0010090131 Thermal Spraying Brees surface engineering as an in situ and ex situ process F Kremsner, R. Polak, Teralab Surface GmbH, Vienna Abstract Thermally sprayed layers can only be successllly used for boiler protection in cases where the combustion processes coincide wih cortosive conditions in « way that flve gas pen. eration can be kep! controfable. Eficien protective thermal spray solutions on super heater lubes and wall material gener ally call for strictly defined manufactusing conditions which ore ‘assured in workshop conditions [ex sit coating} only. ln cases \where thermal sprayed coatings have undergone subsequent thetmal reciments to give completely dense layers, hey ate known to have most effective corrosion protection. Because ofthis conirlled thermal sintering step this process is lalored for ex situ conditions In situ refurbishment work of boilers normally disallows skictly controlled process conditions for spray jobs, As a matter of foc! the qualification of spray personnel becomes much more important for successful protection work. Well trained people, good work preparation ond perfect process supervision are key issues for in stu moinlenance and lost but not least stiong interaction between on-site management and coating team. 1. Introduction High temperature chlorine corrosion s@ challenging problem in biomass or waste incineration. In thisharsh envitonment spe- cial nickel-based materials with chromium and molybdenum (eg, alloy 625] are widely used for protection of tube and ‘wall moterials. Such coatings show « good corrosion-resistont choracter in chlorine-dominated flue gas envionment. They ‘are common for weld or spray coatings in curative (onsite) measure or in preventive new part protection. Thermal spray: ing has become on economic alternative to weld cladding Nevertheless sprayed coatings have a potentially higher risk of sub-surface corrosion in chlorine concitions due 10 its spe: cial layer morphology, Sometimes in cose of weak cohesive binding mechanisms between neighbouring portcles chemical cctive chlorine can migrate through the layer and couse sub- coating corrosion on the pipe material underneath. Difusion processes follow principles which are dependent upon time, temperature and concentration gradient, The pen elration velocity is tiggered by + surface temperature of tube + chlorine concentration inthe flue gos ond + difusion coefficient of the coating. Tube temperature and chlorine concentration are process ‘eleven! factors. The only way o decreose the penetration of flue gos is downgrading the diffusion coefficient. In solid bodies the latter is defined by i} A 0-0, 0 £) where E is the enéigy barrier of the layer agains! penetvation of gos consivents, R the general gas constant (JK-Imol-1} cond T the temperature. Measures 10 slow down the reaction process is minimizing the diffusion coefficient and raising the energy barrier E for gas enty. Total gas lightness [E = 2)is very difficult to reach for spray coatings without thermal sinter ing. Such tis oimed by strict contol of coating parameters 1o establish very high energy barriers for fue gos. The effective diffusion coefficient of porous solids - lke sprayed layers - can also be expressed in the form (2) where D is the diffusion coefficient for gaseous oF fluid me: dium, &; the residual porosity, 8 a retardation coefficient for difusion in fight pores and T a form factor, considering the pote geometry. The time needed for penettating o sprayed layer depends side from the mentioned relations also on the diflusion poth {As, Time is a square function of the layer thickness {3} At = (As?) what means that thicker coatings are more effective than thinner ones.co1D090131 All measures to retard penetration of sprayed coatings by flue goses are primarily conducted to maximize the tighiness of spray coating structures {minimizing the pore content) and optimizing the layer thickness. Limiting fact forthe loyer thick ress isthe negative accumulation of stresses and increasing coating costs. Furthermore also the interlomellar oxide content plays a role in high temperature corrosion of spray layers. Such the spray paromelers cim for lowest particle oxidation, Despite all parameter optimization today the common Final step in coating is to apply sealers, which tend to reduce re- sidual pore volumes by infilratifg the coating Long experience with especially aggressive boiler corrosion has directed TLS in the development of post thermally com pressed [sinlered] coatings. By applying a supplementary thermal slep sprayed alloy is sintered onto the sald tube such forming 0 pertect tight composite. An ani-corrosive shel is produced around the tube. Because ofthis