Trivalent Passivation Systems PDF
Trivalent Passivation Systems PDF
Trivalent Passivation Systems PDF
Introduction
Zinc and zinc alloy plated coatings are applied to fasteners in Figure 1 - Zinc and passivate layers
order to give sacrificial corrosion protection to the base metal.
However, these sacrificial coatings are very susceptible to
corrosion themselves particularly in conditions of high humidity.
Corrosion products formed on zinc type deposits are generally Passivate layer
referred to as white rust. Prevention of white rust is usually
achieved by application of a conversion coating, traditionally based
on hexavalent chromium compounds. These treatments convert
the metal surface into a complex mixture of chromium (including
hexavalent) compounds giving excellent corrosion resistance. Zinc layer
Hexavalent chromium compounds, however, have long
been recognised as carcinogenic. This, coupled with the need
to increase the recyclability of vehicles (ELV Directive) and
consumer electronics (RoHS) led to the adoption of trivalent
based passivation systems in the middle of the last decade, but
the story isnt yet finished as today new regulations, including How passivates protect the zinc layer
REACH (SVHC), are raising questions which may be answered Zinc is a reactive metal, which gets oxidised (corroded) in
by new developments in passivation technology. the presence of humidity and oxygen. Unlike nickel or stainless
steels, the formed zinc oxide is a soft, voluminous and porous
Why pasivate? corrosion product, which does not prevent further corrosion
The primary advantages of hexavalent systems included ease of through the zinc layer (see Figure 2). Therefore, the zinc metal
use, low cost, ability to passivate various deposits (including zinc needs protection by chemically formed mixed metal oxide films.
alloys) and colours. Draw backs consist of factors such as poor The passivate films are hardly soluble in water or water based
application in the supply chain, no advancements to improve corrosion salt solutions used as anti-freezing agents, thus provide a tough
resistance and extremely poor resistance to thermal shock. barrier coating.
Conversely trivalent passivates, which offer at least the same
resistance to white corrosion, have exceptional thermal shock Figure 2 - The stages of zinc corrosion
resistance, a traceable supply line (www.zinklad.com) and
continued advancements to increase corrosion resistance. The 1 2 3 4
various finishes, film thicknesses and relative concentrations
of chromium compounds can be seen in the table below.
1. The typical passivate film thickness of a thin film passivate is Cobalt free - Beside mixed oxides of zinc and trivalent chrome,
about 80nm 100nm resulting in an even blue appearance and passivate films contain small amounts of cobalt zinc oxide
prevents zinc corrosion between 24 hours 72 hours in NSS tests. and cobalt chrome oxide. These oxides increase the hardness
2. Thick film passivate films form about 4 5 times thicker films and temperature resistance of passivate films. By the addition
(thickness between 300nm 400nm) resulting in an iridescent of small amounts of cobalt compounds, the thermal shock
appearance and prevent white corrosion in neutral salt spray resistance of the passivate film is increased to 150C.
in excess of 72 hours for zinc, 120 hours for zinc-iron and However, cobalt salts are under threat of regulation. The
150 hours for zinc-nickel. European CLP (classification of cobalt salt) classifies the toxicity
of several cobalt salts to carcinogen cat. 2. Therefore an increasing
Table 4 Comparative values to 5% white rust for interest on cobalt free passivates has been observed in Europe.
passivated coatings Since 2003, high performance cobalt free, trivalent chromium
passivates have been commercially available for zinc-nickel
Criteria Zinc Zinc-iron Zinc-nickel deposits. Today the first cobalt free black passivates have been
Hours to introduced, also for zinc-nickel deposits. Research continues
>72 >120 >150
white rust to develop similar systems applicable to zinc plated deposits,
particularly in respect to being resistant to thermal shock tests.
Market adoption
So which industries have adopted these systems? Before Chromium free passivates - At this time, the replacement of
the year 2000, trivalent chromium passivates were almost trivalent chrome to non-chrome technologies is being tested
exclusively for zinc plated finishes designed to have chrome like in indoor applications such as electronic components that are
appearances. This would include fasteners for internal automotive used in dry environments. Several patents and publications on
trim and domestic hardware; performance passivation for exterior non-chrome conversion coatings indicate further research on
automotive and construction fasteners being the domain of this topic, particularly to develop passivates for higher volume
yellow, green and black hexavalent chromium. fastener applications such as automotive and construction.