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Assessment of Fire Damage

to Pressure Vessels in a Refinery Unit✫

J.L. Hau*

ABSTRACT fully document findings of any evaluation. In cases

where damage is extensive, the answer may be
A systematic approach is proposed to assess the fitness of straightforward. But in cases where damage is not so
pressure vessels in the alkylation unit of a refinery after fire obvious, the decision to declare a unit suitable for
damage. Techniques used to study a Jan. 11, 1991, fire further service should be supported with more than a
included in-situ metallography; hardness testing; crack written description resulting from a visual inspection.
detection; and measurements of thicknesses, plumb, General guidelines for assessing fire and explosion
circumference, and straightness. Emphasis is placed not on damage and documenting a resultant investigation
conventional techniques such as hardness testing and in-situ
have been issued.1 This paper describes a specific
metallography, but on methods of measuring the affected
vessels and effectively detecting and sizing distortions approach used to assess fire damage and fitness for
caused by the fire. Though these methods have been service for future reference. Concern over proper
available in the past, they are not used in typical fire damage support and quantitative information was emphasized
assessments. because the fire occurred in an alkylation unit which
handled hydrogen fluoride (HF), a lethal substance.
KEY WORDS: circumferential measurements, field hardness
The fire lasted 2 to 4 h and destroyed part of the
testing, fire damage assessment, fitness for service, in-situ
metallography, straightness unit, but fortunately, there were no deaths. The fire
began while a main fractionator reflux pump (P-3B,
INTRODUCTION Figure 1) was being removed. It was caused by an
unexpected gas leak in the suction valve of the
Because of the nature of the process products used in malfunctioning pump. A gas cloud formed and moved
any oil refinery unit, accidental fires occur. When they toward the unit’s furnaces, where it ignited. The fire
do, there is an immediate need to evaluate the unit’s flashed back to pump P-3B. Nearby pumps and
fitness for service. Insurance requirements and a need equipment were involved also.
to keep inspection files updated make it necessary to Damage was observed in piping, support piping
steel structure, I-beams, and steel platforms on
vessels. Concrete fire proofing systems for steel

Submitted for publication August 1992; in revised form, October 1992.
* Refinería ISLA (Curazao), S.A., Affiliated to Petróleos de Venezuela, S.A.
beams were cracked and damaged severely. Three
(PDVSA), P.O. Box 3843, Emmastad, Curacao, Netherlands Antilles. explosions occurred when pipe sections busted. Most

420 © 1993, NACE International CORROSION–MAY 1993

FIGURE 1. Partial plotplant of the affected unit showing the fire zone and the locations of the

of the piping sagged or collapsed when support beams INSPECTION AND EXPERIMENTAL
buckled. The steel platforms attached to vessels within PROCEDURE
the fire zone also sagged, buckled, and/or warped
because of overheating. Ancillary equipment such as Definition of the Fire Zone
electrical wiring, circuit boards, instruments, and A visual inspection was made, and all vessels and
electrical motors burned. Except for the acid relief surroundings were photographed. Every statement in
neutralizer vessel (V-3, a full Monel), vessels and heat the visual inspection report was supported by a
exchangers within the fire zone did not exhibit obvious photograph of the relevant detail. The inspection
fire damage despite the severity of the heat. Their showed that the aluminum (Al) sheets used as jackets
suitability for future service needed to be assessed. for insulation systems in vessels, heat exchangers,
All steel structures, insulation systems, steel columns, and pipes melted in some places. Frozen
platforms, pump foundations, and fire-proofing systems aluminum drops confirmed the melting. By identifying
were demolished and rebuilt. All piping and flange bolts points where melting started, a fire zone was
within the fire zone were removed and replaced. calculated within which the temperature was assumed
Pumps were overhauled. Electrical motors were to have reached the melting point of Al (approximately
rewired and repaired. Ancillary equipment was 657°C). The fire zone is shown in Figure 1. This
replaced. However, all but one vessel were inspected represents a partial plotplant of the unit. Vertical
and repaired. Thus, the pressure vessels were the only vessels (V) are represented as circles. Horizontal
items intended for reuse in the condition the fire left vessels (also V) and heat exchangers (E) are drawn as
them. usual. Columns (C) are represented by circles, while

CORROSION–Vol. 49, No. 5 421


pumps (P) are represented by rectangles. With the insulation system of some vessels was affected to a
exception of a 965 mm and a 1066 mm diameter pipe larger extent than the bottom half. As a result, the
line, both attached to the HF acid settler (V-4), other selected spots on the fire side were always located on
pipe circuits were not included in Figure 1. the upper half. Plastic replication was used for
recording and photomicrography.
Classification of Vessels To estimate heat exposure temperatures, some
by Heat Exposure Severity steel support beams were examined
The vessels were divided into two categories: metallographically, as were two 200 mm core samples
those made of low-carbon steel and those made of removed from the intermediate skirt that joins the HF
Monel 400† (UNS NO4400)(1). The acid relief neutralizer acid settler (V-4 on the top) with HF storage vessel V-5
vessel V-3 (uninsulated) and the HF rerun column C-1 (on the bottom). Skirt vents were welded on the holes.
(insulated) were made of Monel. The rest of the One core sample was removed on the side opposite to
vessels within the fire zone were made of low-carbon the fire zone (the south face of these vessels in Figure
steels. The vessels also were divided into two classes: 1). The other core sample was removed from the north
with and without insulation. For a given degree of fire face to establish a comparison between the steel
exposure and time, uninsulated vessels must have microstructure on the part of the skirt that may have
been affected to a greater extent than those with an become very hot with portions that may have remained
external insulation system. unaffected by the fire.
A preliminary classification was made from the For comparison and to establish the
visual inspection, taking into account whether the steel microstructural changes to be expected after high-
platforms collapsed by heat, whether the insulation temperature heat exposure, steel specimens were cut
system remained in place, whether the insulation from an SA-285 Grade C 25 mm plate and subjected
material (rock wool) burned, whether the aluminum to various temperatures in the laboratory for 30 min
sheets melted, and where the vessels were located and cooled at different rates. A heating time of 30 min
within the fire zone. The zone enclosed some vessels, was used because none of the vessels was exposed to
partially covered others, and only touched some parts the fire’s effects for the full 2 to 4 h it lasted.
of others. The insulation systems of vessels and heat Hardness testing — Hardness testing was used in
exchangers were damaged or destroyed. In others, lieu of tensile testing, which is not done usually
only the aluminum jacket suffered, and the insulation because it would involve removing a sample from the
material remained in place. vessel. In this unit, the most common steel used in the
Every effort was made to ensure the classifications vessels were SA-516 Grades 55 and 60 (for welded
reflected the severity of heat exposure. A rating was ones) and SA-106 Grade B (for seamless heat
assigned based on the evaluation and tests needed for exchange shells). According to the code under which
each particular case. Depending on this classification, these vessels were designed and constructed,2 the
at least two of the seven tests used were performed on minimum ultimate tensile strength of low-carbon steels
each vessel in the fire zone. was used as a basis to determine design stress. Since
the code did not refer to allowable hardness values,
Testing Performed the minimum acceptable hardness values for the
In-situ metallography — In the case of low-carbon evaluation had to be specified. This was done by using
steel vessels, in-situ metallography was used mainly to the specified minimum tensile strength of each grade
examine microstructural changes that occurred and and finding the approximate equivalent Brinell
estimate heat exposure during the fire. For Monel Hardness for steels: 109 HB for SA-516 Grade 55 and
equipment, however, temperatures could not be 121 HB for SA-516 Grade 60 and SA-106 Grade B
estimated based on microstructure. In-situ steels. For equipment constructed of Monel 400 (C-1
metallography was used on Monel equipment to and V-3), a minimum hardness limit of 110 HB was
determine excessive grain growth. specified.
Portable microscopes were used to observe the Field hardness testing was carried out using a
microstructure on selected spots of some vessels and comparison hardness tester. For selected vessels,
heat exchangers. Normally, a spot was chosen on the hardness testing was performed at given distances
surface facing the fire zone and on the opposite side along longitudinal lines drawn on the external surface
for comparison. Damage indicated the upper half of the and separated by an angle of about 90°. The top head
was included, when necessary.
A bench-type testing machine was used to
UNS numbers are listed in Metals and Alloys in the Unified Numbering measure the hardness (HV30) of test pieces, of sam-
System, published by the Society of Automotive Engineers (SAE) and co-
sponsored by ASTM. ples cut from steel beams found within the fire zone,

