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Processes, Physics, Chemistry,
and Metallurgy


Materials Science and Engineering Department
Rensselaer Polytechnic Institute
Troy, NY

WILEY-VCH Verlag GmbH & Co. KGaA

range, the embrittling effect disappears. Similarly, when the temperature is

raised much above room temperature, any embrittlement gradually disappears,
primarily because the increase in temperature increases the diffusion rate of the
hydrogen and promotes its escape to the surrounding atmosphere. The true
fracture stress (i.e., load at fracture divided by the actual cross-sectional area
at fracture) for a construction steel containing hydrogen can be reduced by
35-40% between -60 and +2O"C (-75 and +75"F) and yet show little
degradation at temperatures either far below or significantly above this range.
The rate of plastic deformation has been shown to have a marked influence
on the extent of hydrogen embrittlement as well. Hydrogen embrittlement
disappears at very rapid strain rates (above about lo3 s - l ) and becomes
negligible at very slow strain rates (below loM4sec- '). Insidiously, the embrit-
tlement due to dissolved hydrogen is most severe in the range of strain rates
normally encountered in conventional tensile testing (i.e., to s- ')
and service.
The degree to which hydrogen embrittles a steel has also been shown to be
strongly dependent on the microstructure present. In general, microstructures
produced by transformation of austenite at high temperatures or slower
cooling are less severely embrittled than those that depart significantly from
equilibrium, forming at temperatures well below the equilibrium eutectoid
temperature or at high cooling rates. For example, untempered martensite
loses almost all of its limited ductility in the presence of hydrogen, while
lamellar pearlite loses about 40% of its ductility, and spheroidized pearlite
loses less than 30% of its ductility. Bainite too can exhibit susceptibility to
hydrogen em brittlemen t.
Hydrogen enters the Fe lattice in steels only in atomic form, and occupies
interstitial sites. When in solution in Fe, there is strong evidence that hydrogen
atoms give up their sole valence electron to become a hydrogen ion or proton,
with a single positive charge and an extremely small diameter. Thus, hydrogen
in solution in iron can diffuse very readily and rapidly by migrating in the
lattice from interstice to interstice. In fact, the form that hydrogen ultimately
takes when dissolved in a material depends on the size of the imperfection with
which it associates. At vacancies and dislocation lines, the hydrogen probably
exists in its ionized form as a proton. At dislocation pile-ups and small-angle
grain boundaries, it probably exists as nascent or atomic hydrogen, while at
voids, cracks, and in porosity, it probably exists as diatomic hydrogen (H,)
molecules or as gaseous hydrogen (Bastien, 1961).
Since hydrogen cannot enter the crystal (e.g., iron) lattice except in atomic
or ionic form, reactions that provide a source of such nascent hydrogen or ions
at the surface of a solid (or in liquid iron) can act as potent sources of hydrogen
for embrittlement. Since the solubility of hydrogen varies with both the
temperature and the state of aggregation (i.e., phase) of iron, as indicated in
Figure 11.3, the majority of hydrogen involved in the degradation of properties
of weldments is probably absorbed when the iron is in the molten state. The
solubility of hydrogen in molten iron at 2795F (at 0.0024 w t X ) is roughly 4 x