Materials Science, Vol. 41, No.

6, 2005

SCIENCE FOR PRODUCTION STUDIES ON THE PROPERTIES OF HIGH-VELOCITY OXYFUEL THERMAL SPRAY COATINGS FOR HIGHER TEMPERATURE APPLICATIONS
T. S. Sidhu, S. Prakash, and R. D. Agrawal
Materials operating at high temperatures in corrosive media suffer erosion-corrosion wear, oxidation, and hot corrosion. Among various methods used for the protection of the surfaces against degradation, we can especially mention the technology of application of coatings by high-velocity oxy-fuel spraying, which gives coatings which high strength and hardness, low (less than 1%) porosity, and high erosion-corrosion and wear resistances. The characteristics of the coatings and their protective properties are presented. The role of some high-velocity oxy-fuel coatings in the protection of metals and alloys against degradation at high temperatures in various media is demonstrated.

Protective Coatings In a wide variety of applications, materials have to operate under severe conditions such as erosion, corrosion and oxidation at higher temperatures in hostile chemical environments. Surface modification of these components is necessary to protect them against the indicated types of degradation [1]. Only composite materials are able to meet such a demanding spectrum of requirements: the base material provides the necessary mechanical strength and coatings provide a way of extending the limits of use of materials at the upper end of their performance capabilities by allowing the mechanical properties of the substrate materials to be maintained while protecting them against wear, erosion, or corrosion [2 3]. Even if the material withstands high temperatures without coating, coating enhances the life period of the material in this case. The main advantages of coatings are summarized as follows [4, 5]: very high flexibility concerning alloy selection and optimization for specific resistance to corrosion environments and abrasion/erosion of particles; surface properties can be separated from the required mechanical properties of the structural component; coating systems (multi-layered or functionally graded) can be used by combining, e.g., good adhesion with optimized corrosion and erosion behavior; unique alloys and microstructures can be obtained by thermal spraying which are not possible with wrought materials; these include continuously graded composites and corrosion-resistant amorphous phases;
Metallurgical and Materials Engineering Department, Indian Institute of Technology Roorkee, Roorkee-247 667, India. Published in Fizyko-Khimichna Mekhanika Materialiv, Vol. 41, No. 6, pp. 8095, NovemberDecember, 2005. Original article submitted February 19, 2005. 1068820X/05/41060805 2005 Springer Science+Business Media, Inc. 805

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costs of the coating solution are normally significantly lower than those of highly alloyed bulk materials; thermal spray coatings are of especial interest due to their cost/performance ratio; thermal-spray coatings additionally offer the possibility of on-site application and repair of components, given a sufficient accessibility for the sprayer and his equipment; however, thermal spraying in the workshops is preferred, whenever possible, to achieve optimal results. Table 1. General Property Criteria for Coating Systems for Elevated-Temperature Services [2] Component system criteria / property
Aerodynamic property

Coating criteria / property

Smooth surface finish for coating must conform to the appearance of precision cast component Coating must be resistant to all types of stress (impact, fatigue, creep, and thermal) to which system is exposed Coating/substrate must be compatible without gross thermal or structural mismatch; diffusion rates at the interface must be minimum at operating temperatures just as the compositional changes, development of embrittling phases must be avoided Coating composition must have sufficient reserve of all reactant constituents to meet scale reformation needs without marked deterioration in the protection ability; coating must be ductile and must develop uniform, adherent, and ductile scale at low rates

Mechanical strength and microstructural stability System adhesion, bonding, and interface stability

Surface resistance to erosion and oxidation/hot corrosion

Use of Coatings at Higher Temperatures Protective surface treatments are widely used at low temperature, the use of these at elevated temperature is more recent. High-temperature applications are largely limited to the aerospace industry. An enormous challenge exists to develop and apply these techniques to other high-temperature applications [6]. The demand for protective coatings has recently increased even for almost all types of superalloys, since high-temperature corrosion problem become much more significant for these alloys with increasing operating temperatures of boilers, turbines, and heat engines. The necessities for higher performance and increased efficiency have resulted in the progressive increase in their operation temperatures [79]. As a result, components operating at high temperatures in plants of this sort are coated or surface treated [10]. Although superalloys were designed for higher temperature applications, protective coatings are also applied to enhance their life for using in corrosive environments as they are not able to meet both the high-temperature strength and high-temperature corrosion resistance simultaneously [11] (see Table 1). Coating Techniques There are many available coating-deposition techniques and choosing the best process depends on the func-

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tional requirements, adaptability of the coating material to the intended technique, the required level of adhesion (size, shape, and metallurgy of the substrate), availability and cost of the equipment (see Fig. 1) [12].

