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An Assessment of Thermal Spray Coating Technologies for High Temperature Corrosion Protection GR. Heath’, P. Heimgartner', G. Irons”, R. Miller” and S. Gustafsson! "Eutectic + Castolin, P.O. Box 360, CH-1001 Lausanne, Switzerland ? TAFA Inc., 146 Pembroke Road, Concord, NH 03301, USA Keywords: High temperature corrosion, thermal spraying, coatings, Arc-wire, Plasma, HVOF, SprayHused Abstract: The use of thermally sprayed coatings in combating high temperature corrosion continues to grow in the major industries of chemical, waste incineration, power generation and pulp & paper. This has been driven partially by the development of corrosion resistant alloys, improved knowledge and quality in the thermal spray industry and continued innovation in thermal spray equipment. There exists today an extensive range of thermal spray process options, often with the same alloy solution. In demanding corrosion applications it is not sufficient to just specify alloy and coating method. For the production of reliable coatings the whole coating production envelope needs to be considered, including alloy selection, spray parameters, surface preparation, base metal properties, heat input etc. Combustion, Arc-wire, Plasma, HVOF and Spray‘fuse techniques are reviewed and compared in terms of their strengths and limitations to provide cost-effective solutions for high temperature corrosion protection. Arc wire spraying, HP/HVOF and spray+fiise are emerging as the most promising techniques to optimise both coating properties and economie/practical aspects. Résumé: L'utlisation de revétements obtenus par projection thermique est en continuelle expansion pour combattre la corrosion a haute température dans les principales industries chimiques, papete- ries, incinération de déchets et les centrales. Cette tendance est due, entre autre, au développement dalliages résistant a la corrosion, & Tamélioration des connaissances et de la qualité ainsi qu’ aux innovations continues des équipements dans lindustrie de la projection thermique. Il existe actuelle- ‘ment une importante gamme de procédés de projection, utilisant souvent les mémes types d'alliage. Pour répondre a une application anticorrosion, il n'est pas suffisant d'exiger simplement un alliage et une méthode de revétement. Pour obtenir des revétements fiables, il faut tenir compte de l'ensemble des besoins, comprenant le choix d'un alliage, les paramétres de projection, la préparation de la surface, les propriétés du métal de base, apport de chaleur, etc. Les techniques de projection a la flamme, au fil, au plasma, HVOF et autofusible sont revues et comparées au point de vue de leurs qualités et limitations 4 fournir une solution économique de protection contre la corrosion a haute température. Les projections fil a larc électrique, A haute vitesse et autofusible sont les plus prometteuses tant pour les qualités du revétement que pour les considérations économiques. 1, INTRODUCTION High temperature applications cover a very broad range of different conditions for bulk or coating ‘materials in contact with the specific environments. At low material temperatures of 250-300 °C, local temperature variations can cause condensation of highly aggressive acidic sotutions in the presence of flue gases containing SO; or HCl, For example, such conditions can be found in cement furnaces burning fuels (c.g, solid waste) with higher concentrations of sulphur or chlorine. The metallic structures behind the thick brick insulation can be severely corroded by concentrated acids originating from corrosive gases penetrating through cracks or pores in the lining and condensing at the relatively cooler metal surface. The other extreme is found in gas turbines where metal temperatures can go well above 1000 °C. In this temperature range oxidation is the dominant surface degradation process [1]. In an intermediate temperature range there exists a large number of applications with a wide variety of different corrosive environments. Those are often characterised by a complex interaction of different degradation mechanisms, such as oxidation, sulfidation, carburization, molten salt corrosion, ete., depending on temperature, gas composition and type of material exposed to the gases. In coal fired boilers used for power generation, it is mainly oxidation and sulfidation that may be problematic for the materials exposed, depending on the local activities of oxygen and sulphur (2][3][4] Burning fuels with significant amounts of chlorine or elements such as sodium, potassium, vanadium, zinc and lead can cause the formation of ash and salt deposits with very low melting points; chlorides play a dominant role. If the temperature of the metal surface is above the melting point of the salt’s eutectic composition, very corrosive conditions develop with the molten salts fluxing the protective oxide scales or directly dissolving the metal. This corrosion mechanism is very often encountered in waste incinerators(5}{6][7][8], black liquor recovery boilers in the pulp and paper industry [9][10], fluidized bed boilers burning fuels with higher chlorine contents (e.g. solid waste) and also engine exhaust systems when oils with higher amounts of vanadium