Journal of Analytical and Applied Pyrolysis 92 (2011) 106–110

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

TG–MS analysis of nitrile butadiene rubber blends (NBR/PVC)

A. Pappa a,∗ , K. Mikedi a , A. Agapiou a , S. Karma a , G.C. Pallis a , M. Statheropoulos a , M. Burke b
a
National Technical University of Athens, School of Chemical Engineering, Field Analytical Chemistry and Technology Unit1 , 9 Iroon Polytechniou Street, 157 73 Athens, Greece
b
QinetiQ Farnborough, GU14 0LX, UK

a r t i c l e i n f o a b s t r a c t

Article history: Blends of nitrile butadiene rubber (NBR) with polyvinyl chloride (PVC) are widely used in products such as
Received 28 January 2011 hoses and seals. As part of a project that uses NBR/PVC blends for manufacturing forest fire hoses, blends
Accepted 2 May 2011 of NBR/PVC with various inorganic fillers, such as Mg(OH)2 , china clay (organic modified kaolin) and nano
Available online 11 May 2011
clay (organic modified bentonite) were studied by TG–MS. No significant changes were observed to the
type of the polymers’ decomposition products, compared to that of NBR/PVC blend without additives.
Keywords:
The most remarkable change was the absence of HCl from decomposition products in the presence of the
NBR/PVC
Mg(OH)2 additive.
TG–MS
Polymer blends © 2011 Elsevier B.V. All rights reserved.
China clay
Nano clay
Forest fire hoses

1. Introduction As part of a project that uses NBR/PVC blends for manufacturing

Thermogravimetry (TG) is becoming an increasingly important
technique, especially in the rubber industry [1,2]. The study of the
complicated thermal degradation, the analysis of the evolved gases
and volatiles organic compounds (VOCs) and the determination of
the role of additives, can clearly benefit from the connection of TG
with other analytical techniques. This is particularly true, if ther-
mogravimetry is coupled to an analytical method that will permit
the identification of the products, such as mass spectrometry (MS)
[3].
The main advantage of TG–MS is the acquisition of multiple
information during one run: the weight loss of the sample as a
function of the temperature, the type of the volatile products as
a function of the temperature and in some cases the quantitative
analysis of the evolved gases. Additionally, the TG–MS technique
can be used for revealing the details of the degradation mecha-
nism, for comparative studies of thermal degradation of various
polymers or for studying the role of additives.
In this work, TG was combined with a MS using an in-house
developed TG–MS interface, enabling the study of thermal degra-
dation of rubber blends. The main advantage of employing the
TG–MS interface is the near real-time monitoring of degradation
and the fast, unobstructed transfer of the evolved gases to the mass
detector.
forest fire hoses, blends of NBR/PVC with various inorganic fillers
were studied by TG–MS. In NBR/PVC blends, NBR acts as a per-
manent plasticiser, whereas PVC improves ozone, chemical and
thermal resistance of NBR in applications such as fuel hose cov-
ers [4]. Mg(OH)2 , china clay (organic modified kaolin) and nano
clay (organic modified bentonite) were used as fire retardant addi-
tives. The organic modification of the clays aimed to improve the
compatibility of inorganic composites with polymer blends.
The thermal degradation of PVC has been extensively studied in
the past with various techniques including TG–MS [5,6]. Accord-
ing to our knowledge, there are few studies referred to the thermal
degradation of NBR [7] and NBR/PVC blends [4,7]; however, none
of them uses TG–MS. The aim of the present work is to study the
thermal degradation of NBR/PVC blends used for manufacturing
forest fire hoses by TG–MS. This includes the interpretation of TG
curves, the identification and the profiling of the evolved volatile
products during the different degradation phases. The effect of var-
ious additives on the thermal degradation of the NBR/PVC blends
is also studied.
2. Experimental
2.1. Materials

The following vulcanized rubber samples were supplied from

∗ Corresponding author. Tel.: +30 210 7723193; fax: +30 210 7723188. QinetiQ (Farnborough, United Kingdom): NBR (34% acrylonitrile
E-mail address: athpappa@chemeng.ntua.gr (A. Pappa). content), NBR/PVC (65:35) and NBR/PVC with inorganic fillers
1
http://fiactu.ntua.gr/. according to the following recipes; NBR/PVC with 50 phr Mg(OH)2 ,

0165-2370/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2011.05.003
 A. Pappa et al. / Journal of Analytical and Applied Pyrolysis 92 (2011) 106–110 107

Fig. 4. Mass spectrum at 40.9 min of NBR thermal degradation.

nected to a vacuum source, in order to produce stable laminar

flow conditions. The flow through the intermediate tube has two
Fig. 1. TG and DTG curves of PVC powder.
modes of operation: (1) the idle mode, when the intermediate
tube is flushed with an inert gas (He) in order to prevent evolved
gases from reaching the capillary and (2) the sampling mode,
when the intermediate tube is connected to vacuum in order to
direct the evolved gases to the head of the capillary. Sampling
period and duration are adjusted by an electronically controlled
solenoid valve. When the sampling duration is adjusted to be infi-
nite, then the system operates in a continuous sampling mode.
The TG–MS interface has been successfully used so far for the
TG–MS analysis of synthetic and natural polymers, such as Kraton
1107, cellulose and pine needles [8–11]. Its evaluation (tests for
monitoring the mass-flow stability, gas transfer delay, evolved-gas
condensation effect and the interferences of the coupling system
on TG and MS specifications), is presented in detail elsewhere
[12,13].
Fig. 2. Mass spectrum at 25.1 min of PVC thermal degradation.