Fig. 1. Coating-deposition technologies [12]. From the production point of view, chemical vapor deposition (CVD) from a pack, physical vapor deposition (PVD), and thermal spraying (metal spraying) are in current use [13]. Since the CVD process is a nonlineoff-site technique, proper masking and tooling are the major design considerations. Another shortcoming of the CVD process is the inclusion of pack particles in the coating, which can lead to its failure [14]. Thermally sprayed coatings often have superior properties, lower application cost, and less environmental issues as and when compared to other industrially used coatings, such as CVD, PVD, and hard chromium plating [15]. It is reported that overlay coatings perform better than diffusion coatings at higher temperatures [16]. For depositing overlay coatings, thermal spray technologies are often considered [17]. Thermal Spray Techniques In the early 1900s, Dr. Max Schoop, young Swiss inventor, invented thermal spraying after watching his son playing with a toy cannon. Dr. Schoop observed that the hot lead shots projected out of the cannon stuck to almost any surface, the result of which gave him the idea that if a metal could be melted and projected in a spray-like manner, then a surface could be built up with this material.

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Fig. 2. Schematic diagram of a thermal spray process [19]: (1) materials, (2) gas/air, (3) energy, (4) thermal spray, (5) coated part;
the diamond-jet gun is used as an example [35].

The technology continued but expanded in the 1970s due to the development of thermal plasmas and the increasing demand for high-temperature and wear-resistant materials and coating systems [18]. In thermal spraying, the initial coating material (materials in the form of rods, wires, or powder) is heated, generally to a molten state and projected onto a receiving surface, known as substrate, as shown in Fig. 2 [19]. The thermal spray processes used to deposit coatings for protection against high-temperature corrosion are as follows [5]: flame spraying with powder or wire, electric-arc wire spraying, plasma spraying, spray and fuse, high-velocity oxy-fuel (HVOF) spraying, and detonation gun. The particle speed, flame temperature, and spray atmosphere are the main parameters differentiating various spraying techniques (see Table 2) [12, 1920]. Coating porosity, bond strength, and oxide content are typical properties influenced by the coating procedure. In 1988, METCO introduced the Diamond-Jet HVOF system, which is now the main topic of interest among the researchers and industrialists due to its superior properties as compared to many other thermal spraying processes. High-Velocity OxyFuel Thermal Spraying The HVOF processes belong to the family of thermal spraying technologies and are capable of producing coatings with lower porosity, higher hardness, superior bond strength, and lower decarburization than many other thermal spraying methods [1, 2124]. In recent years, there has been a considerable growth in the use of this spraying process to deposit cermets, metallic and ceramic protective overlay coatings, which are typically 100300 m thick, onto the surfaces of engineering components to allow them to function under extreme conditions [21, 25]. Thermally sprayed coatings previously had limited usefulness as corrosion protection coatings due to the presence of interconnected porosity in the structure. However, HVOF coatings have recently gained popularity and are now extensively studied for their corrosion-resistant properties [26]. So far, several HVOF sprayed coatings have been subjected to corrosion testing in seawater, including cermets [2729] and anticorrosion alloys [3032]. These studies make it possible to conclude that the HVOF method produce coatings with higher corrosion resistance as compared with other spraying technologies. The HVOF sprayed coatings have found wide application in marine, aircraft, automotive and other industries. For reclaiming a wide range of petrochemical-process components, such as storage vessels, heat exchangers, pipe end fittings, and valves subjected to severe erosive, wear, and corrosive conditions, the Amoco Oil Company routinely employs the HVOF process by applying AISI-316-L and C-276 Hastalloy coatings [33]. The HVOF spraying techniques are predominantly used as wear, corrosion, and oxidation resistant barriers resulting in increased lifetimes as compared with the uncoated substrate components [34].

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Table 2. Comparison of the Characteristics for Various Thermal Spraying Processes [12, 19 20] Spray gun temp. (C)
6000

Deposition technique
Electric arc

Heat source

Propellant

Material feed type

Wire

Particle velocity m / sec

240

Coating materials
Ductile materials

Relative bond strength

Good

Porosity level vol. %

8 15

Arc between electrodes Plasma arc

Air

Plasma arc spraying

Inert gas

Powder

16,000

120 600

Metallic, Very good ceramic, to excellent plastic, and compounds Metallic, ceramic, plastic, and compounds Fusible metals Metallic and ceramics Metallic, ceramic, plastic, and compounds Excellent

25

Lowpressure plasma spraying Spray & fuse Flame spraying Detonation gun spraying

Plasma arc

Inert gas

Powder

16,000

900

<5

Powder

Excellent

< 0.5

Oxyacetylene / oxyhydrogen Oxygen / acetylene / nitrogen gas detonation

Air

Powder

3000

30120

Fair

10 20

Detonation shock waves

Powder

4500

800

Excellent

0.11

Highvelocity oxy-fuel (HVOF)

Oxypropylene / Combustion hydrogen / jet propane / LPG

Powder / wire

3000

800

Metallic Excellent and ceramic

0.1 2

The HVOF Spraying Process In the HVOF process (Fig. 3), the powder / wire material is melted and propelled at a high velocity toward the surface with the use of oxygen and fuel gas mixtures. Propylene, propane, hydrogen, acetylene, methane, ethylene, crylene, SPRAL-29 kerosene, MAPP (methyleacetylene-propadiene-stabilized gas), LPG, etc. are used as combustion fuels. The HVOP system consists of a spray gun, powder-feed unit, flow-meter unit, and an air and gas supply unit. The powder feed unit comprises a hopper assembly, air vibrator, feed-rate meter, and control cabinet.

