Coote eo eee eee BRC-CORP 37-74-F 121 Section 25. HYDROGEN BLISTERING Peftuttton vf che Problew Blistering is a form of hydrogen damage which arises from penetration of the maral hy hydrogen generated in a rarrneton reaction at the eurface Hydrogen blistering occurs when steel is exposed to certain aqueous corrosive media in which atomic hydrogen is developed as a result of the corrosion. This phenomenon should not be confused with the other types of hydrogen damage (see Section 27 on Hydrogen Embrittlement .and Section 24 on Hydrogen Attack). This atomic hydrogen permeates the steel and collects in isconcinuities such as inclusion stringers, voids, or rifts, and transforms to molecular hydrogen. When a sufficient amount has collected, pressures are created of sufficient magnitude to either raise a blister on the steel surface or to crack it internally. Lover quality steels having many inclusion stringere are more prone to develop blisters than high quality steels. Di ion of the Problem Theory asserts that during corrosion, hydrogen is generated in atomic form, most of which combines to molecular hydrogen on the metal surface Where it is discharged, The recombination step 1s normally fast, but in the presence of specific poisons (H2S is one), it is very much retarded. The surface concentration of atomic hydrogen thus provides a driving force for diffusion of hydrogen into the metal. Metal structures, being iuperfect, contain mauy microscopic voids or cavities, and even macroscopic laminations or discontinuities, resulting from metallurgical processing. Atomic hydrogen arriving at a defect within the metal i able to recombine to molecular hydrogen in the void spac Exceedingly high pressures of hydrogen are able to build up within these cavities. This imposes severe stress on the surrounding metal which can relax only by plastic yielding, propagation of the lamination laterally, or by rupturing to the surface. Plastic flow from the pressure of molecular hydrogen is the first stage Lu the developueut of @ biieter, The wetel susounding ile vold (in= clusion) can only withstand a small degree of plastic strain without cracking. ‘The amount of strain to fracture normally would be fairly large, but in the Presence of the hydrogen it is markedly reduced (by the hydrogen embrittlenent effect discussed in Section 27). When the maximum local plastic strain is reached, a disk shaped tensile crack develops which must grow outward to increase its size. The actual direction taken by the growing crack in a eoft eteel is one where it meets the least constraint by the surrounding metal. Two possibilities are illustrated in Figure 25-1 ‘The case (b) iu Figure 25-1 offers the least constraint owing co che Presence of the free surface in the vicinity of the crack nucleus. Thus, a crack which is small in size compared to the distance from the free surface may grow tn any Alvertion, hut one located close te the free eurface tendo te develop into a blister, As the flux of hydrogen into the crack continues, the size of the blister increases. At any stage the crack may choose one of two modes of further propagation illustrated by Figure 25-2,12 BRC-CORP 37-74.F Corrosion Environment Corrosion Environment Case of Greatest Constraint b. Case of Least Constraint 10 Opening a Crack to Opening a Crack Figure 25-1 Pomible Directions of Primary Propogation for a Hydrogen Blister Crack in a Soft Steel 2. Crack Growth — Mode f 1B. Clack Growth = Mode IL Figure 25.2 Pomible Modes of Secondary Propegation of Hydrogen Blister Cracks 5 ‘Venting of Hydrogen by Mode II Crack Proposation Se < . Same Area After Metal Removal by Corrosion Figure 25.3 Final Stages of Hydrogen Blister Crack Growth Possibilities % Po ccvccccccscccesBRC-CORP 37-74.F 123 As long as the crack can continue to propagate in Mode I, shown in Figure 25-2, and accomodate the continuous flux of hydrogen, the size of the blister continues to increase, However, the moment propagation by Mode II, shown in Figure 25-2, begina, the end of the fracture process approaches. If & portion of the Mode II crack reaches the surface, venting of the hydrogen terminates the process. Hovever, the corrosion reaction continues, so that after enme perind af time, = Afar ehaped place of ataal unnld he romavad, Jeaving a ring shaped pit as illustrated in Figure 25-3. For each material there 1s some critical ratio of length of crack (L) to its depth (D) below the surface, L/D, corresponding to the start of Mode II crack propagation (this ratio may vary with the depth below the surface). Thus, defects close to the surface tend to develop into blisters more readily than the same defects deep in the material, but these wore easily formed blisters are much smaller in size, A harder steel is more likely to favor lateral growth Mode I and larger blisters. However, the phenomenon is complicated by the fact that erack propagation 