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Thermal Spraying between erosion and corrosion challenges

R. Polak, IRW Technical Ofce, Vienna; F. Kremser, Terolab Surface Ltd., Vienna 1 Introduction Corrosion damage and erosive material losses need adequate overhauling strategies for boiler operators. Thermal Spraying is one of the methods that should generally be taken into closer consideration. No distortion even on already damaged pipe walls and a comparatively high coating performance are among its advantages. As demands on protective measures in the boiler sector have been changing, the demands on thermal spray coatings have also increased. Initially the focus was on those forms of damage characteristic in coal-red power plants but nowadays it is mainly centred on corrosioninicted strain. This is initiated by the increasing chlorine content in the exhaust fumes and presents a signicant challenge for preventive maintenance methods like Thermal Spraying. Apart from the basic properties of materials used for coating applications, procedural parameters determine the expectations in boiler maintenance to a great extent. Thermal Spraying stands out by its wide choice of process variances. It should therefore be of no surprise that differing and sometimes controversial results have been obtained in practical experience with these protective measures. This article is intended to convey a basic knowledge of thermally sprayed coatings for boiler operators. 2 Characteristics of thermally sprayed protective coatings Thermal Spraying is a method for mechanical bonding of coatings composed of single particles, without intensively heating the substrate. In order to achieve sufcient bonding the particles need to have a high energy level at the moment of their impact on the substrate. On impact upon the substrate which has to be protected this energy is transformed into a deforming force which ultimately determines the adhesive strength of the coating being applied. Hence the structural composition of a thermally applied coating differs signicantly from that of casted materials. The latter are heterogeneous in their structure and possess a residual pore volume. As protective coatings, they are not capable of forming a completely gas-proof bond and will eventually be penetrated by combustion atmosphere. Practical results are therefore linked to the penetration resistance of such coatings. The relevant factors for protecting boiler components against the attacks of aggressive smoke gas environments are (1) their order of importance regarding the substantial stability of the materials used and (2) the coatings penetration resistance that can be achieved. The suitability of a coating with added erosion protection is determined by its mechanical properties (e.g. hardness) but also by its chemical resistance. Both factors are connected with the chosen coating process. On the one hand the method used has an effect on a coatings chemical composition, on the other hand the kinetic response parameters determine its penetration resistance [1]. For coating procedures in incinerators plants arc spraying, high velocity spraying and plasma spraying are most commonly employed. There are signicant differences in coating performance and layer quality. Arc spraying yields the highest coating performance. The higher layer thickness accomplished by plasma and high velocity spraying resists smoke gas penetration longer but at a higher process cost. From a maintenance viewpoint a compromise has to be made. 3 Quality relevant process factors Thermal Spraying is based on the mechanical anchoring of highly heated or highly accelerated particles on tube material without heating the substrate itself during the process. Thermal Spraying avoids inducing tension into the construction, which is a crucial motivation for boiler applications. The layer is formed by successive attachment of the sprayed particles whereby velocity and temperature at the moment of impact on the substrate determine adhesion and density respectively. Characteristic data for the above mentioned processes are cited in table 1. Spray deposition rates between
Av. particle Adhesion Oxide Porosity Applicat. Coating velocity content rate thickness m/s MPa % % kg/hr mm Arc Plasma High velocity 100-150 400-700 600-1000 10-30 20-70 >70 10-20 1-3 1-2 5-10 1-2 1-2 6-60 1-5 1-5 0.2-10 0.2-2 0.2-2

Table 1: Characteristic differences in processes.

