environments. The formation of chromium rich oxide scale might have contributed for the better hot corrosion/oxidation resistance in the coated steel. Parkash S. et al, 2005. deposited NiCrAlY, Ni20Cr, Ni3Al and Stellite metallic coatings with plasma spray technology on Ni based Superni-718 substrate. NiCrAlY was used as bond coat in all coatings. Hot corrosion studies were performed on 900C under cyclic

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conditions. The results of SEM/EDAX and EPMA techniques reveals that NiCrAlY provides best protection to the base alloy due to oxides of Ni, Al and NiCr2O4 spinal in the scales. Hot corrosion resistance of Ni3Al coating is less as compared to NiCrAlY and Ni-20Cr but it performs better than the satellite-6 coating. Sidhu H. S. et al, 2010. formulated NiCr and Stellite-6 coatings on ASTM-SA-210 Grade A1, ASTM-SA213 T-11 and ASTM-SA213-T22 boiler tube steels by HVOF technique using LPG as fuel gas. These coatings have been examined for characterization by metallography, SEM/EDAX and XRD techniques for describe the transformations that take place during HVOF spraying. The results of Stellite6 coating were better than NiCr coatings for low value of porosity and surface roughness. Microhardness of the Stellite-6 coating has higher hardness as compared to the NiCr coating, although both coatings have high hardness values compared to the substrate steels. Sidhu B.S. et al, 2005. were used Low carbon steel ASTM-SA210-Grade-A1, ASTMSA213 T-11, and 2 ASTM-SA213-T- 22 steels as substrate material and Ni-20Cr-10Al-1Y bond coat applied on these specimens and Ni-20Cr coating deposited by plasma spraying. The samples were exposed to the combustion gases for atotal of 10 cycles, each consisting of a 100 h exposure followed by 1 h cooling at ambient conditions. The possible mechanism of attack for this coating is shown in Figure 2. XRD,SEM/EDAX Analysis shows top-most scale is rich in nickel, and then a chromium rich layer lying just above the bond coat is followed by an intermediate layer where nickel and chromium are coexisting, which confirms the formation of spinel. The continuous thin band of chromium lying at the bond coatsubstrate interface blocks the transport of species to the substrate, which contributes to the protection of the base steels.

Figure 2: Mechanism of Attack of Oxidation (Sidhu B.S. et al, 2005).

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The uncoated T22 steel showed better resistance to hot corrosion in boiler environment as compared with T11 and GrA1 bare steels. All the plasma sprayed steels have shown better degradation resistance than uncoated steels. Mohsen et al, 2007. Investigated Ni based inconel 738 material and Amdry962 (Ni-22Cr-10Al-1Y) as bond coat and Metco204YSZ (ZrO2-8%Y2O3) coating that deposited by plasma spray technique on the substrate. Hot corrosion studies were performed on 1100C under cyclic conditions for 22, 24 and 100 hours. The results of SEM/EDAX and EPMA techniques reveal that horizontal cracks as shown in Figure 3 and spallation of YSZ layer are due to formation of monoclinic ZrO2 and YVO4 crystals.

Figure 3: SEM Image Showing the Cross-section of the Coating after Hot Corrosion Test (Mohsen et al, 2007).

Bala N et al, 2009 examined SA 516 (Grade 70) uncoated and SA 516 (Grade 70) steels Ni-20Cr coated by Cold spray process .Cyclic corrosion was performed in molten salt (Na2SO4-60%V2O5) at 900C for 50 cycles. The results of XRD,SEM/EDAX shows cold spray coating of Ni-20Cr alloy powder was found to be useful in developing hot corrosion resistance in SA-516 steel in Na2SO4-60%V2O5 environment at 900C due to Ni and Cr in its oxide scale, which are reported to be protective oxides. The uncoated steel showed substantial spallation of its oxide scale during hot corrosion. The Ni-20Cr coating was found to be successful in retaining its continuous surface contact with the substrate steel. Ramesh M.R et al, 2010. examined HVOF process used to deposit NiCrFeSiB alloy powder on boiler tube steels SA210 grade-A1, SA213-T11, and SA213-T22. Thermocyclic oxidation test were performed in static air at 900C in silicon carbide tube furnace up to 50 cycles. The results of SEM/EDAX and EPMA techniques reveal that the microstructure of coatings has a dense and layered structure with porosity less than 0.5%. The superior performance of NiCrFeSiB coating can be attributed to continuous and protective thin oxide scale of

