Multi-colored Stain on Valves

A: You are describing a phenomenon called "rouging," a term that pertains to the multi-colored stain you are seeing. Rouging is a problem that is seen primarily in high-purity water applications or steam. Though more commonly associated with the pharmaceutical and electronics industries, it can occur most anywhere. At the lower temperatures rouge is red or yellowish in appearance, but in high-temperature steam it will be dark gray or black. The FDA has not made any formal opinion about rouging, but pharmaceutical companies are concerned about contamination of their products so they go to great lengths to prevent it and to clean their systems when it occurs-incurring undesired downtime and expense.

The mechanism of rouging is still not fully understood and as a result there are some myths and misconceptions about what it is and how to prevent it. Essentially, rouge is a form of rust, i.e., iron oxide, but different than the heavy rust seen when stainless steel is not cleaned properly after heat treatment or welding. While normal rust is a result of improper cleaning during manufacture, rouge is a much thinner layer that occurs when perfectly cleaned stainless steel reacts with high-purity water environments. Rouge seems to be more prevalent at temperatures in excess or 60° C.

We know that stainless steels achieve their corrosion resistance by developing a very thin microscopic chromium oxide layer. The general consensus about rouging is that certain services, such as high purity water with very low oxygen content, dissolve this protective layer and allow the stainless steel to resume corroding. This corrosion is then responsible for the staining we call rouging. These stains have been analyzed as being various types of iron oxide as well as containing traces of chromium and nickel.

While mainly an aesthetics problem, most people still want to prevent rouge in their systems. One commonly held belief is that the ferrite phase in cast stainless steels or welds causes rouging, and purchasers of valves and other equipment frequently impose strict limits on the ferrite content of cast stainless steels. Since wrought stainless steels with no ferrite also experience rouging, it doesn't appear that ferrite is the culprit.

A study conducted by AvestaPolarit1, found that the water's gas content and a metal's surface finish were influential for rouging. Basically, water with high oxygen and low carbon dioxide content was less likely to cause rouging as were electro-polished surfaces of the metal components. This study also found no significant correlation for the different alloy grades, including duplex stainless steels with their high ferrite content.

Since most people find rouge objectionable in their systems, much attention has been given to its removal. Various acids and chelates are used to clean systems of rouge, but these can leave behind their own contaminates or films. In addition, if acid exposure is not controlled closely, the acid can etch the metal surfaces thus destroying the expensive electro-polished surfaces. Therefore, the most effective way to prevent rouge is by somehow introducing sufficient oxygen to the system, which helps maintain the protective chromium oxide layer.