Thermal Analysis Application No.

UC 303
Thermal Analysis Application
Application published in METTLER TOLEDO Thermal Analysis UserCom 30

Quality control of hard PVC according to

ISO 18373

Introduction
Polyvinylchloride (PVC) has been used
for over 60 years for pipes, window
frames, films, electrical insulation ma-
terial, and countless other applications.
Hard PVC (PVC-U) is especially suitable
for the manufacture of long-lasting prod-
ucts such as water pipes. More than
28 million tons of PVC was produced Figure 1. Schematic diagram illustrating the gelation process.
worldwide in 2001 [1]. In Europe, about
half of all the different types of pipes • PVC products have a good price/per- of agglomerates of primary particles of
(e.g. water, wastewater, and gas pipes) formance ratio. which about 5−10% are crystalline [1].
are made of hard PVC. Arguments for the • PVC can be recycled and used in Hard PVC is produced by mixing the par-
use of PVC, for example for pipes are [2]: new products; its material properties ticles with additives (e.g. stabilizers) at
• PVC has very long-lasting material remain intact. Great efforts are be- a temperature of about 200 °C followed
properties and is continuously being ing made to process used material by extrusion to products such as pipes
developed. directly to make new products. If this or frames. In this process, the particles
• PVC pipes are lighter than pipes made succeeds, the life cycle assessment is “coalesce” or gelate. On cooling, a net-
of other materials but are nevertheless good. Thermal recycling (burning) work consisting of entangled molecules
strong, durable and flexible enough to however remains a difficult problem. and newly arranged, small crystalline
bend without breaking. They are easy domains, is obtained (Figure 1).
to install and are compatible with PVC is polymerized from vinyl chloride in
other materials used in pipe networks. an aqueous emulsion or suspension. The The degree of gelation has a decisive in-
• PVC is resistant to corrosion. Pipes process produces a powder with a grain fluence on the mechanical stability and
have low flow resistance due to their size of about 100 µm. The morphology the fracture behavior of products. The
smooth surface. of the powder is complex and consists higher the processing temperature (Tp)
 the greater the degree of gelation. The
processing temperature must however not
be too high because otherwise degrada-
tion occurs in which HCl is eliminated
(from about 180 °C onward) [3].
Thermal Analysis Application

During the production process, crystallites

with melting points at or above Tp will be
annealed, thus slightly raising their melt-
ing point. Crystallites that melt up to Tp
will recrystallize to form small second-
ary crystallites during the cooling phase
after extrusion. On heating in the DSC,
these will melt at temperatures below the
Figure 2. Schematic presentation of a DSC curve showing the most important effects.
processing temperature Tp [4]. For this Enthalpy of fusion of the small crystallites (shaded area A) and the large crystallites (area
reason, there are relatively few crystallites above B); Tg is the characteristic glass transition temperature.
with a melting point around Tp. This is ob-
served as a melting gap in the DSC curve.

The processing temperature and the de-

gree of gelation are therefore important
quality parameters. Various test methods
such as those involving solubility, hard-
ness and other mechanical character-
istics as well as optical microscopy are
used to determine them. These methods
often require time-consuming sample
preparation or need larger samples. For
this reason, DSC has been used for many
years to investigate the melting behavior
of PVC [e.g. 5-8].

The degree of gelation is defined as the

Figure 3.The three DSC curves measured and evaluated according to ISO Standard 18373
ratio of the amount of small, secondary Part 1 (B-onset) and Part 2 (A-onset and A-endotherm).

Individual sample 1 2 3 Mean Standard

deviation
A-onset in °C 102.03 101.98 101.96 101.99 0.04
B-onset in °C 200.59 200.74 200.16 200.50 0.30
A-endotherm in J/g 6.37 5.42 5.48 5.76 0.53
A-endotherm corrected 6.94
to 83% PVC in J/g
Table 1. Measurement results obtained for three individual samples according to ISO 18373.

METTLER TOLEDO
TA Application No. UC 303 2
 crystallites (melting point below Tp) and Experimental details The corresponding temperatures for the
the amount of large primary crystallites The measurements were performed using A-onset (first peak) and the B-onset (sec-
with melting points above Tp. The con- a METTLER TOLEDO DSC 1. ond peak) are entered in the diagram.
tent of crystallites is determined from the The temperature program specified in The B-onset shows that the maximum
size of the corresponding enthalpies of ISO 18373 is the same for Part 1 and processing temperature of the material
Thermal Analysis Application

