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Abstract
This paper reviews current understanding of mercury induced liquid metal embrittlement (LME) and the mechanism of failure in aluminium
heat exchangers. Natural gas can be contaminated with low levels of mercury, which can concentrate in cryogenic heat exchangers. There have
been several instances where LME has led to major failures and gas leakage in gas processing plant.
q 2006 Elsevier Ltd. All rights reserved.
Keywords: Liquid metal embrittlement; Mercury; Aluminium heat exchangers; Natural gas
Liquid metal embrittlement (LME) is a complex metal The natural gas purchased by consumers consists almost
fracture mechanism that occurs without warning. Liquid entirely of methane, the simplest hydrocarbon. In gas
mercury has been known to have a potentially devastating reservoirs, however, methane is typically found with heavier
effect on aluminium for several decades [1–4], and the hydrocarbons—such as ethane, propane, butane and pentane.
accumulation of mercury in parts of natural gas plants has The raw gas also contains water vapour, hydrogen sulphide,
led to failures. In the 1970s, LME and corrosion of aluminium carbon dioxide, nitrogen and other gases that are removed from
alloys by mercury in liquid natural gas (LNG) industry became the gas stream at processing plants.
a cause for concern. A paper published in 1980 entitled In gas processing plants, hydrocarbons are separated
‘Mercury—LNG’S Problem’ [5] focussed on the potential risk through fractionation—based on the different boiling points
of failures and papers published in Proceedings of GPA Annual of the hydrocarbons in the natural gas liquids (NGL) stream.
Conventions and elsewhere in 1990s discussed failures of The liquids are cooled to temperatures around K50 8C and the
components due to LME by mercury and on methods to combat various fractions are separated as they boil off as the liquids
this [6–8]. temperature is increased in stages in various heat exchangers.
The conditions required for LME to occur are: This cryogenic distillation, separating ethane and heavier
hydrocarbons from sales gas (methane) occurs within cold
(1) the presence of an embrittling liquid metal—with mercury boxes, typically made from aluminium. An example of such a
being a well-known, severe embrittling agent for coldbox is shown in Fig. 1.
aluminium alloys,
(2) the presence of a stress above a threshold value, which can
be as low as 5% of the yield stress under some conditions 3. Forms of Hg attack in aluminium heat exchangers
for aluminium alloys in mercury, and
(3) ‘wetting’ of the substrate by the liquid metal, which in the Mercury can occur in natural gas feed stock, often at very
case of aluminium alloys requires rupture of the oxide film low levels, and can sometimes accumulate in quantities
between the substrate and liquid metal. sufficient to cause severe attack and failure of cryogenic
aluminium heat exchangers. The cooling equipment in a gas
separation process is typically an aluminium plate-fin heat
* Corresponding author. exchanger, the construction of which is often an Al 3003 core
E-mail address: rcoade@hrl.com.au (R. Coade). with Al 5083 or 6061 headers, nozzles and piping. The mercury
0308-0161/$ - see front matter q 2006 Elsevier Ltd. All rights reserved. in the natural gas can degrade the aluminium coldbox materials
doi:10.1016/j.ijpvp.2006.02.022 by three basic mechanisms [6]:
R. Coade, D. Coldham / International Journal of Pressure Vessels and Piping 83 (2006) 336–342 337
(7) Gordon [9] citing the early work of Pinnel and Bennett
[10,11] and Bruce and Wise [12] described the amalgamate of
Al and Hg as a white fibrous corrosion product identified as
either an amorphous form of g-Al2O3 or a form of hydrated
Al2O3 (alumina) or alumina hydroxide. Phannensteil et al. [13]
concluded that it was necessary for ions to be present in the
water for amalgam corrosion to occur. It is probable that these
ions destabilised the protective oxide layer allowing the
mercury to come in contact with the base metal.
(6) Nelson [8] acknowledges that mercury can cause cata-
strophic attack of aluminium in the presence of ‘free’ water,
however, suggests that in cryogenic heat exchangers the
presence of water is extremely unusual, and has not been a
factor in any reported leak occurrence.
phenomenon peculiar to aluminium and discussed in the and adsorption kinetics. Alloy strength is particularly
preceding section. important, and increasing strength can either decrease or
For LME cracks to initiate there must be intimate contact increase susceptibility to LME depending on the circum-
between liquid and solid metals, with no intervening oxide stances. Crack growth rates generally increase, and threshold K
films to prevent wetting and adsorption. Al alloys are covered values for cracking generally decrease, with increasing
by a thin, protective oxide film, and surfaces can be covered by strength [20].
liquid mercury indefinitely without any reaction until the oxide Specific data for welded 5083-0 alloy in liquid mercury at
is damaged. Oxide films can be broken by mechanical 20 8C show that threshold K values are somewhat lower for
processes, e.g. by scribing or abrasion, by chemical processes, 5183 weld material with an equiaxed microstructure than for
e.g. corrosion, or by plastic deformation of the aluminium the 5083 plate (in the T-L orientation), although the crack
resulting in slip steps at the surface. Slip processes can occur growth rate was somewhat higher for the latter for some K
locally in favourable oriented grains at stresses well below the values [21,22]. Limited data on the times to failure for the
macroscopic yield stress, and slip steps can emerge at the welded 5083-0 alloy stressed in mercury at 20 8C show that
surface after long times under stress due to creep processes failure can occur in less than 1 h at high stresses (70% of yield),
(thermally activated dislocation re-arrangements) beneath the and that there is considerable scatter with other similarly
surface. stressed specimens lasting for w20 h. Failures occurred after
The time required for slip-step/oxide-rupture events will, of hundreds of hours at low stresses, with the threshold stress for
course, decrease with increasing stress and, hence, times to cracking being perhaps only w10% of the yield stress.