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Fig. 3. Schematic cross section of a diamond-jet spray gun [35]: (1) powder with nitrogen carrier gas, (2) oxy-propylene, (3) compressed air, (4) gun head, (5) air envelope, (6) shock diamonds due to supersonic spread of the particles, (7) balanced oxyfuel flame, (8) combustion zone, (9) molten powder particles, (10) sprayed material, (11) substrate or forming die.

The desired powder is fed from the powder feed unit by means of a carrier gas to the gun, where combustion occurs. The amount of powder required for deposition can be regulated by using the powder feed-rate meter. In the combustion zone, the powder material enters the flame, where it becomes molten or semimolten, depending on the melting temperature and the feed rate of the material. The flame temperature for the HVOF process is about 3000C [20]. The molten or semimolten particles are then propelled out of the gun nozzle at very high velocities toward the target/substrate, where the material is deposited. Powder particles, typically within the range 1063 m, attain velocities of 300800 msec 1 at the substrate to be coated [12, 22, 3638]. The quality of the coatings significantly depends on the velocity and temperature of the powder particles impinging upon the substrate surface, which, in turn, is associated with the gas pressure developed in the combustion chamber. In the HVOF spray systems of the first and second generations (Continuous Detonation Spraying, Top Gun, Jet-Kote, and Diamond Jet), combustion occurs under pressures of 35 bar and the flame attains a supersonic velocity in the process of expansion at the exit of the nozzle. These systems produce comparable particle velocities with the standard spray parameters and the same fuel gases and powders. Thus, in the course of spraying of a WC17% Co powder in these systems by using particles whose sizes were distributed within the range 45 + 10 m and propane as fuel, the resulting particle velocities were about 450 m / sec [39]. The HVOF systems of the third generation (Diamond Jet Hybrid 2600 and 2700, JP-5000, OSU Carbide Jet, and TOP Gun K) operate at higher combustion pressures within the range of 610 bar. These systems permit higher particle velocities and higher spray rates. Thus, for the WCCo powder, the velocities are about 600 650 m / sec and the spray rates increase up to 10 kg / h or even up to 18 kg / h (in the JP-5000 system) without any deterioration of the coating quality [39]. Advantages of the HVOF System The HVOF process is designed around producing high velocities of spray particles and this contributes to the advantages of the HVOF spraying over the other processes of thermal spraying in terms of particle condition [4041] including: more uniform and efficient particle heating due to the high turbulence experienced by the particles inside the combustion chamber; much shorter exposure time in flight due to the high particle velocities;

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Fig. 4. Characteristics of the HVOF and standard plasma-process coatings [42]: (I) hardness, (II) porosity: (III) oxide content, (IV)
bond strength, (V) maximum thickness.

Table 3. Benefits of Using HVOF Coatings [19]

Coating benefit
Higher density (lower porosity) Improved corrosion barrier Higher hardness ratings Improved wear resistance Higher bond and cohesive strengths Lower oxide content Lower content of unmelted particles Greater chemistry and phase retention Thicker coatings (per pass and total) Smoother as-sprayed surfaces

Main causes of this benefit

Higher impact energy Lower porosity Better bonding, less degradation Harder and tougher coating Improved particle bonding Less in-flight time of exposure to air Better particle heating Reduced time at higher temperatures Lower residual stress Higher impact energies

lower surface oxidation due to the short particle exposure time as compared to other thermal spraying techniques; reduced mixing with ambient air once the jet and particles leave the gun; lower ultimate particle temperatures as compared to other processes, such as plasma or arc guns, as these processes operate at temperatures of 16,000 and 6000C, unlike 3000C in the HVOF (oxygen/propylene mixture) process. Stokes [19] summarized the causes of producing of high-quality coatings by the HVOF process as shown in Table 3. The HVOF coatings have better qualities as compared with those produced by using the standard plasma-spraying process as indicated in Fig. 4 [42].

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Fig. 5. Schematic diagram of a spherical particle impinged upon a flat surface [19]: (1) rim, (2) core (& 0.1 d high), (3) splat, (4) substrate, (5) spherical particle prior to impact [19].

(a)

(b)

Fig. 6. Two morphological forms of lamellae splashed on the substrate: (a) pancake, (b) flower; (1) crack, (2) deformed substrate,
(3) corona, (4) substrate, (5) lamella; (I) top view, (II) X-section view [43].

