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THE
ical attack or molecular degradation. Instead, the
chemical penetrates into the molecular structure
and interferes with the intermolecular forces
binding the polymer chains, leading to accelerated
molecular disentanglement.
The mechanism steps involved in ESC failure are
PLASTIC
similar to those responsible for creep failure, and
include fluid absorption, plasticization, craze initi-
ation, crack growth, and finally fracture. Because
the ESC process depends on the diffusion of the
chemical into the polymer structure, the rate of fluid
absorption is a critical parameter in the rate of both
KILLER
craze initiation and crack extension. The more rap-
idly that the chemical agent is absorbed, the faster
the polymer will be subjected to crazing and sub-
sequent failure.
Recent comparisons have illustrated creep as a
special condition of ESC. Under this model, creep is
Environmental stress cracking simply ESC with air as the chemical agent, the prin-
is involved with some 25% cipal difference being that the presence of an active
chemical agent accelerates the disentanglement
of plastic part failures. process. This acceleration results in a significant re-
duction in the time to crack initiation, and sub-
Jeffrey A. Jansen stantially increases the speed of the extending crack,
Stork Technimet thus shortening the time to failure. Alternatively,
New Berlin, Wisconsin ESC cracking develops at reduced stress or strain
levels relative to creep failure in air.
E
nvironmental stress cracking (ESC) is a It has been theorized that
phenomenon in which a plastic resin is de-
graded by a chemical agent while under “Highly localized fluid absorption is probably the
stress, and it is the leading cause of plastic mechanism for acceleration. The fluid is preferentially
component failure. It is a solvent-induced failure absorbed at sites under high dilatational stress such
mode, in which the synergistic effects of the chem- as a stress concentrating defect, a craze, or the tip of
a crack. The absorbed fluid locally plasticizes the ma-
ical agent and mechanical stresses result in cracking.
terial, reducing its yield strength. Critical strains and
A recent study showed that 25% of plastic part fail- stresses for craze initiation with the most active fluids
ures are related to ESC. can be as low as 0.1% and a few megapascals. Stresses
To adequately understand the ESC failure mech- and strains due to processing and/or assembly can
anism, some background on analogous cracking in often exceed the critical condition.” (Rapra Tech-
air is required. In the absence of chemical interac- nology)
tion, cracking is associated with prolonged static
stress through a creep mechanism. Creep, some- Characteristics of ESC
times called static fatigue, is a brittle fracture mode Environmental stress crack failures share several
in which continuous stress results in molecular dis- typical characteristics:
entanglement within the polymer chains. • Brittle fracture: ESC failures are caused by brittle
The creep failure mechanism involves a series of fracture, even in materials that would normally be
distinct steps. The first step is craze initiation, the expected to produce a ductile yielding mechanism.
second is craze growth that leads to crack initiation, The crack initiation sites for ESC failures are always
then crack extension, and finally catastrophic frac- on the surface. They normally correspond to local-
ture. Creep failure is common within plastic mate- ized areas of high stress, such as microscopic de-
rials at room temperature, but rare in metals. It is fects or points of stress concentration. The initia-
a result of the viscoelastic properties of polymeric tion location is generally related to direct contact
materials. with an active chemical agent, either liquid or gas.
This article details the steps involved with ESC, • Multiple cracks: Multiple individual cracks are
describes the characteristics of such failures, and initiated, and these subsequently coalesce into a
discusses the three factors involved with failure. unified fracture. Numerous crack origins and the
Two case histories illustrating ESC failures are also corresponding unions are illustrative of an ESC
presented. failure mechanism.
• Smooth morphology: The crack origin areas usu-
Steps in environmental stress cracking ally exhibit a relatively smooth morphology, in-
ESC is a phenomenon in which a particular dicative of slow crack growth. However, aggres-
sive chemical agents can produce rapid initiation • Alternating bands: Recent experimentation has
and extension, characterized by more coarse sur- shown that ESC commonly develops by a pro-
face features. gressive crack-extension mechanism. Examination
• Craze remnants: The presence of opened craze of fracture surfaces created under laboratory con-
remnants, either within the crack origin regions or ditions reveals a series of alternating bands corre-
in adjacent areas, is further indication of ESC. In sponding to crack extension cycles, as illustrated
many cases, the final fracture will develop via duc- in Fig. 1. The observed bands are thought to repre-
tile overload after the crack length has reached a sent repeated cycles of crazing, followed by crack
critical size. extension via brittle fracture, consistent with the
• Stretched fibrils: The final fracture zone can in- steps involved in creep and ESC failure mecha-
clude stretched fibrils and other features indicative nisms. This is illustrated in the diagram shown in
of ductile cracking. It is important to note that ESC Fig. 2.
is not a chemical attack mechanism; therefore, fea-
tures that are normally associated with chemically Elements of ESC
induced molecular degradation will not normally Environmental stress cracking follows several
be present. tendencies regarding all three of the essential ele-
Resin type
• Amorphous structure: Amorphous
plastics are considerably more suscep-
tible to ESC than semicrystalline resins.
This is primarily attributed to the sub-
stantially greater free volume associated
with amorphous resins, as compared
with the orderly, compact structure of
semicrystalline resins.
• Low molecular weight: ESC resistance
decreases with reduced molecular weight
of the plastic. This is true in terms of the
material selected, and also in cases where
molecular degradation has resulted in molecular
weight reduction. The superior ESC resistance im-
parted by elevated-molecular-weight resin results
from the increased level of molecular entanglement. Fig. 1 — Scanning electron images show the progressive nature of ESC failure
• Lower crystallinity: Within semicrystalline resin within a polycarbonate laboratory fracture.
families, the level of crystallinity significantly im- • Molecular size: Chemicals with lower molecular
pacts the ESC resistance. In general, higher levels weights are more aggressive ESC agents than
of crystallinity, normally accompanied by an in- higher molecular-weight counterparts. Thus, sili-
creased specific gravity, produce improved resist- cone oil is more severe than silicone grease, and
ance to ESC failure. acetone is more severe than methyl isobutyl ketone.
This results directly from the size of the molecule,
Chemical agent with smaller molecules having a greater ability to
• Hydrogen bonding: Fluids with moderate levels permeate into the molecular structure of the
of hydrogen bonding are generally more aggres- polymer.
sive ESC agents than chemicals with extreme levels
of hydrogen bonding. As such, organic esters, ke- Stress effects
tones, aldehydes, aromatic hydrocarbons, and chlo- • Tensile stress: ESC failure will occur within a
rinated hydrocarbons are more severe than organic material only under conditions of tensile stress. Ten-
alcohols and aliphatic hydrocarbons. sile stresses are required to create the molecular dis-
entanglement that leads to ESC. Compressive
A localized stress field exists stresses, while sufficient to cause mechanical failure
immediately in front of a crack, under some conditions, do not orient the molecules
notch, or defect. in ways conducive to ESC.
• Residual stress: Internal molded-in residual
stresses combine with external stress to produce
Fluid is absorbed into the stress
field and locally plasticizes ESC. In many cases, the magnitude of the molded-
the material. in stress is sufficient to result in ESC. ■
For more information:
Crazes initiate and grow within Jeffrey A. Jansen,
the plasticized stress field. Polymer Science Manager,
Stork Technimet,
2345 South 170 St.,
The crazes coalesce and cracking New Berlin, WI 53151;
initiates and extends beyond the
original stress field. A new stress tel: 262/782-6344;
field is created and plasticized. e-mail: jeff.jansen@
stork.com.
Crazes initiate and grow
within the plasticized stress
field.
Cracking continues in
a progressive manner.