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Materials Science and Technology

ISSN: 0267-0836 (Print) 1743-2847 (Online) Journal homepage: http://www.tandfonline.com/loi/ymst20

Hydrogen attack of pressure-vessel steels

P. G. Shewmon

To cite this article: P. G. Shewmon (1985) Hydrogen attack of pressure-vessel steels, Materials
Science and Technology, 1:1, 2-11, DOI: 10.1179/mst.1985.1.1.2

To link to this article: http://dx.doi.org/10.1179/mst.1985.1.1.2

Published online: 02 Dec 2013.

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Critical Hydrogen attack (HA) is a degradation process occurring in steel exposed to
hot, high-pressure hydrogen. It is caused by the nucleation, growth, and ultimate
assessment link-up into fissures of small methane bubbles - primarily on grain boundaries.
The location and growth kinetics of the submicrometre bubbles during the
incubation period before fissure formation has been studied only in the past few
Hydrogen attack years. Growth is limited primarily by grain-boundary diffusion, though creep of
the ligaments between bubbles can be limiting under certain conditions. The
of pressure- processes limiting bubble nucleation are unclear though there seems to be a
vessel steels critical stress (methane pressure plus applied stress) above which the bubble
density increases greatly. Alloying with Cr enhances the resistance to HA,
primarily by reducing the bubble density rather than by reducing the bubble
growth rate. The process of bubble growth and link-up is completely analogous to
that by which grain-boundary voids link-up to limit the creep ductility of alloys.
Simultaneous HA and creep leads to a marked acceleration of failure, though it is
unclear whether this is caused primarily by the enhancement of nucleation or by
growth. ,. MST/112

1985 The Institute of Metals. Manuscript received 9 August 1984; infinalform


8 October 1984. Professor Shewmon is in the Department of Metallurgical
P. G. Shewmon Engineering, Ohio State University, Columbus, Ohio, USA.
Downloaded by [Universite Laval] at 09:13 09 May 2016

Introduction dioxide bubbles during annealing in an oxidizing


atmosphere has been the subject of recent studies.10,11
The most important difference-between these cases and
Steel exposed to high-pressure hydrogen at temperatures the development of methane bubbles in PV steels is the
above 300C may appear to be unaffected for weeks, or value of the equilibrium gas pressure relative to the creep
even years, and then in a relatively short time can lose strength of the metal matrix. In the cases of copper, silver,
much of its ductility and strength. This is caused by the and nickel the equilibrium gas pressures far exceed the
nucleation, growth, and merging of methane bubbles along creep strength of the metal matrix so that most of the
grain boundaries to form fissures. This process is called incoming solute (hydrogen or oxygen) reacts near the
hydrogen attack (HA). It is distinctly different from the surface to form relatively large bubbles there, Le. bubble
more commonly studied hydrogen embrittlement of steel growth is limited by hydrogen or oxygen supply. This
which occurs at much lower hydrogen pressures and surface layer of large bubbles grows inward in a manner
temperatures. An understanding of the mechanism of HA is resembling that found for the internal oxidation of alloys.
of interest better to predict the behaviour of pressure However, the maximum (equilibrium) methane pressure
vessels containing hot high-pressure hydrogen, and also as that develops in steel leads to only very slow creep, and
another way to study the processes that limit creep thus the strength of the metal matrix greatly slows bubble
ductility in alloys. growth, i.e. bubble growth is not limited by hydrogen
Hydrogen attack was discovered about 60 years ago in supply. As a result the hydrogen will diffuse to a greater
Germany during the development of the process for the depth before it can react to form methane. Thus, bubbles
chemical synthesis of ammonia. 1,2 It has been of primary form homogeneously to an appreciable depth (many
concern to the petroleum industry since they have been the centimetres) beneath the surface of the steel. This matrix
main group who built large pressure vessels (PVs) to carry restraint also accounts for the substantial incubation time
out the hot hydrogenation of feedstock. With the before the bubbles grow to a size sufficient to affect the
consideration of the development of large plants to gasify mechanical properties, or be reliably observed by non-
coal, another group has developed an interest in this destructive examination techniques.
subject. This article begins with a summary of the factors that
Alloying with carbide-forming elements has improved influence the HA of steels and then a more detailed
the HA resistance of low-alloy steels, and allowed industry discussion is given of the models that have been developed
to minimize failures caused by this phenomenon. 3-6 to describe the nucleation and growth of the methane
However, until the last decade there has been relatively bubbles. The discussion is limited to the behaviour of
little study of the atomic processes that limit the nucleation carbon steel and 2'25Cr-lMo steel in a gaseous hydrogen
and growth of the bubbles. These recent studies have been atmosphere. However, exactly the same kind of
motivated by the availability of new experimental degradation and decarburization is found in boiler piping
techniques to study the submicrometre bubbles that grow made of carbon or low-alloy steel,12 and recently the
during the incubation period, as well as by the desire better formation of methane bubbles has been reported in
to address the question of what would limit the life and 18Cr-8Ni stainless steel exposed to a flame.13,14 In both
operating conditions for very large PVs in coal-gasification cases the hydrogen is generated by the oxidation of the
plants. steel by water. The hydrogen potential (chemical activity) is
The growth of internal gas bubbles in a metal through high but unknown.
the inward diffusion of a mobile gas atom and chemical The atomic processes involved in the growth of methane
reaction to form an insoluble gas molecule is a bubbles in steel bear many similarities to the slow growth
phenomenon found in several systems. The embrittlement of grain-boundary voids in the creep of alloys, and the
of oxygen-bearing copper 7 or silverS by the formation of models for methane-bubble growth will draw heavily on
steam bubbles during annealing in a hydrogen-bearing the creep models. Bubble nucleation in HA is less well
atmosphere is well established. The development of understood, as in the case of void nucleation in creep.
nitrogen bubbles and their growth to fissures has been However, it is clear that the bubbles in HA must nucleate
demonstrated in the nitriding of stee1.9 The embrittlement heterogeneously because of the relatively low methane
of carbon-bearing nickel by the formation of carbon pressures available to drive nucleation.