Splat Formation and Building Up an HVOF Coating Depending on the melting temperatures of the particle relative to the flame temperature, the particle may be molten, semimolten, or solid when it impacts a substrate or a precoated surface. The state of the particle as it leaves the combustion zone affects the final microstructure of the coating [1]. The HVOF coatings have lenticular or lamellar grain structure resulting from rapid solidification of small globules flattened upon striking a colder surface at high velocities (Fig. 5). Initially, the particle is melted and propelled out from the gun in the form of a sphere. Then, in its first contact with the substrate, the impact creates a shock wave inside the lamella and in the substrate. Postimpact forms the particle into a pancake shape lamella or splat (associated with moderate particle velocities and moderate heat contents) shown in Fig. 6a or a flower type lamella (connected with an elevated velocity of the particle and an elevated heat content) as shown in Fig. 6b when the process of solidification takes place [43]. When a molten droplet arrives at the surface at a high velocity, the process of spreading of the splat is restrained by surface tension. Otherwise, the extremities of the splat either become weak and break off or form small spherical drops [19].

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Fig. 7. Cross section of the lamella splat depicted in diagram (a) is shown in diagrams (b, c) representing possible microstructures of
the lamellae: (1) layers of lamella, (2) substrate, (3) lamella split, (4) formed columns, (5) brick-wall effect [19].

The surface roughness of the substrate also affects the splat formation and the loss of adherence occurs if an inadequate amount of surface roughness is present whilst spraying [44 45]. Building Up a Coating A coating is the buildup of individual particles striking the substrate. In one pass of the spray gun, a layer of 515 lamellae in thickness is formed depending on the processing parameters, such as the powder feed rate, spray distance, particle size, and linear speed of the torch. Hence, several passes of the spray gun are required to build up a coating across the workpiece. Meanwhile, the layer deposited by the first pass may be subjected to oxidation (for highly oxidizable materials) and cooling. On the second pass, the temperature of the first layer (which may be partially solidified) cools the second layer due to the difference in temperatures between the first and second layers. The final coating may comprise 5 200 passes of the deposited material. Afterward, the coating is allowed to cool down to room temperature. During this period, thermal stresses are generated often leading to crack formation in the coating or separation from the substrate [19]. Once a molten or semimolten particle strikes the substrate or previously deposited material, solidification starts and a columnar structure of the deposit is formed as shown in Figs. 7a, b [19] or changes into a brick-walltype structure depicted in Fig. 7c [1, 19], where a low rate of heat removal is experienced between the particle and the adjoint material interface due to substrate oxidation and/or surface roughness. In either case, the solidification inside each lamella is repeated as the coating is built up to the required thickness. Physical and Mechanical Properties of the Coatings In comparison with the other thermal spraying processes, the HVOF coatings have low roughness, high bond strengths, higher hardness, lower porosity, low oxide content, and higher thickness [4647]. The overall result is a coating with reproducible characteristics and high erosion, corrosion, and wear resistance. Due to high velocity and high impact of the sprayed powder particles, the coatings produced by the HVOF spraying process are less porous and have higher bond strength than the coatings produced by the other methods, such as plasma spraying, flame spraying, and electric arc spraying [48 50]. The high kinetic energy of the particles in the HVOF process deforms the particles in a plastic state rather than in a molten state. As a result, the oxidation of spray metal during flight and flattening is relatively weaker, since oxidation occurs only by a relatively slow diffusion mechanism.

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Fig. 8. Schematic diagram of adhesion of a particle to a substrate asperity [19]: (1) asperities, (2) particle in flight, (3) particle mechanically locked to the asperities of the substrate, (4) substrate.

Despite the plastic state, the high kinetic energy of particles still allows flattening by deformation and leads to a dense and pore-free coating with low oxygen content. This characteristic of the HVOF process is of high importance for spraying mechanically alloyed materials [50 53]. Hamatani et al. [54] reported that the HVOF sprayed carbide dispersed Ni-based alloy (Cr3 C2 NiCr) can have a hardness of 1150 HV and an adhesion strength of 200 MPa. Further, by using Ni Cr of 20 wt. % and a smaller primary powder size, the adhesion strength of Cr3 C2 Ni Cr coating can be improved to 250 MPa. In the case of Ni Cr < 20 wt. %, due to the high carbide rate, the strength of the coating decreases. On the other hand, if Ni Cr > 20 wt. %, then the softer particles could give a decrease in adhesion strength. Further, in the case of using smaller particles, the relatively extensive surface area causing effective kinetic momentum and heat transfer from the gas flame to the particles attributes superior acceleration and heat, which results in better adhesion strength of the coatings. Microstructural Properties. The detailed microstructural examination of HVOF sprayed powders shows that these coatings exhibit characteristic splatlike layered morphologies due to the deposition and resolidification of molten or semimolten powder particles. During HVOF spraying, powder particles contain, generally speaking, three separate zones: fully melted regions, partially melted zones, and the unmelted core. However, the relative proportion formed in an individual powder depends on its particle size, trajectory of motion through the gun, the gas dynamics (velocity/temperature) of the thermal-spray gun, and the type of the gun [5558]. Corrosion Behavior of the Coatings. Dense coatings provide better corrosion resistance than the porous coatings because porosities can do harm to the persistent corrosion resistance of the coating [27, 59 61]. In the HVOF process, the powder particles are propelled out of the gun nozzle at high velocities toward the substrate. Due to high velocities and high impacts of sprayed powder particles, the coatings produced by the HVOF spraying process are very dense. Numerous research workers have reported that the HVOF coatings have higher corrosion resistance than the other thermal sprayed coatings [28, 30, 60 67]. Adhesion of the Coatings. The HVOF coatings have higher bond strengths than the most part of the coatings obtained by the other processes of thermal spraying due to the high kinetic energy attained by the impinging particles [68]. The bond strength observed in the HVOF system is higher than the strength attained in the plasma thermal spraying process by 25% [19]. The adhesion strength of the impinging particle to the substrate depends on the mechanical and metallurgicalchemical mechanisms. An impinging particle flattens, conforms to a suitably prepared surface, and then mechanically locks itself to the receptive asperities as shown in Fig. 8. Subsequently, diffusion or alloying may occur leading to the formation of intermetallic compounds. This is known as the metallurgicalchemical mechanism of adhesion [19, 69].

