QUESTION:

I am handling high purity-water and keep getting a multi-colored

stain on my valves and other equipment. What is this, and how can I
prevent it?
ANSWER:
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.