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End Markets Business Plastics Processing Materials Sustainability

MIT Engineers Develop a Digital

Fiber
JUN 10, 2021
The Materials Analyst, Part 23:Stress
cracking: How to avoid this killer (part 2)
     
admin 1 | Aug 15, 1999

In last month’s article we defined the terms environmental stress cracking and solvent stress cracking, briefly
explained the mechanisms involved, and provided a couple of examples of actual case studies. This month we want
to conclude the discussion with a few more case studies and then discuss tests and material selection techniques
that can keep us out of trouble with this challenging problem.

PEEK for Medical 3D Printing One of the most difficult things to explain to a client who has a stress cracking problem is why every part does not
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fail. However, if we keep in mind that both a certain stress level and a certain degree of chemical exposure are
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JUN 10, 2021
needed to produce the effect, the variability becomes easier to understand. This principle is illustrated in our next
case study.

Study Examines Feasibility of

Recycling 3D-Printing The problem involved some handsets for telephones molded in ABS. Two small threaded brass nuts were molded
Thermoplastic Scrap into the part, and after the customer received the parts he noticed cracks that appeared to be emanating from the
JUN 09, 2021 area around the inserts. The problems appeared in some lots but not in others.

We were baffled until we started to ask the client questions about their assembly process. We discovered that the
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Manufacturer CathX Medical end user of this handset was very particular about the appearance of any marks such as fingerprint smudges. So, to
JUN 09, 2021 clean the surface, all of the parts were wiped down with a solution that was a mixture of ethyl alcohol and ethyl
acetate.

Ethyl alcohol will not cause any problems for ABS, but ethyl acetate can be very aggressive. This still did not explain
Entek Debuts ‘Workhorse’ Twin- the lot-to-lot variability until we obtained a specification for the cleaning solution. It turned out that the solution
Screw Extruder could vary in composition from 75 percent ethyl alcohol/25 percent ethyl acetate to 25 percent ethyl alcohol/75
JUN 09, 2021
percent ethyl acetate. When the solution was predominantly ethyl alcohol, the parts could withstand the cleaning
process. But when the ethyl acetate concentration began to increase, the combination of the solvent and the
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molded-in stress produced by the shrinkage around the brass inserts was enough to produce cracking.
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JUN 09, 2021 Detecting Stress

This instance leads us to a discussion of one of the methods that can be used to test for the presence of stresses in a

Breaking News in Flexible part that might lead to stress cracking. In transparent parts, the easiest way to detect stress is by viewing the part
Packaging with polarized light. Stresses appear as birefringence, a condition manifesting as a series of multicolored bands.
JUN 09, 2021
Qualitative evaluations can be made visually, but a variety of more sophisticated instruments allows the
measurements to be more quantitative. But in many parts, geometry makes such viewing difficult. More
Texas Injection Molder Files Class importantly, the addition of modifiers such as colorants, fillers, reinforcements, and tougheners render many parts
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opaque.
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In these cases, one of the most effective ways to evaluate a part is through a technique known as the mixed solvent
method. In this test, two materials are mixed in varying concentrations. One of the ingredients is relatively inert to
the polymer of interest while the other one is meant to serve as the stress crack agent. The idea is to start with a
solution that is weak in the stress crack agent and move progressively to increasingly aggressive mixtures. A part
that can stand a relatively high level of stress crack agent is considered to be relatively stress free. But if a part fails
while the stress crack agent concentration is still quite low, then the part will likely have problems in the field.

For some materials such as polycarbonate and polysulfone, researchers have even been able to calculate the
approximate stress level associated with failures in certain mixtures.

