SUBJECT: Corrossion problems associated with stainless steel 4-1 The rotating equipment business uses a great deal

of 300 series stainless steel, and as a result we often experience several types of corrosion:

General corrosion Galvanic corrosion Pitting Inter granular corrosion Chloride stress corrosion cracking Erosion- corrosion Fretting Concentrated cell or crevice corrosion Selective leaching Micro organisms

At the end of this aticle is a page titled, "The Galvanic Series Of Metals and alloys". I'll be referring to this chart during our discussion. The basic resistance of stainless steel occurs because of its ability to form a protective coating on the metal surface. This coating is a "passive" film which resists further "oxidation" or rusting. The formation of this film is instantaneous in an oxidizing atmosphere such as air, water, or other fluids that contain oxygen. Once the layer has formed, we say that the metal has become "passivated" and the oxidation or "rusting" rate will slow down to less than 0.002" per year (0,05 mm. per year). Unlike aluminum or silver this passive film is invisible in stainless steel. It's created when oxygen combines with the chrome in the stainless to form chrome oxide which is more commonly called "ceramic". This protective oxide or ceramic coating is common to most corrosion resistant materials. Halogen salts, especially chlorides easily penetrate this passive film and will allow corrosive attack to occur. The halogens are easy to recognize because they end in the letters "ine". Listed in order of their activity they are:

fluorine chlorine bromine iodine astatine (very unstable.)

These are the same chemicals that will penetrate Teflon and cause trouble with Teflon coated or encapsulated o-rings and/ or similar coated materials. Chlorides are one of the most common elements in nature and if that isn't bad enough, they're also soluble, active ions; the basis for good electrolytes, the best conditions for corrosion or chemical attack.

GENERAL OR OVERALL CORROSION. This type of corrosion occurs when there is an overall breakdown of the passive film formed on the stainless steel. It's the easiest to recognize as the entire surface of the metal shows a uniform "sponge like" appearance. The rate of attack is affected by the fluid concentration, temperature, fluid velocity and stress in the metal parts subject to attack. As a general rule the rate of attack will double with an eighteen degree Fahrenheit rise in temperature (10 C.) of either the product or the metal part. If the rotating portion of the seal is rubbing against some stationary component, such as a protruding gasket or fitting, the protective oxide layer will be polished off and the heat generated will increase the corrosion as noted above. This explains why corrosion is often limited to only one portion of the mechanical seal, metal casing. There are many good publications available to help you select the proper metal for any given mechanical seal application. As a general rule, if the wetted parts of the equipment are manufactured from iron, steel, stainless steel or bronze, and they are showing no signs of corrosion, grade 316 stainless is acceptable as long as you do not use stainless steel springs. (see chloride stress corrosion below) GALVANIC CORROSION If you put two dissimilar metals, or alloys in a common electrolyte, and connect them with a voltmeter, it will show an electric current flowing between the two. (This is how the battery in your automobile works). When the current flows, material will be removed from one of the metals or alloys ( the ANODIC one) and dissolve into the electrolyte. The other metal (the CATHODIC one) will be protected. Move down to the end of this aticle and look at the Galvanic Series chart The further apart the materials are located on this chart, the more likely that the one on the ANODIC end will corrode if they are both immersed in any fluid considered to be an electrolyte. Salt water, is one of the best! Example #1. A ship has lots of bronze fittings and a steel hull. Note that steel is located seven lines from the ANODIC end, and bronze is listed at twenty seven rows from the same end. Sea water is a perfect electrolyte, so the bronze fittings would immediately attack the steel hull unless something could be done to either protect the steel ,or give the bronze something else to attack. The classic way to solve this problem is to attach sacrificial zinc pieces to the hull and let the bronze go after them. Again, looking at the chart, you'll note that zinc is found on line three from the top of the chart. In other words the zinc is further away from the bronze than the iron, so the galvanic action takes place between the zinc and the bronze, rather than between the steel and the bronze. Zinc paint is used for the same reason.

Example #2 Nickel base tungsten carbide contains active nickel. When this face material is used in dual seal applications it is common to circulate water or antifreeze between the seals (as mentioned in the beginning of this paper, water can be an excellent electrolyte because of the addition of chlorine and fluorine). You'll note that active nickel is located twenty one rows from the top of the chart. Passivated 316 stainless steel is positioned nine rows from the bottom. This means that the stainless steel can attack the nickel in the tungsten carbide causing it to corrode. The rate at which corrosion takes place is determined by :

The distance separating the metals on the galvanic series chart The temperature and concentration of the electrolyte. The higher the temperature, the faster it happens. Any stray electrical currents in the electrolyte will increase the corrosion also. The relative size of the metal pieces. A large cross section piece will not be affected as much as a smaller one. Many metal seal components are isolated from each other by the use of rubber o-rings or similar materials and designs. Shaft movement that causes fretting of the 316 stainless steel rubs off the passivated layer and exposes the active stainless to the electrolyte until the metal part becomes passivated once more. This is one of the reasons we see corrosion under o-rings, and Teflon wedges. In the following paragraph I'll be discussing another cause of corrosion under rubber parts.