are burnt. Corresponding to the variety of corrosive environments is the number of countermeasures that have been developed to avoid excessive material damage. They can be grouped into the following categories: * alloy selection: a large number of Fe-, Ni- and Co-based alloys exists today specially designed for good resistance to oxidation, sulfidation or corrosion by ash/salt deposits * design aspects: improve temperature distribution (avoid hot spots), avoid excessive deposition of ash and slags by use of soot blowers, rapping, screens * chemical additives: neutralisation of corrosive components in the flue gases by injecting additives such as limestone or dolomite * shielding: SiC tiles in waste incinerators, other types of refractory linings * coatings: different coating techniques are applied to protect critical surface areas from corrosive gases, including co-extrusion, chromizing, weld overlay and thermal spray coatings. 2. PROTECTIVE COATINGS A number of coating failures in the past due to adhesion problems, porosity or unsatisfactory resistance to corrosion and erosion has focused development activities to produce new coating technologies and new coating materials. Today, coating solutions have achieved an important position in combating high temperature corrosion (2][3][8][10][1 1][12]. The main advantages of coatings can be summarised as follows: * Very high flexibility concerning alloy selection and optimisation for specific resistance to corrosive environments and particle abrasion/erosion. Surface properties can be separated from required mechanical properties of the structural component. * Coating systems (multi-layer or functionally graded) can be used, combining, for example, good adhesion with optimised corrosion and erosion behaviour [13][14). * Unique alloys and microstructures can be obtained with thermal spraying which are not possible with a ‘wrought material. These include continuously graded composites [13]{14] and corrosion resistant amorphous phases [15][16]. ‘+ Costs of a coating solution are normally significantly lower than those of a highly alloyed bulk material; thermal spray coatings are specially interesting for 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 work shop is preferred, whenever possible, to achieve optimum results. 2.1. Thermal spray coating procedures ‘The spray processes that have been used to deposit coatings for protection against high temperature corrosion are listed below: ~ Combustion (Flame) spraying with powder or wire ~ Electric arc wire spraying ~ Plasma spraying, including HP-Plasma (PlazJet) and Vacuum Plasma - HVOF spraying and High Pressure HVOF (HVOF: High Velocity Oxygen Fuel) ~ Spray and fuse (restricted to fusible coating materials) Particle speed, flame temperature and spray atmosphere (air, hydrogen, argon, vacuum..) are the main parameters differentiating the above techniques. The most important variable regarding coating quality is probably particle velocity, which ranges from below 100 m/s for powder combustion spraying to above 1000 m/s for HP/HVOF as shown in Fig 1 [17]. Coating porosity, oxide content and bond strength are typical properties influenced by the coating procedure. Coating adhesion is also very sensitive to surface preparation, as it depends on mechanical anchorage to the surface of the substrate. One exception is spray and fused coatings where a metallurgical bond is produced by diffusion, Such a bond has a significantly higher bond strength, Fig. 1: Particle speeds for different thermal spray processes [17] 1000 — 200 zs 800 E 00 B 600 B 500 3 400 Z 300 5 200 = 400 ° Bsa. 2 = ee Ee cs Be zo = § $2 $6 58 gn ge goa 3 f4 zh 8 Thermal Spray Process From the point of view of costs and performance, arc wire spraying, HP/HVOF and spray+fuuse processes are especially interesting for the protection of large surfaces against high temperature corrosion, These methods are described in more detail below. Are wire spraying is a low cost method for coating large areas in a reasonable time[18][19]. The gun design is schematically given in Fig. 2. The possibility of using cored wires opens up a wide field of possibilities with respect to coating composition and incorporation of hard phases for erosion resistance. At low impact angles the presence of a hard material increases erosion resistance. At high angles a ductile Phase is required for good erosion resistance[14][20]. The structure of arc wire sprayed deposits, as shown in Fig. 4a, is typically lamellar with a significant amount of oxides at the particle boundaries and a relatively high porosity (related to the spray material and spray parameters). Coatings of this type should therefore not be used for extreme conditions concerning temperature and aggressivity of the corrosive environment. As reported in [2] this type of coating has performed well under the conditions of ABFB (Atmospheric Bubbling Fluidised Bed) and CFB (Circulating Fluidised Bed) boilers at relatively low temperatures. It has also been used for BLRB (Black Liquor Recovery Boilers). Fig. 2: Electric arc spraying (schematic) suvstrate HVOF and high pressure HVOF (gun of HP/HVOF system JP-5000 is shown schematically in Fig, 3) as a result of high particle speeds produce coatings with a