Analyse of Zeonex 350R

Erasmus student
2017/2018
Thermal analysis is defined by the International Confederation of Thermal Analysis and
Calorimetry (ICTAC) as “a group of techniques in which a property of a sample is monitored
against time or temperature while the temperature of the sample, in a specified atmosphere,
is programmed.” In practice, the temperature of the oven that contains the sample actually is
programmed, while the temperature of the sample in some cases may differ from the
programmed temperature. Exothermic or endothermic reactions or phase transitions in the
sample subjected to the programmed temperature variation may cause variations in the
temperature between the sample and oven up to several degrees.

Two possible processes that can occur during the treatment of a polymer modifying the
temperature are:

 Thermal degradation of polymers: This is molecular deterioration as a result of

overheating. At high temperatures the components of the long chain backbone of
the polymer can begin to be broken (chain scission) and react with one another to
change the properties of the polymer. Thermal degradation can present an upper limit
to the service temperature of plastics as much as the possibility of mechanical
property loss. Indeed unless correctly prevented, significant thermal degradation can
occur at temperatures much lower than those at which mechanical failure is likely to
occur.

The chemical reactions involved in thermal degradation lead to physical and optical
property changes relative to the initially specified properties.

 Depolymerization: Depolymerization is a special category of degradation, it is the

process that converts the polymer into a monomer, into a mixture of monomers or
oligomers. De-polymerization is a process of decomposition of the polymer chain to its
monomers or oligomers. It is usually achieved with high temperature (thermal) or
hydrolytic agents (chemical).

Commonly, thermal depolymerization is classified as the chemical reaction in which

the polymer chain is converted to high temperature monomers.

In this study, the polymer to be analyzed is the Zeonex 350R, which has a cyclic olefin
copolymer structure.

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 Image 1: cyclic olefin copolymer structure (Zeonex 350R)

The main objective of the study is to determine the stability of the polymer after an increase in
temperature over a sample and to observe if its structure changes with the increase in
temperature, so that it can be concluded whether or not it is a good polymer to work with.

To carry out the study, 3 samples of Zeonex 350R were analyzed. The first one was subjected
to an increase in temperature to approximately 600 ° C, while the other two samples were
subjected to a cyclic process for two and four weeks respectively. This cyclic process was
carried out in a heated cabin with a specific temperature increase and for a certain time.

Simultaneous measurement TGA-DTA / DSC heat flux (Differential Scanning Calorimetry) and
weight changes (thermogravimetry) in a material as a function of temperature or time in a
controlled atmosphere. Measuring simultaneously the properties of these two materials, not
only increases productivity, but also simplifies the interpretation of results. The
complementary information obtained allows differentiating between endothermic and
exothermic events not associated with weight loss (for example, fusion and crystallization) and
those that involve weight loss (for example, degradation)

The analysis capacity is improved, since two or more sets of information concerning the
behavior of the sample are always available simultaneously (differentiation between the
transformation and decomposition phase, between the reactions of addition and
condensation, recognition of reactions of pyrolysis, oxidation, and combustion, etc.)

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 110 5.00E+00

90 0.00E+00 "TG"
DTG
-5.00E+00
70
-1.00E+01
Mass/%

50

DTG(%/min)
-1.50E+01
30
-2.00E+01

10 -2.50E+01

-10 10 60 110 160 210 260 310 360 410 460 510 560 610 -3.00E+01
Temperature/ ºC

Graph 1: TG and DTG of Zeonez 350R first sample

Observing the graphical representation 1, it can be deduced that at 380ºC the decomposition
of the given compound begins, since observing the Excel values it is seen that the mass%
begins to decrease. It is taken as the beginning of the decrease of the mass from 100%, since
an amount greater than 100% is not real. This temperature (380ºC) indicates the point at
which the sample begins to decompose, losing part of its mass progressively.

The lower part of the graphic representation tells us that it is a pure compound. There is no
residual mass.

Tº Time/min DTA/(uV/mg) Mass/% DTG/(%/min) DTG/(%/min)

370 39,09984 0,79741 100,26443 -0,28424 1

375 39,59928 0,81076 100,10199 -0,37684 1
380 40,09929 0,83372 99,87432 -0,53789 1
385 40,59977 0,87102 99,55303 -0,77038 1
390 41,10032 0,92024 99,08634 -1,12559 1
395 41,60092 0,9864 98,3628 -1,83124 1
Picture 1: in this table the increase of temperature with the passage of time and the progressive decrease of the compound mass
is shown

Above 440 °C is the maximun decomposition temperature of the compound as shown in graph
1 (blue function). Observing graph 2 it can also be inferred that the maximum decomposition
temperature is around 440º, since the ions that make up the compound have their maximum
at that temperature (see graphs 2 and 3).