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Elevated bond strength depends not only on the applied deposition process but also on the purity (absence of oxides and other foreign elements), adequate roughness, and adhesion to the substrate surface parallel with plastic deformation exhibited by the particle on the substrate surface. Cohesive strength depends on the roughness, temperature difference, and bond/cohesive strength of the previously coated surface. Coating properties are also governed by the splat layering which, in turn, depends on the particle parameters at the impact, the shape and topology of the already deposited layers, the ability of the flattening particle to accommodate their pores, asperities, etc., and finally, on the temperature at the time of impact [70]. The full melting of spray particles does not contribute to the increase in the adhesion of HVOF metallic coatings. On the other hand, the deposition of partially melted large particles contributes to the substantial improvement of adhesion strength to more than 76 MPa, i.e., twice as large as for the coating deposited with completely melted particles [71]. Protective Role of HVOF Coatings at Elevated Temperatures The thermal spray coatings used at higher temperatures must be dense enough so that protective oxides can form inside voids and fill them and thick enough to postpone the diffusion of corrosive species to the substrate material till the formation of protective oxides inside the coating [72]. Guilemany et al. [73] also reported that thicker coatings provide better resistance against corrosion. Splats formed in HVOF coatings are very flat, which is the desired structure of coatings intended for operation in corrosive environments at higher temperatures. Corrosive species mostly propagate along the splat boundaries. In the HVOF coatings, the distance from the coating surface to the coating/substrate interface along the splat boundaries is very long [74]. Alloys and coatings designed to resist oxidizing environments at high temperatures should be able to develop a surface oxide layer, which is thermodynamically stable, slowly growing, and adherent [75]. The performances of some HVOF-sprayed coatings used at higher temperatures (up to 1000C) in corrosive environments have been reviewed. Cr3 C2 Ni Cr Coating. The HVOF-sprayed Cr3 C2 Ni Cr coatings are mainly used at temperatures between 600 and 900C in steam turbine blades or boiler tubes for power generation [59, 76] due to their behavior against aggressive corrosion and erosiveabrasive atmospheres and their thermal stability at high temperatures [77]. In view of of their good resistance to high-temperature corrosion and erosion, these coatings are considered as protective coatings for heat exchanger pipes and fluidized bed combustors [78 79]. The HVOFsprayed Cr3 C2 Ni Cr coatings have high erosion, corrosion, and wear resistance properties [64, 80 84]. Vuoristo, et al [80] reported that plasma spraying, detonation gun spraying, and high velocity oxy-fuel spraying methods are mostly used to apply chromium carbide coatings to work as wear-resistant coatings against abrasion and erosion in corrosive environments at high temperatures up to 900C. The room temperature abrasion and erosion wear resistance of Cr3 C2 + 25% Ni Cr coatings applied by these methods was compared and the high-velocity combustion process was reported to have highest wear resistance. The corrosion resistance of HVOF-sprayed Cr3 C2 Ni Cr coatings protecting the heat exchanger pipes of recuperators used in steel mills was evaluated. It was found that these pipes corroded via oxidation, sulfidation, and molten salt corrosion. Three kinds of corrosion tests under cyclic conditions were carried out: high-temperature oxidation tests in air, cyclic oxidation tests in an SO2-containing environment, and a molten-salt corrosion test. High-temperature oxidation tests were carried out in a box furnace for 50 h at 1000C. Another high-temperature corrosion test was performed in a N2 4.8% O2 0.2% SO2 atmosphere at 1000C for 100 h. The molten-salt corrosion test of the coating was carried out at 700C for 20 h in a sodium sulfate ( Na2 SO4 ) and iron sulfate Fe2 ( SO4 )3 salt environment carrying an O2 0.5% SO2 gas mixture. In this experiment, a plati-