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amorphous SiO2 and Cr2O3 formed on the surface of the oxidized coatings. Sundararajan T. et al, 2004. Investigated 80Ni-20Cr and 50Ni-50Cr coatings that deposited by HVOF (High Velocity Oxy Fuel) process and APS (Air plasma spray) on 9Cr-1Mo steel substrate respectively. Steam oxidation test was carried out at 650C for 100, 1000 and 3000 hours. These coatings have been examined by metallography, SEM/EDAX and XRD techniques that show HVOF coatings of both 80Ni-20Cr and 50Ni-50Cr yielded a good protection till 750C by forming Cr oxide as protective layer as compared to APS. Aalamialeagha M.E. et al, 2003. Reveals that when Ni-20%Cr alloy gas and water atomized powders sprayed BY Topgun HVOF with a gaseous propylene fuel and Met-Jet II HVOF system with liquid fuel (kerosene) on mild steel substrates. The oxide, porosity and the amount of melted material in the coatings were characterised using scanning electron microscopy (SEM) and X-ray diffraction (XRD), whilst the corrosion resistance of the coatings was evaluated by use of a salt spray chamber and potentiodynamic tests. The results observed that greatest corrosion protection to the steel substrate is given by coatings produced from gas atomized Ni-20%Cr powders when sprayed by the liquid fuelled Met Jet II HVOF system Sidhu H.S et al, 2006 examined Cr3C2-NiCr, NiCr, WC-Co and Stellite-6 alloy coatings that were sprayed on ASTM SA213-T11 steel specimens using the HVOF process, liquid petroleum gas was used as the fuel gas. Hot corrosion testing was done on the specimens after exposure to molten salt at 900C under cyclic conditions. The testing techniques shows that NiCr Coating to be most protective followed by the Cr3C2-NiCr coating. WC-Co coating was least effective to protect the substrate steel. In this study it is concluded that the formation of Cr2O3, NiO, NiCr2O4, and CoO in the coatings may contribute to the development of a better hot-corrosion resistance. Sidhu H.S et al, 2006 Investigated The boiler tube steel, ASTM-SA210 grade A1 as substrate and Cr2O3NiCr, WC12Co and stellite-6 alloy powder and Ni20Cr wire coating deposited by HVOF process with oxygen and LPG as the fuel gases. Cyclic oxidation was performed in molten salt (Na2SO460% V2O5) for 50 cycles, The results of XRD, EDAX and EPMA analysis shows the porosity of NiCr coating lies in the range of 13.5% that provided highest resistance to hot corrosion. Sidhu H.S et al, 2006 used Low carbon steel ASTM-SA210 grade A1, 1Cr0.5Mo steel ASTM-SA213-(T11) and 2.25Cr1Mo steel ASTM-SA213-(T22) as substrate and WC12%Co, Cr3C225% NiCr powder coating were deposited by HVOF thermal spraying process with LPG as fuel gas in the thickness range of 350380m.Characterization were done in order to achieve microstructure of coatings. SEM/EDAX and XRD techniques show that WCCo coatings have slightly higher hardness and porosity as compared to the Cr3C2-NiCr coatings that is desired for hot corrosion. Kamal S. et al, 2010 formulated NiCrAlY + 0.4 wt.% CeO2 coatings with D-gun process on Nickel- and Iron based superalloys superni 75, superni 718, and superfer 800H specimens .Hot corrosion studies were performed in a molten salt (40% Na2SO4-60% V2O5) for 100 cycles at 900C under cyclic conditions. The proposed hot corrosion mechanism of the NiCrAlY + 0.4 wt.%CeO2 coated superalloy superfer shown in Figure 4.