Without realizing it, this type of test was being conducted in a haphazard way by our telephone handset client.
Sometimes the operators would use a mild mixture that was mostly ethanol with a small amount of ethyl acetate
and the parts would work well. At other times, the ethyl acetate concentration would be at the high end of the
tolerance, and the parts would fail. Many people find it surprising that a simple wiping of the plastic part is sufficient
to produce the problem, but the mixed solvent technique usually involves relatively brief exposure times. Typically,
a 90-second dip followed by a waiting period of a few minutes is all that is necessary to reveal the problem. If cracks
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 Elusive Solution

The next two case studies show how the mixed solvent method uncovered unexpected problems related to stress
cracking. The first involved some polycarbonate tubes. These tubes were gated at one end with a ring gate that was
machined away after molding. At some point during secondary operations the gate end of the part was swabbed
with a mixture of 1 percent isopropyl alcohol and 99 percent water. Stress cracks would occur occasionally in this
area. Our client’s managers were looking for a cause and a possible solution.

They kept unusually good records and had saved retains from several runs going back five years. They sent us
samples from a variety of these runs and asked us to evaluate the parts.

The mixed solvent test for polycarbonate is well developed. It involves varying concentrations of n-propyl alcohol as
the inert ingredient and toluene as the stress crack agent. The mildest mixture is a 10:1 mix of n-propanol and
toluene. This is followed by a 5:1 blend. And if the parts are good enough to withstand that, a 3:1 mixture is applied.
The exposure time is 3 minutes. If problems are going to occur, they usually appear within minutes of removing the
part from the solution, although it is prudent to check the parts periodically for at least an hour to detect cracks that
may develop slowly.

Now you may be wondering to yourself, if we use the n-propyl alcohol as the inert agent in the stress crack solution,
how in the world is a mixture of 1 percent alcohol and 99 percent water causing the parts to stress crack? Well, that’s
what we wanted to know. We tested all of the various lots that were submitted. Every lot but one passed the
exposure to the first solution.

Normally this is sufficient to expect that field performance will be satisfactory. Most of the sample lots made it past
the second solution and one group even passed the most aggressive solvent mixture. But what about this one lot
that did not make it past the first screening? What was different about it?

Well, all of the parts except the ones from this lot were submitted as molded. But this one lot had been decorated
with a black ink designed to indicate the fluid level in the tube. And the failures in this group were remarkable. We
had received four parts. One part went into each of the three solutions and promptly failed. The fourth part was
never removed from the bag that it came in. But when the failed parts were returned to the bag, the fourth part also
failed just from the casual contact with the other three parts. It was the ink! A check of the composition revealed a
relatively high level of an aromatic petroleum distillate.

The Right Material

A second case study involved a roller bearing housing made of high impact polystyrene. It was gated at one end and
the material had to flow approximately 8 inches to fill the entire part. At the end of the part was a cylindrical detail
into which a bearing was pressed as a secondary assembly operation. This assembly was conducted at the end
user’s plant and was therefore not done until days or even weeks after the part was molded.

A significant number of parts developed cracks within days or weeks of having the bearing inserted. At first it looked
like a straightforward case of weldline failure. Because of the flow path, two weldlines were present on the diameter
that was accepting the bearing and the failure appeared to propagate along these weldlines.

But there was a problem. First, the failure always occurred in a delayed fashion. No one ever saw a part crack
outright at the moment the bearing was inserted. Second, every part we received for review had a greasy residue on
the polystyrene in the vicinity of the bearing. The bearing manufacturer performed a finite element analysis on the
region of the part where the bearing was inserted and showed that the peak stresses were very close to the yield
stress of the polystyrene. That was the stress part of the equation. The solvent appeared to come from the grease.
The identification of the mechanism as stress cracking was confirmed by some photographs of the crack region
taken at very high magnification. Two of these are shown in Figures 1 and 2.

Figure 1 shows the crack magnified by a factor of 20. A close look at this shows that the crack does not start at the tip
of the weldline at the end of the part. Instead, the crack is actually discontinuous and stops in several places and it
does not even extend to the end of the part where we would expect the weldline to be the weakest. This indicates
that the failure is starting in several places simultaneously and that the cracks actually start on the outside diameter
where the stresses are the highest and propagate inward from multiple points of origin.