2 Materials Science and Technology January 1985 Vol. 1


Shewmon Hydrogen attack of pressure-vessel steels 3

NELSON CURVES (API, 1977) several samples under a fixed pressure but at increasing
temperatures. A complete loss in ductility is usually found
over a temperature increment of 50 K.
600 3. Pressure. Hydrogen attack is not observed in carbon
II steel until the hydrogen partial pressure PH exceeds 1 MPa .
.\
C-)
At higher pressures the incubation time decreases slowly
~500
0::
1\. \ 2.25 Cr -1.0 Mo with increasing pressure, or equivalently the temperature
:;::)
t--
I ', . threshold for HA drops (see Fig. 1).
~LoU 400
a...
::E
LoU
t-- 300
< ------- O~MO
---
Steel
4. Alloying. Alloying with carbide-forming elements can'
significantly increase the steel's resistance to HA, that is,
the steel resists attack to a higher temperature. 3,5 The
.- .- .- _ . _. CARBON Steel elements most commonly added for this purpose are Cr
200
-'- and Mo. Reducing the carbon content is not an effective
10 15 20 MPa
approach since steels with only a few hundredths per cent
o 1 2 3 ksi of carbon are still attacked.2, 17 .
HYDROGEN PARTIAL PRESSURE 5. Microstructure. In carbon steel no changes are
Lines suggested by API as .upper limits of tempera-
obvious under the light microscope during the incubation
ture and pressure for use of various steels5 .
stage. However, work with the scanning electron
microscope (SEM) has shown that early in the incubation
period discrete bubbles develop on grain-boundary
carbides (see Fig. 2). These grow and ultimately link up to
Observations form thin fissures along the grain boundariesl8,19 (see
Fig. 3). These fissures in turn link together, and often vent
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methane to the surface.20 As long as the bubbles contain


The outline of the HA phenomenon was well defined by the equilibrium methane pressure, methane forms slowly
Naumann in the late 1930s.2,3 The Germans were then and there is very little decarburization of the matrix.
working with ammonia synthesis at 300-600C, and
However, once the methane in fissues vents to the surface,
21-96 MPa hydrogen pressure, as well as coal liquefaction methane forms as rapidly as carbon can diffuse to the
at 400-550C and up to 69 MPa of hydrogen. 1,2 In the fissure surface, and decarburization of the regions on either
intervening period the operating limits to avoid HA in side of the fissures proceeds rapidly. These decarburized
common alloys have been better defined, but the outlines of regions increase in thickness, and the entire surface layer
the phenomenon are unchanged. The maximum pressures may become 'cracked' and decarburized.
commonly used commercially have decreased, the life of The formation of fissures is not homogeneous, but varies
components has appreciably increased, and the
from one part of the sample to another. Factors which
temperatures have remained roughly the same.
can increase the tendency of a region to fissure formation
Briefly, the characteristics of HA are: are: local cold work,2, 16,20 welding,21 and bands of
1. Incubation time. There is an extended period during inclusions.22,23 If the strings of inclusions run beneath and
which there are no changes in the room-temperature parallel to the external surface, fissures develop parallel to
mechanical properties of the steel exposed to hot, high- the surface, but the methane cannot vent to the surface.
pressure hydrogen. Then, in a relatively short time the This often results in surface blisters,2 which can become
mechanical properties deteriorate markedly, especially quite large.23
the toughness and ductility. 1,15,16 6. Mechanical properties. The easiest way to follow the
2. Temperature. The incubation time decreases rapidly effect of HA is by measuring mechanical properties at
with rising temperature. Equivalently, at any given pressure room temperature. In carbon steel fissuring always occurs
of hydrogen there is a temperature below which the and causes a clear shift in the mechanical properties. The
incubation time exceeds the life of the part, and no HA is effect is the earliest and most pronounced for impact
observed. This is the basis for describing the HA resistance
of alloys as is done in Fig. 1. A commonly used way to
study the susceptibility of an alloy to HA is to anneal

3 Bubble link-up into fissures: in this steel (REM-


treated Fe-O'2C, after 88 h, 450C, PH = 65 MPa)
local bubble density was higher and link-up into
2 Typical methane bubbles in HA of carbon steel fissures came earlier than in Fig. 2; however, the
(Fe-O'3C ESR steel after 88 h, 450C, PH = 65 MPa) methane gas is still trapped in fissures since pearlite
{Ref. 18) dissolution (decarburization) is negligible18