fusion using DSC [3]. In simple terms, Part 2: on extrusion was 200.5 °C. The results
the larger the endothermic DSC peak in • Start temperature: 35 °C are summarized in Table 1.
the range between Ta (about 100 °C) and • End temperature: 225 °C
Tp (about 200 °C), the better the degree of • Heating rate: 20 K/min The main result of ISO 18373 Part 2 is the
gelation (Figure 2). • Gas purge: 20 mL/min nitrogen enthalpy of fusion of the secondary crys-
tals (the A-endotherm). This is measured
DSC is now a well-established and sim- Sample preparation: A rod of PVC-U, by drawing a linear baseline between the
ple test method for quality control. The 3 mm in diameter, was cut into cylindri- A-onset and the B-onset and determin-
ISO 18373 standard covers DSC meth- cal disks 1 mm in height using a sharp ing the area of the endothermic peak.
ods for testing rigid PVC pipes [4, 9]. knife. Two pieces were placed in a 40-µL The mean of the integral gives a value
ISO 18373-1 describes the measurement aluminum crucible so that the flat sur- of 5.76 J/g for the enthalpy of fusion. This
of the processing temperature as the ex- faces rested face-down on the bottom. value must be corrected with respect to
trapolated peak temperature (B-onset). This ensured good thermal contact be- the PVC content of the sample. The con-
ISO 18373-2 describes the measurement tween the crucible and the sample. The tent can be determined by thermogravi-
of the enthalpy of fusion of the small sample mass was 13−16 mg. The crucible metric analysis [3] and is 83% for this
crystallites, the peak area A (the A-endo- was sealed using a lid with a hole. particular sample (calculated from the
therm) in Figure 2. This is easily deter- mass loss in the HCl elimination step).
mined and is a measure of quality for the According to the standard, it is important The enthalpy of fusion of the small crys-
amount of small crystallites and hence that the sample does not move during the tallites is thus 6.94 J/g. This value is used
indirectly for the degree of gelation. measurement. This was done by placing in addition to the processing temperature
the crucible on a flat steel surface and as a further measure of quality for the
The standard mentions the following ad- pressing the lid onto the sample using corresponding PVC product.
vantages of the DSC method: the flat end of a rod.
• Small sample quantities, easy to take Conclusions
from the pipe wall Results The maximum processing temperature
• Possibility of investigating different Figure 3 shows the three DSC measure- and the degree of gelation of PVC-U in
locations in the pipe ments performed with individual sam- finished products are two important pa-
• No specific sample geometry is needed ples. The curves show a step between 70 rameters that have a significant influ-
• Rapid analysis and 90 °C due to the glass transition of ence on the stability and the mechanical
• Older pipes can be sampled and meas- PVC-U. After a small peak between 100 behavior of the particular product. To
ured. and 110 °C, there follows a broad endo- simplify the evaluation, the enthalpy of
thermic effect up to 200 °C. This is due fusion of the small crystallites below the
These methods can also be used to test to the melting of the small crystallites. processing temperature was determined
other PVC-U products. Above 200 °C, the larger crystallites melt in this method instead of the degree of
and degradation begins (not visible in gelation. DSC measurements performed
The following experiments describe the Figure 3). according to ISO 18373 provide a simple
analysis of hard PVC according to ISO According to ISO 18373 Part 1, the ex- and rapid method to determine the two
18373 Parts 1 and 2 to measure the max- trapolated onset temperatures are de- parameters for quality control. Particu-
imum processing temperature and the termined by drawing tangents at the larly advantageous is the fact that only
crystallite enthalpy of fusion. points of inflection of the two peaks. small samples are required for the test.

METTLER TOLEDO
TA Application No. UC 303 3
 This enables samples to be taken from [4] ISO 18373-1:2007 Rigid PVC pipes [8] L.A. Fillot, C. Gauthier, P. Hajji,
− Differential scanning calorimetry A powerful tool to characterise PVC
different locations around the pipe cir- (DSC) method − Part 1: Measurement gelation, Proc. 9th Int. PVC Conf.,
of the processing temperature. Brighton, April 2005, 425.
cumference. [5] M. Gilbert, J. C. Vyvoda, [9] ISO 18373-2:2007 Rigid PVC pipes
Thermal analysis technique for − Differential scanning calorimetry
investigating gelation of rigid PVC (DSC) method − Part 2: Measurement
Literature
Thermal Analysis Application

compounds, POLYMER, Vol. 22, of the enthalpy of fusion of crystallites.

[1] Rogério P. Marques, José A. Covas, August 1981, 1134.
Processing Characteristics of U-PVC [6] H. Potente, S.M. Schultheis,
Compounds, Firmenschrift von „Bestimmung des Geliergrades von
CIRES S.A. (Companhia Industrial PVC mit der DSC”, Kunststoffe 77,
de Resinas Sintéticas), Estarreja, 1987, 401. Publishing Note:
Portugal, 2003. [7] J.W. Teh, et al, Interpretation of This application has been published in
[2] www.pvc4pipes.org DSC Measurements of the Degree the METTLER TOLEDO Thermal Analysis
[3] B. Benzler, Thermal analysis of of Fusion of Rigid PVC, J. of Vinyl
polyvinyl chloride (PVC), UserCom No. 30.
Technology, Vol. 11 No.1 , See www.mt.com/ta-usercoms
METTLER TOLEDO Thermal Analysis March 1989, 33.
UserCom 9, 6−7.

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TA Application No. UC 303 4