PITTING This is an accelerated form of chemical attack in which the rate of corrosion is greater in some areas than others. It occurs when the corrosive environment penetrates the passivated film in only a few areas as opposed to the overall surface. As stated earlier, halogens will penetrate passivated stainless steel. Referring to the galvanic chart you'll note that passivated 316 stainless steel is located nine lines from the bottom and active 316 stainless steel is located thirteen lines from the top. Pit type corrosion is therefore simple galvanic corrosion, occuring as the small active area is being attacked by the large passivated area. This difference in relative areas accelerates the corrosion, causing the pits to penetrate deeper. The electrolyte fills the pits and prevents the oxygen from passivating the active metal so the problem gets even worse. This type of corrosion is often called "Concentrated cell corrosion". You'll also see it under rubber parts that keep oxygen away from the active metal parts, retarding the metal's ability to form the passivated layer. INTERGRANULAR CORROSION All austenitic stainless steels (the 300 series, the types that "work harden") contain a small amount of carbon in solution in the austenite. Carbon is precipitated out at the grain boundaries, of the steel, in the temperature range of 1050 F. (565 C) to 1600 F. (870 C.). This is a typical temperature range during the welding of stainless steel.

This carbon combines with the chrome in the stainless steel to form chromium carbide, starving the adjacent areas of the chrome they need for corrosion protection. In the presence of some strong corrosives an electrochemical action is initiated between the chrome rich and chrome poor areas with the areas low in chrome becoming attacked. The grain boundaries are then dissolved and become non existent. There are three ways to combat this:

Anneal the stainless after it has been heated in this sensitive range. This means bringing it up to the proper annealing temperature and then quickly cooling it down through the sensitive temperature range to prevent the carbides from forming. When possible use low carbon content stainless if you intend to do any welding on it. A carbon content of less than 0.3% will not precipitate into a continuous film of chrome carbide at the grain boundaries. 316L is as good example of a low carbon stainless steel. Alloy the metal with a strong carbide former. The best is columbium, but sometimes titanium is used. The carbon will now form columbium carbide rather than going after the chrome to form chrome carbide. The material is now said to be "stabilized"

CHLORIDE STRESS CORROSION. If the metal piece is under tensile stress, either because of operation or residual stress left during manufacture, the pits mentioned in a previous paragraph will deepen even more. Since the piece is under tensile stress cracking will occur in the stressed piece. Usually there will be more than one crack present causing the pattern to resemble a spider's web. Chloride stress cracking is a serious problem in industry and not often recognized by the people involved. In the seal business it is a serious problem if you use stainless steel springs or stainless steel bellows in your seals. This is the main reason that Hastelloy C is recommended for spring material. Here are some additional thoughts about chloride stress cracking that you'll want to consider:

Chlorides are the big problem when using the 300 series grades of stainless steel. The 300 series is the one most commonly used in the process industry because of its good corrosion resistant proprieties. Outside of water, chloride is the most common chemical found in nature and remember that the most common water treatment is the addition of chlorine. Beware of insulating, or painting stainless steel pipe. Most insulation contains chlorides and piping is frequently under tensile stress. The worst condition would be insulated, steam traced, stainless steel piping.

If it's necessary to insulate stainless steel pipe, a special chloride free insulation can be purchased, or the pipe can be coated with a protective film prior to insulating.

Stress cracking can be minimized by annealing the metal, after manufacture, to remove residual manufactured stresses. Never replace a carbon steel bolt with a stainless steel one unless you're sure there are no chlorides present. Bolts can be under severe tensile stress. No one knows the threshold values for stress cracking to occur. We only know that you need tensile stress, chlorides, temperature and the 300 series of stainless steel. We do not know how much chloride, stress or temperature.

Until I figured out what was happening I had trouble breaking stainless steel fishing hooks in the warm water where I live in Florida. Many cleaning solutions and solvents contain chlorinated hydrocarbons. Be careful using them on or near stainless steel. Sodium hypochlorite, chlorethene. methylene chloride and trichlorethane are just a few in common use. The most common cleaner used with dye checking material is trichloroethane, explaining the reason we sometimes experience cracks after we weld stainless steel and dye check it to inspect the quality of the weld.