very low level of porosity and oxides as shown in Fig. 4b) [21][22][23]. The flexibility with respect to coating composition is comparable to are spraying with cored wires. HVOF coatings are being developed for gas turbines to achieve coating properties similar to those produced by vacuum plasma spraying, but at lower costs [24] Fig. 3: HP/HVOF spraying (system JP-5000), schematic Spray and fuse technique is a two step process comprising the deposition of a coating by e.g. combustion spraying, followed by a fusing procedure in which the coating material is heated above its fusion temperature to give an highly dense coating with a very good bonding to the substrate. Fig. 4c) gives an example of the dense microstructure of a spray and fuse coating. For certain materials it is possible that fusion already occurs during the spray process. The main drawback of this procedure is the fact that only specially designed alloys can be fused after spraying. There is also the possibility that the base metal properties are negatively modified due to the heat input during fusion of the coating. This point must be taken into consideration before coating of specialty steels by running preliminary tests. By precisely controlling heat input and by the use of automated systems, negative effects on the base metal can usually be overcome. Fig. 4: Microstructures of a) are wire sprayed FeCrAl costing (100x), b) HVOF sprayed Inconel 625 coating (10x), ¢) combustion spayed and fused NiCriBSi coating (100x) b) e) 2.2, Degradation of thermal spray coatings in high temperature environments Although the overall composition of a sprayed coating may be very similar to a specific wrought material the corrosion behaviour can be significenily different. This is mainly due to oxidation of the spray particles during the spray process, porosity and inhomogeneities in the distribution of major alloying elements across the coating. These discontinuities, which can be extremely small, can open a path for corrosive gases, melten salts or condensed acids during exposure to the corrosive environment [12]. For spray and fused coatings the comosion behaviour is closer to that of a hulk material of the corresponding composition. ‘The following deterioration mechanisms are essentially responsible for high temperature degradation of thermal sprayed coatings: ~ Internal autzck of the coating caused by oxidation, sullidation, molten salts ele.. The attack normally follows the particle (splat) boundaries or other weak areas in the coating as described above. ‘This kind of deterioration indicates thet the coating, meterial, 2s such, is not resistant enough to the given environment, ~ Penetration of the aggressive components through the coating to the base melal, which is attacked seriously. The coating ean remain more or less unaffected. Finally the coating will spall duc to the formation of voluminous corrosion products at the coating - base metal interface ~ Formation of cracks in the cveting originating ftom stresses in the deposit or at the coatin - base metal interface. The stresses can be a consequence of thermal expansion mismatch between coating. and substrate or excessive coating thickness giving rise to high invemnal stresses in the coating. Through the cracks the corrosive environment can quickly reach the base metal surface and cut its way under the coating to give adhesion loss and spalling. Stresses can also develop with time as a tesuk of ‘mechanical/physical property changes in the coating due to reactions with the corrosive envirorament, The Mechanism of attack and the rate of deterioration strongly depend on coating material proportics, spray technique and, of course, the corrosive conditions encountered. Base material properties, such 2s chemical composition, thermal expansion coefficient and surface preparation, can also have a signific influence on the deterioration prowess, 2.3. Critical coating properties The following coating properties have been found to be important for a good protection against high temperature corrosion: * Coating chemistry must be optimised for the given application (gas composition, temperature, ash/salt deposits, abrasion ...). Iron- nickel- and cobalt-based coating materials with and without hard phases for a broad spectrum of applications are available today as powders and/or (cored) wires. Some of the nickel alloys are specially designed for fusible coatings to be used with the spray and fuse process. ‘* Coating thickness must be matched to the given conditions, the coating material and spray process selected. Thick coatings are desirable for life extension, although too thick coatings can negatively influence adhesion and cause cracking due to high stresses in the deposit. ‘* A dense coating is a very important feature for protection against aggressive gases or liquid phases formed by condensation. If they can penetrate through the deposit, base metal corrosion will quickly cause the coating to spall by voluminous corrosion product jacking mechanisms. Porosity is mainly influenced by the coating procedure, but also by coating material and thickness. ‘* Coating adhesion is one of the most important properties of the coating/substrate system. Influencing factors are surface preparation, coating