DP-MS-75-88

EFFECT OF HYDROGEN ON THE FRACTURE

TOUGHNESS OF 17-4 PH STAINLESS STEEL
by
T. L. Capeletti

Savannah River Laboratory

E. I. du Pont de Nemours and Co .
Aiken, South Carolina 29801

A paper proposed for presentati on at t he

Seaond I nternationa Z Conference on MeahanicaZ
Behavior of MateriaZs in Boston, Mas sachusetts,
on August 18, 1976, and for pub lication in the
Jou:rnaZ of Engineering MateriaZs and TechnoZogy.

This paper was prepared i n connection with work under Contract

No. AT(07- 2)-l wi th the U. S. Energy Research an d Deve lopment
Administration. By accep t an ce of this paper, the pub l i sher
and/or reci pient acknowledges the U. S. Government ' s righ t to
retain a nonexclusive, r oyalty-free license in an d t o any copy-
right covering this paper , al ong with the right t o r eproduce
and to authorize others to re pr oduce all or part of the copy-
righted paper .

.------NOTice- - - - - .
This report was prepared as an account of work
sponsored by the Unit r.d States Government. Neit her
the United States nor the United States Energy
Rt11!'J rr.h a nd Developme nt Administrat io n, nur irnr uf
their employees, nor any of their contractors,
subcontracton , or their employees , makes any
warnnty, express or implied , or assumes any legal
liability or responsibility for the accuracy , completeness
u1 uxfulnus of 1ny information, appanttu.~ . product or
process dlsclosed, or represents that its use wo uld not
ISTRIBUTION OF THIS DOCUVIENT tS UNLIMI
infringe privately o wned rights.
 DISCLAIMER

This report was prepared as an account of work sponsored by an

agency of the United States Government. Neither the United States
Government nor any agency Thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal
liability or responsibility for the accuracy, completeness, or
usefulness of any information, apparatus, product, or process
disclosed, or represents that its use would not infringe privately
owned rights. Reference herein to any specific commercial product,
process, or service by trade name, trademark, manufacturer, or
otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or any
agency thereof. The views and opinions of authors expressed herein
do not necessarily state or reflect those of the United States
Government or any agency thereof.
 DISCLAIMER

Portions of this document may be illegible in

electronic image products. Images are produced
from the best available original document.
 EFFECT OF HYDROGEN ON THE FRACTURE
TOUGHNESS OF 17-4 PH STAINLESS STEEL*

T. L. Capeletti
Savannah River Laboratory
E. I. 'du Pont de Nemours and Co.
Aiken, South Carolina 29801

ABSTRACT

Fracture toughness (K ) of 17-4 PH stainless steel decreased

c
significantly with increased hydrogen test pressure for a variety
of heat treatment conditions: solution annealed, underaged, peak-

aged, and averaged. Minimum toughness (13 MPalm) was obtained

with peakaged samples tested in 69.5-MPa hydrogen; toughness was

maximum (100 MPav'ili) for samples tested in helium. Aging treat-

~ents increased the.hardness from 28 R for solution-annealed

c
material to 42 R for peakaged material and correspondingly
c
decreased the fracture toughness in high-pressure hydrogen (KH)

from 31 to 13 MPaliii·. However, increased hardness had no substan-

tial effect on the K in helium. Fracture mechani.sm changed from

c
predominantly ductile rupture in helium to cleavage in 69.5-MPa

hydrogen, with mixed-mode fractures at lower hydrogen pressure

(3.5-MPa). On the basis of these data,17-4 PH stainless steel

is not recommended for hydrogen service.

* The information contained in this article was developed during

the course of work under Contract No. AT(07-2)-l with the U. S.
Energy Research and Development Administration.
 INTRODUCTION

High-strength, hydrogen-compatible stainless steels have a

large potential utility in hydrogen energy systems, The relatively

low yield strength of austenitic stainless steels (~300 to 500 MPa),

which previously limited the useful design strength range, may be

increased by thermomechanical processing [l].* Higher strengths

are obtained with precipitation-hardened stainless steels, and

good compatibility with hydrogen has been demonstrated for some

of these materials [2].

Yield strengths of 1172 MPa have been achieved with 17-4 PH

stainless steel, an age-hardened, martensitic material [3], which

has been reported as being resistant to hydrogen embrittlement [4].