Materials Science and Technology January 1985 Vol. 1


4 Shewmon Hydrogen attack of pressure-vessel steels

properties, and next most severe for the ductility, while the bubbles. At lower temperatures where methane formation
ultimate tensile strength and the yield stress are last and is slower, and/or at later stages where the bubbles link up
least affected.2,15 to form fissures, the existence of the equilibrium pressure in
In unstressed, quenched and tempered (QT) 2'25Cr-1Mo the bubbles is less clear. However, during the long
steel Erwin24 reported no change in the room-temperature incubation time before bubble link-up the bubbles grow
tensile properties after 5 years at 540C and 21 MPa slowly and it seems quite probably that equilibrium is a
hydrogen even though a bubble volume fraction of between good approximation, at temperatures above 275-300C.
001 and 01 had developed. Under these stress-free Several experimental observations point to this.19,28-30
conditions bubbles form and grow, but fissuring does not The methane that generates HA in steel is formed by the
occur. However, Cuiffreda et al.25 showed that 138 MPa reaction
of hydrogen at 455C reduced the creep ductility
MxC+2H2=CH4+xM (1)
significantly in a test that failed in 6 months. Also, Wanagel
et a1.26 found that modest exposure to hydrogen (14 MPa, For Fe3C in carbon steel the activity of the carbide and the
600C, 20 d) developed methane bubbles sufficient to metal can be taken as unity. The equilibrium constant K
reduce the stress-rupture life materially in subsequent tests for this reaction can be written as
in an inert atmosphere at 600C. Both of these creep tests
were done under hydrogen-exposure conditions that would
1m = KIJ . . . . . . . . . . . . . . . (2)
have developed much less bubble volume by HA alone where 1m and IH are the fugacities of methane and
than was developed in Erwin's long-time tests. hydrogen, and Ao and AM are the activities of carbon and
7. Decarburization. The depth of decarburization in the metal (iron) atoms. For Fe3C, 1m is given by the
normal service 450C) should be negligible unless equation
fissuring develops to aid transport to and from the ambient
In/m=-13'3+13700/T+2InPH (3)
gas. In Cr-Mo steels exposed to hydrogen Masaoka
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et ai.2 7 reported surface decarburization and 'cracks' along where the fugacity of the hydrogen gas has been taken
grain boundaries near the surface. At 450C decarburiza- equal to its partial pressure, i.e~ hydrogen is assumed to
tion was negligible. Even after 1000 h at 600C the depth of behave ideally.31
decarburization was only 0'3-04 mm. The depth of grain- Odette and Vagarali32 have developed an equation of
boundary cracking (fissuring) at 600C increased with the state for methane in this range of temperature and
depth of decarburization and with PH' but was less than pressure. They show that 1m is adequately described by an
the depth of decarburization. equation of the form
(4)
where
Mechanisms C(T) = 2'375/T + 178 x 10- 3 1m > 104 MPa }
= 1187/T+309 X 10-3 (5)
Lengthening the incubation time is the critical factor in 103 <1m < 104 MPa
preventing HA. The use of sensitive dilatometry and the = 0005 1m < 103 MPa
SEM have established that during essentially all of the
The combination of these equations leads to relations
incubation period many small (submicrometre) methane
between PH2 and PCH4 as shown in Fig. 4. Note that at low
bubbles are growing on the grain boundaries of the stee1.19
hydrogen pressures and higher temperatures the lines on
Thus an analysis of the kinetics of this early period
this log-log plot approach the slope of Pm ~ P~, as would
becomes an analysis of the rates of nucleation and growth
be expected for ideal gas behaviour, while at high hydrogen
of these small bubbles. The pressurized bubbles create
pressures and lower temperatures the non-ideality of the
discontinuities in the stress normal to the grain boundaries
methane leads to a nearly constant methane pressure,
that results in a stress gradient exactly the same as that
independent of PH2 This high-pressure behaviour is a
caused by the stress discontinuities formed by voids on
strong contributor to the nearly pressure-independent
boundaries in samples under an external load. Thus the
temperature limit for HA found in Fig. 1.
atomic processes involved in the nucleation and growth of
methane bubbles in steel closely resemble the slow growth
of grain-boundary voids during the creep of alloys, with the
formation of fissures in HA corresponding to the fracture
of the creep sample. 10 ksi Equilib. PMVS PH / II
/ II
Since the methane pressure provides the driving force for d -- [ar bon Steel 1/1
both nucleation and growth, the discussion of mechanisms ~a.. --- Cr-Mo Steel 1//
w
a
1.5 II I /
begins with the calculation of the maximum (equilibrium) 0::: / I /
:::> 3 ksi
methane pressure that can develop as a function of VI
VI
// / /
hydrogen pressure, temperature, and carbide type (carbon w
activity).
0:::
a..
z
w 1ksi
Ac= O.12~~//

/'/'
//> / / "71
II

~a ,/ / /
EQUiliBRIUM METHANE PRESSURE 0:::
/' / /
.",/' ,/,/ /
It is impossible to draw any valid conclusions about the 0
>- 0.5 /
/ / /
/' ,/
mechanism of bubble growth in HA unless the pressure :I: / /
.", /'

driving the expansion of the bubbles is known. The early ~a 0.3 ksi
/
/
.",
/
/'

/'
/'
/ /
--I ,/ .", ./
kinetic models assumed that the methane pressure equalled 0 0/ 550C ,/ 500 /(./450 500C
the methane fugacity. This led to such high driving 0.5 1.5 2 2.5 3 3.5
pressures that one always concluded that bubble growth LOG (METHANE PRESSURE7MPa)
occurred by matrix creep.
4 Methane pressure in equilibrium with steel as
The bubbles in which the methane forms are initially
function of hydrogen pressure and temperature:
very small, and growth is very slow. Thus, it seems clear solid lines are for carbon steels; broken lines are for
that at higher temperatures, and early in the incubation carbon activity 012 and reflect lower carbon
period, the equilibrium pressure is established in the activity found in commercial QT 2'25-1 Mo steel

Materials Science and Technology January 1985 Vol. 1


Shewmon Hydrogen attack of pressure-vessel steels 5

0.3
2 Carbon Activity
(Graphite Std. State)
>-
.....
~ E:20.3 MPa H2 >
"0~ 0 E: \6.9 MPa H2
~
U
X
0.2

~.c z
. 0
w dl
0:::
2
U
0.\
Downloaded by [Universite Laval] at 09:13 09 May 2016

19 20 21
T (20+ I"ogt) x 10-3
5 Activity of carbon, and dilatometric strain rates at 550C as function of tempering parameter36

Alloy steels is, much more iron IS In the carbides than assumed by
In steels alloyed with carbide-forming elements, like Geiger and Angeles. These high Fe/Cr ratios stem
chromium, the activity of carbon is lower than in carbon primarily from the low chromium content of the steel.
steels. Also, dilatometric measurements have established However, it is partly caused by the lack of chromium equi-
that the rate of HA of QT 2'25Cr-IMo is at least three libration between the carbides and regions of the alloy far
orders of magnitude slower than that of carbon steels at from the carbides owing to the slow diffusion of chromium.
the same temperature and hydrogen pressure. 1 7.33 Several
observations indicate the effect of alloying and heat GROWTH KINETICS
treatment on the microstructure and rate of HA: Models
The growth of methane bubbles in a steel requires that'
1. The line on the Nelson curve (see Fig. 1) for
several processes proceed simultaneously:
2'25Cr-lMo is about 200 K higher than for carbon steel.
2. Geiger and Angeles31 found, as have several other (i) the solution and diffusion of hydrogen
authors, 3.34 that the resistance to HA in quenched Cr-Mo (ii) the solution and diffusion of carbon
steels increased appreciably with tempering. They also (iii) the formation of methane gas
concluded that the thermodynamic properties of the more (iv) the movement of iron atoms away from the growing
stable M23C6 and M7C3 carbides formed by tempering bubble.
could be approximated by using the free energy of
formation of Cr23C6 and Cr7C3. From this they concluded Figure 7 shows the steps that must occur sequentially, or in
parallel, for the growth of methane bubbles. Anyone of
that the activity of carbon should drop by roughly three
these processes could be rate controlling, but analysis40-44
orders of magnitude as tempering removed the M3C from
the steel.
3. Baker and Nutting35 report that during extended
tempering of QT 2'25Cr-IMo steel at 690C all of the
M3C disappears and is replaced by M23C6 or M7C3.
Parthasarathy and Shewmon36 have recently measured o XT 1 50
6 XT2
the carbon activity of QT 2'25Cr-IMo steel at 550C as a -15 o XT3
function of the amount of tempering. They did this by XT4 CD
Q
o 8M
equilibrating the steel with pure Ni.37 Results are shown in 1: )(