Trade name. and from the intermediate skirt of vessels V-4/V-5.



Thickness measurements — Thickness detect changes in diameter along the vessel height or
measurements were made with commercial digital length. Circumferential measurements can be taken
ultrasonic thickness gauges. Again, readings were with a steel tape long enough to cover the
taken at given distances along the same longitudinal circumference of the vessel. If external attachments
lines used for measuring hardness. Thickness get in the way of the tape, the circumference may be
measurements were taken to make certain excessive taken in more than one step by measuring the amount
thinning (locally or generally) did not take place during of necessary arc segments and adding them. This
the fire and subsequent cleaning of the unit. The method also has been used in the refinery to estimate
possibility of excessive thinning was considered accumulated creep strain in a vessel operating in the
because of the indiscriminate use of salt water to creep range, but the measurement will not distinguish
control and extinguish the fire and because carbon whether an increase in diameter is uniform, with the
steel is not resistant to diluted HF. original roundness being maintained or due to localized
Plumb check — Eight places around the bulging.
circumference of vessels V-4 and V-5A were checked Crack detection — Liquid penetrant testing was
for vertical plumb. Out-of-plumb can be measured with used to detect cracking on the internal and external
a surveyor’s transit or with a plumb bob. In the latter surfaces of welds on equipment made of Monel 400
case, the bob is suspended by a string from the top of and on external attachment welds in those carbon steel
the vessel at a given offset. The deviation from the vessels where steel platforms and other steel
offset, measured with a scale at the bottom of the structures collapsed during the fire. Wet fluorescent
vessel, should show how far the object is out-of-plumb. magnetic particle testing was used in a few cases to
This test was used only for vessels V-4 and V-5 inspect welds on the internal surface of some vessels
because they are joined by an intermediate skirt and in HF service.
together form a tower 31.5 m in height.
Straightness verification — The plumb check was RESULTS
intended to discern whether vertical vessels remained
vertical, but straightness verifications were intended to Metallography
detect bulging or local distortion not apparent to the Expected microstructural changes — Grain growth
naked eye. A vessel surface may be straight but not was the only expected microstructural change for
necessarily vertical. This verification again was Monel vessels, but this could not be determined
performed only for vessels V-4 and V-5. The because the prior grain size was unknown.
methodology used was similar to that used as a quality For low-carbon steel vessels, long-term exposure
control for vessel tolerance on new constructions. The to temperatures in the range of 600 to 727°C may
method consisted of fixing two support bars of equal cause some degree of spheroidization of the cementite
length to give the same offset x: one just above the V-4 (Fe3C) plates within the pearlite, but this microstructural
top head-to-shell weld seam and the other just below change was unlikely to occur because, as mentioned
the V-5 bottom head-to-shell weld seam. A string was earlier, the fire exposure time was probably near only
then attached to both bars and depth (d) 30 min. The experiment conducted in the laboratory
measurements were taken (with a depth gauge or with with low-carbon steel SA-285 Grade C pieces showed
steel tape) at given distances (y) from the string to the that, for such a short-term heating, microstructural
vessel surface. The shorter the distance between the changes began to be noticed only when heated to or
two measurements, the more accurate and precise the just above the subcritical temperature A1 (727°C) and
actual vessel surface is copied. If the depth is equal to thus when the existing pearlite colonies transformed to
the offset, then this particular point lays on a line that is austenite. The results obtained from this experiment
parallel to the vessel surface; if the depth is larger than are summarized in Figure 2, while the transformation
the offset, there is a depression on that particular spot. processes giving rise to the main microstructural
If the depth is shorter than the offset, there is a bulge changes caused by heating to about 750 to 800°C are
on that particular point. With this information, a profile illustrated in Figure 3. Most of the apparent
of the vessel can be plotted as a “y” vs (x-d) graph. microstructural changes that took place after carbon
The method has been used successfully in the refinery steel was heated to just above the subcritical
to estimate accumulated creep strain in a vessel temperature occurred in the pearlite. That is why they
operating in the creep range. It is particularly effective may not be so evident in cases where the volume
in locating and measuring bulging, depressions, or fraction of pearlite is low, as in an SA-285 low-carbon
other distortions in a vessel. steel.
Circumferential measurements — These The transformation process from pearlite to
measurements were much easier to carry out than austenite during heating to just above A1, and then
profile measurements and mainly were intended to from austenite back to a ferrite-pearlite structure during