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6-60 kg/h favour arc spraying for large-surface repair work, but process-related increase of porosity and oxide content have to be taken into account. The other two processes perform at lower spray deposition rates but with considerably lower levels of oxide content and porosity. The particles thermo-kinetic energy upon impact on a substrate is quality-relevant in Thermal Spraying. Their heat content and velocity at this moment determine the deformation power and thus the coatings porosity. High heat content in the particles, i.e. high thermal energy, raises the coatings oxide content. Both oxide content and porosity are crucial quality features of thermally sprayed coatings. Porosity affects the penetration resistance of ue gas. A high oxide content of coatings permits the penetration of corrosive gases along the particles boundary layers. Applications in the corrosion dominated combustion environment require the coatings to be as dense as possible yet with a moderate oxide content. If the application is intended for erosion protection, hard and wear-resistant properties are the goal. Illustration 1 relates the three thermal spray processes described to the particle velocities achieved. From the particles thermal and kinetic energy content quality differences in coatings can be determined. Arc spraying is based on the attachment of fusing particles on the substrate by compressed air at a relatively low particle velocity. As only a moderate particle velocity is reached, the porosity of these coatings is higher than those of competing processes. A coatings high oxide content resulting from the particles fusibility has an adverse effect on the corrosion resistance of the layer compound. Illustration 2a shows the difference in appearance and structure between NiCr20MoNb coatings applied by arc spraying and high velocity spraying respectively. The varying densities and inherent oxide contents can easily be recognised. High gas temperatures form the basis for plasma spraying.
AS Arc spraying LS Lichtbogenspritzen PS Plasma spraying PS Plasmaspritzen HGS /HVOF Velocity Oxygen Fuel HVOF HighHochgeschwindigkeitsspritzen
Gas Gastemperatur(C) Gas temperature [C] temperature
15000

In order to avoid vaporisation of the sprayed materials the dwell temperatures in the ame have to be kept short. The coatings inherent oxide content remains manageable due to the particles being heated in a jet of inert gas. The higher impact velocity compared to that of arc technology results in lower porosity and thus in higher penetration resistance. In contrast to plasma spraying, the particle temperature in high velocity spraying is kept considerably lower and in turn the particle velocity is further increased. Exceptionally dense coatings of remarkably low oxide content are the result (illustration 2b) with the advantage of improved corrosion resistance. Disadvantageous for plasma and high velocity spraying are the low spray deposition rates and the higher cost of these technologies. High coating performance connected with low process costs is the reason why arc spraying is still rmly established as a boiler protection application. 4 Thermal Spraying for corrosion protection Boiler components in the corrosive environment of refuse and residual waste incineration are subject to accelerated damage due to chlorine induced corrosion. With rising temperatures of the water walls damage is increased. Raised expectations towards thermally sprayed coatings add also to this fact. Comparative analyses of thermally sprayed coatings under realistic conditions in a superheater area (refuse incineration) gave good support [2]. A variety of thermally sprayed coatings produced by arc and high velocity processes were applied in the same superheater environment. Spray and fuse coatings were also examined in this cycle of tests as alternatives. Coatings of this type are subject to a high temperature treatment following the coating, which leads to gas-tight variants. They have been developed especially for superheater tubes (illustration 3). This technology is only suited for pre-coated tubes and cannot be used for the reconditioning of damaged ones.

PS
PS

10000

5000

AS LS

HVOS / HVOF HGS

300 500 700 900

100

Partikelgeschwindigkeit [m/s] Particle velocity [m/s]

Illustration 1: Thermo-kinetics of thermal spray processes.

a) Arc technology b) High velocity Illustration 2: Structural differences in NiCr20MoNb coatings.

