Activity - 1 The Final

Amit R Patel, Manoj Kumar
A Group Activity
on
Degradation of Materials, Various Types of Degradations, Causes, Consequences and Evaluation (Erosion Corrosion, Solid Particle Erosion, Corrosion)
Submitted to Dr. Harpreet Singh Assistant Professor (SMMEE)
Submitted by Amit R. Patel Research Scholar SMMEE Manoj Kumar Research Scholar SMMEE
INDIAN INSTITUTE OF TECHNOLOGY ROPAR RUPNAGAR-140 001 (PB)

November 2011
Definition: According to A.W.Batchlor, Materials degradation can be defined as loss of performance of an engineering system. Loss of performance can relate to many parameters, e.g. loss in mechanical strength of a structural component exposed to a corrosive medium. For the engine with worn cylinders, wear can increase the clearance between piston ring and cylinder to such an extent that there is no compression of combustion gases. In this case the engine can be considered to have failed, as it will no longer be able to pull the car or truck up the hill. A mechanical degradation proceeds at a rate that varies with local conditions and failure occurs if the performance declines to below the critical level. Loss of efficiency occurs if performance declines but remains above the critical level during the service lifetime.
Fig. Graphical definition of material degradation Various types of degradation:There are three basic categories of materials degradation
Physical degradation Chemical degradation Biological degradation 3
Physical origin refers to the effect of force, heat and radiation. Chemical origin relates to destructive reactions between the material and chemicals that contact it. Biological origin includes all interactions between life forms and engineering materials.
Fig. Classification of various types of material degradation Causes of Physical Material degradation Heat thermal damage: All materials are vulnerable to thermal degradation even where other factors such as corrosion or wear are absent. Increases in temperature generally lead to a decline in hardness of materials, which is usually counterbalanced by an increase in ductility. There are exceptions to the trend of declining hardness with temperature where a material may show a limited rise in hardness over a narrow temperature range but the effect is usually minor. Electrical conductivity declines for metals but is increased for nonmetals, e.g. ceramics at elevated temperatures. Most of the changes to physical properties are reversible, e.g. hardness except where microstructural change has occurred. Materials degradation at very low temperatures A reduction in temperature inhibits the chemical reactions that cause many materials degradation problems. Furthermore, when the temperature falls below 0C,
4
freezing of water removes sources of liquid water for electrochemical corrosion. Severe forms of materials degradation are less likely at low temperatures than at high temperatures. However, very low ambient and process temperatures still pose some problems of materials degradation. Steel and many other metals become brittle at low temperatures thus necessitating the use of special alloys that are usually based on nickel. Nickel has the advantage of maintaining toughness at low temperatures. Nonmetals are also prone to low temperature brittleness. Electrochemical corrosion A basic reason why corrosion causes so much damage to machinery and structures is that components of differing materials and shape are placed in close contact with each other. Another reason is that pure metals are rarely used to manufacture components; instead alloys and composite materials are usually selected. These characteristics of mechanical construction and manufacture ensure that a machine or structure contains many electrochemical cells even though in most cases no electrochemical cell was deliberately designed into the system. A simple example of the ease with which electrochemical cells are generated is to consider a steel shaft contacting a bronze bearing when immersed in seawater. Where no electrochemical cell is present, a metal object may last almost indefinitely. An iron column sited in India is observed to have not significantly rusted over many hundreds of years. It is believed that the purity of the iron used contributes to its corrosion resistance by ensuring that electrochemical cells are not formed between the iron and any other metals or carbon that are commonly present in iron. Alloying introduces electrochemical cells on a microscopic scale between grains of different metallic phases. Another factor that heightens corrosion damage is the increasing hostility of the environments to which manufactured items are subjected. There is a continuing demand for ever higher temperature when exposed to increasing concentrations of acids and alkalis. Even when there is no deliberate environmental stress, environmental pollution brings increasing amounts of sulfur compounds and other corrosive agents into contact with manufactured materials. These pollutants combine with atmospheric oxygen and water to generate more potent forms of electrochemical corrosion, which can rapidly destroy equipment and structures. Erosion-Corrosion
5
According to Hodgkiess et al [10], erosion-corrosion is a form of material degradation involving electrochemical corrosion processes and mechanical wear. The total material loss is often significantly in excess of the sum of the separate pure corrosion and wear processes, interactions, or synergism, between the thus signifying important two components. High-temperature
corrosion accompanied by erosion (E-C) caused by the impact of fly ashes and unburnt carbon particles are the main problems to solve in steam generating plants, especially in those regions where the component surface temperature is above 873 K [11]. The free oxygen content in power plant boiler atmospheres is sufficient to account for combined erosioncorrosion process, consisting of an oxidizing gas at elevated temperature carrying erosive fly-ashes which impact against metallic surfaces. These erodent particles can deposit or embed themselves on the test surface in quite significant quantities, and chemical reactions of erodent particles and oxide scales can develop on the eroding surface [11]. Boiler steels are unable to meet these requirements for both the high temperature strength and the high temperature corrosion resistance simultaneously over longer periods of their usage, so protective coatings are used to counter the latter. Coating provides a way of extending the limits of use of materials at the upper end of their performance capabilities, by allowing the mechanical properties of substrate materials to be maintained while protecting them against wear or corrosion [12]. For hot corrosion and erosion-corrosion resistance at elevated temperatures, thermal spray coatings must be hard, dense, sufficiently thick, and tightly adherent to maintain the shielding effect for a long time. They must be resistant to elevated temperatures, thermal cycles and chemical environment and they must also have low internal stresses, low oxide content, and thermal expansion coefficients similar to that of the base material. Coatings should also have small splat size and no cracks [13]. Furthermore, the coatings should have good thermal conductivity. It is strongly believed that the nano-particle coatings could be candidate materials which can provide most of these properties. Among the various surface coating techniques, thermal spray processes such as Detonation Gun Spraying (DS), Plasma Spraying (PS) and High Velocity
6
Oxygen Fuel (HVOF) spraying have been under active considerations in the recent times, whereas Cold Spray Technique is barely out of its infancy. According to Yamada et al [14], thermal spray has e m e r g e d as an important tool of increasingly sophisticated surface engineering technology. It is one of the many methods of applying overlay coatings for applications ranging from protection of materials in harsh environments, to dimensional restoration of worn machine elements [14]. Cold spray has been used to produce protective coatings and performance enhancing layers, ultrathick coatings, freeforms and near net shapes. Cold spray is a relatively young process and still considerable R&D efforts are needed to understand and control the process, as well as develop engineered coatings with desired properties for specific applications. The last few years have seen exponential growth of cold spray R&D around the globe. Considerable R&D efforts are being undertaken at various laboratories, academic institutions, and industries [2]. Cold spray is a solid state process and hence produces coatings with many advantageous characteristics. Since high temperature is not involved, it is ideally suitable for depositing temperature sensitive materials such as nanophase and amorphous materials, oxygen sensitive materials like aluminium, copper and titanium and phase-sensitive materials such as carbide composites. Review of status of Research and Development in the subject International/National status Erosive, high temperature wear of heat exchanger tubes and other structural materials in coal-fired boilers are recognized as being the main cause of downtime at power- generating plants, which could account for 50-75% of their total arrest time. Maintenance costs for replacing broken tubes in the same installations are also very high, and can be estimated at up to 54% of the total production costs. High temperature oxidation and erosion by the impact of fly ashes and unburned carbon particles are the main problems to be solved in these applications. Therefore, the development of wear and high temperature oxidation protection systems in industrial boilers is a very important topic from both engineering and an economic perspective [3]. Coatings provide a way of extending the limits of use of materials at the upper
7
end of their performance capabilities, by allowing the mechanical properties of the substrate materials to be maintained while protecting them against wear or and more fuel-efficient power corrosion [12]. The desire for higher operating temperature, improved performance, extended component lives, and cleaner plant/processes places severe demands on the structural materials used to
construct such a high-temperature plant. As a result, many components operating at high temperature within such plants are coated or surface treated[4]. Porcayo-Calderon et al [5] have reported the use of protective coatings for the superheater/re-heater components of boiler where the material severely suffers on fireside corrosion. According to Taylor and Evans [6], a few earlier attempts have been made on the thermal sprayed protective coatings for fossil power plants though the thermal spray process is extensively used for gas turbine applications. Sundararajan et al [7] also advocated the need for applying thermal spray coatings on the boiler components. From a production point of view, three methods are in current use for depositing coatings, these being chemical vapour deposition (CVD) from a pack, physical vapour deposition (PVD) and thermal spraying (metal spraying). Ilavsky et al [8] have also reported that the thermally sprayed deposits have often superior properties with potentially lower application cost or less environmental issues as and when compared to other industrially used coatings such as CVD, PVD, hard chromium plating. The high resistance of high-chromium, nickel-chromium alloys to hightemperature oxidation and corrosion makes them widely used as welded and thermally sprayed coatings in fossil fuel-fired boilers, waste incineration boilers, and electric furnaces. Modern thermal spray processes such as high velocity oxyfuel (HVOF) and plasma spraying are often applied to deposit high-chromium, nickel coatings onto the outer surface 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 tube [9]. Erosion wear and mechanical properties of nickel- and iron-based as well as chromium-nickel plasma sprayed coatings on carbon steel have been studied by Hidalgo et al [10] in the simulated industrial service conditions in boilers. These types of coatings are used as heat transfer and structural elements in boilers.
8
They have performed experiments in laboratory combustion unit which was simulated to boiler service conditions at 400, 600 and 800C. Coatings were reported to have a moderate to low oxidation indexes. Yamada et al [1] carried out studies to evaluate the high-temperature corrosion resistance of Ni-20Cr, Ni-50Cr and Cr coated boiler tubes in actual refuse incineration plant as well as in laboratory tests. It was observed that detonation sprayed Ni-50Cr coating exhibited the highest corrosion resistance in laboratory test at 873K 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. Recent reports emphasised that the understanding of the degradation and failure mechanisms of high-temperature coatings in the field need to be improved, particularly with respect to the effects of engine operation and environment on the coating performance (e.g., thermal cycling) [11]. In general, the reaction behaviour of protective coatings in environments of their use and their interactions with the substrate during high-temperature performance is not well understood [9]. Ak et al [13] demonstrated the successful application of NiCr coatings on stainless steel applications. substrates using a high velocity oxy-fuel technique for corrosion Preliminary results of fabrication and microstructural
characterization of NiCr coatings were given. These coatings were characterized by means of optical microscope, image analyzer, scanning electron microscope and Xray diffraction (XRD). NiCr powders with a composition of 80% Ni and 20% Cr were deposited by HVOF spraying to give coatings that were approximately 90100m thick. It has been found that the samples produced by HVOF spray process possess porosities. XRD results revealed that the coating had Ni, CrNi2, Cr-Ni, Fe0.93Ni0.056, Ni-Cr-Fe and Fe-Cr phases after the coating process. The microhardness properties of the coatings strongly depended on porosity, oxide, unmelted and semimelted particles, and inclusions and the porosity, oxide and inclusion decreased hardness values[13]. Wang and Shui [14] performed experiment testing boiler tubes using HVOF
9
method and other spraying processes, and observed that all the HVOF carbide cermet coatings showed much higher erosion resistance than 1018 steel and arcsprayed iron-base coatings, when eroded by bed ashes at shallow and steep impact angles [14]. According to Karthikeyan [15] cold spray finds applications in corrosion protection where absence of process-induced oxidation may offer improved performance. In electrical and thermal field where the absence of Aluminum and processaluminum induced oxidation may offer improved conductivity.
alloy coatings are being investigated for repair/refurbishment of space shuttle solid rocket boosters and others (aerospace), repair and retrieval of parts and plate stocks used in aircraft structures (aircraft industry), repair/refurbishment of casings (gas turbine), corrosion protection coatings (petrochemicals) etc. At present, high performance layers such as high temperature oxidation resistant MCrAlY coatings, high conductivity copper/silver coatings, phase pure biocoatings, etc., are produced in Vacuum Plasma Spray systems or Physical Vapor Deposition systems. These systems are extremely expensive to both install and operate. Moreover, cold spray process may lend itself to collect the overspray and reprocess these expensive raw materials. Hence, well founded cold spray technology will be able to compete for a good market share of VPS/PVD electronic/electrical, biotechnology and coatings in turbine, power, other industries. Similarly, cold spray can
produce MMC coatings and freeforms with any dissimilar materials, even with graded properties and hence can achieve a share of the MMC market as well . Wolfe et al [16] explored the potential of cold spray in applying Cr3C2-25 wt.%NiCr and Cr3C2-25wt.%Ni coatings on 4140 alloy for wear-resistant
applications. They observed that cold spray process optimization of the Cr3C2based coatings resulted in increased hardness and improved wear characteristics with lower friction coefficients. The improvement in hardness was directly associated with higher particle velocities and increased densities of the Cr3C2-based coatings deposited on 4140 alloy at ambient temperature. Selective coatings were evaluated using X-ray diffraction for phase analysis, optical microscopy (OM), and scanning electron microscopy (SEM) for microstructural evaluation, and ballon-disk tribology experiments for friction coefficient and wear determination.