Fig. 5, where the degree of tempering ranged from --001


to 100 times that of commercial practice. Note that though
;;;
.5
-16
10 5
e\ll
the carbon activity drops continuously with increasing 5
-17
tempering, there is no sharp drop in the carbon activity or
rate of growth (hydrogen attack) with extended tempering.
Figure 6 shows growth rate v. Pm. STEM analysis of the 5.0 5.2 5.4 5.6 5.8 6.0
carbides confirmed that the extended tempering indeed
eliminated the M3C (Ref. 38) as reported by Baker and \n (P- ..2l:
r
)
Nutting. However, the carbon activity in the tempered
6 Strain rate v. driving force for QT 225Cr-1 Mo
Cr-Mo steel dropped to little less than one-tenth that of (Ref. 36): a slope of 10 corresponds to grain
normalized carbon steel. This is primarily due to the fact boundary diffusion limited growth, while a slope
that the M23C6 and M7C3 formed in the heavily tempered greater than unity would stem from some creep
steel had Fe/Cr ratios of 7: 3 and 6: 4, respectively,39 that control

Materials Science and Technology January 1985 Vol. 1


6 Shewmon Hydrogen attack of pressure-vessel steels

Hydrogen Diffusion Carbide DissolutIon -----2b--------401


to the Bubble t
{ Carbon Diffusion
f (a) 9 b
Methane
f
Generatlon at
t he Bubble Surface

Parallel Process I
( bl
Surface Diffusion
of Fe Atoms
Bubble Growth
Towards Bubble Tip
by Direct Power
t Law or Dislocation
Diffusion of Fe Creep
Atoms Along the
Grain Boundary

(c I
I
I
Accommoda t i on by I
Creep of the I
I
Adja~ent Grains I I I I
II I I
r--- aj-----+-- f3-l--a
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7 Diagram of sequential and parallel steps involved in i+1~


hydrogen attack of steel40
a bubbles of radius a and spacing 2b on grain boundary; arrows
normal to boundary represent sign and magnitude of local stress in
matrix which results from uniform deposition of atoms between
//
bubbles; b bubble which has changed to a disc-shaped bubble; this
and experimental observations17,19,45 all support the occurs with higher stress (Pm+lTn) and greater relative boundary
conclusion that during the incubation stage the growth is diffusion (Obi Os); c representation of discontinuous nature of
'bubbled' boundary segments on grains of diameter d; regions
limited by the movement of iron atoms away from the represented by P must accommodate expansion of bubbled
developing bubble. The discussion here deals only with the boundaries via lattice creep and boundary sliding .
diffusion and creep processes that limit the growth of 8 Diagrams of spacing and distribution of bubbles
bubbles. used to describe bubble growth
Iron atoms can be moved away from a bubble by
diffusing over the bubble surface to the grain boundary
and then along the boundary, or by elongating the region
between the bubbles by lattice creep. Each of these them, d is the grain diameter, Db the boundary-diffusion
processes has been investigated, and equations are coefficient, bb the boundary thickness, and Q the molar
available describing the rate of bubble growth as a function volume. The function h(a/b) is about unity and changes
of the driving pressure and various kinetics very slowly with a until (a/b)2 > 0'5, that is, until quite late
parameters.46-53 in the development of fissures. Note that the rate of growth
It will be assumed that the bubble density is uniform increases as only the first power of P.
with a spacing 2b over an essentially continuous sheet of The bubbles lose atoms only on the plane of the
grain boundaries across the sample, see Fig. 8. This boundary. To maintain the nearly spherical equilibrium
assumption is supported by the observation that after a shape of the bubble, atoms must diffuse over the surface to
relatively short nucleation transient the growth rate replenish those lost down the boundary. If the ratio
observed indilatometric studies is a function only of Db/Ds > 1 (Ds is the surface-diffusion coefficient), and
temperature and hydrogen pressure, being independent of P > 2y/a, then this surface-diffusion adjustment is too slow
time, as well as temperature/pressure excursions. and the bubbles grow into disc-shaped bubbles,46,47 see
Consider first the case of grain-boundary diffusion- Fig. 8. The equation for the observed expansion of a
limited growth. The diffusion equations are solved for the sample then becomes
case in which the atoms diffusing out of the bubble along
E:sd = (fb/d)(DsbsQ/RT)(a/b2)p2j(a/b) ..... (8)
the boundary deposit at a uniform rate over the entire
region between bubbles. where j(a/b) is a different function than h(a/b), but has the
The primary force acting to enlarge the bubble is same properties for our purposes. Here the rate of
methane pressure Pm. This will be resisted by the surface- expansion increases as p2, thus with high forces the
tension pressure 2y/a, where a is the bubble radius and y is bubbles will become crack-like. Such a stage can sometimes
the surface tension. In engineering systems any applied be found in carbon steels, but it has not been observed in
stress develops a stress acting normal to the boundary (in' alloy steels, presumably because Pm is too low. It is worth
which provides an additional force enhancing growth. (Any noting that for these disc-shaped bubbles the rate at which
resulting creep of the PV will accelerate the growth of the the bubble radius increases, da/dt increases as p3 Thus
bubbles still more, but here (in will be considered as a static fissures would develop with a smaller overall external
supplement to the gas pressure.) The total driving force P strain, as one would expect.
will thus be The region between the bubbles is stressed by the high-
pressure methane. If the pressure becomes high enough,
(6)
this can lead to creep of the matrix according to the
The externally observed growth rate for the case of constitutive equation
boundary diffusion is
(9)
E:bd = (fbjdb2)(DbbbQjRT)Ph(a/b). . . . . . . (7)
This leads to an equation for the creep contribution to the
where fb is the fraction of grain boundaries with bubbles on overall growth of the sample under HA of:49

