Using Differential Scanning Calorimetry to Determine the Quality of a PVC Part

Paul Gramann, Javier Cruz and Brian Ralston

The Madison Group
Madison, WI 53711
Abstract

Failure of Plastic Piping and Fittings

Failure of unplasticized poly(vinyl chloride) (PVC-U)

pipes and fittings may be related to many factors, such as,
design, installation, abuse and/or manufacturing. A
successful failure investigation may require detailed
analysis of all these factors to determine the primary
cause of failure. This paper will review current techniques
that use aggressive chemicals to qualitatively assess the
quality of the PVC pipe or fitting. The paper will also
review a technique that utilizes differential scanning
calorimetry (DSC). This technique can accurately
determine the temperature at which the part was
manufactured. It is also able to determine the percent
gelation of the PVC material, which is directly related to
the mechanical properties of the part.

Failure of a piping system can result in large monetary

damages. Water leaks can quickly create substantial
damage, and clean-up cost can be significant due to issues
related to mold. PVC fails for many of the same reasons
that other plastics fail, including:

Poly(vinyl chloride) - PVC

Plastic is a popular alternative to copper, steel, aluminum
and other materials for pipes and fittings. The most
widely used plastic for pipes is PVC, which comprises 66
percent of the water distribution market and 75 percent of
the sanitary sewer market in the US [1]. This material has
distinct advantages over metal piping.
In light of skyrocketing copper costs, plastic can be
significantly less expensive. Labor costs can be as much
as 50 percent lower, due in large part to the use of easy to
apply solvent cements that eliminate the need to solder.
Noise reduction with plastic can be as much as four times
over copper of comparable size. Further, there are fewer
problems associated with condensation. Corrosion
resistance of PVC is typically much greater than steel. It
is estimated that 700 water main breaks occur in North
America with 2.2 trillion gallons of water lost annually in
the US. This results in a $2.98 billion loss in revenue [1].
Possibly the most important advantage of plastic is that it
may eliminate the risk of contamination that can come
from copper and other metals. Medical studies have
shown a direct correlation between copper ingestion and a
number of birth defects, digestive disorders and even
Alzheimers disease [2].

Chemical Attack
Product or System Design
Installation
Manufacturing
Abuse

PVC is considered to have relatively good chemical

resistance. However, like all plastics it can be attacked by
a host of foreign chemicals. Chemicals such as ketones,
aromatic and chlorinated hydrocarbons, esters and
benzene can be very aggressive to a PVC part. Figure 1
shows a pipe that swelled and cracked as a result of
contact with a phthalate ester. Failure as a result of
installation can occur for many different reasons
including: overbelling of the pipes bell during insertion
of the male, incorrect adhesive, improper joining
technique, wrong climate, and inadequate support.
Plastic pipe is manufactured using an extrusion process.
Fittings are primarily produced by injection molding. Like
most plastic manufacturing operations, the processing
conditions determine the quality of the product. Of
particular importance is the temperature of the PVC
during manufacturing. The temperature during processing
influences the degree of PVC gelation. If the processing
temperature is too low, the degree of gelation, or fusion,
will be reduced. If the processing temperature is too high,
degradation of the PVC will occur. Both of these
situations will result in lower than optimal material
properties (e.g. strength, chemical resistance) and may
result in product failure while in the field. Figure 2 shows
a crack in a pipe prior to installation. Such a failure is a
direct result of poor manufacturing techniques. As this
paper will show, inadequate fusion of the PVC was more
than likely the cause of this defect. This paper will
investigate common techniques used to determine if the
correct processing conditions were used during
manufacturing.

Chemical Immersion Techniques to

Determine Degree of PVC Gelation
The degree of gelation of PVC during the manufacturing
process is critical to ensure proper mechanical strength.
Two widely used techniques currently exist to
qualitatively determine the level of gelation. These
techniques follow the standards ASTM D2152 Acetone
Immersion Test [3] and ISO 9852 Dichloromethane Test
[4]. These techniques involve aggressive chemicals and
give a pass/fail result. The part fails if the chemical is able
to attack the PVC. This attack will result in the lifting of
polymer from the surface.
Acetone Immersion Test (AT)

Using DSC to Examine the Quality of PVC

The acetone immersion test and the dichloromethane test
may provide some insight into whether the PVC had
proper gelation. However, these techniques require the
use of aggressive and toxic chemicals, give a subjective
pass/fail result, and do not give information on the
processing history of the PVC.
During processing of a PVC part, as the material is
heated, the smaller grains (crystallites) melt first.
During melting, the grains fuse together forming a
partially-gelled state. The level of gelation is dependent
on the processing temperature, with higher temperatures
yielding a higher degree of gelation.