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num catalyst was used for the fast transformation of SO2 into SO3 . It was found that Cr3 C2 NiCr coatings exhibited excellent corrosion resistance in the molten salt as well as in the oxidation environment. The HVOFsprayed Cr3 C2 Ni Cr coating was recommended as a promising coating for heat exchanger pipes suffering the molten-salt corrosion attack [85]. Wang and Luer [86] reported that HVOF-sprayed Cr3 C2 Ni Cr coatings are used in elevated-temperature service environments including fluidized bed boilers, coal-fired boilers, and municipal waste incinerators, in light of the excellent corrosion and oxidation resistance of the nickel chromium alloy and reasonable wear resistance of chromium carbides at temperatures of up to 900C. They investigated the erosion-corrosion (oxidation) behavior of the HVOF Cr3 C2 Ni Cr coatings at elevated temperature. It was found that the erosion-oxidation resistance of the HVOF Cr3 C2 Ni Cr coating was higher than the resistance of the substrate (1018 steel) and other thermal-spray coatings including FeCr Si B (Armacor M), Ni-base, Cr2 O3 6Si O2 4Al2 O3 (Rokide C), Cr2 O3 12Si O2 2Al2 O3 4Mg O (Rokide MBC), and WC NiCr Co (SMI 712). The high erosion-oxidation resistance of the HVOF Cr3 C2 Ni Cr coating was explained by its low porosity, fine-grained structure, and the homogeneous distribution of hard carbides/oxides which form a skeletal network inside the ductile and corrosion-resistant metal binder. The performance of HVOF-sprayed Cr3 C2 Ni Cr coatings on a Fe-based superalloy in a Na2 SO4 60% V2 O5 environment at 900C under cyclic conditions were evaluated by Sidhu, et al. [87]. The thermogravimetric technique was used to establish the kinetics of corrosion. It was found that the mass gain of the coated superalloy was less than 1 / 5 of the mass gain of the uncoated superalloy. The corrosion resistance of Cr3 C2 Ni Crcoated alloys was reported to be due to the formation of phases like Cr2 O3 , Ni O, and Ni Cr2 O4 . Nickel-Chromium Coatings. Nickel-chromium alloys are used as coatings to deal with oxidation and corrosive environments at high temperatures. When nickel is alloyed with chromium, this element oxidizes to the protective surface oxide Cr2 O3 at rates which could make it suitable for use up to about 1473K [88]. The faster the formation of the surface oxide layer, the better the offered protection [89]. There is an increasing interest in the deposition of Ni-based metallic alloys for protection against corrosion. Ni-based coatings are used in applications, where wear resistance combined with oxidation or hot-corrosion resistance is required [90]. The high resistance of high-chromium nickel-chromium alloys to high-temperature oxidation and corrosion makes them widely used as welded and thermally sprayed coatings in fossil fuel-fired boilers, waste incineration boilers, and electric furnaces [91]. Modern thermal-spray processes, such as HVOF, are often applied to deposit high-chromium nickel coatings onto the outer surfaces of various parts of the boilers, e.g., tubes, to prevent the penetration of hot gases, molten ashes, and liquids to the less noble carbon-steel boiler tubes [92]. Sundararanjan, et al [93] evaluated the steam-oxidation resistance of the HVOF and air-plasma-sprayed Ni 20Cr metallic coatings on 9Cr1Mo-type steel at four steam temperatures within the range 600750C. The results showed that the thick and dense HVOF coating exhibited better steam oxidation resistance than the thin and porous APS coating. The formation of continuous protective oxide scale of Cr2 O3 was observed on the surfaces of the HVOF coatings, despite their low concentration in the coating material. The diffusion of nickel from the coatings to the substrate and iron from the substrate to the coatings for longer exposures to steam oxidation was also noticed. The diffusion rates of Ni and Fe were found to be almost similar. The diffusion of iron led to the formation of Fe2 O3 scale which was suggested to be the cause of nonprotectiveness of the coatings for longer exposure times. In the case of Ni 50 Cr coatings, the HVOF coating formed a complete Cr2 O3 healing layer, which prevents the growth of scale. In addition, in the presence of an APS coating, the initiation of scale was also observed on the interface of the coating and the substrate. At the same time, in the HVOF coating, it was absent [94]. The high-temperature corrosion resistance of Ni 20Cr, Ni 50 Cr and Cr coated boiler tubes in the actual refuse incineration plant, as well as in the laboratory tests, was evaluated by Yamada, et al. [95]. It was observed that the detonation-sprayed N i 50Cr coating exhibited the highest corrosion resistance in laboratory tests at