CORROSION–Vol. 49, No. 5 423


(a) (b) (c) (d)

FIGURE 2. Microstructure found in SA-285 Grade C steel specimens: (a) as-received condition; (b) heated to
750°C and air cooled; (c) heated to 800°C and air cooled; (d) heated to 1000°C and air cooled. All were etched
in 2% Nital and shown at 100X. Measured hardnesses are indicated for comparison.

ferrite grains. After cooling, new ferrite grains nucleated

at the grain boundaries (i.e., nucleation sites) of each
austenite grain and then grew until reaching the
subcritical temperature A1. The remaining carbon-
enriched austenite transformed to pearlite colonies
much smaller in size than the original ones. That is
why the final microstructure of the low-carbon steel
heated to 750°C (Figures 2b and 3c) has a ferrite-
pearlite microstructure finer in places where the total
volume fraction of ferrite increased at the expense of
pearlite. However, since bulk decarburization of the
steel was not considered, the total quantity of Fe3C
and/or of carbon remained unaffected. Thus, it is the
redistribution of Fe3C within the steel after the thermal
cycle that caused an apparent reduction of the volume
fraction of pearlite.
The original ferrite grains were not greatly affected
except when the heating temperature was increased to
800°C. Several new austenite grains began nucleating
at existing ferrite grain boundaries (Figure 3d), and
those that formed already grew deeper into the
surrounding ferrite grains. Upon cooling, each
FIGURE 3. Schematic representation of the partial phase
austenite again gave rise to several ferrite grains,
transformations that occurred during heating to about 750 and which resulted in a ferrite grain size much smaller than
800°C and then cooling to room temperature. the original. This is illustrated in Figure 2c, where
approximately 50% of the structure is the
untransformed original ferrite grains and the other 50%
cooling, involved nucleation and growth. The pearlite is a finer structure formed from the austenite grains
colonies gave rise to several austenite grains because that existed at about the heating temperature and that
pearlite comprises several alternated layers of Fe3C consisted of ferrite with smaller pearlite colonies. If not
plates and ferrite and, thus, contains many nucleation much time is allowed for grain growth to take place and
sites at each boundary. The newly formed austenite heating proceeds until the critical temperature A3
grains grew into and at the expense of the surrounding (about 850 to 900°C), which is the necessary



temperature level for the complete transformation of previously cited. For low-carbon steel vessels, it was
this steel to austenite, the final resulting microstructure assumed that temperatures could not have risen higher
upon cooling to room temperature will be a finer ferrite- than 727°C, based on the above findings and on the
pearlite structure than the original. In this sense, heat fact that significant microstructural changes start at
exposure to temperatures in excess of A3 for low- 727°C for low-carbon steel.
carbon steel, will have a similar or even greater Of all the evaluated vessels, the butane
refinement effect that a normalizing treatment, potassium hydroxide (KOH) treater (V-8) and the
noticeable grain growth being evident only when the propane KOH treater (V-10) were assumed to be the
steel is heated to much higher temperature levels, for most affected, with suspected vessel wall temperatures
example, to 1000°C, as in Figure 2d. higher than 727°C. Those vessels handled gas instead
Microstructure in vessels — The microstructure of of liquid, where most of the incoming heat would have
the lower cylindrical portion of the acid relief been spent by the latent heat of vaporization of the
neutralizer, vessel V-3 made of Monel, was normal and liquid. They also were completely within the fire zone
was considered acceptable for reuse from a (Figure 1) and were not insulated. The steel platform
metallographic standpoint. In the rerun column C-1, on top of these vessels appeared to have been
also made of Monel, the average grain size was larger exposed to temperatures as high as 1000°C (Figure 4).
than in the previous case, but actual grain growth The metallographic method only provided an
during the fire could not be established. This column is upper bound of heat exposure for the vessels of less
relatively small and was enclosed by the fire (Figure 1). than 727°C. The only indicator of lower bound
The aluminum jacket melted away, but the insulation temperatures was the fact that the caustic beds for
material remained in place. Spots that could have both KOH treaters melted during the fire. This indicated
remained colder or become hotter than other spots on actual internal temperature equal to or in excess of the
the same column could not be identified, as was melting point of KOH, which is approximately 360°C.
necessary for comparison. Thus, the maximum temperatures at which these two
With respect to low-carbon steel vessels, the fact vessels were heated must have been between 360
that heat exposure higher than 850 to 900°C could and 727°C. As described later, deformation twins were
have produced grain refinement rather than grain observed on vessel V-8 on the opposite side of the fire.
growth made it difficult to estimate heat exposure Therefore, at least one explosion took place before this
temperatures based on grain size. There was no way vessel was heated by the fire, otherwise twinning
to be certain a fine grain structure was actually in would not have formed.
original condition or the result of heat exposure during Distortion of structural steel — Metallographic
the fire. This uncertainty could be overcome examination was used to estimate the heat exposure
sometimes by comparing the microstructure with and provide a reference for vessels. Examination of
another taken on the same vessel but on the selected samples removed from steel beams provided evidence
spots that most likely remained cold during the fire. In of heat exposure to higher temperatures than A1.
general, the metallographic results were not easy to Gross deformation of low-carbon steel T- and I-beams
interpret, particularly when examining the shell heads and steel platforms indicated much higher
in vessels and the shell covers, both of which are hot- temperatures than those estimated for vessels. Gross
forged typically. Also, in-situ metallography was used deformation occurred because low-carbon steel gets
to examine the planes parallel to the plate surface very soft when heated to high temperatures. Figure 5
instead of the most commonly known transverse shows the high-temperature, short-time yield strength
metallographic planes, perpendicular to the plate or properties of low-carbon steel.3-5
head surfaces. When uncommon features were Figure 4a shows the microstructure of a
observed, the first question was whether the metallographic specimen taken from a steel beam that
microstructure really represented the bulk metal. This exhibited no sign of being heated by the fire. For
dilemma made it necessary to repeat the analysis on a comparison, the microstructures found in grossly
metallographic plane deeper into the metal wall. deformed steel platform beams, where there is clear
Seven vessels, three heat exchangers, and one evidence of grain growth, also are shown in Figure 4.
column were selected for metallographic examination. Hardness values taken on these metallographic
Microstructural changes caused by high temperature specimens are shown as a reference.
exposure or subsequent water quenching were not The occurrence of grain growth indicated, as
found in any of the inspected equipment. In all cases, described earlier, heat exposure of 950 to 1100°C for a
the microstructure was considered acceptable. relatively short time (less than 1 h). The samples of
Estimation of heat exposure in vessels — badly damaged steel beams were taken from the
Metallographic temperature estimation could not be platforms of vessels V-8 and V-4. Heat exposure of at
done for the equipment made of Monel for reasons least 1000°C was assumed to have occurred.

