Structural Integrity of a Standpipe

Levi de O. Bueno Component in a Petrochemical

Luiz Marino
Department of Materials Engineering,
Universidade Federal Sao Carlos,
Rodovia W. Luiz, km.235,
13565-905 Sao Carlos(SP), Brazil
Flavio A. S. Serra
Fernando T. Gazini
PETROBRAS/REPLAN,
Rodovia SP 332, km 132
13.100 Paulinia (SP), Brazil
Catalytic Cracking Unit: Part
1—Assessment of Creep Rupture
Properties
During a shutdown for general maintenance of a catalytic cracking unit, intergranular
cracks were observed to occur during welding of the regenerator’s standpipe component
manufactured from 2 1/4 Cr-1Mo steel. The cracking was observed to be related to
intensive carbide precipitation in grain boundaries. To overcome the problem it was
decided to heat-treat the relevant section of the component to dissolve these carbides and
make possible its welding to a new virgin section of the tube. Samples of the material in
its various conditions (virgin, ex-service, heat-treated and welded) were taken to check
the efficiency of the thermal treatment in reducing the embrittlement effects and to carry
out a general assessment of the remaining life of the component related to creep behavior
considering smooth bar creep specimens. 关S0094-4289共00兲00403-5兴

Introduction
During a shutdown period for general maintenance of a cata-
lytic cracking unit in Brazil, with the unit completing 149,800
hours of operation 共17.3 years兲, and approaching its design life of
20 years, it was found necessary to weld a pressure gauge con-
nection of the standpipe, an internal component of the regenerator
unit, manufactured of 2 1/4 Cr-1Mo steel. Figure 1 presents a
drawing of the components of the petrochemical cracking unit.
The welding operation was observed to be ineffective because
during cooling of the welding zone extensive cracks were detected
on the base metal. The problem led to a closer examination of a
larger area of the material around the pressure gauge connection
which revealed a substantial reduction in wall thickness of the
pipe and the existence of a long crack around the connection. The
pipe was about 20 m height, 1 m diameter, and 25 mm wall
thickness. Service oxidation and erosion due to the high flux of
matter flowing up the column resulted in severe local metal loss.
Thus, the measured average thickness was about 15 mm, with
local regions being about 10 mm at the lower extremity of the
pipe.
Field metallographic examination of the material showed inter-
granular cracks associated with massive carbide precipitation on
grain boundaries, suggesting dangerous embrittlement of the ma-
terial. A similar problem had already been experienced at another
cracking unit. To overcome the problem it was decided to replace
about 5 meters of the lower extremity of the standpipe, where the
the loss in wall thickness was most severe. A section of about 40
cm of the remaining extremity was then submitted to a partial
carbide resolubilization heat treatment which enabled the welding
of a new virgin tube segment to the deteriored standpipe material.
This resolubilization treatment consisted of a 5 hours plateau at
950°C followed by temper at 750°C, as shown in Fig. 2.
To verify the safe operation conditions of the unit, a general
program of laboratory examination of the material was made to
check possible embrittlement effects associated to residual car-
bides still present in the microstructure and also a general assess-
Contributed by the Materials Division for publication in the JOURNAL OF ENGI-
NEERING MATERIALS AND TECHNOLOGY. Manuscript received by the Materials
Division October 15, 1999; revised manuscript received March 7, 2000. Guest Edi-
tors: Raj Mohan and Rishi Raj.
ment of its remaining life related to creep behavior. This article
gives a description of the creep strength of the material in the
following metallurgical conditions: virgin, ex-service, heat-treated
and welded, determined basically with smooth bar creep speci-
mens. In Part 2 of this work, an assessment of the problem is also
made considering notched bar creep specimens.
Methodology
The 2 1/4 Cr-1Mo steel was studied in four different metallur-
gical conditions:
• Virgin 共V兲: as extracted from a sample of the standpipe with
no service at all in the unit, in a typical annealed condition.
• Serviced 共S兲: as extracted from a sample of the pipe after
service for 17.3 years in the unit;
• Restored by heat-treatment 共R兲: as extracted from a sample of
the serviced material which was heat-treated under the se-
quence shown in Fig. 2;
• Welded 共W兲: as extracted from a sample having a weldment
between the virgin and the heat-treated material.
Hardness measurements were made with a VEB Brinell/
Vickers apparatus and impact data with a Mohr-Federhaff Charpy
pendulum.
Data on room and hot tensile tests were obtained with a Instron-
1127 testing machine, and creep tests were carried out on standard
constant load creep machines 关1,2兴, according to ASTM E 139.