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The compound to be analyzed, Zeonex 350R, has a cyclic structure since it is a cyclic olefin
copolymer, which can be decomposed in different ions. Some of the located ions are:

4.5E-09
m:15

m:18
4E-09 m:28

m:29
3.5E-09 m:39

m:42

3E-09 m:43

m:53

m:55
2.5E-09
m:56
Mass %

m:65
2E-09 m:66

m:68
1.5E-09 m:78

m:79

1E-09 m:81

m:82

m:97
5E-10
m:98

0
0 50 100 150 200 250 300 350 400 450 500 550 600 650
-5E-10
Temperature ºC

Graph 2: it shows the different ions in the sample

2.00E-08
1.80E-08
1.60E-08
1.40E-08
1.20E-08
Mass %

1.00E-08 m:32 m:41

8.00E-09
6.00E-09
4.00E-09
2.00E-09
0.00E+00
25 55 85 115 145 175 205 235 265 295 325 355 385 415 445 475 505 535 565 595
Temperature ºC
Graph 3: it shows the different ions in the sample

Mass Ion
15 -CH3
18 H2O
28 CO
29 -CH2-CH3
32 O2
43 -CH2-CH2-CH3

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The presence of CO indicates that a reaction has occurred between the methyl group and the
O2 present during the analysis. The O2 is present during the analysis since the sample is
entered manually, so there are a few seconds in which the O2 can come into contact with the
sample. CO2 is not produced, since it does not appear in graph 2.

After the analysis of the first sample, the analysis of two more samples was carried out but
subjecting them to a cyclic temperature variation during 2 and 4 weeks respectively.

The second sample was subjected during 2 weeks to a cycle consisting of the following parts,
the process was started at a temperature of 40 ° C which was kept constant for 6 hours, then
the temperature was increased linearly for another 6 hours up to 80 ° C and It remained
constant for 6 hours. Finally the temperature decreased approximately 25 ºC to later return to
the initial point of the cycle and this can continue for 18 times.

The third sample was subjected during 4 weeks to a cycle consisting of the following parts, the
process was started at a temperature of 40 ° C which was kept constant for 6 hours, then the
temperature was increased linearly for another 6 hours up to 80 ° C and It remained constant
for 6 hours. Finally, the temperature decreased approximately 25 ºC to later return to the
initial point of the cycle and this can continue for 36 times.

In order to make a comparison between the analysis of the three samples, three graphic
representations were carried out in which they were grouped: TG, DTG and TIC.

TG comparation
120

100

80
DTG(%/min)

60

40

20

0
0 100 200 300 400 500 600 700
-20
Temperature (ºC)

TG-1 TG-2 TG-3

Graph 4

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In the graph 4 it can be seen that the functions that represent the samples are practically the
same and do not show a great variation between them, besides the section parallel to the x
axis between 500 and 600 ºC is linear, so there is no residual mass. This similarity in the result
of the samples indicates that a good stable polymer.

DTG comparation
5.00E+00
0.00E+00
0 100 200 300 400 500 600 700
-5.00E+00
DTG(%/min)

-1.00E+01
-1.50E+01
-2.00E+01
-2.50E+01
-3.00E+01
-3.50E+01
Temperature (ºC)

DTG-1 DTG-2 DTG-3

Graph 5

In graph 5 we can see that the three functions coincide practically one on the other, which
indicates the thermal and structural stability of the polymer. It is observed that the
decomposition temperature is the same for the three samples, around 440 ºC.

TIC comparation
1.80E-07
1.60E-07
1.40E-07
1.20E-07
1.00E-07 TIC-1
TIC/A

8.00E-08 TIC-2
6.00E-08 TIC-3
4.00E-08
2.00E-08
1.00E-22
-2.00E-08 0 100 200 300 400 500 600
Temperture (ºC)
Graph 6

In Figure 6 we can see that the shape of the functions that represent the three samples are
similar but not exact. However, in the three representations we can see that at the beginning

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of each function an elevation is observed that corresponds to the water present during the
process. It can be seen that the maximum peak is at the same point in the three
measurements.

After performing the analysis of the three samples and obtaining the graphs of TG, DTG and
TIC, it can be concluded that given the similarity in the results obtained in the three samples
after making various temperature variations the Zeonex 350R is a stable polymer at high
temperatures , since its structure does not vary; so it is a good polymer to work with him.