CORROSION–Vol. 49, No. 5 425


(a) (b) (c)

FIGURE 4. Microstructure in samples from steel beams found in the fire zone: (a) unaffected; (b) taken from the
V-8 platform; (c) taken from the V-4 platform. Etched in 2% Nital and shown at 100X. Measured hardnesses are
indicated for comparison.

Structural steel heated at this temperature has little From those results, it was concluded that the north
resistance to yielding (Figure 5), which explained why face side of the skirt was heated to 775 to 800°C
the platforms collapsed under their own weight. during the fire. According to Figure 5, the steel at this
V-4/V-5 intermediate skirt — Microstructures found temperature had a minimum yield strength of only
in these two core samples are shown in Figure 6. about 2.1 kg/mm2 (3000 psi). Although a rough
Since the paint on the external surface of the sample estimate of the total dead weight supported by the skirt
taken on the side opposite to the fire (South face, resulted in a compressive stress still lower than
Figure 1) was almost intact, it was assumed the fire did 2.1 kg/mm2, the skirt could have buckled under the
not affect this side of the skirt. As expected, a typical combined action of this compressive stress and short-
ferrite-pearlite microstructure was found on this term creep. Visual inspection performed on this skirt
sample. In contrast, some degree of pearlite banding showed some areas were distorted, indicating the
was apparent in the microstructure of the core sample onset of what might have been a plastic failure of the
taken from the fire side (north face), while the pearlite skirt and a collapse of the top vessel. The fact that the
itself looked somewhat fragmented, as if it had been skirt did not fail may have be attributed to the additional
heated to between 750 and 800°C. To confirm this support provided by the cold side of the skirt and of the
finding, a piece cut from the sample on the opposite two large pipes attached to the vessel – one on the
side to the fire was heated for 2.5 h to 775°C in a west side (15 mm thick, 1066 mm in diameter) and the
furnace, removed, and allowed to cool freely in still air. other on the bottom head (15 mm thick, 965 mm in
The microstructure of this sample is shown in Figure 7. diameter), both of which remained cold during the fire.
Apart from a lesser degree of pearlite banding, the The skirt was reinforced with five struts (90o angle
other microstructural changes resembled those beams), welded on both vessels (top and bottom) on
features observed in the core sample removed from rectangular reinforcement pads with rounded corners.
the fire side of the skirt. Since the degree of banding A fire-proofing layer 50 mm thick also was installed.
developed in a particular steel is a function of its most This consisted of a concrete mix (Portland cement
recent thermal cycle into the austenitic region, it is Type 1 and sand) applied on the skirt’s internal and
obvious that the cooling of the small metallographic external surfaces. This system also covered the struts
sample did not match exactly that of the skirt heated by and the reinforcement pads on both vessels.
fire. The appearance of pearlite banding because of a High pressure shock — Some deformation twins6
thermal cycle involving reaustenitization was not in the ferrite (also known as Neumann bands) were
surprising. Pearlite banding also can be eliminated by observed (Figure 8). These twins were recognized
fast cooling, in cases where the steel is first fully because they formed within the ferrite grains, were
austenitized.6 The 2.5 h of heating at 775°C did not relatively thick, had a lenticular shape, had generally
cause any grain growth. straight boundaries, and never extended across the



boundaries. Similar twins formed in the cold side (north

side) and middle part of the butane KOH treater
(vessel V-8) (Figure 8b). On the vessel surface facing
the fire (southeast), no twins were detected.
The deformation twins in ferrite develop only under
certain circumstances, when the shear stress required
to start deformation by dislocation movement is greater
than that required for twinning. In iron ferrite, this can
happen only with the imposition of plastic deformation
at very low temperature (e.g., –196°C) or when
deformation occurs at very high strain rate. In this FIGURE 5. Published data for high-temperature yield strength
particular case, the most likely cause of twin formation of some low-carbon steels.3-5
was shock waves produced by the explosions. That
part of the vessel or steel beam must have remained
cold (at room temperature) because higher
of 301 HV (equivalent to about 284 HB) and the other
temperatures would have promoted slip deformation
of 203 HV (equivalent to about 191 HB).(2) Despite the
instead of twinning. It should be noticed that this
difference in hardness, there were no significant
deformation involved insignificant total strain. Changes
differences in microstructure apart from a slight
in dimension due to deformation twinning were not
difference in etching response. The softer specimen
was etched faster in 2% Nital and was slightly darker
than the harder specimen (Figure 10).
Hardness Testing
Figure 10 also shows the microstructure of the
Once minimum values are specified, hardness
specimen quenched from about 800°C. Although the
may be considered a test for acceptance or rejection of
dark-etching features may appear to be pearlite
vessels. If the hardness level indicates the occurrence
colonies, they are not. The constituent is known as
of softening below an acceptable limit, action is
troostite,6 a transformation product that forms from the
required normally since the vessel may no longer be in
austenite.(3) Because of fast cooling, ferrite does not
compliance with the minimum tensile requirements of
form, so the troostite occupies the exact location of all
the construction code. However, some caution should
pre-existing austenite. In this sense, water quenching
be exercised. The design stresses below 343°C
had the effect of freezing the structure that existed at
(650°F) are normally one-quarter of the specified
800°C. Since austenite was present in all the places
minimum tensile strength, according to the code under
where troostite was found, the resemblance of the
which the vessels were constructed.2 However,
structure in Figures 10c and 10d, with the schematic
hardness testing methods that produce an indentation
representation shown in Figure 3d, is obvious. There
by plastically deforming the metal at the point where it
was a tendency for the austenite to form along
is applied depend on the yield stress rather than the
preferential bands parallel to the rolling direction of the
ultimate tensile strength. This means a reduction in
plate. This process created the pearlite banding seen
hardness may correspond to a reduction in yield
in Figures 6c and 7a. The hardness measured on this
strength but not necessarily to a reduction in the
specimen was 180 HV (equivalent to about 171 HB).
ultimate tensile strength. The discovery of low
Although this hardness does not exceed the limit of
hardness values may indicate a need to remove a core
210 HV, this is an undesirable mixed microstructure
sample to check tensile properties rather than rejecting
because its presence may impair the toughness of the
the metal based on hardness alone.
Expected hardness variation — Low-carbon steels
Results obtained in vessels — Because of the very
only turn hard and brittle if austenitized during the fire
low carbon equivalent (CE) of the carbon steel used to
and cooled very rapidly by firefighting water. For this
particular unit, the limit on maximum allowable
hardness was 200 HB (equivalent to 210 HV). To (2)
The difference in hardness arose because of the time elapsed between
establish a reference for the evaluation (Figure 2), removing the specimen from the furnace and quenching in water and also
because of the severity of quenching. The one with the highest hardness
experiment results were added from specimens that was not only quenched within 3 to 5 s after removing it from the furnace,
were doused with water to simulate the effect of but it also was agitated when immersed in the water. A problem of
firefighting efforts. As illustrated in Figure 9, one of the gripping the other specimen was experienced and this further delayed the
process of transporting it from the furnace to the water container. This, in
three specimens heated to 1000°C cooled freely in air addition to the fact that no agitation was used while water quenching,
(Figure 2d), and the other two were doused with water. (3)
made this specimen softer than the previous one.
Actually, troostite is an old term no longer in common use. Now it is known
The one cooled in air had a hardness of 130 HV; one to be composed of bainite, unresolved and very fine pearlite or even
of the two water-quenched specimens had a hardness martensite. For the sake of simplicity, the use of the term troostite is used.