The specimens for the constant strain rate tensile and constant
load creep tests were of the same shape and dimensions, accord-
ing to Fig. 3共a兲.
Some creep tests were also carried out on specimens having a
welded joint between the virgin and the restored material, simu-
lating the situation of the standpipe after the welding process. In
this case, the creep specimens had the weld metal portion situated
in the center of the specimen gauge length, as shown in Fig. 3共b兲.
The creep tests with specimens of the virgin, ex-service and
restored material were all carried out with extensometry, which
enabled generation of creep strain versus time data during the test
until rupture. For each test a number of about 100 strain: time
readings were selected to define the creep curve in each condition
of the material.

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 Fig. 1 Schematic view of the pretrochemical cracking unit
Fig. 2 Heat treatment schedule carried out on the ex-service
material to enable welding operation of a new segment of the
standpipe component
Fig. 3 „a… Constant strain rate tensile and creep test smooth
bar specimens; „b… cross-weld creep test specimens
The specimens for both constant strain rate tensile and creep
tests were always extracted from the longitudinal direction of the
pipe.
Results
As shown in Table 1, chemical analysis revealed that the aver-
age compositions of the virgin and ex-service material were
within the ASTM limits for A387, grade 22 steel, except for the
the ex-service material which had a much higher carbon content
than the specification.
The effect of the heat-treatment on hardness was remarkable, as
shown in Table 2. The ex-service material showed an average
level of 141 HV20 , which was close to the hardness level of 151
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HV20 for the virgin material. The heat-treated material exhibited
higher values around 378 HV20 , which should be related to the
bainitic microstructure with high supersaturation of carbon.
Room temperature tensile tests of the ex-service material
showed that only its elongation values were outside the ASTM
standards. Comparisons with data from the virgin material, how-
ever, revealed a greater loss of ductility and also some reduction
on the yield stress and tensile stress levels, as shown in Table 3.
Hot tensile data of the heat-treated material also shows much
lower elongation and much higher tensile strength values than the
ex-service material, as mentioned in Table 4. The strength level of
the heat-treated material was found to be equivalent to data pub-
lished by Watanabe et al. 关3兴 for a 2 1/4 Cr-1Mo steel with 80,000
hours use at temperatures of 560–570°C, as shown by Fig. 4. It
should be pointed out, however, that in this case both the virgin
and ex-service materials had the same chemical composition 共2.23
Cr-0.97 Mo-0.09 C-0.28 Si-0.49 Mn-0.014 P-0.005 S兲.
The results of the creep tests are shown in Table 5, where T is
⬘ is minimum creep rate, t r is rupture
temperature, ␴ is stress, ␧ min
time, and ␧ r is the elongation at fracture. According to the
fracture-mechanism map for annealed 2 1/4 Cr-1Mo steel by
Ashby and co-workers 关4兴, the above range of stress and tempera-
Table 1 Chemical composition of the virgin and the ex-service
standpipe material
Table 2 Hardness data for the 3 conditions of the material
JULY 2000, Vol. 122 Õ 265
 Table 3 Room temperature tensile results
Table 4 Hot tensile results
ture conditions are within the region of transgranular creep frac-
tures tending to the border of the intergranular creep fractures at
the lower stress levels. The temperatures levels explored 共600–
650°C兲 could be considered as situated in the low temperature
range 共T/Tm⬍0.6兲, and the stress levels in the intermediate stress
range for creep ( ␴ /E⫽10⫺4 ⫺10⫺3 ).
As expected, the results of the ex-service material reveal a no-
ticeable decrease in creep life compared to the virgin material. On
the other hand, the data of the heat-treated material presented the
same or even greater levels of creep strength compared to the
virgin material. This fact, therefore, led to a decision to consider a
more detailed evaluation of the creep behavior of the ex-service
Fig. 4 Constant rate tensile data for 2 1Õ4 Cr-1Mo, for virgin
and ex-service conditions, according to Watanabe et al. †3‡
Table 5 Creep results for 2 1Õ4 Cr-1Mo standpipe steel using
smooth bar specimens
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Fig. 5 Minimum creep rate x stress: „a… for the ex-service ma-
terial at 600, 625, and 650°C; „b… for the other conditions of the
material at 600°C; „c… and at 650°C
material rather than of the heat-treated material. The welded ma-
terial on the other hand, exhibited levels of creep strength between
the virgin and ex-service material.