10
The results obtained strongly suggested that cold spray is a versatile coating technique capable of tailoring the hardness of Cr3C2-based wear-resistant coatings on temperature sensitive substrates [16]. Kim results et al [17] that deposited WC-12~17%Co powders there is with nanoand microstructures by cold spray process using nitrogen and helium gases. The showed no detrimental phase transformation and/or decarburization of WC by this method. It was also observed that nano-sized WC in the feedstock powder is maintained in the cold sprayed coatings. The nano-sized WC is advantageous over micro-sized WC for cold spray deposition because higher particle velocity can be obtained with the same gas velocity. It was also demonstrated that it is possible to fabricate the nano-structured WC-Co coating with low porosity and high hardness (2050 HV) by cold spray deposition with reasonable powder preheating [30]. Lima et al [18] used the cold spray process to prepare nano structured WC-Co coatings. A 10 nm thick coating was achieved. It was concluded that the WC-Co cold sprayed coating has a high density and microhardness when compared to those of nanostructured feedstock. There was no significant difference between the average grain size of the nanostructured feedstock and coating. They concluded that it is possible to produce pure and well bonded nanostructured WC-Co coatings via cold spray processing. Agarwal etal [19] explored the existing knowledge of erosion, high temperature erosion, and high-temperature Coal Gasification Atmosphere (CGA) erosion-corrosion (EC) phenomena. Experimental results and interpretive analysis of impingement angle effects in alloys 310 and 6B exposed to simulated CGA EC atmosphere at 1500 F are presented and discussed. These results clearly demonstrate the utility of the interpretive analysis in developing better cause and effect and mechanistic understanding of the CGA EC phenomena. Uusitalo etal. [20] carried out series of hot erosion and erosioncorrosion (E C) tests on thermal sprayed coatings, diffusion coatings and boiler steels using a burner-rig type elevated temperature EC tester in order to evaluate the possibility to utilise thermal sprayed coatings in shielding of boiler components. Test conditions simulated the EC conditions in the super heater section of a circulating fluidised bed
11
combustor (CFBC). Carbide containing HVOF coatings performed well in erosion tests, as expected. Also diffusion coatings and nickel-based, high-chromium HVOF coatings performed well. In EC tests in presence of chlorine, nickel-based HVOF coatings performed the best, whereas carbide containing HVOF coatings and diffusion coatings wore away. Flores etal. [21] explored the materials and machinery components handling corrosive slurries are exposed to erosioncorrosion (EC) processes that significantly reduce their service lifetime. Difficulties predicting material loss in industrial machinery, financial and security impacts due to early failure of worn components and the necessity of managing highly aggressive slurries (e.g. oil sands), have motivated the application of surface engineering solutions to reduce the negative effects of erosioncorrosion processes. The erosioncorrosion resistance of nickel base and iron base metal matrix composites (C Ni and C Fe MMCs, respectively) coatings was studied in this paper. The behavior of the MMCs compared with their non-reinforced matrices (NRMs); tungsten carbides (WC) particles were used to reinforce the NRMs. The microstructures of the NRMs and MMCs were analyzed by microscopy techniques and the effects of adding a reinforcing phase to the matrices are reported and linked to their EC resistance. The EC resistance was assessed at different sand contents (10 and 50 g/l) and temperatures (20 and 65 C) using a submerged impinging jet (SIJ) apparatus; the MMCs were also studied under EC at 5, 10 and 14 m/s to analyze the structural integrity of the reinforcing phase. The results shown that, the C Ni was the more EC resistant coating under most of the experimental conditions, at 5 m/s the EC degradation mechanism was dominated by matrix degradation with the WC showing little damage and the CFe was negatively affected by corrosion, especially at 65 C. Interestingly, the MMCs were more susceptible to changes in temperature whereas, for the NRMs EC resistance was more affected by the sand content of the slurry. M.Kaur etal [22] explored the Detonation-gun (D-gun) spray technology and found it a novel coating deposition process which is capable of achieving very high gas and particle velocities approaching 45 times the speed of sound. This process provides the possibility of producing high hardness coatings with strong adherence. In the present study, this technique has been used to deposit Cr3C2NiCr coating on
12
T22 boiler steel. Investigations on the behaviour of this coating subjected to hightemperature oxidation in air and oxidationerosion in actual boiler environment at 700 10 C under cyclic conditions have been carried out. The weight change technique was used to establish the kinetics of oxidation. X-ray diffraction (XRD), field emissionscanning electron microscopy/energy-dispersive spectroscopy (FE-SEM/EDS) and EDS elemental mapping techniques were used to analyse the oxidation/oxidation erosion products. The uncoated boiler steel suffered from a catastrophic degradation in the form of intense spalling of the scale in both the environments. The Cr3C2NiCr coating showed good adherence to the boiler steel during the exposures with no tendency for spallation of its oxide scale. V. Chawla etal. [23] explored Hot corrosion and erosion problems in coal based power generation plants in India. The coal used in Indian power stations has large amounts of ash (about 50%) which contain abrasive mineral species such as hard quartz (up to 15%) which increase the erosion propensity of coal. Hot corrosion and erosion in boilers and related components are responsible for huge losses, both direct and indirect, in power generation. An understanding of these problems and thus to develop suitable protective system is essential for maximizing the utilization of such components. These problems can be prevented by either changing the material or altering the environment or by separating the component surface from the environment. Corrosion prevention by the use of coatings for separating material from the environment is gaining importance in surface engineering. C.Xu etal. [24] developed a halide-activated pack-cementation method but at a temperature (600 C) noticeably lower than normal, an -Fe2Al5 coating and two Ni2Al3 coatings with and without dispersions of CeO2 nanoparticles were developed respectively on a low-carbon steel and the steel pretreated with an electrodeposited film of Ni or NiCeO2. The erosioncorrosion (EC) performance of the three aluminide coatings during 100 h exposure at ~600 C in a coal-firing laboratory-scale fluidized-bed combustor (FBC) was investigated, by mounting the aluminized samples onto a rig which maintained rotation for accelerating the relative impacting speed of flying solid particles (mainly SiO2 bed materials). The -Fe2Al5 and the CeO2-free Ni2Al3 coatings experienced an unacceptable recession rate. Compared to the two CeO2-free aluminide coatings, the CeO2- dispersed -Ni2Al3 coating offered
13
profoundly improved EC resistance, because the latter coating was not only strengthened by the CeO2 dispersion and grain refinement, it also could grow a more adherent alumina scale. Shimizu etal [25] investigated the high temperature erosion characteristics of two types of surface-treated SUS410 steels; overlay welding and forging of the base metal. Two-layer overlay welding of 6 mm and forging with a 10% reduction, were used on a base metal of SUS410, to prepare specimens. High temperature solid particle erosion tests using a test temperature of 1173 K were performed using 1 mm alumina particles, with impact angles between 30 and 90 and a particle velocity of 100 m/s. Erosion rates, especially at shallow angles of 30, were dramatically different for all specimens. Compared with the base metal of SUS410, the erosion rate was reduced by 50% for overlay welded material, and 30% for forged material. High temperature hardness measurement and the observation of the eroded surface by scan electron microscopy were undertaken to analyse the erosion behaviour. An increase in the erosion rate of the specimen was related to a decrease in the high temperature hardness. Although the hardness was reduced to approximately 70% at 1173 K for all specimens, this suggested that the wear resistance of the overlay welding material was improved by restraining the plastic flow because it was harder at high temperatures. The forged material was suggesting that the plastic flow of eroded surface was restrained by the refinement of the microstructure and the residual stress near the surface, which reduced erosion rate regardless of this lower hardness. Nickel based alloys represent a significant part of overall thermal spray business. These materials are widely used as bond coats and as top coats in number of applications requiring combination of properties, such as good wear resistance and corrosion resistance at the same time. There is an increasing interest in the deposition of Ni based metallic alloys such as Ni-20%Cr, Inconel 625 for protection against corrosion. Ni based coatings are used in applications where wear resistance combined with oxidation or hot corrosion resistance is required [26-30]. Nickelchromium oxidizing environments alloys at have been used as coatings nickel is to deal alloyed with with high temperature. When
chromium, this element oxidizes to Cr2O3, which could make it suitable for use, up
14
to about 1200C. However, in practice its use is limited to temperatures below 800C. The thermal sprayed 50/ 50 nickel chromium alloy is usually recommended as an erosioncorrosion protection for boiler tubes in power generation applications [31]. References:Yamada, K., Tomono, Y., Morimoto, J., Sasaki, Y., Ohmori, A., (2002), Vacuum 65 (3-4) 533-540. J. Karthikeyan, Cold Spray Technology: International Status and USA Efforts, ASB Industries, Inc, 2004. Hidalgo V. H. et al., Wear 247 (2001) 214-222. Nicholls, J.R., JOM Jan. (2000) 28-35. Porcayo-Calderon, J., Gonzalez-Rodriguez, J.G., Martinez, L., J. Mater. Eng. Perform. 7 (1998) 79-87. Taylor, M.P., Evans, H. E., Mater. Sci. Forum 369-372 (2001) 711-717. Sundararajan, T., Kuroda, S., Itagaki, T., Abe F., ISIJ Int. 43 (1) (2003) 95-103. Illavsky, J., Pisacka, J., Chraska, P., Margandant, N., Siegmann, S., Wagner, W., Fiala, P., Barbezat, st G., Proc. 1 Inter. Thermal Spray Conf., Montreal, Quebec, Canada, May 8-11 (2000) 449-454. 9. Tuominen, J., Vuoristo, P., Mantyla, T., Ahmaniemi, S., Vihinen, J., Andersson, P.H., J. Therm. Spray Technol. 11 (2) (2002) 233-243. 10. Hidalgo, V. H., Varela, J. B., Calle, J. M. de la, Menendez, A. C., Surf. Eng. 16 (2) (2000) 137-142. 11. National Materials Advisory Board, Coatings for High-Temperature Structural Materials: Trends and Opportunities, National Academy Press Washington D.C., http://www.nap.edu/openbook/0309053811/html, (1996) 1-85. 12. Chatterjee, U. K., Bose, S. K., Roy, S. K., Environmental Degradation of Metals, (2001), Pub. Marcel Dekker, 270 Madison Avenue, New York. 13. Ak, N. F., Tekmen, C., Ozdemir, I., Soykan, H. S., Celik, E., Surface and Coatings Technology 173-174 (2003) 1070-1073. 14. Wang, B. Q., Shui, Z. R., Journal of Materials Processing Technology 143-144 (2003) 87-92. 15. Karthikeyan, J., Cold Spray Technology: International Status and USA Efforts, ASB Industries, Inc, USA (2004). 16. Wolfe, D. E., Eden, T. J., Jaroh, A. P., Journal of Thermal Spray Technology 15 (3) (2006) 400-412. 17. Kim, H.J., Lee, C.H., Hwang, S.Y., Surface and Coatings Technology 191 (2-3) (2005) 335-34. 18. Lima, R. S., Karthikeyan, J., Kay, C. M., Lindemann, J., Berndt, C. C., Thin Solid Films 416 (2002) 129135. 19. Agarwal S.C., Erosion-Corrosion of Materials in High- Temperature Environments: Impingement Angle Effects in Alloys 310 and 6B under Simulated Coal Gasification Atmosphere. 20. Uusitalo M.A., Vuoristo P.M.J., Mntyl T.A., Wear 252 (2002) 586594. 21. Juan. F. Flores, A. Neville, N. Kapur, A. Gnanavelu, Wear 271 (2011) 1331 1340. 22. Kaur Manpreet, Singh Harpreet, Prakash Satya, Surface & Coatings Technology 206 (2011) 530541. 23. Chawla Vikas, Chawla Amita, Puri D., Prakash S., Gurbuxani Prema G and Sidhu Buta Singh, Journal of Minerals & Materials Characterization & Engineering 10(4) (2011) 367-385. 24. Xu C., Peng X., Zheng L., Wang F., Surface & Coatings Technology 205 (2011) 45404546. 25. Shimizu K., Xinba Y., Ishida M., Kato T., Wear 271 (2011) 1349 1356. 26. Edris, H., McCartney, D.G., Sturgeon, A.J., J. Mater. Sci. 32 (4) (1997) 863-872. th 27. Knight, R., Smith, R.W., in: Berndt, C.C. (Ed.), Proc. 13 International Thermal Spray Conference, Orlando, Fl, USA (1992) 159. th 28. Dorfman, M.R., DeBarro, J.A., in: Ohmori, A. (Ed.), Proc. 14 International Thermal Spray Conference, Kobe, Japan (1995) 562. th 29. Harvey, M.D.F., Sturgeon, A. J., Blunt, F.L., Dunkerton, S.B., in: Ohmori, A. (Ed.), Proc. 14 International Thermal Spray Conference, Kobe, Japan (1995) 531. th 30. Nordmand, B., Liao, H., Landemarre, O., Coddet, C., Pagetti, J., in: Coddet, C. (Ed.), Proc. 15 International Thermal Spray Conference, Nice, France (1998) 69. 31. Sidhu, H. S., Sidhu, B. S., Prakash, S., Surface & Coatings Technology 200 (2006) 53865394. 1. 2. 3. 4. 5. 6. 7. 8.
Solid Particle Erosion Solid particle erosion (or erosive wear) implies the removal of material from component surfaces due to successive impact of hard particles travelling at substantial
15
velocities. It is to be noted that solid particle erosion is different from the other forms of erosion like liquid impact erosion, slurry erosion, cavitation erosion, etc. Material removal due to solid particle erosion is a consequence of a series of essentially independent but similar impact events. Thus, the contact between the hard particles and the component surface is of a very short duration. From this point of view erosion is completely different from the other closely related processes like sliding wear, abrasion, grinding and machining wherein the contact between the tool/abrasive and the target/work-piece is continuous. Degradation of materials due to solid particle erosion, either at room temperature or elevated temperature, is encountered in a large variety of engineering industries as illustrated in Table 11-12. At the same time, the erosion process has been used to advantage in a number of situations like sand blasting of castings, shot peening of rotating components, cutting of hard and brittle materials by abrasive jets and rock drilling13-15. Thus, the technological and commercial significance of erosion cannot be overlooked. Over the years the state of the information on solid particle erosion has been reviewed by Engel16, Preece and MacMillan17, Hutchings18, Finnie and McFadden19, Tilly20, Ruff and Wiederhorn21, Shewmon and Sundararajan22, Sundararajan23, Kosel24 and Levy25. Room temperature erosion (a) Impact velocity of the erodent particle has the most dramatic effect on the erosion rate. The erosion rate of a material (E) is usually defined as the ratio of weight loss suffered by the eroding material to the weight of the erodent particles causing the loss. The velocity dependence of erosion rate is characterized by the velocity exponent p given by: E = E 0Vp where E0 is a constant and V is impact velocity.
16
