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 / °C2.4. 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.
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