NBR/PVC with 10 phr nano clay and NBR/PVC with 10 phr china
clay. In addition, a Hydro grade of PVC powder was used.

2.2. Instruments and methods

The TG–MS analysis was carried out using a thermogravimet-

ric analyzer (TA Instruments, TGA 2050) and a quadrupole mass
selective detector (HP-5972). An in-house developed interface con-
sisting mainly of three coaxial tubes was used for the connection
of the two instruments. The inner tube is a capillary transfer line Fig. 5. Evolution profiles of ions at m/z 27, 53, 67, 93, 107 of NBR thermal degrada-
connected to the MS detector ion source. The outer tube is con- tion.

Fig. 3. TG and DTG curves of NBR. Fig. 6. TG and DTG curves of NBR/PVC.
108 A. Pappa et al. / Journal of Analytical and Applied Pyrolysis 92 (2011) 106–110
Fig. 7. Evolution profiles of ions at m/z 27, 36, 53, 67, 78 of NBR/PVC thermal degra-
dation.
Fig. 8. TG curves of NBR/PVC and NBR/PVC with inorganic additives: Mg(OH)2 , china
clay and nano clay.
The transfer line of the TG–MS interface was a 2.15 m long
uncoated fused silica capillary column 0.15 mm id (Varian, USA).
The temperature of the TG–MS interface was 200 ◦ C and the
temperature of the transfer line was kept at 210 ◦ C. The inert gas
used was helium with a flow rate of 100 cm3 min−1 in the ther-
mobalance. The continuous mode was selected. Gas flows were
adjusted at 60 cm3 min−1 for the port A and 40 cm3 min−1 for the
port B of the interface system. The samples, approximately 5 mg
(1 mg for PVC), were heated in the thermobalance from 50 to 600 ◦ C
with a rate of 10 ◦ C min−1 at helium atmosphere. The MS interface
was heated at 280 ◦ C. The electron impact source was tuned at 70 eV
and the scan rate was 0.45 scans s−1 . The mass range for the MS data
acquisition was set at 2–300 amu.
Fig. 9. Evolution profile of ions at m/z 18 (H2 O) and m/z 36 (HCl) in the thermal
degradation of NBR/PVC with Mg(OH)2 .
3. Results and discussion
3.1. TG–MS of PVC
In Fig. 1, the TG and DTG (derivative thermogravimetry) curves
of PVC revealed two main degradation steps, in agreement with
literature [14,15]. A mass loss of 65.2% at about 210–370 ◦ C was
observed in the first stage. The second degradation step of PVC
took place around 370–530 ◦ C, corresponding to the mass loss of
29.7%. In Fig. 2, the mass spectrum at 25.1 min, corresponding to
the temperature of maximum rate of mass loss is presented. Peaks
at m/z 36 and 38 are attributed to HCl and m/z 78 to C6 H6 . The mass
spectra (not shown) of the second degradation step (370–530 ◦ C),
presented a peak at m/z 91, which could be attributed to toluene or
to a fragment of other alkyl-benzenes. The above observations are
in agreement with the known mechanism of PVC degradation; the
first step is dehydrochlorination and formation of macromolecules
with conjugated double C C bonds, whereas, on the second step
degradation continues with cracking and pyrolysis to low hydrocar-
bons of linear or cyclic structure [15,16]. According to the literature,
Fig. 10. TIC of (a) NBR/PVC with nano clay and (b) NBR/PVC with china clay, during
their thermal decomposition.
Fig. 11. Mass spectrum at 20.2 min of the thermal degradation of NBR/PVC with
nano clay.
 A. Pappa et al. / Journal of Analytical and Applied Pyrolysis 92 (2011) 106–110
HCl is the main volatile degradation product of the first step. Small
quantities of benzene and other hydrocarbons are also emitted. In
the second step, up to 527 ◦ C, more aromatic products are evolved
than aliphatic [15].
3.2. TG–MS of NBR
The TG and DTG curves of NBR are shown in Fig. 3. The mass loss
in the range 120–300 ◦ C (8.6–26.3 min) was too low to be detected
by the MS. The main mass loss of NBR (87.7%) took place at one
step at about 300–500 ◦ C. During the thermal degradation of NBR
chain scission is occurring. Considerations of the bond strengths
indicate that the thermal cleavage takes place preferentially at ter-
tiary carbon atoms and at bonds beta to the CN bond [17]. This is
reconfirmed from the mass spectrum at 40.9 min (Fig. 4), corre-
sponding to the temperature of maximum rate of mass loss, where
ions at m/z 27, 53, 67, 93, 107, 110, 160 were recorded. Some of
these masses arise from the pyrolytic degradation of acrylonitrile
polymer such as m/z 53 (acrylonitrile, C3 H3 N), m/z 67 (butenen-
itrile, C4 H5 N), while others are characteristic of poly butadiene
polymer as m/z 110 (ethylene-cyclohexane, C8 H14 ). Moreover,