In the case of metallic materials, a detailed analysis of a large amount of experimental data by Hutchings26 has shown that under oblique impact conditions, the mean velocity exponent is 2.4. A similar analysis of the experimental data by Sundararajan and Shewmon27 indicated a mean value of 2.55 for p for erosion under normal impact. The above values of p are in contrast with the values of around 3 reported for ceramics and values in excess of 5 observed in polymer matrix composites28. The velocity exponent is also influenced by other parameters such as impact angle, particle size, etc. Goodwin et al.29 noted a decrease in the velocity exponent with decreasing particle size. The velocity exponent has also been observed to be a function of erodent particle shape30,31. (b) Impact angle is defined as the angle between the target material and the trajectory of the erodents. Dependence of erosion rate on the impact angle is largely determined by the nature of target material. As shown in Fig 1a, ductile materials (like metals and alloys) exhibit a maximum in the erosion rate at intermediate impact angles (e.g. 15, 30). In contrast, the maximum erosion rate of a brittle material (like glass) is usually obtained at normal impact angle i.e. at 90 (see Fig 1a). Among the erodent-related variables, erodent particle shape has a dramatic influence on the erosion rate-impact angle behaviour. Cousen and Hutchings31 and
17
Reddy and Sundararajan32 noted a maximum in the erosion rate at normal impact angle, even with ductile materials like mild steel and copper, when a spherical erodent was used. At present there exists insufficient data regarding the effect of impact velocity, size, friability and hardness of erodent particle on the variation of erosion rate with impact angle. (c) Particle size is an important variable which influences the erosion behaviour. According to Goodwin et al29, as illustrated in Fig 1b, the erosion rate increases with an increase in particle size up to a limiting size (50 to 100 m) beyond which erosion rate becomes independent of particle size. Similar observations have been made by Montgomery and Clark33, Wood and Espenschade34, Sheldon and Finnie35, Zhou and Bahadur36, Yerramarredy and Bahadur37 and Levy38. Bahadur and Badruddin39 also observed that in the case of a 18Ni (250) maraging steel eroded with SiC, Al2O3 and SiO2 particles, the erosion rate of the maraging steel increased with increasing particle size of SiC and Al2O3 while the opposite was true when SiO2 particles were used as the erodent. A number of theories have been put forth to explain the size effect as observed above34-39, but no consensus has yet emerged.
18
Fig. 1 (a) Schematic diagram showing the influence of impact angle on the erosion rate in the case of ductile and brittle material20 (b) variation of erosion rate of steel with particle size at normal impact at different impact velocities29 (c) influence of impact angle on erosion rate in the case of spherical and angular particles; (d) influence of flux rate of erodent particles on the erosion rate of a 1018 stee148 (d) The influence of particle shape on the erosion rate has been studied by several investigators31,32,39-41. Brown et al.40, Cousen and Hutchings31, Levy and Chik41 and Liebhard and Levy42 observed significantly higher erosion rates in many metallic materials when eroded with angular particles rather than spherical particles. According to Kleis43, the impact angle corresponding to maximum erosion rate shifted to an impact angle of 90 from 30 when the glass beads replaced crushed glass as the erodent. Reddy and Sundararajan32 observed a maximum in the erosion rate in Cu and Cu based alloys at normal impact angles when a non-friable, spherical steel shot was used as the erodent. Their observation is presented in Fig 1c. In contrast, when an angular
19
SiC is used as the erodent, the same Cu and Cu alloys exhibited a ductile response with regard to erosion behavior (Fig 1C 44). Thus, as the angularity of the erodent particle increases, the erosion rate increases and in addition, the erosion rate-impact angle behavior shifts more towards a ductile response. e) The influence of the hardness of the erodent particles on the erosion rate of steel has been studied by Wellinger and Uets and Levy25. They noted that as long as the hardness of the erodent particles was at least twice that of the target material, the erosion rate was independent of the particle hardness. The erosion rate decreased remarkably when the hardness of the erodent particles became comparable to that of the target material25,44. It was also observed that the use of friable erodent particles can result in a higher erosion rate45. (f) Usually, the flux rate of erodent particles does not have a significant influence on the erosion rate of metallic materials. However, at very high flux rates, due to interference with other particles and also with the rebounding particles, the erosion rate decreases. Such behaviour has been reported by Mills and Mason46, Montgomery and Clarke33, and Young and Ruff47. Anand et al48 have modelled the above interference effect due to particle rebounding and have come to the conclusion that the erosion rate should decrease exponentially with an increase in flux rate (Fig 1d). (g) The effect of the various strengthening mechanisms on the erosion rate of single phase metals and alloys has been summarized in Table 243,49-57. It is clear from Table 2 that none of the strengthening mechanisms like cold work, grain size hardening and solid solution strengthening available for single phase materials are effective in improving the erosion resistance of the eroding material. Figure 2a illustrates the influence of solid solution strengthening on the erosion rate. In the case of Cu, addition of solutes like Zn and Al increases the hardness/strength and the erosion rate44. In the case of Ni, addition of 20 wt% of Cr increases the strength/hardness but decreases the erosion rate56.
20
The results of the numerous investigations related to the erosion rate and strengthening mechanism for multiphase alloys are compiled in Table 337,56,58-74 Even in multiphase alloys, though the various strengthening mechanisms result in a substantial improvement in material strength, the erosion rates change only marginally. The erosion behaviour of dispersion strengthened alloys is presented in Fig. 2b56.70-72 it is clear that the erosion rates of the dispersion strengthened alloys are generally higher compared to the same alloy without the dispersion. The erosion behaviour of alloys based on intermetallics, presented in Fig. 2c, indicates that the erosion rates of various intermetallics are comparable in spite of their varying crystal structure and melting point. However, erosion rates of inter metallics appear to be lower than that of the base material (see Fig. 2c for comparison of the erosion rates of Ti 3Al based alloys with Ti). A large number of investigators have characterized the erosion behaviour of a variety of quenched and tempered steels
51, 58-60
. One such work is that due to McCabe
21
et al59. These authors studied the erosion behaviour of a plain carbon steel having two different carbon contents and a variety of microstructures. Among the various microstructures, spherodized steel exhibited the maximum erosion resistance while the martensite microstructure showed minimum erosion resistance. Pearlite and tempered martensite structure had intermediate erosion rates. The steel having higher carbon content had a lower erosion resistance. Both steels, irrespective of their microstructure, exhibited a ductile erosion behaviour. The only exception was the steels with martensite microstructure since they showed brittle erosion response especially in the higher impact velocity erosion tests. Balan et al characterized the erosion behaviour of grey, malleable and nodular cast irons having a variety of microstructures. Their observations clearly indicated that the nodular cast iron exhibited the lowest erosion rates while grey cast iron had the highest erosion rates. The malleable cast iron exhibited intermediate erosion rates. In terms of the matrix microstructure, a spherodized matrix generally exhibited a lower erosion rate as compared to cast irons having pearlitic or tempered martensitic matrix microstructures.
22
Fig. 2 (a) Influence of solid solution strengthening on the erosion rate of Ni-base and Cu-base alloys (b) bar diagram illustrating the effect of dispersion strengthening on the erosion rates of various Ni-base, iron-base and Al-base alloys56,68,70,71
23
Fig. 2 (c) Bar diagrams illustrating the erosion rates of Ti base, iron-base and Ni-base inter metallics61, 72-74 Elevated temperature erosion (a) The variation of erosion rate with temperature for a number of metals and alloys is presented in Figs 3a and 3b 75,76. The erosion data presented in these figures pertain to high impact velocities and mostly with angular particles. The observed temperature dependence of erosion rate can be conveniently classified under three groups. In the first group, the erosion rate initially decreases with increasing temperature, reaches a minimum and then starts increasing with increasing temperature. Materials such as 5Cr24
OSMo, 17-4PH, 41OSS, Alloy 800, Ti-6Al-4V and tungsten, etc., belong to this group. The second group comprises metals like Ta, lead (oblique impact) and alloys like 310SS (oblique impact) 1018 steel, 1100 aluminium (normal impact) which exhibit a temperature independent erosion rate up to a critical temperature followed by an increasing erosion rate with increasing temperature. Finally, the group III materials show an ever increasing erosion rate with increasing temperature. Into 600, carbon steel, 12Cr-lMo-V steel and 2.25Cr-1Mo steel, lead and 2024 Al are some typical examples in this group. (b) At present there exists insufficient data relating to erosion rate and impact angle at different temperatures. However, most of the metallic exhibit a ductile behaviour, i.e. a maximum erosion rate at oblique impact angles (10 to 30). The universality of such an observation is shown in Figs 3c and 3d, wherein the data from a large number of investigations have been presented77-83. Levy84 obtained a higher erosion rate at normal impact than at oblique impact for 9Cr-1Mo steel at 850C using rounded Al2O3 (130 m) erodent observations are presented in Fig 3e. However, at a low impact velocity of 20 m/s, a maximum in the erosion rate occurred at oblique impact angles. Observations due to Chang et al85 (Fig 3f) indicated that the peak erosion rate of Co at a test temperature of 780C occurred at an impact angle of 60 when impacted with 20 km angular alumina particles at the impact velocities of 70 and 140 m/s. However, when the erosion test was carried at 600C (V=140m/s) the erosion rate peaked at an impact angle of 30C (Fig 3f). Thus, there apparently exists conflicting observations regarding the erosion rate-impact angle behavior.
25
Table 3 Effect of various strengthening mechanisms on room temperature erosion of multiple phase material
26
*Generally valid for erosion tests carried out with angular erodent particles.
Fig. 3 (a) Variation of erosion rate with test temperature in the case of 2.25 Cr-1 Mo, 5 Cr-0.5 Mo, 1018 steels and 304, 310, 410 and 17-4 PH stainless steels 75 (b) effect of test temperature on the erosion rate of a number of pure metals (Ta, W, Pb) and alloys (Ti-6Al-4V, 2024 Al, 410 SS) at two impact angles (30 and 90) 75 However such observations can be rationalized the basis of erosion-oxidation interaction mechanisms as will be demonstrated in a later section. (c) The velocity exponent (p) obtained by various investigators is plotted in the velocitytemperature space in Fig 4a. The value of velocity exponent covers a wide range from
27
0.9 to 2.88. The velocity exponent decreases with an increase in erosion test temperature for 304SS to values as low as 0.9 at low impact velocities. At relatively higher impact velocities, p appears to lie in the range 2 to 3. Levy and Man86-87 obtained velocity exponents for erosion of 9Cr-1Mo steel at 650C using angular SiC particles. According to them, the velocity exponent initially remained constant and then increased with an increase of erodent size especially at low impact velocities. However, at high impact velocities p went through a minimum at an intermediate size of the erodent. (d) Tabakoff and Vitta80 carried out erosion tests on Inco 600 alloy using quartz particles in the size range of 70 m to 800 m. Their results, presented in Fig 4b, indicate that the erosion rate increased marginally with the increase of particle size. Zhou and Bahadur82 investigated the effect of particle size of SIC on the erosion rate of 304SS at 650C (impact angle: 30; impact velocity: 65 m/s). Their results (Fig 4c) indicate a particle size independent erosion rate beyond a particle size of 40 m. Levy and coworkers86-88 however, noted an increase of erosion rate with an increase of particle size for a 9Cr-1Mo steel eroded at a temperature of 650C and also for a 1018 steel eroded at 450C. (e) There is very limited data available on the influence of particle shape on elevated temperature erosion. Levy et al84, 86-87, 89 investigated the erosion rate of number of Cr containing steels at 850C with angular SiC and spherical Al203 as erodent particles. A typical result valid for a 9Cr-1Mo steel, is presented in Fig. 4d. the erosion rate is considerably higher when SiC is used as the erodent. In addition, the velocity dependence of erosion rate is itself influenced by the type of erodent used. (f) Zhou and Bahadur90 have investigated the influence of particle flux rate on the erosion of 304 and 430 SS over a large temperature range. their results shown in Fig 5a indicate that upto a temperature of about 500 C, a lower flux rate actually resulted in a substantially higher erosion rate. As will be shown subsequently, the sudden manifestation of a particle flux rate dependent erosion behavior beyond 500 C can be related to the mechanisms of interaction between erosion and oxidation. (g) The influence of eroding material properties on the erosion behavior of metallic materials at elevated temperatures has been investigated only to a very limited extent. In addition, the interpretation of the available data is also complicated by the fact that the behavior of oxide scale under erosion conditions need to be considered in addition to the behavior to the behavior of metallic material per se. The fact that the various strengthening mechanisms discussed in relation to erosion at room temperature becomes less important or even unimportant at elevated temperatures leads to further difficulties with respect to the analysis of the experimental erosion data.
28
Fig 3. Continued (d) influence of impact angle and test temperature on the erosion behavior of (i) 304 SS (ii) 410 SS and 316 SS77,79,80 References
[1]. [2]. Bitter J.G.A. Wear 1963, 6, 5 Bitter J.G.A. Weur 1963, 6, 169
29
[3].
[4].
Lehrke W.D. and Nonnen F.A. 1st Int. Conf. on Protection of Pipes, BHRA. Durham. UK 1975. paper G2 Forse C. and Ball A. Proc. of 6th Iilt. Cot$ on Erosion by Liquid and Solid impact. (Eds. Field J.E. and Come,; N.S.) Cavendish Laboratory, Cambridge University, September; 1983, Cambridge, UK Neilson J.H. and Gilchrist A. Wear 1968. 11, 123 Wright I.G. Mater. Sri. Engg. 1987, 88, 261 Thimot G. American Society for Mechanical 6zgineer.y Forum on Practical Erosion Problems in Fluid Systems and Machinery, Niagara Falls, New York, June 21 1979 Carson S.E. and Rnnnels O.D. D.O.E. Report Coo-0003-28, U.S. Dept. of Energy, 1978 Rademarkers P.L.F., Bos L., Van Wortel J.C. and Kotster B.H. Proc. Conf. on Fluidized Combustion, institute of Energy, London, 1984 Stringer J. and Drenier S. Proc. Am. Power. Conf. 1981, 43, 913 Sage W. and Tilly G.P. Aerorzaut. .I. 1969. 73, 429 Tilly G.P. 8th ICAS Congress, Amsterdam, 1972 Black P.H. Met. Engg. Q.. August 1972, 46 Finnie I. and Oh H. Proc. 1st Gong. of Int. Sot. Rock Mechanics 1966, 2, 99 Summers D.A. Treatise on Materials Science and Technology (Ed. Preece C.M.) Academic Press, New York, Vol. 16, 1979,395 Engel P.A. Impact wear of materials. Wear 1978. 48, 18 . . . Tilly G.P. Treatise on Materials Science and Technology, (Ed. Scott D.) Academic Press, New York, Vol. 13. 1979. 287 Ruff A.W. and Wiederhorn S.M. Treatise on Materials Science and Technology (Ed. Preece C.M.) Academic Press, New York, Vol. 16, 1979, 69 Shewmon P. and Sundararajan G. Ann. Rev. Mater. Sri.1983, 13, 301 Sundararajan G. Trans. Indian Inst. Metals December 1983, 36, 3 Kosel T.H. Metals Handbook. Vol. 18. ASTM International, The Materials Information Society, 1992, 199 Levy A.V. Solid Particle Erosion and Erosion-Corrosion of Materials, ASM International, Materials Park. Ohio, USA, 1995 Hutchings I.M. Proc. Conf. on Corrosion/Erosion of Coal Conversion System Materials (Ed. Levy A. V.) NACE, Houston.1979, 393 Sundararajan G. and Shewmon P.G. Wear 1983, 84, 237 Manish Roy, Vishwanathan B. and Sundararajan G. Wear 1994, 111, 149
[5]. [6]. [7].
[8]. [9].
[10]. [11]. [12]. [13]. [14]. [15].
[16]. [17]. [18]. [19]. [20].
[21].
[22]. [23]. [24]. [25].
[26].
[27]. [28].
30