CORROSION–Vol. 49, No. 5 427


(a) (b) (c) (d)

FIGURE 6. Microstructure found in the intermediate skirt of vessels V-4 and V-5: (a) on the cold side, 178 HV;
(b) the same as in (a) but at higher magnification; (c) on the fire side, 136 HV; (d) the same as in (c) but at higher
magnification. All etched in 2% Nital.

145 HB for steel grade 55; and between 121 and

150 HB for steel grade 60.
A relatively high percentage of the hardness
measurements were near the specified minimum
hardness value used in this evaluation. Lower values
were found only on two vessels. On one vessel, a
single value of 104 HB was found, with a minimum
allowable of 109 HB. Figure 11 shows results for the
other vessel, the feed drier V-2A, for which a minimum
hardness of 121 HB was specified. The external
insulation system of this vessel was almost destroyed,
so the fireproofing effect provided by the insulation was
lost in the fire. The top platform on this vessel (V-2A) is
shared with butane the KOH treater (vessel V-8). The
platform was heated to about 1000°C (Figure 4b). As
(a) (b) seen on all faces where hardness was measured, at
least one spot had a value reaching the minimum
FIGURE 7. Microstructural changes produced by heating to specified limit. On the northwest side, two points were
about 775°C for 2.5 h and air cooling cold-side steel specimens
found to have even lower hardness. Because these
cut from the V-4 and V-5 intermediate skirt. Hardness 128 HV.
Etched in 2% Nital. values were located on the face opposite the fire side,
it was concluded that these were original values and
not a consequence of softening during the fire. In fact
manufacture these vessels, it is doubtful whether (Figure 9), for short-term heating as equipment in this
portions of the actual vessels could have been unit experienced, softening might not occur without
hardened by heating and cooling during the fire to the very high temperatures, as in the cases of the steel
extent achieved by the above experiment. The cooling platform beams in Figures 4b and 4c. In-situ
rate must have been very fast to cause the phase metallography was performed on the supposedly soft
transformations seen in Figure 10 and to result in side of this vessel, but the microstructure was normal.
hardness levels in excess of 200 HB (210 HV). Of the
one column, 13 vessels and three heat exchangers Thickness Survey
tested, only a few had isolated maximum hardness No excessive thinning attributable to the fire was
values of 162 to 173 HB. Most readings were between found. This was ascertained by comparison with
110 and 140 HB for Monel vessels; between 120 and previous thickness records.



Measurements carried out during this evaluation

were more systematic and exhaustive than normally
performed in a turnaround and gave a better general
view of the actual conditions of the vessels. Of the 13
vessels, two columns, and three heat exchangers
tested, only one had a thickness below the retirement
value. The results obtained for this vessel are shown in
Figure 12, which also illustrates a typical form of
presentation of the thickness survey data. A total of 72
thickness measurements were taken, 18 for each of
the four inspected sides. The hardness values were
included and correlated with the thickness values.
The affected vessel was the propane KOH treater,
which contains an internal caustic flake bed to
neutralize the last traces of HF in a propane stream
before storage. According to inspection files, the (a) (b)
bottom course of this vessel was replaced in 1984
because of excessive thinning. This section was harder FIGURE 8. Deformation twins (some indicated by arrows)
than the original as a result of the material used. This is observed on the surface of (a) an otherwise intact steel T-
a corrosion problem and not a consequence of the fire. beam removed from the fire zone and (b) the cold side of vessel
The bottom course was scheduled for replacement. V-8. Etched in 2% Nital.

Of eight results obtained from verification of
vertical plumb on vessels V-4 and V-5, four are shown
in Figure 13. The out-of-plumb in the other four results
not shown did not exceed 41 mm. Maximum deviations
of 76 and 78 mm were found on the northwest and
southeast sides, respectively. The magnitude of the
measured out-of-plumb condition was not significant in
comparison with an overall length of 31,500 mm,
including both skirt lengths.

