Intergranular Corrosion
Intergranular
corrosion
Intergranular corrosion is a form
of attack in which corrosion proceeds preferentially along grain
boundaries with the result that relatively little total corrosion
can cause serious loss of strength. As a possible problem with
brasses in service it is restricted to aluminium brass of
abnormally high phosphorus content in service in
sulphide-polluted water. Provided that the phosphorus impurity
level is below 0.015% no trouble is experienced. No maximum for
phosphorus is given in standards for aluminium brass but
commercial material is normally well below the 0.015% level.
Pitting
corrosion
Pitting corrosion, which some
years ago was a rather common cause of failure of copper water
pipes in some districts, is not a serious problem with brasses.
Alpha brasses inhibited against dezincification can however
suffer pitting under some circumstances. As in copper, the
pitting produces very localised attack often in approximately
hemispherical form beneath a small adherent mound of green
corrosion product. If this mound is carefully removed, crystals
of red cuprous oxide can usually be seen in the cavity. Service
in slow-flowing sulphide-polluted sea water is most likely to
produce pitting in aluminium brass but this alloy sometimes
develops pitting corrosion in fresh water service. The number of
examples of this that have been reported are too few to establish
the range of water composition and service conditions that are
necessary to cause it and it is therefore advisable to use
admiralty brass instead of aluminium brass for all fresh waters.
Galvanic
corrosion
When different metals or alloys
are in contact with one another in an electrolyte (sea water,
fresh water, rain, dew, condensation, etc.) they affect one
anothers resistance to corrosion. Usually one - the more
"noble" - will cause some degree of accelerated attack
(galvanic corrosion) on the other and will itself receive a
corresponding degree of protection. Figure 8 shows lists a number
of common metals and alloys in their order of nobility in sea
water and may be used to give some indication of the possible
galvanic corrosion effects of coupling brasses to other metals.
In general the further the other metal is from the brasses in the
electrochemical series the greater the effect will be.
Fig 8: Galvanic series for common
metals and alloys in sea water

The relative positions of the
different metals indicated in Table 29 are different in a
different environment or even under prolonged stagnant conditions
in sea water, where the passive films on stainless steels could
break down and sulphide films could form on the copper alloys.
The series shown can however be taken as representing the
majority of service conditions.
Among the brasses themselves there
are small differences of electro-chemical potential, those of
highest copper content being more noble. In particular, the alpha
brasses are somewhat more noble than the beta brasses; this shows
itself in the tendency for the beta phase in alpha-beta brasses
to suffer preferential attack but the difference between the two
is not great.
Relative area effects
The extent to which additional
(galvanic) corrosion takes place on brass coupled to a more noble
metal depends not only upon the difference between them in the
galvanic series but also upon their relative areas, exposed to
the sea water or other electrolyte, sufficiently close to one
another for significant corrosion currents to flow through the
electrolyte between them. If the effective area of more noble
(cathodic) metal greatly exceeds that of the brass, galvanic
attack on the brass may be severe but if the area of cathodic
metal is smaller than that of the brass the effect will be
negligible. For example stainless steel or Monel trim in a brass
valve is quite acceptable but brass bolts on a stainless steel
structure would certainly not be.
In a water system with brass
valves and fittings and copper or stainless steel pipes, the total
area of the cathodic metal greatly exceeds that of the brass but,
because of the limiting influence of the electrical resistance of
the water, significant corrosion currents flow only between the
brass and the copper or stainless steel very close to it.
Consequently the effective areas of brass and copper or
stainless steel are not very different and the extent of any
galvanic action between them is small. A brass fitting in a
copper or stainless steel tank, on the other hand, would come
under the influence of a much larger area of cathodic metal and
severe galvanic attack would be expected.
Similarly, naval brass tubeplates
can be used with copper-nickel tubes in sea water cooled
condensers because the effective cathodic area of the tubes does
not extend more than a few tube diameters from the tube plate
surface. If, however, the copper nickel tubes are replaced by
titanium, which is much further from the brasses in the galvanic
series, deep attack on the tubesheet will occur.
Beneficial effects
Just as coupling to a metal above
it in the galvanic series will generally cause additional
corrosion of brass, coupling to a metal below it can reduce
attack. The prime example of this is the use of galvanic anodes
for cathodic protection. A less obvious example is the successful
use of high tensile brass spindles in cast iron valves. In
gunmetal valves the galvanic action between an HTB spindle and
the valve body causes accelerated dezincification of the spindle,
but in a cast iron valve the galvanic action reduces the
corrosion of the spindle and this combination is generally
satisfactory in service.
Prevention by insulating or
coating
It is possible, but often wrongly
assumed to be easy, to prevent galvanic corrosion by electrically
insulating the more noble and less noble metals from one another.
The difficulty arises because the metallic connection (more
accurately, the electronically-conducting connection) between the
two members of the galvanic couple does not have to be by direct
contact between them. The possibility of galvanically accelerated
dezincification of an alpha-beta brass valve bolted to a flange
on a large copper vessel is not eliminated, or even reduced,
simply by fitting an insulating gasket between the two, since
they will remain connected through the bolts. It is necessary
also to fit insulating washers under the bolt heads and
insulating bushes in the holes drilled in the flange of the
valve. Even then there remains the possibility of the valve and
vessel being in electronically-conducting connection with one
another though the pipework and supporting steel work. Whenever
steps are taken to insulate the two members of a potential
galvanic couple from one another it is important to check, before
they are brought in contact with the water or other electrolyte
for which they are to be used, that the desired absence of
electrical continuity between them has been achieved.
As an alternative to insulating
the two members of a couple from one another, one or both of them
can be isolated from the electrolyte by coating or painting. In
some cases the anodic member needs to be painted or coated to
protect it from corrosion that would take place even in the
absence of the galvanic effect - for example ferrous water boxes
of condensers with brass tubes and tubeplates. In principle,
however, galvanic corrosion is more safely prevented by painting
or coating the cathodic member. This follows from the relative
area effect. If a coating applied to the anodic member is only
90% complete, the total amount of galvanic corrosion will remain
the same but it will all be concentrated on the exposed 10%, i.e.
the situation will actually have been made worse. If, on the
other hand, a coating applied to the cathodic member is 90%
complete the total amount of galvanic corrosion will be reduced
by 90%.
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