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Figure 4: Schematic Diagram Showing Proposed Hot Corrosion Mechanism of the NiCrAlY + 0.4 wt.%CeO2 Coated Superalloy Superfer 800H at 900 C in Na 2SO4 + 60% V2O5 after 100 Cycles (Kamal S. et al, 2010).

The SEM/EDAX, XRD results reveals that bare and coated Fe-based superfer 800H superalloy showed least and highest resistance to the hot corrosion, respectively. D-gunsprayed NiCrAlY + 0.4 wt.% CeO2 coating found to be effective in imparting hot corrosion resistance to superfer 800H in the molten salt environment Pint B. A. et al, 2001 investigated Fe-9Cr-1Mo (ferritic alloy),and an austenitic stainless steel, 304L as substrate material and iron-aluminide coating were deposited by Chemical vapor deposited (CVD). High temperature cyclic oxidation testing in air with 10 0.5vol.%H2O was done in an automated test rig with a cycle consisting of 1h at 800C temperature and 10min cooling at room temperature. The XRD, SEM/EDAX results show that CVD aluminized coatings have excellent resistance to environments containing water vapor but do not appear to have sufficient Al for long-term resistance to low oxygen, high sulfur environments. The high coefficient of thermal expansion of 304L may be more compatible with Fe3Al coatings while the ferritic substrates should avoid the intermetallic phase formation Lasota B. S. et al, 2005 examined composite coatings FeAl- FexAly strengthened by a fine dispersive Al2O3 were thermally sprayed by HVOF process. The cyclic corrosion behavior of coatings with FeAl intermetallic matrix was investigated in N2 + 9% O2 + 0,2% HCl +0,08% SO2 aggressive gases at 600C for exposure times of up to 500 hours. Model of the corrosion mechanism of intermetallic coatings in aggressive gas. Mixture is shown in Figure 5. One portion of intermetallic coatings was sealed with an inorganic phosphate seal. The results of SEM/EDAX, XRD show that an adherent alumina scale and iron oxide layers were formed on all studied coatings. A stable Al2O3 phase on the surface of the studied

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Figure 5: Model of the Corrosion Mechanism of Intermetallic Coatings in Aggressive Gas Mixture: N2 + 9 vol.% O2 + 0.2 vol.% HCl + 0.08 vol.% SO2 (Lasota B. S et al, 2005)

coatings ensure high oxidation resistance. All the results confirm good heat proofness of HVOF sprayed coatings with an intermetallic FeAl matrix. 3. CONCLUSION Degradation of metals is a severe problem in the industrial applications. It is not possible for single material to have different properties to meet the demand of todays industries. So alloy and composite materials is required to provide the necessary mechanical properties and protective surface layer which immune the substrate surface from hot corrosion, wear and erosion also. The formation of chromium rich oxide scale might have contributed for the better hot corrosion/oxidation resistance in the coated steel. NiCrAlY provides best protection to the base alloy due to oxides of Ni , Al and NiCr2O4 spinal in the scales. Alloy and composite coatings has high hardness and low value of porosity as compared to substrate steel that is desirable in hot corrosion resistance. In order to improve the corrosion resistance of coatings, post-treatments are often used to eliminate the inherent defects in the ceramic coatings, such as liquid metal impregnation, Sealing treatment .sealing is to close or fill open structural defects connecting to the surface and make the sealants penetrate into the coating as deep as possible. Sealing treatment is an effective method to improve the corrosion resistance of porous materials. Therefore high temperature oxidation and hot corrosion behaviour of alloy and composite coatings need to be further investigated to understand the behaviour and performance of these coatings at higher temperature in different corrosive environment. REFERENCES
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