Figure 2 provides a view of the surface exposed by the crack magnified by a factor of 200. The top of the photograph
is the outside diameter of the part and the multiple cracks travel in parallel lines as the failures move from the outer
to the inner diameter. The lack of any evidence of chemical attack on the crack surface confirms that this is not
simple solvent damage. Once the stress is relieved by the initiation of the crack, the material does not undergo any
further chemical attack.

Two solutions were posed to this problem. The first option was to change to a filled polypropylene. Polypropylene is
semicrystalline and therefore has much better chemical resistance than polystyrene. It is much less likely to stress
crack in the presence of the grease. The use of fillers is primarily designed to match the shrinkage of the amorphous
polystyrene. Although this was not actually implemented in production, tests run on samples indicated that this
material change would solve the problem.

The second fix was to move up the amorphous polymer performance ladder to ABS. Since the ABS could still
encounter problems from the grease, we also wanted to reduce the stress component from the bearing insertion. So
wetoran
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question was, which method developed less stress on the plastic? For this we turned to a mixed solvent test.
 Stress Crack Resistance

One of the best chemicals for checking stress crack resistance in ABS is concentrated acetic acid, called glacial acetic
acid by chemists. It is very aggressive and usually produces cracks in all but the most stress-free ABS parts. Vinegar,
on the other hand, is 5 percent acetic acid and the rest is mostly water. It rarely causes stress cracks in ABS moldings.
So our mixed solvents are glacial acetic acid and water. We used 95 percent, 65 percent, 35 percent, and 5 percent
solutions of glacial acetic acid to test the two sets of assemblies.

The 95 percent acetic acid solution caused both sets of parts to crack, although a close examination showed that the
cracks were more severe and occurred more rapidly in the parts where the bearing had been installed after the part
was cool. This was confirmed at the 65 percent solution. At a 65 percent acetic acid concentration, the parts
assembled hot showed no problems while the parts assembled cold still produced some cracking. We also noticed
that the grease was actually coming from the bearing. When the bearing was inserted into the cold part, the
interference between the outside diameter of the bearing and the inside diameter of the molded part cause some of
the bearing grease to squeeze out onto the plastic. This did not occur when the bearings were inserted into warm
parts.

Rules of Prevention

Now the good news is that all of these field problems had a solution or at least an obvious cause to the problem. The
bad news is that a lot of time and money were spent uncovering the problem, recalling product, and arriving at
these solutions. It is much better to learn the rules for preventing stress cracking in the first place.

The first rule to remember is that amorphous materials are more likely to have problems with this type of failure
than semicrystalline polymers. If you cannot use a semicrystalline material because of other considerations, a blend
containing a semicrystalline and an amorphous component may be a good compromise. All things being equal, an
alloy of polycarbonate and polyester will work better than a straight polycarbonate.

Second, reduce the stress inherent in the design of the part. Eliminate drastic changes in nominal wall thickness,
sharp corners due to insufficient radiuses, and gates and weldlines located in regions where high levels of external
stress will be applied.

Third, avoid incorporating part features that force the processor into bad decisions regarding molding conditions. A
thick wall placed at the end of the flow path will lead to the use of excessive packing pressure in an attempt to
reduce sink marks. This will build high levels of stress near the gate.

Fourth, when checking chemical resistance data, look for tests that have incorporated some applied stress into the
evaluation. If the addition of 1 percent strain causes a material to fall several notches in the rankings when exposed
to a chemical in your application, look for another material or find a way to protect your chosen material from that
chemical.

Fifth, add reinforcement to improve the performance of a material. As little as 10 percent glass fiber can reduce
problems with stress cracking in materials like polycarbonate and polysulfone. And finally, as is the case with so
many properties, molecular weight is critical. The higher molecular weight materials will resist stress cracking for
much longer and at higher critical stress levels. Once you have selected the appropriate molecular weight, make
sure your process conditions preserve it.

Stress cracking is a frequent problem in plastic applications. But there are methods for getting to the root of the
problem. To avoid problems, select your material with care and employ the fundamental rules of good design and
processing.

Use this link to read Part 1 of this article.

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