Materials Science and Technology January 1985 Vol. 1


Shewmon Hydrogen attack of pressure-vessel steels 7

t:cr = (fb b/d) B((3/2n)/(b/a)3/0 -lJo po. . . . . . (10) inferences can be drawn about the rate-controlling
processes if the rate data are described with the equation
Note that the force is raised to the power n, which in the
case of iron is '" 7. E=AP~exp(-Qm/RT) (12)
Dyson has noted that voids form on only a fraction of
the grain boundaries in a sample undergoing creep, and Note that Qm reflects only the temperature dependence of
that if this fraction is small enough a cage of grains with the diffusion process limiting the motion of iron atoms,
uncavitated boundaries will surround any cavitated while QH contains both the temperature dependence of the
boundary.48 The cavitated boundary and the surrounding diffusion process and the dependence of methane pressure
cage of void-free grains must expand at the same rate, so on temperature at constant hydrogen pressure. The
the cage may restrain the growth of the cavitated pressure exponent m in equation (12) should be directly
boundary. It is possible that the same cage effect would comparable with the exponents of P in the model rate
occur in restraining the growth of discrete bubble-covered equations, equations (7), (8), or (10).
grain boundaries in samples undergoing HA, especially in Carbon steel Several steels have been studied using
the more creep and HA resistant alloys like the Cr-Mo dilatometry and the data fit with equation (12). Domains of
steels. different rate-controlling processes have been observed. If
Whether or not this type of restraint occurs is an the bubbles nucleate uniformly over a continuous surface
important question in the development of more HA of many grain-boundary segments, then the rate of growth
resistant steels. Increasing the chromium content reduces of the sample will be given by the equations for Ebd, or Esd
the equilibrium methane pressure Pm, but also reduces the However, there will be some segments of grain boundary
alloy's creep resistance somewhat. A higher creep strength with no bubbles, and these regions will have to
can be obtained with addition of Ti or V (Ref. 54). accommodate the expanding boundaries on either side via
Parthasarathy49 argues that in the HA of commercial lattice creep. Steels apparently differ in the degree to which
Cr-Mo steels the fraction of boundaries with bubbles is the bubbled grain-boundary segments form a continuous
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sufficiently high for the cage restraint not to exist. Also, he path across the sample. This difference might be
obtains good agreement between his model and the represented by the ratio of the average values of IX and f3 in
observed data without including the restraint effect. It is Fig. 8e. If this ratio is 1 then the bubbled boundaries will
also noteworthy that there was a drop from 218 to 154 in form an essentially continuous path across the sample, and
the Vickers hardness between the two most highly the rate of growth will be given by Ebd' If the ratio is less
tempered samples in Fig. 5, yet the change in theHA rate than unity the initial expansion may be given by Ebd or Esd,
is negligible, that is, E is proportional to the activity of but after the bubbles on the bubbled segments grow to
carbon, but does not change with a change in matrix link up the next stage of growth will be controlled by
strength. lattice creep in the regions between the bubbled segments.
The values of Qm and m that should go into the
Experiment equations for E have not all been well determined for pure
Following the growth of submicrometre bubbles during the iron, but the best values are given in Tablel. They are
incubation period of HA requires either a very sensitive followed by one question mark if the value is based on
dilatometer (strain sensitivity less than 10- 5) or high- somewhat uncertain data, and two question. marks if the
magnification microscopy (over x 2000), Le. an SEM. It is values are educated guesses. It is possible that the grain-
only within the last few years that such techniques have boundary data are markedly influenced by the adsorption
been used to study HA. Work done previously could of impurities, as has been reported for nickel,56 but there
establish only the incubation time, that is, when the are no reliable data on the subject for steel.
bubbles link up and the expansion becomes rapid. McKimpson and Shewmon 19 measured the rate of HA
It has been demonstrated by dilatometry that at the of an ESR carbon steel (O'3%C) with a capacitance
hydrogen pressures of engineering interest (> 7 MPa) the dilatometer. They found appreciable change in the
bubble density quickly reaches a steady-state value, and the temperature and hydrogen-pressure coefficients, QH and u
growth rate t: becomes time independent, that is, E is a (equation (11)), on going from low Pm (high T, low PH) to
function only of temperature and hydrogen pressure during high Pm (low T, high PH)' In fact, QH increased from
the incubation period. 17.19 The results obtained can then 115 to 210 kJ moi -1, and the hydrogen-pressure exponent
be described by the expression u decreased from 19 to 0,6. This is what one would expect
t: = CP~exp(-QH/RT) (11)
from the non-ideality of methane (Fig. 4) if the same
process controlled the rate at both high and low Pm. If
where PH is the hydrogen pressure. these rate data are described in terms of Pm (equation (12)),
Since the methane pressure Pm is the actual driving force the Qm values for the two domains of Pm are essentially
that enters the mechanistic equations given above, clearer equal to 220 and 225 kJ mol- 1, while the values of mare

Table 1 Model predicted* and observed rate coefficients for hydrogen attack

Om(mod), m(obs),
Steel Control process kJ mol-1 m(mod) kJ mol-1 m(obs) A, }lm Ref.

Carbon Creep 290 7(7) 280 98 45


Grain-boundary diffusion 190(7) 1 250 17 1 1 45
225 12 045 17
10 Pm 220 16 20 45
10Pm 220 15 055 19
Surface diffusion 130(??) 2 115 33 45
225Cr-1 Mo (BM) 225 17 65 55t
(WM1) 313 66 55
(WM2) 249 34 5 55

* ? and?? after constants used in the model equations reflects the relative uncertainty in the experimental data available
for steel.
t Average of two BM heats.