However, the available data do not include effects of hydrogen

exposure on crack growth behavior. Since flaws can develop in·

service due to cyclic load conditions, crack propagation rates

must be well defined in materials for critical components of

hydrogen energy systems. This report summarizes results which

show that high-pressure hydrogen environments adversely affect

the fracture toughness of 17-4 PH stainless steel.

TEST PROGRAM

Fracture toughness data were obtained from tensile tests on

17-4 PH stainiess steel using single-edge notch samples [5),6.35

cm long, 1.59 cm wide, and 0.40 cm thick (Figure 1). Nominal

* Numbers in brackets designate References at end of paper.

- 2 -
composition of the 17-4 PH material was as shown in Table 1 [4].

It consisted of a 17Cr-4 Ni martensitic matrix strengthened by a

copper-rich precipitate. All samples were annealed 2 hours at

1340°K, water-quenched, and aged as indicated in Table 2 to produc_e

hardness values ranging from 28 to 42 Re: Following heat treatment,

the samples were polished with 600-grit sand paper and fatigue

pre-cracked in air at ambient temperature to produce a total crack

length (including notch) of approximately 0.673 cm. The pre-cracked

samples were then tested to fracture in one of three environments:

3.5-MPa hydrogen, 69.5-MPa hydrogen, or b~.~-MPa helium.

Critical stress intensities for crack propagation were cal-

culated from loading data and sample configuration using the

relationship [5]

where

w = Specimen width
B = Specimen thi ckne.s .s
a = Total crack length
.) p Crack propagation load

RESULTS AND DISCUSSION

Fracture Toughness
The fracture toughness of 17-4 PH stainless steel decreased

significantly with increased hydrogen test pressure for all heat

treatments (Table 3). Minimum toughness (13 MPaliil) was obtained

- 3 -
with peakaged samples fractured in 69.5-MPa hydrogen; maximum

toughness (approximately 100 MPav'iii) was obtained with samples

fractured in helium. Toughness values in Table 3 are averages

of 2 or 3 samples for each test condition.

Aging treatments increased the hardness from 28 Rc for

solution-annealed material to 42 Re for peakaged material and

correspondingly decreased the fracture toughness in 69.5-MPa

hydrogen from 31 to 13 MPaliii. A similar decrease in toughness,

71 to 29 MPalm, was obtained with samples tested in 3.5-MPa hydrogen.

Tn contrast to tho hydrog~n data, im:rl:lased hardfiess had no

significant effect on the Kc in 69. 5-MPa helium. Toughness values

in helium average approximately 100 MPalm for all heat treatment

conditions tested.

Compared to the results of the helium tests (Table 3), tough-

ness was substantially reduced at a relatively low hydrogen pressure,

particularly for underaged and peak aged conditions. For example,

toughness in the peakaged condition decr·eased from 97 MPali11 in

helium to 29 MPaliii in 3.5-MPa hydrogen. For averaged and solution-

annealed materials, reductions in toughness at 3.5-MPa hydrogen

were much less severe. However, increased hydrogen test pressure

from 3. 5 to 69. 5 MPa significantly decreased the toughness for

all heat treatments.

Hydrogen compatibility generally decreased with increased

hardness. Peakaged material exhibited the highest hardness and

was also most sensitive to the hydrogen environment. However,

at similar hardness levels, the underaged material (38 R ) was

c

4 -
more Sl!SCeptible to hydrogen embri ttlement than was the overaged

material (35 Re). These data may indicate an important effect

due to condition of the particle-matrix interface. The incoherent

interface produced by overaging was a more effective trap for

hydrogen than the coherent interface produced by underaging.

Increased trapping resulted in improved hydrogen compatibility.

Fractography
Fracture mechanism changed from predominantly ductile r~pture

in helium to cleavage in 69.5-MPa hydrogen, with mixed-mode failures

in 3. 5-MPa hy4rogen. Typical macro graphs illustrating the effect

of hydrogen on fracture morphology for underaged (1 hour at 710°K)

material are shown in Figure 2; Samples tested in helium exhibited

45° shear-lips over a large portion of the fracture surface, but

~amples tested in hydrogen exhibited flat fracture surfaces with

littl~ or no shear-lip fqrmation. Scanning electron micrographs

illustrating the transition from ductile rupture of the underaged

materiai in helium to cleavaie fracture in hydrogen are contained

in Figure 3.