This technique follows ASTM D2152 [3] and is used to

determine the adequacy of PVC gelation of extruded PVC
pipes and injection-molded fittings. Samples that are
taken from the pipe or fitting must be removed without
modifying the structure of the PVC. A mechanical saw
should not be used since the friction generated could
substantially increase the temperature of the plastic. This
may change the degree of gelation and give erroneous
results. A knife or Buehler Isomet low speed saw are two
methods that can be used to ensure that the degree of
gelation is not altered.

Information on these events can be captured using DSC.

According to Gilbert and Vyvoda [5], and Vanspeybroeck
and Dewilde [6], the degree of gelation and the processing
temperature of a PVC part can be determined using DSC.

High quality acetone with a low level of moisture should

be used for the test. The prepared samples are completely
immersed in the acetone for 20 minutes. The samples are
then examined for lifting, raising or removal of any PVC
material from the surfaces. The standard states that at
least 50% attack of the inside, outside, or mid-wall
surface or at least 10% attack on more than one surface
shall be considered indicative of inadequate fusion.

The first transition observed between 80-85oC represents

the glass transition temperature (Tg) of the PVC. Area
A, which is an endothermic response, represents the
melting of the partially gelled crystallites or the level
gelation that was present in the part. Area B represents
the melting of crystallites that did not gel during the
processing of the PVC part.

It is important to note that this test only detects inadequate

gelation and does not determine the over-all quality of the
PVC pipe or fitting. This test cannot differentiate between
thermally degraded and adequately fused PVC. This
technique cannot be used to give actual physical
properties, such as burst and impact strength.
Dichloromethane Immersion Test (DCMT)
This technique follows ISO 9852 [4]. This technique is
very similar to the acetone immersion test to determine
the adequacy of gelation. As with the AT test, sample
preparation should ensure excessive heat is not generated
and the degree of gelation is not modified. Again, a knife
or Buehler Isomet low speed saw are two recommended
methods.
The samples should be immersed in high quality
dichloromethane for 30 minutes. After removal from the
test apparatus, the sample should be examined for signs of
attack which may involve lifting, raising or removal of
material from its surface.

Gilbert and Vyvoda processed PVC compounds at various

temperatures using controlled conditions. Thermal
analyses using DSC were conducted on the processed
samples. The samples were heated from room temperature
to 240oC at 20oC per minute. Figure 3 shows several DSC
thermograms of PVC processed at various temperatures.

As stated above, the degree of gelation is dependent on

the processing temperature, which can also be seen in
Figure 3 [7]. The inflection point found between areas A
and B indicates the processing temperature. The DSC
thermogram shows good correlation between the
processing temperature stated in [5] and the inflection
point.
The degree of gelation can be estimated as [6]:

Degree of Gelation

Area A
Area A Area B

The mechanical properties such as impact strength, tensile

strength and relative elongation of the PVC part are
related to the degree of gelation [6, 8, 9].
The authors conducted a study to understand how well
DSC can predict the processing temperature of PVC.
Samples of PVC parts were heated and cooled in the DSC
cell at controlled conditions. Figure 4 shows the results
o
of a sample heated at 10 C/min to a temperature of 190oC

and then slowly cooled. The sample was then reheated at

a rate of 10oC/min. The figure illustrates that the
inflection point between Area A and Area B is the same
as the temperature that the sample was raised to (190oC)
during first heat. This would represent the processing
temperature of a PVC part during manufacturing. Similar
runs were conducted in which the part was heated to
various temperatures during first heat. These runs also
showed that DSC was able to accurately determine the
processing temperature.

this may have contributed to failure. There are clear

benefits of using DSC to analyze PVC, including:

Trials were also run using a faster cooling rate, which

would represent more realistic manufacturing conditions.
Figure 5 shows the DSC thermogram during first heat to
195oC. Also shown is the DSC thermogram of the second
heat after cooling at a rate of 40C/min. Again, the DSC
accurately shows the maximum temperature (195oC)
during first heat.

Additional research will focus on determining how Area

B should be measured and the relationship between the
degree of gelation to mechanical properties.