1e influenced by the local ductility, which In turn is influenced by the presence of hydrogen. Also, the distribution of defects usually is not uniform, either in type or in depth below the surface Figures 25-4 and 25-5 illustrate various types of crack propagation. Methods of Checking for the Probl The reactions which cause hydrogen to permeate steel are dependent upon many chemical factors in the environment. The complexity of the solutions involved and the difficulties of accurate chemical analysis and interpretation make it diffieult, 4£ nct dmposetble, to predict with certainty whather hydragen blistering will occur. A simple hydrogen probe has been developed for installation in operating or test equipment, to detect those environments conducive to hydrogen damage, The penetration of the outer steel tube by hydrogen cat the pressure to increase inside the probe which is subsequently measured with an attached pressure gauge. Thus, changes in the corrosive environment, which may influence the rate of hydrogen penetration, may be detected and studied. Another simple device which has proved useful is a plain sheet steel can, painted on the outside with rubber base paint. If a corrosive aqueous eolution conducive te hydrogen attack de placed dn euch a painted can, emall hydrogen blisters form under the paint film. A semi-quantative comparison can be made from observing the time for blisters to form in the paint film and the frequency of the blisters formed. There are also new, electrochemical, laboratory techniques which have been used to study hydrogen blistering. Inspection methods normally used to detect the presence of blisters in- clude ultrasonics and visual examination. The appearance of a pressure vessel wall containing hydrogen blisters is shown in Figure 25-6. Methods of Eliminating the Problem Blistering damage is permanent and irreversible. At present, it can rarely be predicted before it occurs, Efforts should be made to control key factors in the mechanism of blistering to prevent its occurence, In sour aqueous environments, the factors tending to produce blistering are: 1) a corrosion reaction giving rise to hydrogen evolution, 2) the presence of a Cee erro cen sce ge1 BRC-CORP 37-74.F Potoon, such as lydivgen sulfide, cyaniaes, arsenates, arsine, and carbon disulfide, and 3) the presence within the steel of inclusions or defects which jct_ as sites for hydrogen accumulation, Elimination of any of these factors helps to prevent blistering. Chemical inhibition has been successfully applied to stress corrosion cracking and blistering problems in sour aqueoua environments. Determination of the effectiveness of an inhibitor can be investigated experimentally in the laboratory for any particular corrosion system. This is done by correlating the rate of hydrogen transmission through a thin steel menbrane with the rate of hydrogen absorption which will cause cracking in the presence and in the absence of the inhibitor. Inhibitors appear to act in the formation of a film by preferential surface adsorption, or formation of a corrosion product which dloplscee the podeone preseat. Use of cleaner steels can reduce the tendency toward blistering. Fully killed steels are preferred. Rimming ateele and ocmi-killed or partially deoxidixed steels are more prone to laminations and to blistering. Steels containing continuous bands or stringers should be avoided. Ultrasonic inspection of plates is recomended, prior to fabrication into a vessel. Another approach is to use more resistant alloys, e.g., Type 304 stainless steel, clad over the carbon steel plate. Sonetines it may be possible to effect proc corrosion and thus reduce the tendency tovard blistering. changes which influence A commonly employed method of controlling (but not eliminating) the blistering problem is to drill into the blisters, thereby relieving internal Pressure and arresting their growth. Pitfalls If attempts are made to prevent hydrogen blistering by employing chemical inhibitors, for example, then all of the pitfalls that need to be considered in the application of an inhibitor, such as improper distribution, need to be recognized. Before hydrogen blisters are drilled, the specific service conditions should be evaluated to determine 1f nthar probleme, ouch aa concentrativ cell corrosion (see Section 10) beneath the blisters, could arise. e e e e e e e e e e e e e e e PocccccccccscccceseBRC-CORP 37-74-F 125 e e e e e e e e e e e e e e @ oe ee 254 (Cross Section Through Hydrogen Blisters Showing Various Types of Crack Propogation Magnification: 1X. eee128 BRC-CORP 37:74.F Figure 255 Cross Section Through # Hydrogen Blister Showing One of Several Different Possible Types of Crack Propogation Magnification: 1X. Pisvocccvecesccese eovcPrcccccecccsoccceBRC-CORP 37-74.F Ww 7 Figure 26-6 View of Pressure Vessel Wall Showing Hydrogen Blisters Magnification: 4X