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After just 1000 hours of operation at a superheaters temperature of 425C distinct undercorrosion due to penetrating fumes was observed on arc sprayed coatings on a boiler tube (illustration 4b). At a superheater temperature of 500C the attack by fused salt corrosion on the coating materials becomes obvious (illustration 4c). High velocity coatings on the same superheater exhibit hardly any disposition for penetration, even after 1000 hours at 425C. Corrosive effects are mainly determined by the attack on the coating material leading to a distinct reduction of the coatings thickness. With rising surface temperature in the superheater, the attack on the coatings increases, driven by fused salt corrosion. These mechanisms ultimately determine the expectations for success of high velocity coatings. Complete gas sealing is the distinctive feature of spray and fuse thermal spray coatings, where signs of undercorrosion have never been found. Corrosion attacks on such coatings are solely determined by the chemical reaction which only affects the outside of a pipes coating. The application of arc spraying to prevent chlorine-induced corrosion in residual waste incinerators cannot be successful at high pipe wall temperatures. At lower wall temperatures, e.g. for wall protection of nned tubes, good results have been reported nevertheless, even with the interaction of erosion in some cases. It is also common practice to impregnate the coatings with sealers to close the open porosity volume for increased penetration resistance. Reports with the results concerning arc and high velocity coatings used for protecting nned walls are also on hand. An example of successful repairs with arc spray technology can be seen in the results of boiler ue 3 at the refuse incineration plant of AV Augsburg, Germany. Since it was brought into service in 2002 sealed spray coatings have been examined both visually and by sample taking. Noteworthy coating degradations could not

Illustration 3: Spray and fuse boiler tubes for superheater operation.

be found (illustration 6a). Four years after being put into operation the beginnings of a corrosion attack under the coating could be detected (illustration 6b). Since 2005 the high velocity process has also been employed as a supplement to arc spraying. 5 Erosion protection Erosion protection by means of thermally sprayed coatings requires above all appropriate resistance against mechanically acting surface damage as well as sufcient corrosive resistance adapted to the boiler atmosphere. With these applications damage to boiler tubes always occurs in the form of substantial abrasion rates, thereby reducing the tube walls thickness. Showcases are various applications with circulating and stationary uidised bed furnaces [4] as well as water walls above linings in grate-red plants, zonal effects on soot blowers, ow-sided tube damage due to large dust loads coupled with high ow velocities.

a) Initial state b) 1000h / 425C c) 1000h / 500C Illustration 4: Arc sprayed coatings after varying superheater exposure periods.

Illustration 5: Spray and fuse coating at 1000 h / 425C.

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Thermal Spraying for erosion protection depends on outstanding wear resistance properties of the coatings applied. The primary question is mechanical resistance the process technology used is only of secondary importance, especially since the influences of varying procedures on erosion resistance are not so significant as the coatings consistency and substantial composition. This is demonstrated in illustration 7 where an identical coating material is applied both by arc and by high velocity spraying. The resulting wear resistance is very similar. Arc spraying as an economical alternative can be used in such cases. This is shown in illustration 8 where the erosion resistance of a selection of coatings is compared to boiler tube material at 450C with an impact angle of 30 and 90 [5]. All these coating systems are far superior to the boiler tubes material whose resistance against abrasive influences declines with rising temperatures. Procedural arguments come into play when flow induced erosion occurs in a distinctly corrosive environment, which is the case in the area of firebrick linings and soot blowers (illustration 9). In connection with thermal coatings, the question of thermal conductivity is often raised. Illustration 10 provides the measured variables between 5 7 W/mK for Ni and Fe based coating systems applied by arc and plasma process. These values lie in the region of 20% of the pipe materials approximate value of 30 W/mK. Yet the coatings low heat conductivity does not cause any technical problems.

16 14

Ni22CrAl Ni22CrAl 550C; Korund; 90 Impact Angle 90 550C; Korund; Impact angle
size Particles Particle size

200 m 200 m

Thickness loss (m) Thickness loss (m)

12 10 8 6 4 2 0

Temp.: : 20C Temp. 20C

Temp.: : 550C Temp. 550C

size Particles Particle size

600 m 600 m

Arc Arc sprayed Sprayed

HVOF HVOF sprayed Sprayed

Arc Arc sprayed Sprayed

Illustration 7: Erosive wear subject to process technology used.