[29]. [30]. [31]. Goodwin J.E., Sage W. and Tilly G.P. Proc. Inst. of Mech. Engg. 1969-70, 184, 279 Ives L.K. .I. Eng. Mater. Tech. Trans. ASME 1977, 99, 126 Cousens A.K. and Hutchings I.M. Proc. 6th Int. Conf. on Erosion by Liquid and Solid impact (Eds. Field J.E. and Corney N.S.) Cavelzdish Laboratory, Cambridge University, September 1983, Cambridge, UK Reddy A.V. and Sundararajan G. Wear 1986, 111, 313 Montgomery J.E. and Clarke J.M. SAE Summer Meetings, New York. 1962, paper 538A Wood C.D. and Espenschade P.W. SAE Summer Meetings, New, York, 1964, paper 880A Sheldon G.L. and Finnie I. Trans. ASME 1966, 88B, 387 Zhou J.R. and Bahadur S. Wear 1989, 132, 235 Yerramareddy S. and Bahadur S. Wear 1991, 142, 253 Levy A.W., Wang B.Q. and Geng G.Q. Mater. Sci. Engg. 1989, A121, 603 Bahadur S. and Badruddin R. Wear 1990, 138, 189 Brown R., Kosco S. and Zun E.J. Wear 1983, 88, 181 Levy A.V. and Chik P. Wear 1983. 89, 151 Liebhard M. and Levy A.V. Proc. Int. Conf on Wear of Materials, (Eds. Ludema K.C. and Bayer R.G.) ASME 1991,245 Kleis I. Wear 1966. 13, 199 Manish Roy, Tirupataiah Y. and Sundararajan G. Mater. Sci. Engg. 1993. A165, 51 Ives L.K. and Ruff A.W. ASTM STP 664, (Ed. Adler W.A.) ASTM, Philadelphia, PA, 1979, 5 Mills D. and Mason J.S. Proc. 6th Int. Conf. on Erosion by Liquid and Solid impact, (Eds. Field J.E. and Corney N.S.) Cavendish Laboratory, Cambridge University, September 1983, Cambridge, UK Young J.P. and Ruff A.W. J. Engg. Mater. Tech., Trans. ASME 1977. 99, 121 Anand K., Hovis S.K., Conrad H. and Scattergood R.O.Wear 1987, 118, 243 Finnie I. Wear 1960, 3, 87 Kleis I. Z. Werksto~ech. 1983. 15, 49 Soderberg S., Hogmark H., Engman U. and Swahn H. Tribol. Inter. December 1981, 333 Goretta K.C., Arroyo R.C., Wu C.T. and Routbort J.L.Wear 1991, 147, 145 Foley T. and Levy A.V. Wear 1983. 91, 45 Behrendt A. Proc. 3rd Ini. ConJ: 517 Rain Erosion and Allied Phenomenon, (Eds. Fvall A.A. and King R.B.) Royal Aircraft Establishment, UK, 1970 Reddy A.V. and Sundararajan G. Metall. Trans. 1987,18A, 1043 Manish Roy, Tirupataiah Y. and Sundararajan G. Mater. Sci. Technol. 1995, 11. 791
[32]. [33]. [34]. [35]. [36]. [37]. [38]. [39]. [40]. [41]. [42].
[43]. [44]. [45]. [46].
[47]. [48]. [49]. [50]. [51]. [52]. [53]. [54].
[55]. [56].
31