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873K followed by HVOF among the detonation-gun-sprayed, plasma-sprayed, and HVOF-sprayed coatings. The detonation-sprayed Ni 50Cr coated tubes performed very well for seven years of testing in the actual plant without any problems and were expected to have a longer life. The authors also conclude that the Incolloy-825 and Inconel-625 with high content of nickel possess higher corrosion resistance than stainless steels. The high-temperature corrosion behavior of HVOF-sprayed Ni / Cr coatings on ferritic and austenitic boiler steels was studied in an oxidizing atmosphere of 500 vppm HCl, 3% O2 , 14% CO2 , 20% H2 O, and argon as balance for 1000 h . It was discovered that the Ni 49Cr 2Si coating performed well because no corrosion products were detected on the coating surface. No internal attack or attack on the substrate through this coating was observed. At the same time, the Ni 57Cr Mo Si B and Ni 21Cr 9Mo Fe coatings proved to be poor in resisting high-temperature oxidation as the substrates were attacked by corrosive species through the voids and oxides [74]. The high-temperature behavior of the same HVOF coatings in the presence of a salt environment of 40% Na2 SO4 40% K2 SO4 10NaCl 10KCl was again investigated in two environments, namely, in an oxidizing environment of N2 20H2 O 14CO2 3O2 500 vppm HCl and a reducing environment of N2 20H2 O 5CO 0.06H2 S 500 vppm HCl . It was found that corrosion was more severe in oxidizing environments than in reducing environments. Active oxidation was responsible for the accelerated corrosion in oxidizing environments. The coatings were prone to chlorine attack in both atmospheres through the interconnected oxide network on the splat boundaries. The Ni 57CrMoSi B coating was the only material forming a protective oxide layer. At the same time, under reducing conditions, the materials with high chromium content were found to be able to form a protective layer containing chromium, sulfur, and sodium. The corrosion resistance of this layer increased with its chromium content. The corrosion resistance of nickel-based high chromium coating materials was found satisfactory in the testing conditions [96]. Lianyong, et al [97] reported that oxidation, sulfidation, and molten-salt corrosion are the main high-temperature corrosion problems for the water-wall tubes of boilers used in thermal power plants, where the most severe corrosion occurs in molten-salt corrosive environments. They studied the corrosion resistance of high-velocity electric-arc-sprayed (HVAS) coatings. By comparison, they recommended NiCr (Ni 45Cr 4Ti) as a promising alloy coating for the water-wall tubes, which can resist the molten-salt corrosion attack. They found that the corrosion resistances of Ni Cr and Fe Cr Al coatings were much better than the corrosion resistance of 20 g steel. The Ni Cr coatings showed the best anticorrosion properties and had a slightly lower porosity than Fe Cr Al coatings. The authors also concluded that the corrosion resistance of the coatings was mainly determined by the chromium content, whereas the microstructure of the coating is as important as the chemical composition of the material. The HVOF-sprayed Ni 20Cr wire coatings have a dense and nearly uniform lamellar microstructure with porosity less than 1% and hardness varying within the range 600630 Hv [58]. Sidhu et at. [87] examined the performance of this coating on a Fe-based superalloy in a Na2 SO4 60% V2 O5 environment at 900C under cyclic conditions. The thermogravimetric technique was used to establish the kinetics of corrosion. The authors reported that the Ni 20Cr wire coating showed high corrosion-resistance behavior and successfully reduced the mass gain by 90% as compared with the gain observed for bare superalloys. The corrosion resistance of this coating may be caused by the presence of nickel and chromium oxides and their spinels. Ni Cr B Si Coatings. The largely employed Ni-based powder belongs to the NiBSi system with the addition of other alloying elements. The addition of chromium improves the oxidation and corrosion resistance at elevated temperatures and increases the hardness of the coating by the formation of hard phases. Boron decreases the melting temperature and contributes to the formation of hard phases. Silicon is added to increase the self-fluxing properties. Carbon produces hard carbides with elevated hardness, thus improving the wear resistance of the coatings [98 99]. The microstructural characterization of the HVOF-sprayed Ni Cr BC coating applied to low-carbon mild