Figure 5 shows data of minimum creep rate versus stress for the
various conditions of the material in this work. The minimum
creep rates for the ex-service material are compared to a data basis
for 2 1/4 Cr-1Mo typical virgin steel in the normalized and tem-
pered condition, reported by Parker 关5兴, as shown in Fig. 5共a兲 at
three different temperature levels. According to this author, a
single value of stress exponent n is appropriate for only a limited
range or applied stress, with n changing from about 8 at high
stress accelerated laboratory tests to 3 at conditions approaching
those of service in plant. For the ex-service material in this work,
the n values varied as depicted in Fig. 5共a兲 according to the three
different temperature levels investigated. Figures 5共b兲 and 5共c兲
compare the results on the other conditions to the ex-service ma-
terial data, at 600 and 650°C, respectively. The minimum creep
rates exhibited by the material in the virgin, heat-treated, and
welded conditions are considerably lower than those of the ex-
service material.
Figure 6 shows data of stress versus rupture time and Fig. 7
shows the variation of minimum creep rate as function of inverse
temperature. Despite the scarce amount of data, a tendency for
inflexion was noticed for the two isostress sets of data with 3
points of the ex-service material indicating a possible decrease in
apparent activation energy of the material at the higher tempera-
tures 共Q f ⬃575 kJ/mol at 600°C and Q f ⬃197 kJ/mol at 650°C兲.
The lines joining the two point isotress sets of the other conditions
have slopes varying from 281–431 kJ/mol. Of course, the data are
too scarce to obtain precise values of this parameter in each case,
but an overall average apparent activation energy value seems
more reasonable to be estimated from the whole set of data, which
gives an estimate of Q f ⬃318 kJ/mol for all conditions of the ma-
terial. This value is in good agreement with data reported for this
parameter for Cr-Mo steels tested in similar range of stresses and
temperatures 关6兴.
Figure 8 shows data of minimum creep rate versus rupture time
for the various conditions of the material. A straight line could be
satisfactorily fitted to the whole set of data including all material
and test conditions in the form of the Monkman-Grant relation-
ship trm•␧ s⬘ ⫽K 关7兴. The best values of these constants were m
Fig. 6 Stress x rupture time; „a… for the ex-service material at
600, 625, and 650°C; „b… for the other conditions of the material
at 600°C; „c… and at 650°C
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 Fig. 9 Variation in stress-rapture strength of 2 1Õ4 Cr-1Mo
steel under different heat-treatment conditions, plotted accord-
Fig. 7 Minimum creep rate versus inverse temperature for ing to the Larson-Miller parameter, as reported by Viswanathan
isotress tests †12‡

curves vary for four different heat-treatment conditions, according

to Viswanathan 关8兴. Remarkable straight lines could be fitted to
the data for the two quench and tempered conditions.
Viswanathan 关8兴 analyzed his data in the form of a stress x P plot,
as seen in Fig. 9, but usually such curve are presented in the form
of LOG (stress) x P. The normalized/tempered and the annealed
materials exhibited lower strength than the two quench tempered
conditions on most of the range stress/temperature studied. For
longer rupture times, however, there is a clear tendency for this
situation to be reverted.
An attempt was made to analyze the creep rupture data of this
work also according to the Larson-Miller methodology 关11兴. The
Fig. 8 Minimum creep rate versus rupture time data for all
two isostress regression lines by the 3 points of the 51.7 MPa and
conditions of the 2 1Õ4 Cr-1Mo steel in this work. Also shown
scatter band „dotted lines… according to Reference †8‡ 68.9 MPa data of the ex-service material data were verified to
produce values for the constant C very close to 20, as shown in
Fig. 10, which agrees with values usually taken for 2 1/4 Cr-1Mo
⫽1.026 and K⫽0.111, which agree well with data published by steel 关12,13兴. It was also observed that the values of the intercepts
Viswanathan 关8兴 for the same steel in the virgin condition. The of the two-point-isostress regression lines for the rest of the data
value of K in the present work was somewhat higher than the of the ex-service, virgin and heat-treated material had also good
value of K⫽0.044 mentioned by Viswanathan 关8兴, as shown in agreement with the constant C value of 20, as seen in Fig. 10. It
Fig. 8. The value of K⫽0.111 is closer to a value of K varying was also interesting to notice that an average of C⫽20.74 was
from 0.7 to 0.75 reported by Ahila and co-workers 关9兴 on a com- obtained for the whole set of isostress data, including the results
parative study of creep behavior of 2 1/4 Cr-1Mo steel as base of tests on notched specimens.