[57]. [58]. [59]. [60]. Trilok Singh and Sundararajan G. Wear 1991, 145, 77 Finnie I., Wolak J. and Kabil Y. J. Mater. 1967, 2, 682 McCabe L.P., Sargent G. and Conrad H. Wear 1985. 105,257 Levy A.V. and Jahanmir S. In Corrosion-Erosion Behaviour of Materials, (Ed. Natesan K.) Met. Sot. AIME. Philadelphia, 1979, 177 Manish Roy and Sundararajan G. Unpublished work. Defence Metallurgical Research Laboratory, Hyderabad,India, 1995 Balan K.P., Reddy A.V., Joshi V. and Sundararajan G.Wear 1991, 145, 283 Emiliani M. and Brown R. Wear 1984, 94, 323 Shin Y.W., Sargent G.A. and Conrad H. Metall. Trans. 1987, 18A. 437 Salik J. and Buckley D.H. Proc. Int. Conj Wear of Materials, (Eds. Rhee SK., Ruff A.W. and Ludema K.C.) ASME, New York, 1987, 592 Naim M. and Bahadur S. Wear 1986, 112, 217 Rao D.R.K., Venkataraman B., Asundi M.K. and Sundararajan G. Surf. Coat. Technol. 1993, 58, 85 Levy A.V. Wear 1981, 68, 269 Manish Roy, Subramanyam M. and Sundararajan G. Tribol. Int. 1992, 25, 272 Conrad H., Smith J.P. and Shin Y.W. Proc. Int. Conf. on Trihological Mechanism and Wear Problems in Materials, (Eds. Santhnnam A.T. and Linga Murthy K.) ASM, Materials Park, ohio,1987,23 Liebhard M., Levy A.V. and Verpoort C. Proc. Corrosion-Erosion-Wear of Materials at Elevated Temperature, (Ed. Levy A.V.) Berkeley, California, 1991, 381 Manish Roy, Ranganath S., Venkataraman B., Subramanyam J. and Sundararajan G. Unpublished work, Defence Metallurgical Research Laboratory. Hyderabad, India. 1990 Howard R.L. and Ball A. Wear 1995, 186-187, 123 Sahoo M., Lui A., Morin G. and Sikka V.K. Mechanical Properties and Erosion Behaviour of Nickel Aluminide. Report MTL 89-68 (J), Canada Centre for Mineral and Energy Technology. CANMET, 1981 Levy A.V., Yan J. and Patterson J. Proc. Int. Conf. on Wear of Materials, (Ed. Ludema K.) ASME, New York, 1985, 708 Gat N. and Tabakoff W. Wear 1978, 50, 85 Shayler P.J. and Yee K.H. Wear 1985, 98, 127 Finnie I., Levy A.V. and McFadden D.H. ASTM STP 664, (Ed. Adler W.F.) Philadelphia, PA, 1976, 36 Shida Y. and Fujikawa H. Wear 1985, 103, 281 Tabakoff W. and Vittal B.V.R. Wear 1983, 86. 89 Gat N. and Tabakoff W. J. Testing Eval. 1980. 8, 177
[61].
[62]. [63]. [64]. [65].
[66]. [67]. [68]. [69]. [70].
[71].
[72].
[73]. [74].
[75].
[76]. [77]. [78]. [79]. [80]. [81].
32