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steel shows that the coatings has layered morphologies due to the deposition and solidification of successive molten or semimolten splats. The microhardness of the coatings is found to be 6.0 GPa [55]. Cha, et al. [100] studied the high-temperature corrosion behavior of HVOF-sprayed Ni 20Cr, Ni Cr BSi and Cr3 C2 Ni Cr coatings applied to 15Mo3 high-temperature steel in a corrosive atmosphere of HCl H2 O O2 N2 at 500C. They revealed that the Ni 20Cr coatings are more corrosion resistant than the Ni Cr BSi and Cr3 C2 Ni Cr coatings. Further, they discovered that the Cr3 C2 Ni Cr coatings exhibited slightly better corrosion-resistant behavior than the Ni Cr BSi coatings under similar conditions. It was also shown that the HVOFsprayed Ni 20Cr, Ni Cr BSi and Cr3 C2 Ni Cr coatings are resistant to corrosion at higher temperatures. Cha and Wolpert [101] again studied the high-temperature erosion and corrosion behavior of the HVOFsprayed coatings on 15Mo3-based materials in the environment containing HCl, H2 O, O2 , and Ni at a temperature of 500C for 168 h. The coatings were fabricated from Colmonoy-62 Ni-based (Ni Cr Fe BSi) and T800 Co-based materials. The authors reported that T800 Co-based coatings showed poor corrosion resistance as compared to Colmonoy-62 Ni-based coatings. They further indicated that Colmonoy-62 applied by the HVOF and APS processes exhibited almost the same corrosion rate. However, the HVOF process produced less oxides, especially along the fusion line, and the coalescence of oxides was stronger for the AP process. Miguel, et al. [102] studied the wear resistance and the mechanisms of wear of Ni Cr BSi coatings obtained by spray and fuse and as-sprayed coatings obtained by atmospheric plasma spraying (APS) and HVOF spraying. They found that both the HVOF-sprayed and sprayed-and-fused coatings performed well, whereas the plasma sprayed coatings showed the worst sliding wear resistance. Electrochemical tests were used to evaluate the corrosion resistance of HVOF-sprayed Ni Cr BSi coatings on the steel substrate. It was found that HVOF-sprayed Ni Cr BSi coatings have excellent corrosion resistance in alkali solutions because their surface can be kept in the self-passivation condition. It was reported that the effects of porosities on the early corrosion of the coating are not serious unless there are penetrating porosities. However, the presence of porosities can do harm to the persistent corrosion resistance of the coating [60]. Cobalt-Based Coatings. Cobalt-based alloys containing chromium, tungsten, and carbon, are known as Stellite alloys. One of the common Co-based alloys in use is Stellite-6 [56]. In Stellite-6 alloys, Cr provides oxidation and corrosion resistance, as well as strength by the formation of M7 C3 and M23 C6 carbides. Refractory metals, such as Mo and W, are known to be solid-solution hardening elements and also contribute to strength via precipitation hardening by forming MC and M 6 C carbides and intermetallic phases, such as Co3 (Mo, W). Further, the alloying addition of Ni, C, and Fe promotes the stability of the fcc structure of Corich matrix, which is stable at high temperatures up to the melting point (1495C), whilst Cr, Mo, and W tend to stabilize at low temperatures in the hexagonal close-packed (hcp) crystal structure, which is stable at temperatures below 417C. Stellite-6 has high hardness at high temperatures, high corrosion resistance, and high wear resistance [103104]. However, there is a very little discussion in the literature on the performance of HVOFsprayed Stellite-6 coatings at elevated temperatures [105]. Kong, et al. [56] studied the microstructural characterization of HVOF-sprayed Stellite-6 coatings deposited on low-carbon mild steel. It was revealed that the microstructure of the as-sprayed coatings comprised, in general, a microcrystalline fcc Co-based metallic matrix with some regions accounting for 20% of the exhibited partially melted dendritic structure. A small fraction of unmelted feedstock powder particles was also present in the coating. It was also reported that the M7 C3 carbide phase was not present in the coatings, although it was present in the original feedstock powder. The authors suggested that its formation in the coatings might have been suppressed by high cooling rates occurring in the course of splat solidification. The high-temperature erosion and corrosion were studied for thermally sprayed coatings on 15Mo3- and 13CrMo44-based materials. The coatings made of Ni-based materials, like Colmonoy-62 (Ni Cr Fe BSi) and Ni Cr BSi / WC, and T800 Co-based material were fabricated by thermal-spray processes, such as HVOF, flame

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spraying and sintering (FS/sinter) and APS. The corrosion studies in the environment containing HCl, H2 O, O2 , and N2 at a temperature of 500C indicated that Colmonoy-62 applied by the HVOF and APS processes revealed the same corrosion rates. The HVOF-sprayed T800 coating experienced the highest corrosion rate. The Ni Cr BSi / WC coating formed by the FS/sinter method proved to be a fair combination of erosion and corrosion resistance [101]. Sidhu, et al. [87] investigated the performance of HVOF-sprayed Stellite-6 coatings on a Fe-based superalloy in the Na2 SO4 60% V2 O5 environment at 900C under cyclic conditions. The authors demonstrated that the Stellite-6 coating was successful in decreasing the mass gain to about one-fourth as compared with the uncoated superalloy. The protection exhibited by this coating was reported to be due to the formation of chromium oxides and chromium and cobalt spinels. CONCLUSIONS The HVOF coatings have higher bond strengths than the most part of the coatings obtained by the other processes of thermal spraying. Moreover, they are higher than for the plasma-spray coatings by 25%. The better adhesion strength of the HVOF coatings is attributed to the better mechanical interlocking of the sprayed droplets with the substrate (as well as with each other) due to the high kinetic energy experienced by the impinging particles. Corrosive species mostly propagate along the splat boundaries. Due to the high velocities and high impacts of sprayed powder particles, the HVOF coatings are very dense and the splats formed in this case are very flat. Thus, in the HVOF coatings, the distance from the coating surface to the coating/substrate interface along the splat boundaries is very long. This is the desired structure if the coatings are intended for operation in corrosive environments at higher temperatures. Hence, the HVOF coatings can perform very well in corrosive environments. The studies performed by some researchers revealed the protective behavior of HVOF coatings at higher temperatures. However, the formation of oxides during HVOF spraying may affect the performance of the coatings in corrosive environments. Therefore, high-temperature oxidation and hot-corrosion behavior of the HVOF coatings need to be further investigated to understand the behavior of these coatings at higher temperatures in various corrosive environments. REFERENCES
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