metal, induction pressure and manual metal arc weldments. At-
tempts to do linear regression to separate sets of data according to
the same temperature level or material condition resulted in minor
variation of the constants K and m which could not be confirmed
anyway due to the short amount of data available. In the present
case, the data for the welded material can be seen to show some
rather systematic trend to a slightly lower slope in Fig. 8. The
Monkman-Grant relationship considering only the data for the
welded material would present values of K⫽0.030 and m
⫽0.806, whereas for the other conditions (V,S,R) taken together
the Monkman-Grant relationship would have constants K
⫽0.217 and m⫽1.129. The validity of the Monkman-Grant rela-
tionship has recently been confirmed by Evans 关10兴 for different
batches of 2 1/4 Cr-1Mo steel tubes in a statistical detailed study.
Evans noticed that temperature conditions do appear to influence
the intercept log K.

Discussion
The creep strength behavior of 2 1/4 Cr-1Mo steel is highly
dependent on the microstructural condition of the material accord-
ing to different heat treatments which can be carried out for dif- Fig. 10 Isotress LOG„rupture time… x inverse temperature data
ferent application. Figure 9 shows how parametric Larson-Miller for the virgin, ex-service, heat-treated and welded material

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Fig. 11 Larson-Miller analysis for the creep results of the
standpipe material
It must be emphasized, however, that according to Pink 关14兴 the
Larson-Miller methodology is in agreement with the theoretical
equation for low temperature deformation only and cannot de-
scribe the high temperature properties accurately. Extrapolations
using this method to predict properties at high temperatures are
spurious for the precise reason that this parameter applies only to
low temperature deformation. The method becomes totally unac-
ceptable as soon as diffusional flow sets in at low stresses, which
can be clearly detected at viable times only at the highest tem-
peratures near melting point, which are not of practical relevance.
That the Larson-Miller parameter is widely accepted may be due
to its use within a phenomenological procedure which provides a
fairly accurate description of rupture properties in the lower part
of the high temperature range where the transition to diffusional
flow starts only after exceedingly long times. This and other tra-
ditional extrapolation methods have two serious limitations: 共a兲
steady-state creep is assumed to be the only mode contributing to
deformation—primary and tertiary creep do not enter the evalua-
tion; 共b兲 their basic equations do not take account of possible
changes of the structure during the creep process, since they rely
on steady-state conditions. A realistic extrapolation of creep rup-
ture times can only be possible when formulations for all the
deformation mechanisms, which are known to operate over a wide
range of temperatures and stresses, are taken into account 关15兴.
This, in connection with the incorporation of modern damage
mechanisms, may allow predictions of the rupture times.
Figure 11 shows the parametric data for all creep results, ac-
cording to the Larson-Miller analysis 关11兴. The figure also con-
tains the line of average values of the 2 1/4 Cr-1Mo steel pub-
lished by the ASTM Data Series 关16兴. It can be verified that the
results of the virgin material show good agreement with the lit-
erature data, The curve of the ex-service material, however, is
displaced downwards indicating a noticeable reduction in creep
strength, but with an approximately similar trend of decrease in
resistance with the Larson-Miller parameter. The points referring
to the virgin material and the welded material are situated much
closer to the ASTM master curve for 2 1/4 Cr-1Mo steel data.
The standpipe component was designed to work at a maximum
operational temperature of 650°C and a stress of 15 MPa at the
critical section of the component, mostly due to the pipe self
weight. According to a simple procedure of extrapolation of the
data referring to the ex-service material in Fig. 11, a remaining
life of about 10 years 共corresponding to P⬵41,500兲 could still be
expected for the component in relation to creep effects, which was
rather superior than the four years programmed for the next unit
shutdown.
The curve for the heat-treated material is situated clearly above
the points of the virgin material, but presents a much faster trend
of drop in resistance with the Larson-Miller parameter compared
to the other conditions. Since only a sector of only 5 meters of the
268 Õ Vol. 122, JULY 2000
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entire standpipe was substituted on its lower extremity, calcula-
tions indicated a level of stress of about 1/3 of the level of 15 MPa
at the region of the weldment carried out between the heat-treated
material and the new virgin segment of the pipe, which would
lead to a life of at least 10 years, for the heat-treated material,
again higher than the scheduled four years period for the next
shutdown.
Conclusions
The accelerated creep tests have indicated a residual life of
about 10 years, for the ex-service material under the initial design
conditions of the structure. The heat-treated material has shown
the worse trend of creep strength loss with time. The level of
critical stress which should be acting on the material in this con-
ditions, however, would lead to rupture only for times also well
superior to the programmed time for the next shutdown. The be-
havior of the welded material was verified to be in between the
virgin and the ex-service material and therefore did not bring
much concern as well.