Materials Science and Technology January 1985 Vol. 1


8 Shewmon Hydrogen attack of pressure-vessel steels

15 and 12, respectively. The values of m and Qrn agree m = 1 in heavily tempered steel, and thus supporting grain-
satisfactorily with those expected for boundary-diffusion- boundary diffusion as the rate-limiting process, at least in
controlled growth, and Parthasarathy found that such a soft Cr-Mo steels.
model fitted the data wen over the entire range with a There are few data on the HA resistance of welds for QT
bubble spacing b = 05 Jlm and a bubble radius 2'25Cr-1Mo, and these results differ. Table 1 includes
a = 005 Ilm (Ref. 49). growth data on the HA kinetics of two commercial weld-
Panda and Shewmon45 used dilatometry to study an Al- metal samples (WM 1 - shielded metal arc and WM2 -
killed carbon steel that nucleated bubbles on an submerged arc).55 Both WM samples grew up to ten times
appreciably smaller fraction of the grain-boundary faster than the base metal (BM in Table 1). Erwin24
segments than McKimpson and Shewmon's, and indeed studied the HA of ESR welds and detected no difference
most steels that have been studied.1s The bubbles between the BM, WM, and HAZ. Sakai and Kaji57
nucleated on these boundary segments initially seemed to reported a bubble density orders of magnitude higher in
grow by surface-diffusion control until they linked up to the HAZ of a welded plate than in the BM. Masaoka et
form a single bubble over the grain-boundary segment. The al.27 coarsened the austenite grain size of 2'25Cr-1Mo
values of Qrn and m for this initial stage are given in steel, called it 'simulated HAZ' and reported essentially no
Table 1 under 'Surface diffusion'. In the second stage the change in HA kinetics at 600C. Clearly, the variability in
large bubbles covering isolated grain-boundary segments the HA of welds is greater than that found in BM, but
grew with Qrn and m values much larger than in the first beyond that there are too few data, or too little
stage. These data are given in Table 1 under 'Creep' as the understanding, to draw firm"conclusions.
controlling process. Effect of creep Modern PV design emphasizes the use of a
The obse~ved values of Qrn and m given in Table 1 for ductile material so that local stress concentrations will be
grain-boundary and surface-diffusion controlled bubble eliminated by localized plastic flow without introducing
growth agree reasonably with those of the model cracks. For PVs in which creep is unimportant room-
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predictions, but are consistently somewhat higher than the temperature elongation provides a good indication of
values expected. This could be explained by a small lattice- adequate ductility. However, with longer time service at
creep contribution from the regions between the individual higher temperature, creep becomes a factor and creep
bubbles on a bubbled boundary,49 or from creep ductility is necessary to relieve local stress concentrations.
accommodation of the unbubbled boundary segments Creep elongations of 015-020 are typical for QT Cr-Mo
shown in Fig. 8c. steels, the elongation being limited by the growth and link-
225Cr-1Mo steel To produce a loss of room-temperature up of voids on grain boundaries.
mechanical properties in QT 2'25Cr-1Mo steel requires In samples undergoing HA, failure (bubble link-up into
exposure to extreme conditions of temperature and fissures) can occur with all strain arising from the
pressure, for example, PH = 30 MPa at 600C for 1000 h or distribution over the boundary of all of the atoms that
more. However, if the steel is inadequately tempered, HA is were initially in the volume occupied by bubbles. In this
observed at lower temperatures and pressures. 55 case the strain at fracture is approximated by
The dilatometric study of HA in this steel requires
greater sensitivity than in carbon steel, but has been
err = bfb/2d . . . . . . . . . . . . . . (13)
successfully carried out. QT 2'25Cr-1Mo steels are similar where it has been assumed that link up occurs when a
to carbon steels in that e = f(T, PH) over the great majority grows to b/2. Typically for carbon steel b = 05 Ilm,
of the incubation period. However, the behaviour of the d = 20 Jlm, and fb = 01, or err = 0'001, which agrees well
two steels differs fundamentally in the initial (bubble with the observed value of strain at the end of the
nucleation) stage of attack. At 500-550C a freshly QT incubation period in carbon steel.19
Cr-Mo steel exposed to 20 MPa of hydrogen expands at a In creep studies one would thus expect a significant
steadily decreasing rate until after a few days e stabilizes (at reduction in err if HA played a role in developing the
550C) or becomes immeasurably small (at 500C). This boundary fissures. This is indeed found to be the case, as
initial strain reflects the build-up of methane in existing was described above in the section 'Observations'. The
voids in the Cr- Mo steel as opposed to the nucleation of surprising thing is how mild the hydrogen exposure can be
many new bubbles in carbon steels. This difference between and still have a significant effect on the creep ductility. In
the two types of steel is discussed further in the next unstressed samples exposed to PH = 20 MPa, one observes
section. a drop in room-temperature elongation after 1000 h only
Dilatometric data on QT 2'25Cr-1Mo steel plate are after exposure at 600C or above. However, in a
given in Table 1 (labelled 'BM' for base metal). The values stress-rupture test (O'n = 310 MPa) run in Pm = 20 MPa
of Qrn and m are comparable to those found in carbon steel hydrogen there was clear evidence of a hydrogen-induced
when boundary diffusion limits growth. The orders-of- loss in ductility on exposure at only 455C (failure in
magnitude slower growth in the Cr-Mo steels (at the same 4500 h).25 If hydrogen does not change the number of
temperature) can be explained as follows. For primarily voids/bubbles on the grain boundaries this would represent
boundary-diffusion-controlled growth the rate e is propor- an increase of about 100 in the rate of bubble growth. The
tional to (1/b2d)F1'7 The reduction in carbon activity gives effect of creep probably results both from an enhanced
a drop in Pm = F of about 3, which raised to the 17 power bubble growth rate, and an enhanced nucleation of
is a factor of 6. The bubble spacing along boundaries b is bubbles, but to date no studies have been made indicating
about 10 times larger in the Cr-Mo steel than in the the relative contributions of the two effects.
carbon steel, and the grain diameter d is about 25 times The enhancement of diffusion-controlled bubble growth
larger in the Cr- Mo steels. Multiplied together these by lattice creep would be entirely consistent with the
factors account for a difference in rate of 1500 between the theories of creep ductility in the literature. In the case
two types of steel. Alternatively, with a Qm of 225 kJ mol-1 of O'n = 0, the main force resisting bubble growth by
the Cr-Mo steel will attain the same e as the carbon steel grain-boundary diffusion stems from the requirement that
at 150 K higher temperature. However, since the bubbles the material leaving the bubbles diffuse and deposit
must grow further to merge in the Cr-Mo steel, 150 K uniformly over the entire region between the bubbles
understates the difference in useful temperature for the two (Fig. 8a). However, the strain rates observed in samples
steels. Figure 1 indicates an about 200 K difference. undergoing HA are only about 1% of that typical of
Figure 6 indicates a continuous drop in the force samples undergoing creep. Thus even relatively small rates
exponent m (equation (12)) with Pm' reaching a value of of creep due to an external stress could open up space