[82]. Zhou J. and Bahadur S. Corrosion and Particle Erosion at High Temperature, (Eds. Srinivasan V. and Vedula K.) The Minerals, Metals and Materials Society, USA. 1989, 315 Trilok Singh. Ph.D Thesis. Banaras Hindu University, Varanasi, India, 1952 Levy A.V. Corrosion and Particle Erosion at High Temperature, (Eds. Srinivasan V. and Vedula K.) The Minerals, Metals and Materials Society, USA, 1989, 207 Chang S.C., Pettit F.S. and Birks N. Oxid. Metals 1990, 34, (l/2), 47 Levy A.V. and Man Y.F. Wear 1986, 111, 173 Levy A.V. and Man Y.F. Wear 1989. 131, 53 Levy A.V., Wang B.Q. and Geng G.Q. Mater. Sci. Engg. 1989, A121. 603 Levy A.V. and Wang B.Q. Wear 1989, 131, 71 Zhou J. and Bahadur S. Proc. Corrosion-Erosion Wear of Materials at Elevated Temperature, (Ed. Levy A. V.) Berkeley, California, 1991, 13-l
[83]. [84].
[85]. [86]. [87]. [88]. [89]. [90].
1.
CORROSION The corrosion processes follow the basic laws of thermodynamics. Corrosion is
an electrochemical process. Under controlled conditions it can be measured, repeated, and predicted. Since it is governed by reactions on an atomic level, corrosion processes can act on isolated regions, uniform surface areas, or result in subsurface microscopic damage. Complicate these forms of corrosion with further subdivisions, add just basic environmental variables such as pH, temperature, and stress, and the predictability of corrosion begins to suffer rapidly. 2. FORMS OF CORROSION There are nine basic forms of corrosion that metallic materials may be subject to: 1. 2. 3. 4. 5. 6. 7. 8. 9. Uniform corrosion Intergranular corrosion Galvanic corrosion Crevice corrosion Pitting Erosion corrosion Stress corrosion cracking Biological corrosion Selective leaching
33
2.1
Uniform Corrosion Although other forms of attack must be considered in special circumstances,
uniform attack is one form most commonly confronting the user of metals and alloys. Uniform or general corrosion, which is the simplest form of corrosion, is an even rate of metal loss over the exposed surface. It is generally thought of as metal loss due to chemical attack or dissolution of the metallic component into metallic ions. In hightemperature situations, uniform metal loss is usually preceded by its combination with another element rather than its oxidation to a metallic ion. Combination with oxygen to form metallic oxides, or scale, results in the loss of material in its useful engineering form; scale ultimately flakes off to return to nature. Fig. 1 shows how corrosion attacks the cover of a tank.
Fig. 1 Cover of tank attacked by uniform corrosion A metal resists corrosion by forming a passive film on the surface. This film is naturally formed when the metal is exposed to the air for a period of time. It can also be formed more quickly by chemical treatment. For example, nitric acid, if applied to austenitic stainless steel, will form this protective film. Such a film is actually a form of corrosion, but once formed it prevents further degradation of the metal, provided that the film remains intact. It does not provide an overall resistance to corrosion because it may be subject to chemical attack. The immunity of the film to attack is a function of the film composition, temperature, and the aggressiveness of the chemical. Examples of such films are the patina formed on copper, the rusting of iron, the tarnishing of silver, the fogging of nickel, and the high-temperature oxidation of metals.
34
There are two theories regarding the formation of these films. The first theory states that the film formed is a metal oxide or other reaction compound. This is known as the oxide film theory. The second theory states that oxygen is adsorbed on the surface, forming a chemisorbed film. However, all chemisorbed films react over a period of time with the underlying metal to form metal oxides. Oxide films are formed at room temperature. Metal oxides can be classified as network formers, intermediates, or modifiers. This division can be related to thin oxide films on metals. The metals that fall into network-forming or intermediate classes tend to grow protective oxides that support anion or mixed anion/cation movement. The network formers are noncrystalline, whereas the intermediates tend to be microcystalline at low temperatures. Uniform corrosion of steel under the high pressure of CO2 environment is very critical problem faced on shore and also off shore at oil wells. Crolet et.al. [2] throw light on analyzing the various effects of CO2 on corrosion in general, based on this work a policy for fighting corrosion in offshore wells can be made, not only that it helps in precisely predicting the mechanisms of local CO2 attack, and a method of predicting the risks of CO2 corrosion in wells as well. Under this work the current knowledge of CO 2 corrosion, starting with descriptions of the various effects of CO 2 on corrosion in general and the diversity of the definitions of corrosivity is discussed. Methods for predicting the risks of CO2 corrosion are proposed as outcome of this work. Nesic [3] also worked on a predictive model was developed for uniform carbon dioxide (CO2) corrosion, based on modeling of individual electrochemical reactions in a water-CO2 system. The model takes into account the electrochemical reactions of hydrogen ion (H+) reduction, carbonic acid (H2CO3) reduction, direct water reduction, oxygen reduction, and anodic dissolution of iron. The required electrochemical parameters (e.g., exchange current densities and Tafel slopes) for different reactions were determined from experiments conducted in glass cells. The corrosion process was monitored using polarization resistance, potentiodynamic sweep, electrochemical impedance, and weight-loss measurements. The model was calibrated for two mild steels over a range of parameters: temperature (t) = 20 C to 80 C, pH = 3 to 6, partial pressure of CO2 (P-CO2) = 0 bar to 1 bar (0 kPa to 100 kPa), and omega = 0 rpm to 5,000 rpm (v(p) = 0 m/s to 2.5 m/s). The model was applicable for uniform corrosion
35
with no protective films present. Performance of the model was validated by comparing predictions to results from independent loop experiments. Predictions also were compared to those of other CO2 corrosion prediction models. Compared to the previous largely empirical models, the model gave a clearer picture of the corrosion mechanisms by considering the effects of pH, temperature, and solution flow rate on the participating anodic and cathodic reactions. The effect of inert atmosphere on the corrosion is studied by Jin Huang et. al.[4]. Here uniform CO2 corrosion of mild steel under inert solid deposits is studied. The effect of an inert solid deposit on uniform CO2 corrosion of mild steel is modeled based on a mechanistic electrochemical CO2 corrosion model. Laboratory testing has shown that the dominant factors introduced by the inert solids deposit are related to surface coverage, where both anodic and cathodic reaction rates are decreased because of less active surface area being exposed. The inert solid deposits also create a mass transfer barrier for corrosive species which limits the rate of the cathodic reactions. An existing mechanistic electrochemical model was modified to account for these effects and was capable of capturing the features of uniform CO2 corrosion of mild steel under inert solid deposits. The iron is protected from the corrosion environment by a thin oxide film 14 mm in thickness with a composition of (Fe2O3)0.5/ Fe3O4. Jiabin Han, et al. [5] applied SEM, XRD and GIXRD (grazing incidence XRD) were applied to characterized and identify the protective/passive film. It is noted that under the usual mode of data collection in XRD technique involves symmetric theta/2theta geometry wherein the angle of incidence and angle of diffraction increases continuously during the data collection. In such a mode the beam can penetrate deeper into the sample compared to GIXRD with a fixed small incidence angle. These small and large incidence angles for XRD and GIXRD are catalogued by the critical incidence angle. Both the schemes are explained herewith with a basic schematic as Figure 2 & 3.
36
Fig 2. Scheme for XRD with larger incidence angle
Fig 3. Scheme for XRD with grazing incidence angel (GIXRD) The electrochemical corrosion processes of iron in a borate solution have been investigated by, Jing Li [6] with the help of in situ electrochemical atomic force microscopy (ECAFM). A freshly polished iron surface is passivated electrochemically in a borate solution to give a film which is different from the oxide layer which forms on the iron surface in air. Study revealed that most areas of the passive film are uniform, but some defects still exist in the film which allows localized corrosion to occur. In situ ECAFM are used to examine these defects directly and to observe the initial corrosion processes in which ferric oxide particles are both formed and reduced by cyclic voltammetry. The passive film on nickel can be formed quite readily in contrast to the formation of the passive film on iron. Corrosive surface on nickel was obtained by localized
37
corrosion of Ni(111) surfaces passivated in a chloride-free sulphuric acid solution and subsequently exposed to chloride (0.05 M) are reported by In situ scanning tunnelling microscopy measurements, by V. Mairice, et al. [7]. The result evident the deterministic role of the structure of the passivated surface on the dissolution in the passive state, independent of the addition of chloride in the electrolyte. The atomic lattice of the passive film formed in the absence of chloride remained intact even after the addition of chloride. At the investigated potential of +0.85 VSHE (0.05 V below the stable pitting potential), the dissolution proceeds by a two-dimensional step flow process that is dependent on the step orientation, the steps oriented along the closed-packed directions dissolving much less rapidly than the steps oriented along no well-defined directions of the oxide lattice. The dissolution rate of the oxide lattice is around 6 NiO molecules s1, independent of the presence of chloride. The comparison with the rate of dissolution that can be estimated from the measured electrochemical current density in the passive state suggests that the dissolution of the oxide lattice of the passive film is not the major anodic reaction in the passive state. Most of stainless steels are used under the ambient atmosphere including indoor and outdoor environments, but not in aqueous solution. However, certain researchers, [8] have studied passive films that are formed in electrolytic solutions. As commonly recognized, the excellent protection ability of stainless steel derives from the highly Cr enriched passive film which is formed as a result of selective dissolution of Fe into the balk solution. On the other hand, the passive films formed under atmospheric conditions do not necessarily exhibit Cr enrichment, because the amount of the solution on a stainless steel as an adsorbed thin water layer is not sufficient for selective dissolution of Fe. Therefore, the modification of passive films may occur as tiny mass transfer between hydroxide layer and oxide layer of the passive films, and/or occasional replace of the adsorbed thin water layer. In the present work, in order to discuss atmospheric corrosion, passive films on stainless steels formed under humid atmospheric environments were characterized using X-ray photoelectron spectroscopy. Most of passive films formed for various period of exposure up to 3 months in humid environments with/without a wet and dry sequence, and without solution supply during exposure has the cation content equivalent to substrate steel, and exhibits
38
almost no change with time. This is reasonable because mass transfer is limited to among the most surface of the steel, passive film and adsorbed water layer. Slight increase in Cr content in the inner oxide later was recognized. During the exposure, Fe+ + in oxide layer may transfer into outer hydroxide layer. On the other hand, gradual changes in cation content with time was observed for the specimen on which small amount of pure water or especially salt solution was supplied periodically during exposure. Supply of chloride stimulates Cr enrichment, because formation of salt or complex may accelerate transfer of Fe++ into solution layer. Study of protective film is very relevant for the protection of steel for the application of reinforcement corrosion [9]. Reinforcement corrosion has become the most serious cause of premature deterioration of concrete structures. Especially, for structures exposed to high environmental aggressiveness and with a long design service life, it is necessary to provide additional preventive measures. The use of corrosion resistant reinforcement materials, such as stainless steel, is an important technical approach which offers many advantages as a preventive measure, such as, reduced maintenance and increased durability. With the increased application of stainless steel reinforcement, the attention to the research in this area is increased. A fundamental area is the development of new stainless steel alloys, such as high manganese alloys, with suitable mechanical properties and high corrosion resistance. Besides its stated importance in the development of new alloys, the corrosion resistance characterization is also essential to allow a thorough selection, of the distinct stainless steel alloys available, for a given application. The structure of the passive films is considered to be a crucial factor in localized corrosion events, the determination of its properties being an important tool for evaluating the electrochemical behavior of passive metallic alloys. The structure of the passive films in this case has been studied by capacitance measurements using the Mott-Schottky approach. The studied passive films were formed under distinct conditions: with and without pre-polarization, both in alkaline solutions with and without chlorides. The stainless steel passive films have shown a bilayer structure of two space charge depletion layers (n- and p-type semiconductors). Generally, the passive films formed on low nickel alloys have higher donor doping
39
densities than those of the Fe-Cr-Ni based alloys. The doping densities in chloride containing solution are also higher than those in alkaline solution. 2.2 Intergranular Corrosion Intergranular corrosion is a localized form of corrosion. It is a preferential attack on the grain boundary phases or the zones immediately adjacent to them. Little or no attack is observed on the main body of the grain. This results in the loss of strength and ductility. The attack is often rapid, penetrating deeply into the metal and causing failure. Typical corrosion under this category for aluminum and carbon steel is as shown in Figure 4.
Figure 4 Exfoliation of aluminum and carbon steel Exfoliation is a form of intergranular corrosion. It manifests itself by lifting up the surface grains of a metal by the force of expanding corrosion products occurring at the grain boundaries just below the surface. It is visible evidence of intergranular corrosion and most often seen on extruded sections where grain thickness is less than in rolled forms. This form of corrosion is common on aluminum, and it may occur on carbon steel. Intergranular corrosion (IGC) can also be defined as the phenomena in which the corrosion rate of the grain boundary is higher than that of the bulk grain body. Austenitic stainless steels can become sensitized to this type of corrosion when the bulk metal
40
experiences a temperature excursion above that necessary to make chromium carbides dissolve.[10] As the metal cools, chromium carbide preferentially precipitates at the grain boundaries causing the local Cr concentration adjacent to the grain boundary to decrease relative to the Cr concentration in the bulk of the grain (Figure 5). This relative drop in Cr concentration adjacent to the grain boundary is called sensitization or segregation. A single loop electrochemical potentiokinetic reactivation (SLEPR) method, originally developed for the nuclear industry and now an ASTM Standard, will be used to quantitatively measure the DOS of material in each array. A modification of this test can be made to show that IGC could occur in sensitized stainless steel adjacent to pits that grow by the acid-pitting mechanism.
Figure 5 Relative Cr concentrations near a sensitized Grain Boundary 2.3 Galvanic Corrosion This form of corrosion is sometimes referred to as dissimilar metal corrosion, and is found in unusual places, often causing professionals the most headaches. Galvanic corrosion is often experienced in older homes where modern copper piping is connected to the older existing carbon steel lines. The coupling of the carbon steel to the copper causes the carbon steel to corrode. The galvanic series of metals provides details of how galvanic current will flow between two metals and which metal will corrode when they are in contact or near each other and an electrolyte is present (e.g., water). Figure 6 gives the corrosion because of dissimilar metal.
41