sintering step this coatings are reserved for exsitu applications 1 :Stucturalfeotuies of harmally spayed layers [osspayed "faa elt poakeowprassed tal Fig, | shows the quali of sintered coating compared with not sinterd, diferenily applied spray structures. Smoll oxide inclusions in the layer have no negative influence on quality. Under aggressive environmental conditions, lke presence of chlorine, the fused layer systems are always beneficial 2. Coating techniques approved for ex situ application Reproducible good layer qualities con be realised under work: shop conditions onl, The manufacturing steps of the cooting process con be controlled and monitored in such @ way that aTLS surface engineering high quality coatings ore obicined. Very sophisticated coat ing procestes lke high-velocity or plasma sproying can be ‘vimmed to porosity levels < 1%, Mechanised torch movement, instrumented process diagnostics and proper dust extraction systems assure these qualities. Also the surface preparation by biasing can meet optimal citric, ‘The advanced process management delivers quality standards 0s high as possible. Nevertheless the final sealer infiltration is standard today except of tubes wit sintered coatings. De spite all sophisicated process management the aggressive corrosion in waste incineration makes it difficult, to achieve solstactory life cycles without sintering In view of thot fact, TIS began long ago to work on the development of sinleted soluions for superheater tubes. Ac- tually sintered, gastight coatings of high corrosion resistance [>500pm thick} are produced around the tubes by thermal treatment of the prior sprayed alloy. Corrosion below the coo! ing such connot take place. This clearly is ilustated by the superheater tube of Fig. 2, where severe damaging corrosion ctlocks the unprotected tube material ‘An important step on the path iowards chemically resistant loyers for waste incineration planis was provided by the development of corosionesistant alloy systems suitable for sintering. Me(C1)BSi systems, where Me is « placeholder for ‘one ore more of he elements Ni, Fe or Co, have shown good benchmark in pracice. Via special Cr and Mo balancing the necessary cortosion resstonce could be achieved. Extended studies of cortosion choracterisics under oxidising ond reduc ing condltions have accompanied the development of these alloys. In the lower diagrom of Fig. 3 the direct relationship Fig. 2: Simard lay offected by corrosion o he tonsiion to the uncoated hue [new condition tp] acl0010090131 of the chrome conten! for cotrosion resistonce in he oxidising medium is shown. On the other hand, paricular imporlonce ‘ttaches lo molybdenum in reducing corrosion media. Here the tesistance-effecive weighting factor of Mo amounts to roughly thiee times that of chromium. Boron and silicon ore important ‘additional elemeni in these alloy systems, Silcon, in particular, has 0 positive effec! on chemical esistonce, Better benefitcan be derived from increosed olloy-specifc Si contents in the ronge of>4% for these sinter able alloys. Corrosion protective layers hove been developed in his way with results equivalent to those of cladding. On the other hand, slicon contents with increased alloying technology prove beneficial to cosrosion inetio in @ high temperoture rvironment Korrosion im reduzierenden Milieu 10%m HCLTO"C, 168, weight loss (moltest) CrviyMost,"B rt") Korrosion im oxidierenden Milieu 40%m HNOS.70°C, 188 characterise of postcompressed Nibosed elloys 1p and oxidising eet conditions Suitability of he process for use in boilers is proven by wide- ranging mechanical tesling and extensive experience in the field, TLS hos developed process technology for industiok scale production, Thsisimplemented in the shape of complete protection of supetheater components |Fig. 4). Increasing Corrosion strain caused by the chlorine burden of biomass and waste material incineration hos led lo ¢ revival ofthe industiol Use of sintered layers. One goal of development is curenlly to make sintered coatings applicable to joint welding, while nother resides to meet more stringent corrosion citeia, Both of hese ate @ testimony to growing industiol demand. aTLS surface engineering fig. 4 large-scale technical pplication of sintred layers 3. On-site boiler refurbishment ~in situ coating ‘Whereas in the case of ex situ conditions, the manufacturing environment enables quality-elevant spray conditions to be obtained, this does not generally exis for in situ coatings in the bollriself [or is only possible with a very high invest men Environmental conditions are an important facto in determining quality during thermal spray workin the plant That isthe reason why results