Vessel Profiles
Results of the straightness check on the surface of
vessels V-4 and V-5 are shown in Figure 14. The fire
side was in the north face of the vessels, and the fire FIGURE 9. Hardness variation brought about by heating steel
did not appear to have touched the south face (Figure samples for about 30 min to various temperatures and cooling
1). The surface on the north face appeared relatively in still air or quenching in water.
straight, with the exception of the intermediate skirt,
where a ridge is seen just below the skirt-to-V-4 bottom
head girth weld and another just above the skirt-to-V-5 section on the east face (29 mm). For vessel V-5, there
top head girth weld. Such ridges, also evident on the was only one significant deviation of 34 mm on the
east face, were apparent to the naked eye and were upper section of the west face.
detected during the visual inspection. The intermediate This technique gave a fairly precise idea of the
skirt was heated partially to 775 to 800°C and, there- actual shape of the vessels. If the situation had been
fore, was deformed locally and distorted by the fire. worse, a decision would have been made to draw as
If each vessel is considered individually, maximum many additional profiles as necessary to find the most
deviations can be derived by subtracting the depth of critical side. Since the distortions (lack of straightness)
the lowest “valley” from the height of the highest “hill.” were not large and original profiles were not available
These maximum differences are indicated in Figure 14. for comparison, it was not possible to ascertain
Since they are relatively small, the presence of such whether these relatively small “hills and valleys” were
irregular vessel profiles was not a cause of concern. formed as a consequence of the fire, were due to
For vessel V-4, the maximum differences were overheating or were caused by local (cold) distortions
detected on the lower section of the south and west from uneven heating and cooling. These vessels were
faces (31 and 35 mm, respectively) and on the upper constructed under a specification allowing a maximum

CORROSION–Vol. 49, No. 5 429


(a) (b) (c) (d)

FIGURE 10. Microstructure of SA-285 Grade C steel specimens after water quenching from: (a) 1000°C; (b)
1000°C; (c) 800°C; and (d) the same but at higher magnification. All etched in 2% Nital. Measured hardnesses
are indicated for comparison.

found, a stress analysis might have been required for


Circumferential Measurements
Circumferential measurements were made only for
five vessels and one column. In all but one case, there
was no significant difference in circumference,
suggesting the fire caused no distortion.
Figure 15 shows results for the vessel where a
significant variation was found. This was the butane
KOH treater (V-8). Except for the first measure taken
on the top of the vessel, circumferential measurements
suggested a normal condition without bulging. The
mean external circumference of 4423 mm departed
from the one based on the nominal inside diameter
(1372 mm) and the actual wall thickness (mean value
15 mm) by only 18 mm. This implied a difference
between the actual mean internal diameter and the
nominal internal diameter of about 6 mm, which was
still within the tolerance of construction of the vessel.
The top circumferential measurement departed
from the mean value by 47 mm. The upper part of the
top course may have swelled because of the internal
pressure and high temperature creep, but this could
FIGURE 11. Typical presentation of results from field hardness not be confirmed. In-situ metallography would have
testing performed on a vessel.
been useful in this respect, but the metallographic
examination on this vessel was done lower on the
of 25 mm out-of-straightness, but the corresponding vessel.
certificates were not found in the inspection files. Even This made it obvious that circumferential
if they had been found, the actual deviations (i.e., measurements should have been taken first because
actual measured—maximum allowable one) would not they can provide information required to pinpoint areas
have exceeded 10 mm and would have been too small where hardness testing and in-situ metallography
to be considered critical. If larger deviations had been would be most useful.



FIGURE 12. Typical presentation of the results of hardness and thickness measurements obtained in a vessel.

The method still is sufficiently precise to reveal any air.7,(4) The vessel was composed of two cylindrical
general distortion on a vessel. The vessel profiles to sections. The bottom had a larger diameter, and the
verify straightness could have provided further two were joined by a conical section. The top section
information to precisely locate the distortion, but these had to be replaced, and the conical section had to be
were not drawn for this vessel. The vessel was repaired. The bottom section was reused after
returned to service. Even if the distortion was creep refurbishing. Since this type of cracking also was found
deformation, it would represent only 1.06%, which during a 1990 turnaround,(5) it was not considered a
does not seem critical for a vessel that is intended to consequence of the 1991 fire.
work well below creep conditions.

Crack Detection (4)

However, this information was misleading. Vessel V-3 was stress relieved
during construction and operates almost at atmosphere pressure. During
Cracks visible to the naked eye were detected in service, the bottom cylindrical portion is completely filled with a 5%
the fillet weld of a support ring in the propane KOH caustic solution because it is the acid relief neutralizer of the unit, and yet
treater (V-10) and on the attachment welds of the sieve extensive cracking was found in areas (mainly welds but also found in
base metal far away from the welds) totally immersed in this solution.
trays in the HF acid settler (V-4). These cracks were (5)
By that time, crack removal and repairs were done only on the conical
attributed to the fire because they probably formed section and the top part of the vessel because it was there where the
vapor phase is present. This time, extensive repairs were done in areas
from excessive stresses introduced by differential below the liquid level. In both occasions, the vessel was again stress
thermal expansions when the shell expanded but the relieved after repairs, but inspection revealed further cracking in those
welds and areas that have not yet been repaired, such as the internal
internals did not. The internals were kept cooler by the surface of the manhole neck. The vessel is scheduled for repairs for the
boiling liquid inside V-4 and by superheated propane in forthcoming turnaround. The cracking mechanism is suspected to be an
vessel V-10. underdeposit corrosion process rather than a stress corrosion one, with
sulfur playing the main role. The deposit is a blackish and a hard one,
Cracks were not detected in the other inspected firmly adhered to the Monel surface, and whenever it was removed, the
vessels except for the acid relief neutralizer, vessel V-3 cracking with a striated or tree-bark appearance became very much in
evidence underneath the deposit. The most effective way to remove it
(a full Monel vessel). It showed cracking with a striated was by grit blasting, which was needed anyway for a proper surface
or tree-bark appearance. This type of cracking has preparation before liquid penetrant testing. For every turnaround,
thorough cleaning to remove all blackish and hard deposits found on the
been reported as stress corrosion cracking of Monel in Monel surface was specified as a measure to avoid recurrence of the
the presence of HF in the vapor phase, moisture and same problem in the future.