EROSION CORROSION This is an accelerated attack resulting from the combination of mechanical and chemical wear. The liquid velocities in some pumps prevents the protective oxide passive layer from forming on the metal surface. The suspended solids also remove some of the passivated layer increasing the galvanic action. You see this type of corrosion very frequently at the eye of the pump impeller. FRETTING CORROSION This type of corrosion is easily seen on the pump shaft or sleeve. You'll see the damage on the shaft under:

The grease or lip seal that is supposed to protect the bearings. The packing used to seal the fluid. The dynamic Teflon or elastomer used in most original equipment seals. The vibration damper used in rotating metal bellows seals. The rubber boot used in low cost seals, if it did not attach to the shaft properly.

As mentioned earlier, 300 series stainless steel passivates its self by forming a protective chrome oxide layer when ever it is exposed to free oxygen. This oxide layer is very hard and when it imbeds into a soft elastomer it will cut and damage the shaft or sleeve rubbing against it. The mechanism works like this:

Oxygen passivates the active stainless steel forming a protective ceramic layer. The seal or packing removes the oxide layer as the shaft or sleeve rubs against it. The ceramic passivated layer sticks into the soft elastomer turning it into a "grinding surface". The oxide reforms when the active metal is exposed and the process starts all over again. A visible groove is cut into the shaft, or sleeve that will cause seal leakage and "hang up".

CONCENTRATED CELL OR CREVICE CORROSION This corrosion occurs any time liquid flow is kept away from the attacked surface. It is common between nut and bolt surfaces, under O-rings and gaskets, and between the clamps and stainless steel shafts we find in many split seal applications. Salt water applications are the most severe problem because of the salt water low PH (8.0&endash;9.0) and its high chloride content. Here is the mechanism:

Chlorides pit the passivated stainless steel surface. The low PH salt water attacks the active layer that is exposed Because of the lack of fluid flow over the attacked surface, oxygen is not available to passivate the stainless steel. Corrosion continues unhampered under the rubber and tight fitting clamp. The inside of the o-ring groove experiences the same corrosion as the shaft or sleeve.

SELECTIVE LEACHING The process fluid selectively removes elements from the piping or any other part that might be exposed to the liquid flow. The mechanism is:

Metals are removed from the liquid during a de-ionization or de-mineralizing process. The liquid tries to replace the missing elements as it flows through the system. The un-dissolved metals often coat them selves on the mechanical seal faces or the sliding components and cause a premature seal failure. Heat accelerates the process.

MICRO ORGANISMS These organisms are commonly used in sewage treatment, oil spills and other cleaning processes. Although there are many different uses for these "bugs", one common one is for them to eat the carbon you find in waste and other hydrocarbons, and convert it to carbon dioxide. The "bugs" fall into three categories:

Aerobic, the kind that need oxygen. Anaerobic, the kind that do not need oxygen. Facultative, the type that goes both ways.

If the protective oxide layer is removed from stainless steel because of rubbing or damage, the "bugs" can penetrate through the damaged area and attack the carbon in the metal. Once in, the attack can continue on in a manner similar to that which happens when rust starts to spread under the paint on an automobile.

The Hendrix Group Reporter

February 1, 2004 (Vol. XIII No. 1)

Chloride Stress Corrosion Cracking of Types AISI 304SS and 316SS

We have had inquiries regarding the relative resistance of types 304SS and 316SS to chloride stress corrosion cracking (Cl SCC). Due to the increased resistance of type 316SS to pitting corrosion, as compared with 304SS, some may think that 316SS is also a useful upgrade to resist chloride SCC when 304SS fails. We do not recommend 316SS as an upgrade to 304SS when environmental conditions have caused failure of 304SS. First, a brief introduction to chloride stress corrosion cracking of the austenitic stainless steels. Stress - corrosion cracking is a generic term describing the initiation and propagation of cracks in a metal or alloy under the combined action of tensile stresses (applied and/or residual) and a corrosive environment. Temperature has a very important influence on the chloride cracking of austenitic stainless steels. Experience has shown that cracking does not occur at room temperature. Chloride cracking does occur at temperatures above ambient, generally at temperatures above 60 C (140 F). As the temperature increases above this limit, the time to fracture decreases, other factors being constant. Normally, chloride cracking is transgranular; however, they can crack intergranularly, if sensitized. Factors that influence the rate and severity of cracking include chloride content, oxygen content, temperature, stress level, and pH value of an aqueous solution. It has been established that oxygen is required for chloride cracking to occur. The severity of cracking increases with temperature. The stresses required to produce cracking can be assumed to be always present. Residual stresses from forming, bending, or joining operations are sufficient for cracks to form. Thermal stress relief treatments at 870 C (1600 F) can effectively prevent cracking if done correctly and without the necessity of subsequent cold working (to correct distortion, for example).