The rel~tive amount of cleavage fracture increased with

increased hardness and with increased hydrogen pressure. Samples

tested in 3.5-MPa hydrogen exhibited mixed mode fractures with

large secondary cracks, as illustrated for overaged (1 hour at

865°K) material in Figure 4a. In 69.5-MPa hydrogen (Figure 4b),

the extent of secondary cracking was diminished. Fracture

-s-
occurred predominantly by cleavage with some indications of

intergranular failure. All fractures in helium were predominantly

ductile rupture, regardless of heat treatment condition.

REFERENCES

l B. C. Odegard and A. J. West, "On the Thermo-Mechanical Behavior

and Hyd;rogen Compatibility of 22-13-5 Stainless Steel," to be

published in Mat(friaZ Science and Engineering.

2 A. W. Thompson and J. A. Brooks, "Hydrogen Performance of

Precipitation-Strengthened Stainless Steels Based on A-286,"

Met. Trans., Vol. 6A, No. 7, 1975, p. 1431.

3. H. J. Rack artd David Kalish, ''The Strength, Fracture Toughness,

and .Low Cycle Fatigue Behavior of 17-4 PH Stainless Steel," Met.

Tran~., Vol. 5, No. 7, 1974, p. 1595.

4 . J. Wolf (Edi tor), "Ferrous AUoys," Aerospace Structural Metals

Handbook, Vol. 1, 19 76, Code 1501, pp. 1 and 2.

5. J.E. Srawley and W. F. Brown, Jr .. , "Fracture Toughness Testing

Methods," Fracture Toughness Testing and Its Application. ASTM

STP 381, 1965, p. 190.

- 6 -
 Table l. Nominal Composition of 17-4 Stainless Steel

Composition, wt %
Element Minimum Maximum

Carbon 0.07
Manganese 1. 00
Phosphorus 0.04
Sulfur o. 03
Silicon ". 1. 00
Chronium 15.50 17. so
Nickel· 3.00 5.00
Copper. 3.00 5.00
Co~umbium
+ Tantalum 0. 15 0.45
Nitrogen
Iron R<1l;mrP Balance

Table 2. Heat Treatments for 17-4 PH Stainless Steel

Heat Treatment Hardness,

Condi ti on TemEerature,a °K (°F) R

Underaged 710 (800) 38

Peak aged 780 (950) 42
Over aged 865 (1100) 35
Solution-Annealed 28

a. All samples ·were solution-annealed 2 hours at 1340°K prior to

aging l hour at the indicated temperatures.

Table 3. Fracture Toughness of 17-4 PH Stainless Steel

Average Toughness, MPaliil

l.ondition 69.S~MPa He 3.5-MPa H2 69.5-MPa H2

Un de raged 104 31 20
Peak aged 97 29 13
Overaged 57 34
Solution-Annealed 97 71 31
LIST OF FIGURES

1 Single-edge notch (SEN) sample geometry used for fracture

toughness investigation

2 Macrographs illustrating effect of test environment on

fracture morphology for underaged (1 hr at 710°K) 17-4 PH
stainless steel

3 Scanning electron micrographs illustrating the transition

in fracture mode of 17-4 PH stainless steel from (a) ductile
rupture in helium to (b) and (c) cleavage in hydrogen (test
environments as indicated)
4 S.canning electron micrographs illustrating effect of increased
hydrogen test pressure on the fracture morphology of 17-4 PH
stdnless steel
 2cm

Fig. 1 Sinqle-edge notch (SEN) sample used

for fracture toughness investigation
Fatigue Tensile fracture

c. 69.5-MPa hydrogen

b. 3.5-MPa hydrogen

a. 69.5-MPa helium
lcm

Fig. 2 Macrographs illustrating effect of test

environment on fracture morphology for underaged
(1 hr at 710°K) 17-4 PH stainless steel
a. 69.5-MPa helium b. 3.5-MPa hydrogen

c. 69.5-MPa hydrogen

Fig. 3 Scanning electron micrographs illustrating the

transition in fracture mode of 17-4 PH stainless steel
from (a) ductile rupture in helium to (b) and (c)
cleavage in hydrogen
..

cracks

a. 3.5-MPa hydrogen

----Secondary cracks

b. 69.5-MPa hydrogen

Fig. 4 Scanning electron micrographs illustrating effect

of increased hydrogen test pressure on the fracture
morphology of 17-4 PH stainless steel