CORROSION–Vol. 49, No. 5 431


Actual Heat Exposure
Apart from the steel platforms, T- and I-beams, the
V-4 and V-5 intermediate skirt, and all steel structures
that were found warped or distorted, metallographic
temperature exposure estimation could not be
performed successfully in vessels, columns, and heat
exchangers. Because of their location within the fire
zone and their badly distorted steel platforms, vessels
V-3, V-4/V-5, V-8, and V-10 (none of which had
external insulation systems) were likely to be the most
affected, but this was not found to be true. Except for
repairs to the conical and bottom cylindrical portion of
V-3 and the attachment welds of some internals in
vessels V-4 and V-10, the remaining vessels were
returned to service without further testing or repair.
Questions regarding the actual temperatures to
FIGURE 13. Results from out-of-plumb measurements made which each vessel was really heated were left
on vessels V-4 and V-5. unanswered. At first, the temperature appeared to
have been high, based on the condition of the steel
platforms. The lack of microstructural changes showed
none of the examined low-carbon steel vessels could
have reached temperatures above 727°C. Because of
the melting of the internal KOH beds in vessels V-8
and V-10, they heated to at least 360°C. A heat
exposure between 360 and 727°C (680 and 1341°F)
includes, according to the terminology used in
literature,1 Zones IV (204 to 427°C) and V (427 to
732°C), which are referred to as medium and heavy
heat exposures, respectively. The steel platforms,
then, heated to Zone VI (727°C and above), which is
defined as severe heat exposure.
If the operating pressure and the process fluids in
the vessels are assumed to have been maintained
during the fire, it is possible to estimate the hoop stress
(usually the largest one) on each vessel. The
calculation was made for several vessels (Table 1).
Figure 16 shows the variation of the Larson-Miller
parameter with stress for creep rupture of carbon steel
plate.5 The conditions of stress rupture and
temperature were computed from the Larson-Miller
parameter master curve for a rupture time of 2h and
30 min. Results are shown in Figure 16b. Hot-yield
strength values taken from Figure 5 were included for
comparison. Although an extrapolation to such a short
exposure may not be accurate and the steels for which
the curve was plotted do not correspond exactly to
those used in the vessels, Figure 16 illustrates what
should be expected for a low-carbon steel subjected to
conditions of creep. For the calculated stresses in
Table 1, creep rupture is expected to occur from
30 min to 2 h when the temperature reaches values
between 570 and 612°C. Since stress rupture is
FIGURE 14. Profiles derived from depth measurements ob- preceded by considerable creep strain, the hottest
tained during the straightness check for vessels V-4 and V-5.
portion of a vessel should have exhibited some degree



of measurable deformation if temperatures on that

particular area had approached those required
for rupture. Even if the vessel did not rupture,
considerable creep strain was expected to have
occurred if the vessel had been exposed to
temperatures just below this range. This was not
observed. The actual heat exposure may have been
from 360 to 570°C or lower.
The relief valve is set typically at the design
pressure. During the fire exposure, the liquid in the
vessel must have started to boil. If the vessel
contained gas instead of liquid, it must have become
superheated. In both cases, the pressure should have
increased until the relief set pressure. Had this been
the actual pressure in the vessels at the time of the fire,
then the stresses would have been higher than
9.7 kg/mm2 (13,750 psi) and hence, the maximum
exposure temperature must have been lower than
540°C or creep deformation or rupture would have
Several large leaks may have developed during
the fire when pipe collapsed or busted. It was possible
that pressure within some vessels dropped to
atmospheric pressure as the gas escaped. However,
this does not seem to have occurred. As in the case of
the V-4/V-5 intermediate skirt (which could be
considered as an empty vessel open to the FIGURE 15. Typical presentation of circumferential measure-
ment results made on a vessel.
atmosphere), an empty vessel was likely to have
heated much higher because it would not have fluid to
cool it. If that occurred, it was in the later stage of the
fire, with insufficient time for the vessels to heat. The fact that a vessel is no longer within given
Heating or uneven heat flux to a portion of a dimensional tolerances does not necessarily have to
vessel can cause severe residual stresses to develop lead to a rejection of the vessel. To know what
during thermal expansion and contraction. Since there dimensional changes, out-of-plumb, lack of
is no available field testing method to measure residual straightness, and/or local distortions to accept before
stresses, the guidelines for assessing fire damage deciding to repair, refurbish, or scrap a pressure
state that localized metal temperatures in excess of vessel, it may be necessary to develop criteria on a
538°C (1000°F) may introduce potentially harmful case-by-case basis using engineering judgment, local
residual stresses and, therefore, a field stress relieving regulatory guidelines, and plant policy. If proper
heat treatment may be necessary to reduce uneven or support is required for the decision, it may be
undesirable residual stresses.1 This is particularly necessary to conduct a stress analysis in concert with
relevant to carbon steel vessels in HF service because a vessel design engineer. This will only be possible if
of the potential problem of hydrogen embrittlement accurate and precise dimensional measurements are
and/or hydrogen stress cracking. Because of the available to evaluate the effect of out-of-plumb or to
relatively low hardness level measured during this characterize the bulge, the depression or the local
evaluation and the fact that the maximum exposure in distortion in a vessel. However, procedures for
the vessels was estimated to be lower than 540°C, dimensional checks are not specified in the available
field stress relieving heat treatment was not deemed refinery guidelines for assessing suitability for further
necessary. service of vessels after fire exposure. Since the
methods used here were found to be quite suitable for
Fitness for Further Service this purpose, they will be recommended as standard
The process of determining the fitness of pressure practice at this refinery.
vessels after a fire is not straightforward. Except for The microstructure of a steel may show some
new construction specifications, no new information degree of spheroidization of the Fe3C or even evidence
was found regarding acceptable deviations for of partial austenitization, which modifies the distribution
dimensions, straightness, and out-of-plumb conditions. and size of the pearlite colonies. None of these

CORROSION–Vol. 49, No. 5 433


Calculation of the Hoop Stress Acting in Some Vessels in the Unit,
Based on the Operating Pressure
Inside Diameter Actual Mean Operating Pressure Hoop Stress(A)
Equipment (mm) Thickness (mm) kg/cm2 psi kg/mm2 psi

V-2A 1830 22 15.0 213 6.24 8865

V-4 3948 24 8.1 115 6.66 9464
V-8 1372 15 15.0 213 6.86 9748
V-10 742 15 28.5 405 7.05 10017
The stress was calculated using the theoretical expression for Hoop Stress = (p D) / (2 t), where p is the internal pressure,
D is the diameter, and t is the wall thickness.