Fig. 6 corrosion because of dissimilar metal corrosion caused by a stainless steel screw causing galvanic corrosion of aluminum 2.4 Crevice Corrosion Crevice corrosion is a localized type of corrosion occurring within or adjacent to narrow gaps or openings formed by metal-to-metal-to-nonmetal contact. It results from local differences in oxygen concentrations, associated deposits on the metal surface, gaskets, lap joints, or crevices under a bolt or around rivet heads where small amounts of liquid can collect and become stagnant. Crevice corrosion may take place on any metal and in any corrosive environment. However, metals like aluminum and stainless steels that depend on their surface oxide film for corrosion resistance are particularly prone to crevice corrosion, especially in environments such as seawater that contain chloride ions. The gap defining a crevice is usually large enough for the entrapment of a liquid but too small to permit flow of the liquid. The width is on the order of a few thousandths of an inch, but not exceeding 3.18 mm. The material responsible for forming the crevice need not be metallic. Wood, plastic, rubber, glass, concrete, asbestos, wax, and living organisms have been reported to cause crevice corrosion. After the attack begins within the crevice, its progress is very rapid. It is frequently more intense in chloride environments. Prevention can be accomplished by proper design and operating procedures. Figure 7 shows the basic mechanism for the crevice corrosion and its industrial occurrence.
42
Fig. 7 Crevice corrosion basic mechanism and its occurrence Crevice corrosion is very relevant for the sea boat sailing in the sea water[11]. In order to understand the effect crevice corrosion tests were carried out in order to evaluate the performance of some conventional and high alloy stainless steels in Arabian Gulf seawater at 25C and 50C using specimens having three different surface conditions namely as received wheel ground and 180 grit SiC ground. Immersion tests of 150-180 days duration and accelerated tests were employed to investigate the crevice corrosion behavior. Immersion test results show that crevice corrosion of 3127 hMo, Remanit 4565, 654 SMO, and Monit 44635 initiated as surficial corrosion with virtually no measurable depth of attack; 254 SMO, Duplex 2205, Remanit 4575, 904L and 317L corroded on l-2 sites attack. Crevice corrosion attack was most predominant at 50C in 180 grit SiC finished surfaces and there was no evidence of crevice corrosion attack in as received samples at room temperature. A method based on Oldfield and Sutton9 mathematical modelling of corrosion in chloride media has been applied for determining critical crevice solution pH (CCSpH), an important parameter which delineates the transition between passive and active states. The CCSpH appears to be a linear function of PREN (PREN = %Cr + 3.3x%Mo + 16x%N) indicating the strong influence of Cr, MO and N additions on the crevice corrosion characteristics of steels. Figure 8 gives the PREn v/s CCSpH for various materials stated. A linear fit is observed for the various materials.
43
Fig. 8 Plot of PREN v/s CCSpH value for steels in natural sea water and NaCL solution The simplest method for preventing crevice corrosion is reducing crevices in the design of the structure When it is not possible to get rid of crevices, improving drainage and sealing of edges or keeping crevices as open as possible and therefore preventing entrance of moisture is the best protective action A protection method called hot wax dip is commonly used in automotive industry.[12] In this method faying surfaces that will make crevices are usually painted before assembly. In aerospace industry sealing the faying surfaces with a polysulfide is known to be an effective method for preventing crevice corrosion. Cathodic protection could be an effective method against crevice corrosion, but anodic protection is often improper as shown in Figure 9. Another common protection method is using alloys which are less vulnerable to crevice corrosion. Addition of inhibiting substances to bulk solution is also a protection method. Application of passivating compounds such as chromate and nitrate is well practiced to prevent crevice corrosion. Overlaying susceptible areas with an alloy which is more resistant to crevice corrosion is another protective measure.
44
Fig 9: Mechanism of active and passive corrosion and its corresponding Anodic and Cathodic reactions in crevice corrosion 2.5 Pitting Corrosion Pitting corrosion is in itself a corrosion mechanism, but it is also a form of corrosion often associated with other types of corrosion mechanisms. It is characterized by a highly localized loss of metal. In the extreme case, it appears as a deep, tiny hole in an otherwise unaffected surface. The initiation of a pit is associated with the breakdown of the protective film on the metal surface. The depth of the pit eventually leads to a thorough perforation or a massive undercut in the thickness of the metal part. The width of the pit may increase with time, but not to the extent to which the depth increases. Most often, the pit opening remains covered with the corrosion product, making it difficult to detect during inspection. This, along with a negligible loss in weight or absence of apparent reduction in the overall wall thickness, gives little evidence as to the extent of the damage. Pitting may result in the perforation of a water pipe, making it unusable even though a relatively small percentage of the total metal has been lost due to rusting. Nickel-aluminium bronze (NAB) is widely used in marine applications because of its high toughness and erosion-corrosion resistance. NAB is used for high performance propellers and seawater handling systems seawater valves and heat exchangers. Pitting and crevice corrosion for copper-based alloys is often attributed to a metal-ion
45
concentration cell. Areas exposed to high copper-ion concentrations are considered to act as cathodic sites (with copper deposition sometimes observed).[13]
Figure 10 Pitting corrosion occurrences at propeller at marine applications NAB may encounter corrosion related problems under in-service conditions. NAB can encounter variability in corrosion performance worldwide, i.e. different local environments. NAB components in naval vessels can be affected by their operational cycles (open / dock type seawater) long periods in the dock compared with commercial vessels. Corrosion problems can lead to expensive repairs to NAB propellers and seawater intakes. Propeller replacement costs is exorbitantly high where as dry dock costs are also significant component. For this a study by Balic et al. is carried out to a detailed study[13]. Since NAB is known to be susceptible to localised corrosion, e.g. crevice corrosion rates as high as 0.7 to 1.0 mm.y1 have been reported - compared with 0.25 mm y1 for type 304 stainless steel. NAB is prone to selective phase corrosion (SPC), and this SPC may initiate pitting corrosion. The study concludes the following: On exposure the copper-rich -phase was initially (during the first 6 months) susceptible to corrosion leaving the unattacked -phases to create an adherent skeletal lattice.
At localised sites, SPC occurred and due to the continuous nature of the III-phase this resulted in the accumulation of corrosion products / deposits at these locations.
46
The formation of a micro-environment beneath the deposit developed into a pitting type phenomenon after prolonged exposures (within 15 months).
Overall, the pitting mechanism is characterised by very wide although relatively shallow corrosion features. 2.6 Erosion Corrosion The term erosion applies to deterioration due to mechanical force. When the factors contributing to erosion accelerate the rate of corrosion of a metal, the attack is called erosion corrosion. Erosion corrosion is usually caused by an aqueous or gaseous corrodent flowing over the metal surface or impinging on it. The mechanical deterioration may be aggravated by the presence of a corrodent, as in the case of fretting or corrosive wear. The attack takes the form of grooves, i.e., scooped-out rounded areas, horseshoe-shaped depressions, gullies, or waves, all of which often show directionality. At times, attack may be an assembly of pits. Ultimate perforation due to thinning or progression of pits, and rupture due to failure of the thinned wall to resist the internal fluid pressure are common. All equipment exposed to flowing fluid is subject to erosion corrosion, but piping systems and heat exchangers are the most commonly affected. Erosion corrosion is affected by velocity, turbulence, impingement, presence of suspended solids, temperature, and prevailing cavitation conditions. The acceleration of attack is due to the distribution or removal of the protective surface film by mechanical forces exposing fresh metal surfaces that are anodic to the uneroded neighboring film. A hard, dense adherent and continuous film, such as on stainless steel, is more resistant than a soft brittle film, as that on lead. The nature of the protective film depends largely on the corrosive itself. Erosion-corrosion is often accelerated at pipe elbows, tube constriction, and anywhere fluid flows are altered and there is an increase in turbulence. Other aspects that increase erosion corrosion are the corrosivity of the flowing corrodant, a two-phase flow, such as steam and water, or a flow in which suspended solids are flowing with the fluid [14], as shown in Figure 11.
47
Figure 11: Erosion-corrosion of brass condenser tubing showing individual teardrop shaped pits with under cutting in the downstream direction. In 1982, Heitmann and Kastner published the results of erosion corrosion
experiments of KWU Siemens. Some years after this publication KWU-Siemens has processed these experimental results in a model and made the software programme WATCHEC which is applied in many power stations over the world. [15] With the help of the calculation model influence of various factors can be estimated rather well. Cr and Mo were incorporated in the correlation formula of KWU Siemens. Other elements as Cu and C were neglected. From the extensive erosioncorrosion experiments of KEMA it was proven that Cu had a 40% more erosioncorrosion resistant effect than Cr. The relative erosion-corrosion resistance of C-steels and 15Mo3 was expressed in the Cr equivalence formula (Cr-equivalent = Cr +1.4 Cu + 0.3 Mo - 0.3 C > 0.09). By comparing the Cr equivalence of steels from failures and non-failures it appeared that steels from failures generally had a Cr-equivalence less than 0.09.
48
Fig 12 Steam blanketing at the inner side and erosion corrosion at the outer side of the bellow having Cr - 0.005, Cu - 0.02, Mo - 0.005, C - 0.12, and Cr-eq.for this combination is 0.0015. The dominant factor for the erosion and corrosion is water chemistry, water velocity, and chemical composition of the steel the suspended iron oxides. Huijbregts [16] worked on the relationship between the chemical composition of steel and erosion corrosion resistance. This relation-ship has been neglected in the past because water chemistry and velocity were thought to be the dominant factors. Especially in steamwater circuits may cause trouble in both conventional and nuclear power stations. This happens rather often; e.g., corrosion in conventional boiler evaporators, corrosion in PWR steam generators and deposition of iron oxides on fuel elements in nuclear reactors. In view of these problems, it is recommended that the iron content in steam water circuits be kept as low as possible. This iron comes from erosion-corrosion, the major sources of which are water separators, wet steam pipes, preheaters, and evaporators. Erosion-corrosion depends on water chemistry, water velocity, and chemical composition of the steel. The resistance against erosion-corrosion in wet steam was determined for 58 steels in a laboratory test. Minute quantities of chromium, copper, and molybdenum increase the resistance against erosion-corrosion. The erosion-corrosion resistance (R) can be calculated by the regression equation R = 0.61 + 2.43 Cr + 1.64 Cu + 0.3 Mo.
49
Steels from in-service erosion-corrosion failures showed low resistance against erosioncorrosion in the laboratory test. No failures were found in steels with a calculated resistance value R of more than 1.0. Figure 13 shows schematic of experimental set-up for the same.
Figure 13 - Design of the erosion-corrosion loop. Power companies provided various erosion-corroded specimens. They came from steam sieves, a spindle, switch levers in feed water pumps, and a control valve housing. All the corroded steels had low Cr, Cu, and Mo content. Case 1. In the experimental boiler, erosion-corrosion occurred in a steam pressure drop vessel in which steam expands and a water steam jet hits the vessel wall. After 10 years of operation, there was a leakage. The vessel wall had a protecting steel plate opposite the steam inlet tube. The steel plate (10 mm thick) and the vessel wall (5 mm thick) were corroded and leakage occurred. The resistance R calculated for the steel plate was 0.90. Case 2. A number of steam sieves suffered erosion-corrosion. Chemical analyses showed that three different steel heats were applied. The calculated resistances were rather low (0.70).
50
Case 3. A spindle from a condensate effluent valve of a low pressure preheater was coated only partly with a 9% chromium steel. On top of the spindle. This coating was lacking. Erosion-corrosion was observed there. Again low Cr. Cu, and Mo values were found, and the resistance value R amounted to 0.75. Case 4. The switch lever of a supply water pump had been attacked severely by erosion-corrosion. Steel No. 58 appeared to have suffered a high weight loss in the laboratory test, i.e. number of specimens 116 mg. The operation time of this lever was 10,000 hours. Another lever from an identical pump at the same station after 40,000 hours showed less corrosion. The Cr, Cu, and Mo content of this steel is slightly higher. The calculated R values of the two levers amounted to 0.65 and 0.73, respectively. Case 5. There was heavy erosion-corrosion in control valve housing, resulting in leakage. This steel No. 57 suffered a high weight loss in the erosion-corrosion test, 107 mg. Cr, Cu, and Mo content was low, and the resistance value R was 0.67. Case 6. A pipe behind the BWR water separator was constructed by welding bent steel plates The wet steam pipe after the pre-water separator. The pipe was welded of bent steel plates. One plate had been corroded severely (R = 0.67). The adjacent noncorroded plates had higher resist-ances (R = 0.89). Case 7: Steel part from the PWR water separator as shown in Figure 14. One steel plate had suffered erosion-corrosion, and much oxide was deposited on the other. The resistance value of the erosion-corroded steel was much lower than that of the noncorroded steel (0.65 to 1.20).
51
Fig - 14 Steel part from the PWR water separator 2.7 Stress Corrosion Cracking (SCC) SCC is defined as the delayed failure of alloys by cracking when exposed to certain environments in the presence of static tensile stress. The importance of a conjoint action of corrosion and stress is reflected in the definition; an alternate application of stress and corrosive environment will not produce SCC. The stress level at which the failure occurs is well below the stress required for a mechanical failure in the absence of corrosion. The minimum stress below which SCC will occur is called the threshold stress, but this may be as low as 10% of the yield stress in some systems. Corrosion alone in the absence of stress does not cause SCC. SCC occurs at points of stress. Usually the metal or alloy is virtually free of corrosion over most of its surface, yet fine cracks penetrate through the surface at the points of stress. Depending on the alloy system and corrodent combination, the cracking can be intergranular or transgranular. The rate of propagation can vary greatly and is affected by stress levels, temperature, and concentration of the corrodent. A simplified stress corrosion test fixture with a round tensile specimen installed is illustrated on Figure 15 in a simulated corrosion environment.[17] A masking material is applied to the test fixture to ensure that the specimen alone is exposed to the corrosive environment. The tensile specimen is stressed to a desired level (typically 25, 50, 75 or 90 percent yield strength). The specimen is then submerged in a 3.5 percent NaCl alternate immersion bath, in a 5 percent NaCl salt spray (fog), or in a 90-95 percent
52
relative humidity test. Test duration is typically three months for low alloy steels and aluminum alloys, and six months for stainless steel. The resistance of metals to SCC is always less when tension is applied in a transverse direction. It is least for the short transverse direction. Stress corrosion is aggravated when tensile stresses due to assembly have been applied in the short transverse direction. Table 1 lists typical materials and environments that may cause stress corrosion.
Fig. 15 Stress Corrosion Test Setup for the SRB Forward Separation Bolt Table 1 Environments That May Cause Stress Corrosion of Metals and Alloys
53