reported from the field offen seem contradictory. That in turn does not make it any easier for the plant operator to take « decision ‘Maintenance work on boiles is typified by the folowing experience * coating work is requenily decided al very short notice fier detecting the extent of he domage by visual rmeons so that edequate planning lecchimes are not ovaiiable; + site octvity requites del review and coordination with ther refurbishment activites + the work hos to be done under severe pressure of time + compromises have to be made in access to the working zones. Previous efforts to fully mechonise process technology for large area protective measures give rise to recognition of the fact that the siength of thermal spraying resides in its mobility ond therefore allowing a flexble domoge-tiggered ‘mainlenance management. In sity refurbishment work offen has © patchwork character becouse it is used on damaged surfaces or components at different locations (see Fig. 5] Mechanisolion aids do not help because of the necessary setup times; preference is therefore given io manual process management. Performing work of good quality under these0910090131 peripheral conditions conlionts the coating service provider swith enormous challenges. Process control in the tradiional sense is not the quolty criterion here, but rather the perform once of manual work to « high standard under constantly changing and physically arduous condiions. Years ago when his tend become clear, TLS had aliecdy placed the human quality factor al the heart ofits in sity philosophy because i was aware of is growing importance. The quaification of he ating leam is bosed on 0} sound professional knowledge, in particular ofthe influences which determine the quality cof manual process work b) inhouse raining on real components with a quolty €}_ field taining under supervision, end 4d] regular retraining By placing o constant emphasis in the market on quality brought about by expertise, boiler managers became con: fident in high quality in stu service ovoilable ot short notice cand with o flexible response. fag. 5:_ st elthmat bythe be we ef ¥ Another important element of he mobile in stu philosophy is the constant development ofknowledge about borderline ctria for thermal spray layers in boiler operation ond a systematic developmen of knowledge of diferent performance profiles pecial types of sealing. Regular inspection, investigation of layer somples via travel me and deisiled documentation of cases of damage ore all pat ofthe TIS servic. In his woy, on the basis of o portnership between the boiler operator and the service provider corrosion speci key performance values are determined for ihermolly sprayed protecve layers mT lL surface engineering cond embodied in a benefi-oriented maintenance shotegy. This makes thermal spraying on integral part of economical plant management 4 Summary ‘When corrosion protection measures are token by thermal spraying, domage coused by corrosion below the coating is repeatedly encountered in the highly corrosive operating environment, This citcumsiance is explained by the fact thot ‘aggressive chlorine penetrates rough the spray structure and cotrodes the lube substote. All attempts to achieve improve. menis with non-post treated spray layers ore explained by process technical endeavous fo prevent difusion mechanisms by achioving the fightest possible layer structures. Ex situ in the production environment, wide-ranging process monitoring does enable the manufacturing conditions to be approximated ithe ideal situation in such @ way as to minimise the penetra tion effect. Higher wall temperatures couse rising difusbiliy for chlorine, so placing limits on the as-sproyed layers os fu on of femperoture The complete prevention of diffusion for thermal spray layers has so far been achieved only by thermal post-compression ofthe different layers. This coating technology i sitable for component protection prior to boiler installation ond is con firmed by process technology verification ond wideronging experience of insilled boilers. Postcompressed spray are based on a different alloying concept and achieve a level of performance comparable to that of cladding layers Thermal spraying in curave boiler care is based upon sealed assproyed layers, Refurbishment coatings ore increasingly ap: plied in he light ofthe specific condition and particular needs. To that exten, in sit coating is lergely dependent upon monval intervention. The route leading to compliance with quality i teria for process technalogy though this development callsfor igh level of expertise on the part of the implementing work team ond an effective partnership with the boiler operator. 5