procedure, coating and base metal chemistry and stresses in the coating or at the substrate interface. If necessary, adhesion can be improved by specific bond coats, although the implications of this additional coating to the system (e.g. regarding corrosion behaviour) must be carefully assessed. * Thermal expansion coefficients of coating and base metal should be matched to avoid stresses at the coating/base metal interface that can lead to a weakening of the bond and subsequent spalling. Fig. 5 gives an example of a coating (A) showing a very similar thermal expansion behaviour to the boiler ‘tube steel. Coating B, on the other hand, has a significantly different expansion coefficient at the operating temperature of the boiler tube which would cause stresses and eventually cracking of a brittle coating. Fig, 5: Thermal expansion coefficient Alpha as a function of temperature for a boiler tube material and two different coatings (A: spray+fused Ni-base alloy, B: combustion sprayed Fe-based alloy) 15 >-— ta] 13 12 11 10 (Tube 7 -2- Coating A. 6 —=-CoatingB | 0 100 200 300 400 500 600 Alpha /10°-K* o Temperature / °C 2.4. Quality control measures Reliable thermal spray corrosion protection solutions can only be realised if'a QC system is integrated into the programme, QC can touch many areas of a coating project, some of which are listed below: ~ Coating recommendation: Proper evaluation of conditions to be expected for the coated components. They include chemical, thermal and mechanical loads as a function of time and also consideration of extreme operating conditions (e.g. during shut down phases). Using this information, together with evaluations of any previous coating failures, a suitable coating material and coating process can be selected. ~ Consumable and equipment control: control of powder/wire composition, particle size distribution, nozzle dimensions, etc. ~ Process control: Periodic or if possible continuous control of spray parameters such as gas flow, electric parameters and spray distance. (Benefit of automated spray systems). ~ Coating assessment: Intermediate and final assessment of coating properties (such as coating thickness and hardness) in order to check the deposition progress and identify eventual modifications of spray parameters. This should also include the coating of test pieces during the coating process as a reference. ~ Reporting of all decisions, evaluations and controls in a written or computer based documentation system. 2.5. Economic considerations Choosing a thermal spray coating process also includes economic aspects, although the performance and probable life expectancy of a coated system should have first priority for the selection. Among others the following factors have an influence on costs to be considered for the different procedures: ~ Capital costs for spray equipment: ~15,000$ (stand-alone arc wire) to ~250,000$ (HVOF or plasma with complete ancillary equipment, such as spray booth, robot, turntable, exhaust system ...) [22][25]. ~ Operating costs (gases, electricity ..): between ~1 S/h (are wire) and ~80 $/h (HVOF, Hydrogen) [27]. ~ Costs for spray material: alloy (Fe,Ni,Co based) in the form of powder, wire or cored wire. ~ Deposit efficiency (<50 to >90%) and deposit rate (<3 kg/h to >50 kg/h). ‘Taking into account these factors, the costs to produce a coating of similar composition and thickness can vary considerably [24][25][27]. For example, the relative costs to deposit one kg of austenitic stainless steel as a coating material would roughly amount to 15 $ for arc wire, 29$ for HP/HVOF (Kerosene), 55 $ for plasma spraying (air) and 70 $ for HVOF (Hydrogen). These figures include capital, labour, operating and consumable costs and are added to give an idea of the cost relation between different Processes. (The above values are only indicative and pertain to the US market in 1993). 3. CONCLUSIONS ‘+ Thermal spray coatings are becoming increasingly and successfully used for a broad variety of high temperature corrosion applications. * Recent developments in thermal spray coating procedures and coating chemistries have brought important improvements in coating quality and reliability, opening a wide field for new applications. Among the numerous spray procedures arc wire spraying, HP/HVOF and spraytfuse processes are emerging as the most promising techniques regarding coating properties and economic/practical aspects. + Experience has demonstrated the need for a coating system approach for successful corrosion control. ‘The coating procedure significantly influences the protective properties that can be achieved with a specific coating material. Additionally, base metal properties and economic factors have to be considered to identify the best solution to satisfy the customer's demands * Quality control measures have to be planned with every coating application to ensure a proper coating selection, consumables of a controlled quality as well as optimised and controlled spray conditions. These measures also include the careful evaluation of any previous coating failures. 4. REFERENCES 1. BAUMANN G., FELLER H.G. and WIENSTROTH U., Metall 46 (1: 1992) 448 2. GUSTAFSSON S., STEINE H.T. 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