FIGURE 16. Creep rupture properties of carbon steel plate.5

changes necessarily mean that the vessel should be applicable code. Thus, although hardness testing and
rejected. These microstructural changes influence the in-situ metallography are probably the most common
creep properties of a low-carbon steel but have little tools recommended for assessing fire damage and
effect on the room temperature properties of these suitability for further service, the results they provide
steels, particularly with respect to the ultimate tensile may be limited and difficult to interpret.
strength used as a basis to determine the design A better method may rely more on the results of
stress of the vessel in this refinery. Since none of the proper measurements of the actual shape of the
vessels, columns, and heat exchangers in this unit selected vessels (Figure 17). If the vessels do not
operated in the creep range, high temperature exhibit any distortion, they have not been affected by
properties of the steel were not relevant. the fire, and the metallography and hardness tests
Excessive softening, detected by field hardness become redundant. With dimensional measurements,
testing, might be a good reason to reject a vessel, but it will be possible to detect and measure distortions
softening may not occur in short-term heating of low- and pinpoint the most relevant zones, where
carbon steels, unless heated to very high metallography and hardness testing can be useful in
temperatures. In that event, plastic or creep deciding the next action required.
deformation would cause an evident distortion. If The procedure is based on the fact that the range
hardness testing indicated softening below an of heat exposure likely to begin causing damage on
acceptable limit, the required action would be to low-carbon steel vessels coincides with the range
remove samples for tensile testing to verify compliance where creep deformation or ruptures occur under the
with minimum tensile requirements specified in the effect of the internal pressure. For those cases where,



FIGURE 17. Proposed fire damage assessment procedure for low-carbon steel pressure

CORROSION–Vol. 49, No. 5 435


for some abnormal reasons, there is no pressure in The methods used to derive profiles on the vessel
the vessels during the fire, damage can occur only surface, to plot the circumferential measurements vs
at much higher heat exposure, where low-carbon the distance along the whole length or height of the
steels become so weak that some distortions or vessel and that used for measuring out-of-plumb, were
deformations become evident. This was the case of suitable for this purpose. They provided additional
the steel platforms that collapsed under their own quantitative information of the direct effect of the fire
weight. and the damage that might have occurred as a
The criteria are defined better in terms of consequence, even in those cases where there was
thickness, but excessive thinning caused by a fire is no noticeable change in hardness and microstructure.
unusual. In any case, if thicknesses are below the These measurements were essential in cases where
retirement thickness, a decision will have to be made stress analysis was judged necessary for acceptance
to repair, replace, or rerate the vessel to comply with or when a vessel was returned to service without
construction code requirements.(6) In this case, there repair.
are usually regulatory guidelines or company policies ❖ The apparent inconsistency of having external
disallowing operation of pressure vessels with steel structures that were badly warped and distorted
thicknesses below the retirement value. The actual due to a very severe heat exposure (estimated to be
measured thickness used to verify whether thickness is in the order of 1000°C or higher) and the fact that the
lower than the allowable minimum must be an average vessels on which these structures were supported,
taken according to proper procedure, as specified in through steel lugs welded directly on their surfaces,
existing guidelines.8 were simultaneously subjected to only medium heat
exposure with temperatures not higher than probably
CONCLUSIONS 540°C, was attributed to the cooling effect of the fluid
that remained in the vessels. In the case of liquid,
❖ Because of the duration of the fire, only short-term much of the supplied heat was used to cause boiling
heating was considered to have occurred. Under of the liquid at the internal pressure of the vessel and
these circumstances, hardness testing and/or in-situ this must set a limit on the increase in vessel wall
metallography of the low-carbon steel grades used to temperature.
build the vessels might not provide necessary infor- ❖ In the case of vessels that contained only gas or
mation to declare suitability for further service. These gaseous mixtures, whether proper for a normal
low-carbon steels may get neither significantly harder operation condition or produced by temperature
nor softer, even if exposed to high temperatures. This increases during the fire, the situation was less
indicated few microstructural changes. understood, particularly in the uninsulated vessels
The use of hardness testing and in-situ such as V-8 and V-10. However, because of the
metallography were even more limited on Monel condition of the molten aluminum sheets used as
vessels. Except for grain growth, no other jackets for external insulation systems in the adjacent
microstructural change took place in Monel when vessels located farther from the center of the fire, it
accidentally heated to high temperatures, but actual was clear that either direct flame impingement or
grain growth could not be established easily unless radiant heating was such that the temperature was
grain size is known beforehand for an unaffected able to reach at least the necessary level for
portion of the same metal. aluminum to melt. The fact that there was no
❖ Since the required heat exposure to produce the evidence suggesting vessel temperatures reached the
significant microstructural or hardness changes was same level of heating must be related to a cooling
expected to be in the range where the strength of effect of the gas or gaseous mixtures contained within
unprotected Monel or carbon steels was considerably the vessels at the time of the fire.
reduced, a more effective way to assess fire damage ❖ With the exception of one vessel that was
was to make dimensional checks on the affected refurbished because of evident fire damage and
vessels and thus determine and measure any repaired because of an in-service corrosion
distortion. phenomenon which gave rise to areas with crack-like
features having a striated or tree-bark appearance,
the rest of the vessels, heat exchanger, and the
column evaluated were returned to service without
The action must be taken despite the fact that a thickness below the major repairs or further testing. Except for a few low
minimum permissible limit does not mean that the vessel will fail in
service. Minimum allowable shell thickness is calculated based on the hardness values, considered to be original ones
design pressure, which is always higher than the operating pressure, and rather than a consequence of the fire, the results did
on the design stress, which is far away from the stress required for the
onset of plastic deformation and still farther away from that required for not show the occurrence of any serious fire damage
fracture. in the evaluated pressure vessels.



2. ASME Boiler and Pressure Vessel Code: Section VIII, Pressure Vessels,
ACKNOWLEDGMENT Division I (New York, NY: ASME, 1986).
3. ASME Boiler and Pressure Vessel Code: Section VIII, Pressure Vessels,
Division 2, Table ACS-2 (New York, NY: ASME,1986), p. 88.
The author acknowledges the contribution of 4. Steel for Elevated Temperature Service (Pittsburgh, PA: United States
Refinería ISLA (Curazao), S.A., affiliated to Petróleos Steel, 1949): p. 30.
de Venezuela, S.A. 5. G.V. Smith, An Evaluation of the Elevated Temperature and Creep-
Rupture Properties of Wrought Carbon Steel, ASTM Data Series DS
11S1 (Philadelphia, PA: ASTM, 1970).
REFERENCES 6. L.E. Samuels, Optical Microscopy of Carbon Steel (Metals Park, OH:
American Society for Metals, 1980): pp. 27, 129, and 175.
1. Guidelines for Assessing Fire and Explosion Damage, MTI Publication 7. H.R. Copson, C.F. Cheng, Corrosion 12 (1956): p. 647.
no. 30 (St. Louis, MO: Materials Technology Institute of the Chemical 8. Pressure Vessel Inspection Code, API 510, 2nd ed. (Washington, DC:
Process Industries Inc.,1990): p. 29. American Petroleum Institute, April 1981).

CORROSION–Vol. 49, No. 5 437