Understanding the level of gelation and its relation to the

final mechanical properties of PVC can be a powerful tool
to evaluate the quality of parts, and for failure analysis.
A study of a PVC pipe failure (Pipe #1), which exhibited
a circumferential crack on its interior surface (Figure 2),
utilized the DCM chemical test, as well as, DSC. Figure 6
shows the coupon after the DCMT. Severe lifting of the
PVC is seen. According to the ISO Standard 9852[4] the
PVC failed the test and is considered to be inadequately
fused. A sample from the same cracked location of the
pipe was analyzed using DSC. The sample was heated at
a rate of 10oC/min to approximately 230oC. Figure 7
shows the DSC thermogram of this sample with gelled
(Area A) and ungelled (Area B) indicated. The T g was
found to be 84.8oC and the processing temperature 177oC.
The degree of gelation was calculated to be 55.9%.
A pipe that cracked axially while in service was also
examined (Pipe #2). The sample after the DCM chemical
test is shown in Figure 8. Again, severe lifting is observed
in this photograph. The DSC thermogram of a sample
taken near the crack is shown in Figure 9. The T g was
found to be 84.7oC and the processing temperature 177oC.
The degree of gelation was calculated to be 53.9%.

Conclusion
This paper reviews a technique that utilizes DSC to
determine the quality of unplasticized PVC parts. This
technique allows one to accurately determine the
temperature at which the part was manufactured. It is also
able to determine the percent gelation of the PVC
material, which is related to the mechanical properties of
the part. This technique has clear advantages over
commonly used methods that use aggressive chemicals.
Further research needs to be completed to relate the
degree of gelation to mechanical properties in the PVC
parts.

References
1.
2.
3.

4.

5.

6.

An exemplar (not cracked) PVC pipe (Pipe #3) was also

analyzed. No lifting of the PVC was observed during the
DCM chemical test. Figure 10 shows the DSC
thermogram for this pipe. The T g was 84.9oC and the
processing temperature during manufacturing of the pipe
was found to be 195oC. The degree of gelation was
calculated to be 97.1%.
Though this is not an exhaustive study on the comparison
of the DCMT and DSC methods, nor the validity of the
DSC method, it does show that the cracked pipes have a
lower degree of gelation than the uncracked exemplar and
1

6 Charlotte PVC Pipe. Type 1. Sch 40.

Controlled conditions
Small sample size
Localized/specific sample selection
Ability to determine degree of gelation
Ability to determine the processing temperature
Does not use aggressive chemicals
Quantitative results (instead of pass/fail)

7.

8.

9.

UniBell, Inc., PVC Pipe Superior Performance in

Critical Systems, 2004
Massel, T. Future of Plumbing Industry Seen in
Hybrid Systems, Plumbing Engineer, Sept. 2008.
ASTM D2152, Adequacy of Fusion of Extruded
Poly(vinyl Chloride) (PVC) Pipe and Molded Fittings
by Acetone Immersion, 2003.
ISO 9852, Unplasticized Poly(vinyl chloride) (PVCU) Pipes Dichloromethane Resistance at Specified
Temperature (DCMT) Test Method, 1995.
Gilbert, M., and Vyvoda, J., Thermal Analysis
Technique for Investigating Gelation of Rigid PVC
Compounds, Polymer, Vol 22, 1134-1136, 1981.
Vanspeybroeck, P., Dewilde, A., Determination of
the Degree of Gelation of PVC-U Using a DSC,
ISO 18373-1, Rigid PVC Pipes Differential
Scanning Calorimetry (DSC) Method. Part 1:
Measurement of the Processing Temperature, 2007.
Zajchowski, S., Mechanical Properties of Poly(vinyl
chloride) of Defined Gelation Degree, Polimery,
2005.
ISO 18373-2, Rigid PVC Pipes Differential
Scanning Calorimetry (DSC) Method. Part 2:
Measurement of the Enthalpy of Fusion of
Crystallites, 2008.

Figures

Figure 1 Chemical attack of a plastic pipe.

Figure 2 Circumferential crack in PVC pipe prior to

installation.

Figure 3 DSC thermograms of PVC samples manufactured at various temperatures.

Figure 4 DSC thermogram of a PVC sample heated to 190 oC and then cooled slowly.

Figure 5 DSC thermogram of a PVC sample heated to 195 oC and then cooled quickly at 40oC/min.

Figure 6 PVC sample of failed Pipe #1

after immersion in dichloromethane.

Figure 7 DSC thermogram of failed Pipe #1.

Figure 8 PVC sample of failed Pipe #2

after immersion in dichloromethane.

Figure 9 DSC thermogram of failed Pipe #2.

Figure 10 DSC thermogram of Exemplar Pipe #3.