Materials SCience and Technology January 1985 Vol. 1


Shewmon Hydrogen attack of pressure-vessel steels 9

version of the API Nelson curve60 for carbon steel showed


a lower pressure limit for welded and/or cold-worked steel
L
o
than for annealed material. This would be consistent with
+ enhanced nucleation by both of these forming operations.
o Cold work also enhances the density of bubbles that
develops in Cr-Mo steels.61
Clugston et al.62 argued that the enhanced rate of
nucleation on boundaries was due to the inhomogeneity of
T ferrite deformation around the ends of carbides (especially
On
at grain boundaries). They give microscopic and analytical
-.L- -PM-lt- evidence to support this. A similar effect had previously
been reported for nickel-based superalloys. 63,64 In nickel
~g

'
b diff-. -""*I-----I(reep~

11r----------j1
alloys, cold work resulted in an increased void density at
grain boundaries and a significantly reduced creep
ductility.

{=
::Z:1 z:::L??::z:? n? 9 b
b-a------, r-!
b-a---I t
Carbon steels
Pishko et al. 18found that the HA of carbon steels develops
a mean bubble spacing of 1 /lm on the grain boundaries
that form the fracture surface, but found no inclusions
9 Creep v. grain-boundary (gb) diffusion coupling
under influence of external stress Go: for Go = 0 entire
inside these bubbles after fracture. These bubbles form at
relaxation is by gb diffusion over a distance b- a, carbide/ferrite interfaces. Their density is much higher than
while with an applied stress of Go > 0, the stress in the density of any inclusions visible with the optical
Downloaded by [Universite Laval] at 09:13 09 May 2016

lattice normal to gb, cr(r), rises but is limited by creep microscope or SEM. Thus these fine bubbles must form in
in central region; reduction of gb diffusion distance a way that is fundamentally different from those found at
from b- a to b'- a allows matching of rates of the large (10-1000 /lm) inclusions in older dirtier steels.
diffusion- and creep-limited regions Using a two-stage replica technique, Wang65 showed
that. only a negligibly small density of voids existed in
annealed steel before hydrogen exposure. The development
along the boundary for the material leaving the bubbles, of a high density of bubbles on exposure to high-pressure
and thus substantially shorten the required diffusion hydrogen is shown by the kinetic studies of Panda and
distance (see Fig. 9). The effect of lattice creep on void Shewmon,45 who found that if a carbon steel was heated
growth under an externally applied stress has been treated under 20 MPa of hydrogen no growth occurred on heating
by several authors.50-53 These authors find that in an in stages (over 6 d) from 275 to 350C. However, at 375C
intermediate range of applied stress the rate of void growth growth started and in a few hours the rate increased by
by boundary diffusion is appreciably enhanced because of over two orders of magnitude. Following this surge of
the shortened diffusion distance for atoms leaving nucleation the bubble density did not change measurably
boundary voids, and the concentration of the applied load with time or further HA at various temperatures and
in the region b - b' of Fig. 9. This results in a higher creep hydrogen pressures. This stable array of nuclei allowed
rate around the plane of the boundary than in the matrix, growth to be measured subsequently down to 275C.
and though the sample expands by creep, the localization McKimpson and Shewm'on19 had earlier obtained similar
of the creep results in a low-ductility fracture. results and initially exposed samples briefly to a high
Wanagel et al.26 have shown that a pretreatment with hydrogen pressure (20 MPa) at 375-400C to establish a
13 MPa hydrogen at 600C significantly decreases the stable bubble density.
stress-rupture ductility of 2'25Cr-lMo subsequently tested At low hydrogen pressures the nucleation of bubbles
in air. Thus the effect of HA on creep ductility seems to be proceeds more slowly but is an essential first step to HA.
due both to enhanced nucleation and growth of the Wang65 has measured the initial growth of annealed
bubbles. samples at low hydrogen pressures (2 MPa) and
400-500C. She found the rate to rise in successive stages
NUCLEATION or steps from an initially undetectable level to an easily
As was seen above in the discussion of growth, the density observable one. Presumably, this was caused by the
of bubbles that nucleate is one of the most important spreading of the stable high-density (one per square
variables in determining the rate of HA of a steel. It is also micrometre) layer of bubbles over sheets of grain
the least well understood aspect of the mechanism of HA. boundaries across the entire cross-section of the samples.
A summary of the observations is given as a preliminary.
Chromium-molybdenum steels
Inclusions In contrast to carbon steels, when Cr-Mo steels are
The steels in common use up to a decade ago contained a exposed to high-pressure hydrogen (20 MPa), there is no
much larger volume of larger inclusions than is found in initial rise in the rate of growth that would reflect the
the structural steel currently being produced. Gas bubbles nucleation of additional bubbles. In fact at 500C an"
easily form at stringered sulphide or silicate inclusions of a 20 MPa of hydrogen the growth initially starts at an easily
size easily observed in the light microscope. 2,20,22,58This measurable rate and then over a period of a few days drops
is probably due to pre-existing voids or lack of cohesion at to a negligible rate.33 The indications all point to a pre-
these interfaces. existing set of voids that fill with methane on exposure to
hydrogen. Using a two-stage replica technique Lopez and
Cold work Shewmon66 have shown that in QT 2'25Cr-1Mo steel a
Cold working an annealed carbon steel greatly increases high density of voids is formed at the tips of carbides
the rate of HA. This leads to earlier fissuring along the during tempering, especially between grain-boundary
grain boundaries20 and an enhanced rate of growth for the carbides. The methane-bubble density that subsequently
decarburized surface layer.2,22 Shih showed that heavy gives rise to HA is much lower, and this density remains
cold work by swaging leads to the development of bands of essentially constant independent of time during hundreds
methane bubbles within pearlite colonies. 59 The 1970 of hours of exposure to hydrogen at 20 MPa (Ref. 67).