In alkaline solutions, the likelihood of chloride SCC is greatly reduced. Consequently, austenitic stainless steels are frequently used for equipment exposed to amine

solutions in gas-treating and sulfur recovery units. A survey of plant experiences has shown no reported instances of cracking despite the fact that chloride contents as high as 1000 ppm were measured in the circulating amine solution. In theory, one would need only a single chloride ion in water, with sufficient oxygen and residual stresses present, to cause cracking . In practice, however, the permissible limits on chloride ion content are higher. In researching the relative susceptibility of 304SS and 316SS to chloride SCC, it becomes clear that results from different tests sometimes contradict one another. For instance, Figure 1, to the left, suggests that 316SS exhibits greater resistance to chloride SCC in the 42% boiling MgCl 2 test. One reason cited for the perceived increased resistance of 316SS to chloride SCC vs. 304SS is its demonstrated better resistance to pitting corrosion. There is some controversy whether chloride SCC cracks typically initiate from the bottom of pits. It has been our experience that detectable pitting is not required for chloride SCC to occur. Our experience also suggests that any laboratory-based results showing a difference in the decreased susceptibility of 316SS vs. 304SS cannot be safely be transferred to field conditions. This opinion is supported by the following sources:

The Sandvik Handbook of Stainless Steels shows the results of testing different alloys in oxygen bearing neutral chloride solutions (Figure 2). The figure shows no difference in the performance between 304SS and 316SS. Testing was done using constant load tests in an autoclave at different chloride contents and temperatures. The sources states "This method gives very reliable results and is often used as a guideline when material selection is made." Volume 13, Corrosion of the ASM Handbook, 9 th Ed., in a paragraph discussing stress corrosion cracking states that "all austenitic stainless steels, especially AISI types 304SS and 316SS, are susceptible to some degree."

MTI manual No. 1, Guidelines for Control of Stress Corrosion Cracking of Nickel-Bearing Stainless Steels and Nickel-Base Alloys, in discussing the 300-series stainless steels, states that with respect to 304SS: "Molybdenum varying variants having greater general corrosion resistance in certain environments (although usually no more resistant to SCC) are Types 316and 316L" Corrosion/99, Paper No. 385, Experience Survey of Chloride Resistant Alloys in Process Plants, cites, " As reported elsewhere, criterion curves of 300's SS for SCC occurrence in T CL diagrams were proposed for heat exchanger cooling water systems. In the present study, such a tendency was not found. SCC occurrences were widely scattered in T Cl- diagrams for both 304SS and 316 SS and no significant difference between the two materials was observed ." In summary, we caution the industrial community when considering an upgrade alloy to combat chloride SCC. As we have previously stated in private communications to a client, " The references share the opinion of this writer in that upgrading to 316SS when a 304SS component has failed due to chloride SCC would invite the real risk of additional, similar failures."

Chloride Stress Corrosion Cracking

(Chloride SCC)
What is Chloride Stress Corrosion Cracking? Chloride Stress Corrosion Cracking creates small cracks in metal. Especially SS316 is sensitive for this type of corrosion. It is a slow process, which finally will end with a line break. This has occurred a few times unfortunately at NAM production facilities, e.g. with Instrument Impulse Lines (SS316 Tubing).

Picture of Chloride Stress Corrosion Cracking

Above is a picture (100 x enlarged) of Chloride SCC in a 316L heat exchanger tube, caused by 400 ppm Chloride and 175 C process temperature. What creates Chloride SCC? Chloride Stress Corrosion Cracking is created under the following circumstances:

Stress in the metal Oxygen [ppb] Chloride [ppm] - See diagram below Above a certain temperature: SS316 at temperatures > 50 C Duplex at temperatures > 150 C Inc825 at temperatures > 250 C

Graphical representation of limits for Chloride Stress Corrosion Cracking

How to avoid Chloride SCC? Firstly, try to avoid that temperatures are exceeding certain limits. Due to the wrong selection of Process Heat Tracing, to be installed on Instrument Impulse Lines, temperatures above 50 C can occur during warm weather. When possible, dimensioning of heat tracing should be such that this can not occur. Vendors of heat tracing can calculate the generated temperatures at various ambient temperatures. When Incoloy 825 tubing is used for Instrument Impulse Lines it is almost impossible that Chloride Stress Corrosion Cracking can occur, because at NAM's Production Facilities there are no process temperatures above 250 C. The price difference between Inc825 and SS316 is negligible.