100

Erosion of Thermal Spray coatings Erosion thermischer Spritzschichten 450C; ;vv= 30 m/s 450C = 30 m/s
Impact angle 30 Auftreffwinkel30

Thickness loss (m] thickness loss (m)

80

Impact angle 90 Auftreffwinkel90

60

40

20

13CrMo44 13CrMo44
Tube material Rohrwerkstoff

Fe30CrB Fe30CrB
Arc Spray arc spray

Ni21Cr9MoNb Ni21Cr9MoNb
Arc Spray arc spray

Ni45CrTi Ni45CrTi
Arc Spray arc spray

Illustration 8: Abrasion rate of varying coatings at 450C Bild 8: Abtragraten verschiedener Spritzschichten compared to boiler tube material.

bei 450C im Vergleich zu Rohrwerkstoff

a) Coating sample after 3 years b) Boiler tube sample after 5 years Illustration 6: Sealed coating used at AV Augsburg.

HVOF HVOF Sprayed sprayed

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6 Summary The disadvantage of the low penetration resistance of thermal spray coatings is a common issue with high chlorine content. Therefore, only dense coatings can succeed at increased temperatures as they occur in superheater applications for instance. High velocity spraying comes close to fullling this demand but with plasma sprayed coatings it is hard to meet. With increased thickness the danger of penetration declines regardless of the process being used. Coating thicknesses of under 500 m for high-energy spray processes and below 800-1000m for arc spraying have established themselves as economic standards. Certainty about complete gas-proofness can only be achieved by treating the coatings with an additional thermal sintering process. Coatings of such quality are mainly used for corrosion protection on superheater pipes. Corrosion protection on the walls of nned tubes is less critical as the corrosion mechanisms progress more slowly. Therefore, processes with a residual porosity can be used. As such applications are usually employed with plant overhauls, economical high-performance processes like arc spraying come to the fore. When applied on residual waste and refuse incinerators additional sealing processes are necessary for increasing the penetration resistance. Especially as work conditions in boiler overhauling cannot entirely exclude mistakes (see illustration 11) rectications of thermally sprayed coatings are common. Mobile process variants meet the requirements to a great extent.

In plants with low chlorine loads, such as in thermal power stations, uidised bed or alkali combustors, low-energy processes are sufcient for achieving long maintenance intervals. In such plants there is often the additional need for erosion prevention. Here, boiler tube failure usually occur from abrasive processes caused by soot blowers, uidised bed masses and high dust loads in the gas ow. Thermal Spraying with all its process variants has established itself as an indispensable preventive maintenance method.

Wrmeleitfhigkeit thermischer Spritzschichten Thermal conductivity

10

Thermal Spray coatings (W/mK) Thermal Spray Coatings (W/mK)

NiCr25Fe / Arc spray NiCr25Fe/arc spray NiCr29Mo / Plasma NiCr29Mo/plasma

NiCr25Fe / Plasma NiCr25Fe/plasma NiCr29Mo / Arc spray FeCr13/arc spray

0 0 100 200 300 400 500

Temperature (C)(C) Temperatur

Illustration 10: Thermal conductivity of Thermal Spray coatings.

Illustration 9: Erosion protection next to a lining.

Illustration 11: Local coating defect.

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Literature [1] P.Heimgartner: Interaktion von Beschichtungsprozess, Werkstoff und Umfeldbedingungen im Korrosionsverlauf bei Taupunktsunterschreitung; Experten- und Diskussionsforum zu Ausgewhlte Manahmen zur Betriebssicherheit industrieller Verbrennungsanlagen; Wien 2004 [2] R.Polak, S.Gustavsson: Assprayed and Densied Thermal Spray Coatings under Superheater Conditions; Terolab Report, Lausanne 2004 [3] B.Wielage, et.al.: Verbesserung der Bestndigkeit von TS-Schichten durch umweltvertrgliche Nachbehandlungsmethoden; Abschlussbericht zum AiF-Projekt; 1998 [4] N.G.Solomon: Erosion-Resistant Coatings for Fluidized-Bed-Boilers; NACE Conference Corrosion/97 , New Orleans,1997 [5] M.Rehberg, G.Heath: Temp. and Velocity Effects on Erosion-Corrosion of Fe- and Ni-Based Coatings in Gaseous Environments; Interim Report Castolin Eutectic, 1994