The stress corrosion cracking (SCC) of stainless steel is one of the biggest problems for maintaining atomic power and chemical plants and occurring widely. However the mechanism has not been solved because of difficulty in observing hydrogen movement. In order to solve this problem, the author has developed a new SCC test method that enables the super Kelvin force microscope (SKFM) and the Kelvin force microscope (KFM) observations. By using this test method, the crack tip deformation and surface potential distribution on SUS316L stainless steels were observed by SKFM and KFM. The existence of hydrogen-induced martensite was examined by the magnetic force microscope (MFM) observations. The results showed that a less noble potential region existed near the crack tip. MFM and KFM observation showed hydrogen induced martensite existed at the less noble potential region. Repeated SKFM observations revealed that the crack is formed by the movement of hydrogen-induced martensite.[18] Fasteners are susceptible to many forms of embrittlement, with stress corrosion cracking generally considered to be the most complex failure mechanism. Stress corrosion cracking is a type of localized corrosion characterized by fine cracks (as seen
54
in the two photographs in Figure 16) that propagate quite rapidly leading to failure of the component and potentially the associated structure.[19].
Fig. 16 Typical appearance of stress corrosion cracking failure.
Fig.17 End cap application of pipelock Pipelocks and the Mechanical Stress Improvement Process (MSIP) have been applied in BWRplants. Pipelocks restore the 'integrity of the weldments with identified cracks. MSIP removes residual tensile stresses from weldments, thus, preventing
55
initiation of cracks or retarding growth of pre-existing flaws 1n piping systems. MSIP was applied for various geometries of weldments including nozzle-to-safe-end Joints. Extensive verification has been carried out by United States Nuclear Regulatory Commission EPRI and the Argonne National Laboratory. Basic concepts and practical application of MSIP and Pipelocks are presented[20]. The Pipelock is a mechanical device which is designed to prevent pipe break under the assumption of a throughwall IGSCC crack around the entire circumference of the pipe weld. It is simple and easy to apply as shown in the Fig. 17 where shell end of a small shell and tube type heat exchanger is shown. The arrangement is additionally applied over the pipe. At the time of the inspection it can be removed quickly without stopping of the power plant. This eliminates inter granular stress corrosion cracking. 2.8 Biological Corrosion Corrosive conditions can be developed by living microorganisms as a result of their influence on anodic and cathodic reactions. This metabolic activity can directly or indirectly cause deterioration of a metal by the corrosion process. This activity can
1. 2. 3. 4. 5.
Produce a corrosive environment Create electrolytic cells on the metal surface Alter the resistance of surface films Have an influence on the rate of anodic or cathodic reaction Alter the environmental composition Because this form of corrosion gives the appearance of pitting, it is first
necessary to diagnose the presence of bacteria. This is also referred to as microbial corrosion. The term microorganism covers a wide variety of life forms, including bacteria, blue-green cyanobacteria, algae, lichens, fungi, and protozoa. All microorganisms may be involved in the biodeterioration of metals. Pure cultures never occur under natural
56
conditions; rather, mixed cultures prevail. Of the mixed cultures, only a few actually become actively involved in the process of corrosion. The other organisms support the active ones by adjusting the environmental conditions to support their growth. For example, in the case of metal corrosion caused by sulfate-reducing bacteria (SRB), the accompanying organisms remove oxygen and produce simple carbon compounds, such as acetic acid and/or lactic acid, as nutrients for SRB. Bacteria are the smallest living organisms on this planet. Some can only live with and others without oxygen. Some can adapt to changing conditions and live either aerobically or anaerobically. There is a wide diversity with regard to their metabolisms. They are classified as to their source of metabolic energy as given in Table 2: Table - 2 Energy Source and its classification
These six terms may be combined to easily describe the nutritional requirements of a bacterium. For example, if energy is derived from inorganic hydrogen donators and biomass is derived from organic molecules, they are called microtrophs (chemolithoorganotrophs). Microorganisms can directly or indirectly affect the integrity of many materials used in industrial systems. Most metals, including iron, copper, nickel, aluminum, and their alloys, are more or less susceptible to damage. Only titanium and its alloys appear to be generally resistant. [21] Viable microorganisms can be found over a surprisingly wide range of temperature, pressure, salinity, and pH. In the 1950s, pioneering work by Zobell isolated sulfate-reducing bacteria (SRB) that grew at 104C (219F) and pressures of 1000 bar from oil-bearing geological formations deep underground. Microbial communities exist in
57
environments as diverse as subzero snowfields to deep ocean thermal vents. Halophiles evolved to live at extreme salinities turn pink the evaporation pans used to win salt from seawater. Sulfur-oxidizing bacteria create very acidic conditions (pH < 1) by producing sulfuric acid as an end product of their metabolism, while other microorganisms survive the opposite end of the pH scale. Given these examples, it should not be surprising that microorganisms have been implicated in the accelerated corrosion and cracking of a correspondingly wide range of industrial systems. For example, the involvement of thermophilic SRB in the severe intergranular pitting of 304L stainless steel condenser tubes in a geothermal electrical power plant operating at 100C (210F) has been reported. In another example, microbiological activity and chloride concentrated under scale deposits were blamed for the wormhole pitting of carbon steel piping used to transport a slurry of magnesium hydroxide and alumina at pH 10.5. Whatever the environmental conditions, microorganisms need water, a source of energy to drive their metabolism, and nutrients to provide essential building materials (carbon, nitrogen, phosphorus, trace metals, etc.) for cell renewal and growth. An understanding of these factors can sometimes help in failure investigations. Energy may be derived from sunlight through photosynthesis or from chemical reactions. The importance of photosynthetic metabolism is limited in the context of this article to aboveground facilities or submerged structures that receive sunlight. For closed systems and buried facilities, microbial metabolism is based on energy derived from oxidation reduction (redox) reactions. Under aerobic conditions, reduction of oxygen to water complements the metabolic oxidation of organic nutrients to carbon dioxide. Under anaerobic conditions, electron acceptors other than oxygen can be used. Figure 1 illustrates the range of pH and redox potential where anaerobic forms of microbial metabolism tend to be found. Whatever the metabolism, electrochemical reactions catalyzed by enzymes provide energy for cell growth. Many of these reactions are not important under abiotic conditions, because they are kinetically slow in the absence of organisms. By promoting these reactions, microbes produce metabolites and conditions not found under abiotic conditions. In some cases, electrons released by the oxidation of metals are used directly in microbial metabolism. In other cases, it is the chemicals
58
and conditions created by microbial activity that promote MIC. Secondary effects can also be important. These include such things as the biodegradation of lubricants and protective coatings designed to prevent wear or corrosion in an operating system, or the alteration of flow regimes and heat-transfer coefficients due to the biological fouling of metal surfaces. Given the potential impact of MIC on a wide range of industrial operations, it is not surprising that microbiological effects are of significant concern in failure analysis and prevention. Microbially induced corrosion problems afflict waterhandling operations and manufacturing processes in oil and gas production, pipelining, refining, petrochemical synthesis, power production, fermentation, waste water treatment, drinking water supply, pulp and paper making, and other industrial sectors. Microbially induced corrosion is also a concern whenever metals are exposed directly to the environment in applications including marine or buried piping, storage tanks, ships, nuclear waste containers, pilings, marine platforms, and so on. Corrosion Mechanisms Involving SRB. Perhaps the best-known mechanism of MIC involves corrosion cells generated and sustained on steel surfaces by the action of anaerobic SRB. Evidence for direct MIC based on other electron acceptors is limited. Microorganisms can influence the corrosion process by a number of less direct mechanisms. Depolarization Mechanisms. Buildup of hydrogen on the cathodic surface can stifle the corrosion process through cathodic polarization. Microorganisms with hydrogenase enzymes are able to use hydrogen and have been widely cited as accelerating anaerobic corrosion through cathodic depolarization. Even though this concept has been challenged, commercial kits for hydrogenase activity are available for assessing MIC in practical applications. Metabolites, such as organic acids produced by acid-producing bacteria (APB), may alleviate anodic polarization. Organic acids can form soluble chemical complexes with metal ions released by the corrosion process, reducing the buildup of Mn on anodic surfaces. Considerable evidence indicates that bacteria and other organisms frequently initiate or accelerate corrosion of metal- Microorganisms accelerate corrosion by producing hydrogen sulfide or acids, both of which are highly corrosive to iron and steel. Thiobacills thioOxidans, the bacteria which convert sulfides or free sulfur to sulfuric acid,
59
may cause the extremely rapid corrosion of steel waterfront structures in the intertidal zone; but this has not been established by experimental evidence.[22] Experiments were undertaken at the U. S. Naval Civil Engineering Laboratory to ascertain if the presence of microorganisms is necessary for corrosion to occur. It was shown that, in aerated sea water, iron corrodes fairly rapidly whether or not microorganisms are present; but that in sea water from which oxygen is excluded, iron rusts very slowly unless sulfate-reducing bacteria or their metabolic by-product, hydrogen sulfide, is present. To induce rapid anaerobic corrosion, the bacteria must be supplied with carbohydrates or other nutrients. Anaerobic conditions and bacterial nutrients might both be found in the layer of slime that accumulates on the surfaces of structures placed in the ocean. Another experimental finding at the U. S. Naval Civil Engineering Laboratory was that the carbonic anhydrase inhibitor, acetazolamidet is an effective inhibitor of sea water corrosion. 2.9 Selective Leaching When one element of a solid alloy is removed by corrosion, the process is known as selective leaching, dealloying, or dezincification. The most common example is the removal of zinc from brass alloys that contain more than 15% zinc. When the zinc corrodes preferentially, a porous residue of copper and corrosion products remains. The corroded part often retains its original shape and may appear undamaged except for surface tarnish. However, its tensile strength, and particularly its ductility, are seriously reduced. Dezincification of brasses takes place in either localized areas on the metal surface, called plug type, or uniformly over the surface, called layer type. Low-zinc alloys favor plug-type attack while layer-type attack is more prevalent in high-zinc alloys. The nature of the environment seems to have a greater effect in determining the type of attack. Uniform attack takes place in slightly acidic water, low in salt content and at room temperature. Plug-type attack is favored in neutral or alkaline water, high in salt content and above room temperature. Crevice conditions under a deposit of scale or salt tend to aggravate the condition. A plug of dezincified brass may fall out, leaving a hole, whereas water pipe having layer-type dezincification may split open. Conditions that favor selective leaching are:
60
1. 2. 3.
High temperatures Stagnant solutions, especially if acidic Porous inorganic scale formation
Corrective measures that may be taken include: Use of a more resistant alloy. This is the more practical approach. Red brass, with less than 15% zinc, is almost immune. Cupronickels provide a better substitute in severely corrosive atmospheres. 2. 3. 4. Periodic removal of scales and deposits from the inside surfaces of pipelines. Removal of stagnation of corrosives, particularly acidic ones. Use of cathodic protection.
REFERENCES:
[1]. [2]. [3]. [4]. [5]. [6]. [7]. [8]. [9].
P.A. Schweitzer. 2004. Corrosion Resistance Tables, Vols. 14, 5th ed., New York: Marcel Dekker. Crolet, Jean-Louis, Bonis, M.R., Elf Aquitaine, Prediction of the Risks Of CO2 Corrosion in Oil and Gas Wells, Journal Society of Petroleum Engineers, Vol. 6, Number 4, pp 449-453, Nov 1991. S. Nesic, J. Postlethwaite, and S. Olsen, An Electrochemical Model for Prediction of Corrosion of Mild Steel in Aqueous Carbon Dioxide Solutions, NACE International Journal of corrosion, Volume 52, Number 04, April, 1996. Jin Huang et. al. Prediction of Uniform CO2 Corrosion of Mild Steel Under Inert Solid Deposits, NACE International conference on Corrosion 2011, March 13 - 17, 2011 , Houston, Texas. Jiabin Han, David Young, and Srdjan Nei, Characterization of the passive film on mild steel in CO2 environments, 17th international corrosion congress, Paper no. 2511. Jing Li, Dale J. Meier, An AFM study of the properties of passive films on iron surfaces, elsivier Journal of Electroanalytical Chemistry 454 (1998) 5358. V. Maurice, L. H. Klein, P. Marcus, Atomic-scale investigation of the localized corrosion of passivated nickel surfaces, Surface and Interface Analysis, Volume 34, Issue 1, pages 139 143, August 2002. Shinji Fujimoto, and Rock-Hoon Jung, Passive Films Formed on Austenitic Stainless Steels under Humid Atmospheric Environments, ICE transaction. M. J. Correia, M. M. Salta, I. T. E. Fonseca, Corrosion Resistance and Passive Film Characteristics of Austenitic Stainless Steel Alloys in Alkaline Solution, ICE transaction.
61
Amit R Patel, Manoj Kumar [10]. [11]. [12]. [13]. [14]. [15]. [16]. [17]. [18]. [19]. [20]. [21]. [22].
C. S. Wichman, J. R. Scully, Investigation of Intergranular Corrosion Propagation Promoted by Interactions between Sensitized Grain Boundaries using Closely Packed Electrode Arrays. Anees U. Malik, Nadeem A. Siddiqi and Ismaeel N. Andijani, crevice corrosion performance of some commercial stainless steels in arabian gulf seawater, Issued as Technical Report No. SWCC (RDC)-28 in August, 1993 Navid Rashidi, Seyed Alavi-Soltani, Ramazan Asmatulu, Crevice Corrosion Theory, Mechanisms and Prevention Methods, Proceedings of the 3rd Annual GRASP Symposium, Wichita State University, 2007, pp 215-216 R.C. Barik, J.A. Wharton, R.J.K. Wood, K.R. Stokes, Nickel-aluminium bronze pitting corrosion in seawater, Environment and Mitigation [f] Jones, Denny A., Principles and Prevention of Corrosion, 2nd Edition, New Jersey: Prentice Hall, Inc., 1996. Excel programme for calculation of FAC (Flow Assisted Corrosion = Erosion Corrosion) on the basis of the publication of Kastner and Riedle (1986), 65 FAC-Calculation model engels www.hbscc.nl. [e] W. M. M. Huijbregts, Erosion-corrosion of carbon steel in wet steam, Materials Performance October, 1984, pp 39-45. Controlling stress corrosion cracking in aerospace applications, NASA, Marshall space flight center, Document Practice No. PD-ED-1227, pp 1 of 5. Fastener Failures Due to Stress Corrosion Cracking, Daniel H. Herring, The Heat Treat Doctor, President The Herring Group, Inc., Fastener Technology International/August 2010. Hiroyuki Masuda, Stress Corrosion Crack Growth Mechanism on SUS316L Stainless Steel, The Open Corrosion Journal, 2009, 2, 204-210. J. S. POROWSKI, W. J. O'DONNELL, M. L. BADLANI, E. J. HAMPTON, Advanced Methods of Improving Resistance to Stress Corrosion Cracking in BWR Piping Systems, pressure vessel and the Piping conference, Pittsburg, Pennsylvania-June: 19-23. 1988 Thomas R. Jack, NOVA Chemicals Ltd., Biological Corrosion Failures, ASM Handbook Volume 11: Failure Analysis and Prevention (#06072G). Harold P. Vind, Ph. D., and Mary Jane Noonan, biological corrosion at naval shore facilities, technical note n-831, u. s. naval civil engineering laboratory Port Hueneme, California, 20 July 1966
62

Activity - 1 The Final

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Activity - 1 The Final

Uploaded by

Copyright:

Available Formats

Amit R Patel, Manoj Kumar

Submitted to Dr. Harpreet Singh Assistant Professor (SMMEE)

Amit R Patel, Manoj Kumar

INDIAN INSTITUTE OF TECHNOLOGY ROPAR RUPNAGAR-140 001 (PB)

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

. One such work is that due to McCabe

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

[5]. [6]. [7].

[10]. [11]. [12]. [13]. [14]. [15].

[16]. [17]. [18]. [19]. [20].

[22]. [23]. [24]. [25].

Amit R Patel, Manoj Kumar

[43]. [44]. [45]. [46].

[47]. [48]. [49]. [50]. [51]. [52]. [53]. [54].

Amit R Patel, Manoj Kumar

[62]. [63]. [64]. [65].

[66]. [67]. [68]. [69]. [70].

[76]. [77]. [78]. [79]. [80]. [81].

Amit R Patel, Manoj Kumar

[85]. [86]. [87]. [88]. [89]. [90].

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Fig 2. Scheme for XRD with larger incidence angle

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar

Amit R Patel, Manoj Kumar