Materials Science and Technology January 1985 Vol. 1


10 Shewmon Hydrogen attack of pressure-vessel steels

600 In the 225Cr-1Mo steel Lopez and Shewmon66 have


shown that the carbon-diffusion-limited growth of M3C
could force open voids at the tips of growing carbides, and
indeed find more than enough such voids in the tempered
c.J 500
~~ steel. This is a quite credible method of formation.
a::
=> However, it is not at all clear what keeps these voids from
!<t
a::
lLJ
sintering shut during the tempering operation before
~ 400 hydrogen exposure.
I-
Surface cracking has been reported in the vicinity of
nozzle attachments and girth welds in higher strength
QT 2'25Cr-1Mo steel after one year of service under
300 10 20 30 (MPa) conditions that were below the Nelson curve limits.71 The
2 3 4 5 (ksi) steel had been tempered to a tensile strength of over
HYDROGEN PRESSURE 900 MN m - 2 700 MN m - 2 is more typical and gives
satisfactory service). Surface cracking indicates local
10 Postulated operating limits for 225Cr-1 Mo based fissuring. The Pm generated by PH = 12 MPa at 450C is
on dilatometric data and limit of AVIV = 0001 at about 400 MPa and is not sufficient to cause fissuring.
50000 h. The two curves for two weld metals are However, the residual stress, and thus O"n, in the surface
for no external load (O'n = 0) and for an external
layer could be as high as the yield at this temperature (400-
load giving an elastic stress of O'n = 100 MN m-2
The limit lines are not extended above PH = 30 M Pa
500 MN m - 2) (Ref. 72). Thus in welds and around nozzles
because of a possible increase in bubble density Pm + O"n would have exceeded the critical value of about
and growth rate in this region 600 MPa postulated as required for the nucleation of a
high density of bubbles. If such a limit exists then efforts to
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raise the strength of Cr-Mo steels 73 must be accompanied


Similar behaviour was seen for the base metal, weld metal, by a reduction in Ac and Pm to keep (Pm + O"n) < 600 MPa
and heat-affected zones of this PV steel. even in regions of high residual stress. (Such a limiting
The only evidence of bubble nucleation during HA of stress postulate would be consistent with the findings of
2'25Cr-1Mo steel is that of Thygeson and Molstad.68 They others 74,75 for the formation of cavities at inclusions
reported the development of grain-boundary fissures during ductile fracture.)
following exposure to 100 MPa hydrogen at 500C. In
carbon steel there is a threshold Pm of about 600 MPa
required to nucleate a high density of bubbles Predicting vessel performance
(PH = 3 MPa at 400C). If the Pm required to nucleate a
high density of bubbles in 2'25Cr-1Mo is the same, Fig. 4
The prediction of PV performance, and the criteria to be
indicates that a PH of about 30-35 MPa would be required
set for such performance are too complex a topic to discuss
for a carbon activity of 012. (The degree of tempering of
here. But it is clearly a primary goal of the work reviewed
the steel used by Thygeson and Molstad was unspecified, here (see Ref. 54). An approach to life prediction using the
but Ac = 012 seems reasonable.) dilatometric data is to choose a certain bubble volume as
defining the 'life' of the vessel and then calculate the time,
Mechanisms temperature, and PH conditions which would reach this.
Two processes seem to be important in the nucleation of
Figure 10 shows the limiting conditions of T and PH
bubbles during HA.
predicted by this approach for a bubble volume fraction of
1. Active nucleation of a high density of bubbles 0'001, a time of 50000 h (6'2 years), and O"n = 0 or
(b < 1 Jlm) on many grain boundaries to form a more or 0" n = 100 MN m - 2. Curves are given for the BM as well as

less continuous surface of bubbles through the sample. This the WM 1 and WM2 data shown in Table 1. It is seen that
leads to fissuring at relatively low sample strains (0001). It the weld-metal limits are clearly lower than for the base
clearly develops in carbon steels, and apparently develops metal, and that the effect of 100 MN m -2 static stress is
in QT 2'25Cr-1Mo steels at high pressures. It is postulated small.
that such active nucleation occurs at values of Such an approach ignores several factors; some are
F > 600 MPa in both carbon and low-alloy steels. helpful and some are not. It tends to underestimate the life
2. The formation of voids during the tempering of because:
2'25Cr-1 Mo, and the persistence of many of these through
(i) vessels have hydrogen on only one side and
long tempering operations to give rise to bubbles in HA.
hydrogen diffuses out the other side so that HA
This is the dominant process for F < 600 MPa.
proceeds only from one side. of the vessel
In carbon steel occasional voids are present at the ends (ii) vessels are usually clad with stainless steel and the
of carbide lamellae. The high density of bubbles nucleates requirement that the hydrogen diffuse through this
and spreads for Pm > 600 MPa and temperatures at or cladding to compensate for the hydrogen that
above 375C. The critical radius (2y/P m) for Pm = 600 MPa diffuses through the vessel lowers the hydrogen
is about 5 nm. If methane formed inside a void of this size activity in the PV steel beneath that for the PH in the
at say 400C it would force iron atoms into the boundary vessel.
tending to wedge open the interface at the next carbide
particle. If a void of > 25 nm were present there the This approach tends to overestimate the life because:
combined action of the methane inside the bubble and the (i) it neglects the accelerating effect of creep on the
wedging action of the atoms from the first void would bubble growth, and bubble nucleation
make it grow.41 These two bubbles would raise still further (ii) it neglects the local effect of residual stress and stress
the stress intensity in the surrounding boundary, and make concentrations around discontinuities which may
spreading of the bubbled region easier.69 Such a model be appreciably higher than 100 MN m - 2 in some
would require residual stress or small voids at the ends of regions
the carbides, but would allow the bursts of nucleation that (iii) there is no allowance for the scatter expected
are observed as well as the observed changes in the between different heats and different welds, and thus
morphology of bubble distribution.70 no lower bound on the variation to be expected .

. Materials Science and Technology January 1985 Vol. 1


Shewmon Hydrogen attack of pressure-vessel steels 11

33. P. G. SHEWMON and z. s. YU: in 'Advanced materials for


Acknowledgments pressure vessel service with hydrogen at high temperatures and
pressures', (ed. M. Semchysen), 85-92; 1982, New York,
American Society of Mechanical Engineers.
This work was performed under the continuing sponsor- 34. T. MITSUO, K. YAMATO, and T. SAITOH: in 'Advanced materials
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