LME initiation will also decrease with increasing stress. The
kinetics of LME crack initiation and growth depend not only on 4. Breaching the aluminium protective oxide
stress (or stress-intensity factor) but also on many other
variables such as the composition of the liquid, the amount of For LME cracks to initiate there must be intimate contact
liquid, the composition, microstructure, and strength of the between liquid and solid metals, with no intervening oxide
substrate alloy and temperature [19]. films to prevent wetting and adsorption. Al alloys are covered
The amount of liquid metal is important for several reasons. by a thin, protective oxide film, and surfaces can be covered by
Firstly, increasing surface coverage of the substrate by the liquid mercury indefinitely without any reaction until the oxide
liquid metal could decrease the time to crack initiation, since is damaged. Oxide films can be broken by mechanical
the probability of potentially weak sites in oxide films exposed processes, e.g. by scribing or abrasion, by chemical processes,
to the liquid would be increased. Secondly (and more e.g. corrosion, or by deformation of the aluminium resulting in
importantly), cracks can ‘run out of’ liquid metal if there is slip steps at the surface.
only a limited supply because films of liquid metal are left on In LNG plant, Gordon [9] favours the abrasion on the
fracture surfaces behind crack tips. Crack-arrest can therefore surface by hard particles in the gas or liquid streams as the key
occur providing the stress-intensity factor, K, is below the oxide breaching mechanism. He suggests that as the gas
critical K for fast fracture in the absence of environmental entering cryogenic equipment usually consists of mainly
effects. methane, CO2 and hydrogen, it is oxygen-free. Hence, the
Cryogenic heat exchangers are often manufactured from reducing atmosphere of the gas stream may prevent any
aluminium alloy 5083, an aluminium–magnesium alloy. reformation of the protective oxide layer once damaged from
Magnesium silicide can contribute to age-hardening in these hard particles in the gas stream has occurred.
alloys. At room temperature, aluminium can hold w1% Mg in Others suggest that the differential thermal expansion
solution although heat exchanger alloys typically contain 4.5% between the aluminium substrate and the alumina oxide
Mg. The aluminium rolling mills anneal this material at being a factor of around 3 could cause the oxide to crack
w455 8C to dissolve all the Mg. Then the rolled stock is when the heat exchangers is warmed.
quenched to room temperature to hold the magnesium in solid It is known that slip processes can occur locally in
solution. This results in a metastable solid solution that wants favourably oriented grains at stresses well below the
to precipitate Al3Mg2. The kinetics of precipitation is so slow macroscopic yield stress, and slip steps can emerge at the
at room and cryogenic temperatures, that for all practical surface after long times under stress due to creep processes
purposes, the alloy is stable. (thermally activated dislocation re-arrangements) beneath the
However, when the alloy is welded, the temperature of the surface. It is possible that such activity could lead to breaks in
heat affected zone can facilitate the precipitation of Al3Mg2. the oxide film. The time required for slip-step/oxide-rupture
This can result in a continuous or semicontinuous film of events will, of course, decrease with increasing stress and,
Al3Mg2 being precipitated at the grain boundaries. The weld hence, times to LME initiation will also decrease with
structure is also subject to grain boundary precipitation because increasing stress.
of the solidification pattern and reheat from multi-pass welds.
Alloy composition and ‘temper’ can affect LME through 5. Metallography of LME cracking in heat exchangers
effects on strength, and grain-boundary microstructure (and
grain-boundary composition if segregation occurs), which can The coldbox on a cryogenic heat exchanger typically
affect creep rates and strain localization (hence, oxide-rupture), includes a distribution manifold with several nozzles from
R. Coade, D. Coldham / International Journal of Pressure Vessels and Piping 83 (2006) 336–342 339
Fig. 3. Section showing multiple cracking near the surface of the longitudinal
fracture and near the end of the delamination crack. 165!.
Fig. 2. Photograph showing the surface of the longitudinal crack and the
delamination cracks, which are more visible in the macroscopic view of a
section through the primary crack after polishing showing the nature and length Fig. 4. Examples of delamination cracking that has deviated and intersected the
of cracking. internal surface, with alumina whiskers clearly exposing the cracks.
340 R. Coade, D. Coldham / International Journal of Pressure Vessels and Piping 83 (2006) 336–342
Fig. 6. Cracks at the outer surface of the circumferential weld and within the Fig. 7. Fracture surface of cracking in the circumferential weld showing the
weld showing extensive branched intergranular cracking. 100!95/141!. intergranular and branched nature of cracks.
R. Coade, D. Coldham / International Journal of Pressure Vessels and Piping 83 (2006) 336–342 341
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