Acknowledgments
The authors are grateful to PETROBRAS-Petroleo Brasileiro
S/A./REPLAN, for obtaining permission to publish these results.
Dr. Luiz Marino is thankful to RHAE/CNPq for a grant received
during the experimental work and Prof. L.O. Bueno wishes to
express his gratitude to UFSCar and FAPESP for their financial
support during the analysis and preparation of this article while at
the University of Wales Swansea, U.K. Prof. L.O. Bueno is also
grateful to Profs. B. Wilshire and J.D. Parker for their helpful
comments on the article.
References
关1兴 Bueno, L. O., 1987, ‘‘Máquinas protótipos para ensaios de fluência em metais
a altas temperaturas, Part 1 and Part 2,’’ Proc. of II ETUAN-Encontro para
utilizaçāo de aços nacionais, Rio de Janeiro, pp. 916–948.
关2兴 Bueno, L. O., 1991, ‘‘Desenvolvimento de máquinas para ensaio de fluência
em metais a altas temperaturas, Part 1 and Part 2,’’ Proc. of 46°. Congresso
Anual da ABM, São Paulo, 4, pp. 1152–1170.
关3兴 Watanabe, T., Sato, K., Biss, V. A., Wada, T., and Miyano, K., 1982, ‘‘El-
evated temperature tensile strength of Cr-Mo pressure vessel steels after long
term service,’’ Proc. of Advanced Materials for Pressure Vessel Service with
Hydrogen at High Temperature and Pressure, Louisiana, ASME Publication
MPC-18, pp. 237–257.
关4兴 Fields, R. J., Weerasooriya, T., and Ashby, M. F., 1980, ‘‘Fracture-mechanics
in pure iron, two austenitic steels, and one ferritic steel,’’ Metall. Trans. A,
11A, pp. 333–347.
关5兴 Parker, J. D., 1985, ‘‘Prediction creep deformation and failure for 1/2 Cr-1/2
Mo-1/4 V and 2 1/4 Cr-1Mo steels,’’ ASME J. Pressure Vessel Technol., 107,
pp. 279–284.
关6兴 Viswanathan, R., 1993, ‘‘Damage Mechanisms and Life Assessment of High-
Temperature components,’’ ASM International, 2nd Printing, Ohio.
关7兴 Monkman, F. C., and Grant, N. J., 1963, ‘‘An empirical relationship between
rupture life and minimum creep rate,’’ Proc. ASTM, Vol. 56, p. 595.
关8兴 Viswanathan, R., 1974, ‘‘Strength and ductility of 2 1/4 Cr-1Mo steels in
creep,’’ Met. Technol., 1, pp. 284–293.
关9兴 Ahila, S., Ramakrishna Iyer, S., and Radhakrishnan, V. M., 1994, ‘‘Compara-
tive study of creep behavior of 2 1/4 Cr-1Mo steel and its weldments,’’ Int. J.
Pressure Vessels Piping, 58, pp. 289–293.
关10兴 Evans, M., 1997, ‘‘Some interpolative properties of the Monkman-Grant em-
pirical relation in 2 1/4 Cr-1Mo steel tubes,’’ Int. J. Pressure Vessels Piping,
72, pp. 177–191.
关11兴 Larson, F. R., and Miller, J., 1952, ‘‘Time-temperature relationship for rupture
and creep stresses,’’ Trans. ASME, 74, pp. 765–775.
关12兴 Scifo, A., 1991, ‘‘Embrittlement phenomena and remanent life assessment for
Cr-Mo steels—Part 2,’’ Welding Int., 5, No. 2, pp. 102–117.
关13兴 Liaw, P. K., Saxena, A., and Schaeffer, J., 1989, ‘‘Estimating remaining life of
elevated-temperature steam pipes, Part 1,’’ Eng. Fract. Mech., 32, No. 5, pp.
675–708.
关14兴 Pink, E., 1994, ‘‘Physical significance and reliability of Larson-Miller and
Manson-Haferd parameters,’’ Mater. Sci. Technol., 10, pp. 340–344.
关15兴 Evans, R. W., and Wilshire, B., 1985, Creep of Metals and Alloys, The Insti-
tute of Metals, London.
关16兴 Smith, G. V., 1971, ‘‘Supplemental report on the elevated-temperature prop-
erties of chromium-molybdenum steels,’’ ASTM Data Series Publication DS
6S2, New Jersey.
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