ions with m/z 93, 107, 160 correspond to 1-cyano-2,4-pentadiene
(C6 H7 N), 1-cyano-2,4,-hexadiene (C7 H9 N) and 1,7-dicyano-4,7-
octadiene (C10 H12 N2 ), respectively. These masses are associated
with both acrylonitrile and butadiene molecules [17]. As these are
unique to the pyrolytic degradation of NBR rubbers, they allow
the positive identification of these rubbers. The hydrogen cyanide
(HCN) with mass 27 originates commonly from the evolved degra-
dation products of NBR like 1-cyano-2,4-pentadiene with m/z 93,
which have labile hydrogen atoms [17]. In Fig. 5, the evolution pro-
files of all the above mentioned ions at m/z 27, 53, 67, 93, 107
show that these products are evolved in the temperature range
300–500 ◦ C.
3.3. TG–MS of NBR/PVC blends
In Fig. 6, the TG and DTG curves of NBR/PVC, indicate that the
mass loss takes place in two steps. In the first degradation step,
a mass loss of approximately 17% with a maximum rate around
250 ◦ C (21.5 min) takes place. A second mass loss of almost 55%,
with a maximum rate around 430 ◦ C (39.2 min) is also observed. The
total char residue of NBR/PVC blend is around 27%. This is higher
than the char residue of pure PVC and NBR degradation which are
around 5% and 8%, respectively (Figs. 1 and 3). The char residue
was probably increased in NBR/PVC blends due to a synergistic
effect of the blend components leading to a more stabilized product
compared to the individual components.
The evolution profiles of characteristic ions, presented in Fig. 7,
imply that the first mass loss corresponds to PVC decomposition
(ions at m/z 36 and 78 are evolved between 21 and 30 min). How-
ever, the intensity of m/z 78 relatively to m/z 36 is lower than
the one during decomposition of pure PVC. The second mass loss
corresponds to NBR decomposition (ions at m/z 27, 53, 67).
3.4. TG–MS of NBR/PVC blends with inorganic fillers
In Fig. 8, TG curves of NBR/PVC blends with 50 phr Mg(OH)2 ,
10 phr china clay and 10 phr nano clay together with the TG curve
of NBR/PVC are presented. The presence of PVC, which acts as sta-
bilizer for NBR [4], leads to 27% char residue in the NBR/PVC blend
instead of 8% at 600 ◦ C in case of pure NBR. The presence of inor-
ganic fillers leads to a slight increase in the mass of residue at 600 ◦ C
compared to the mass of residue of NBR/PVC. The mass residue at
350 ◦ C, where the PVC decomposition has been almost completed,
is increased from 81% for NBR/PVC blend to 91% for NBR/PVC with
Mg(OH)2 filler and to 84% for NBR/PVC with china clay. Taking into
109
account the portion of the fillers in the samples, there seems to be
a remarkable increase of the mass residue at 350 ◦ C for the blends
with Mg(OH)2 and china clay. Thus, Mg(OH)2 and china clay seem
to significantly suppress PVC decomposition, confirming the role of
the above fillers as thermal barriers.
The mass spectra of the polymer blends with inorganic additives
did not reveal any significant changes on the type of decomposition
products of the polymers, compared to that of NBR/PVC blend with-
out additives. The most characteristic differentiation is the absence
of HCl in the evolved products in the presence of Mg(OH)2 filler,
until approximately 40 min, corresponding to 450 ◦ C as the evo-
lution profile of m/z 36 indicates, according to Fig. 9. This may
be attributed to the chemical reaction between Mg(OH)2 and the
HCl evolved from PVC hydrochlorination. As the evolution pro-
file of the ion at m/z 18 shows (Fig. 9), H2 O formed from this
reaction is evolved firstly in the temperature range 250–350 ◦ C
(20–30 min), which is connected with the decomposition area of
PVC. It seems that H2 O is also evolved in the range 410–500 ◦ C
(36–45 min), which is connected with the decomposition of the
remaining Mg(OH)2 . The last is also in agreement with the litera-
ture [18]. The evolution of HCl (m/z 36) above 450 ◦ C (40 min) might
be due to the oxidation of MgCl2 [19]. The later is produced by the
reaction between Mg(OH)2 and HCl of PVC dehydrochlorination.
Although in the present work, an inert atmosphere was used, a
small amount of air might have been present in the TG furnace, as
it was not absolutely air tight.
In the cases of nano clay and china clay, the total ion current (TIC)
diagrams show a small peak at around 20 min, just before the peak
of PVC decomposition that occurs with a maximum rate at 22 min
(Fig. 10a and b, respectively). The mass spectrum of NBR/PVC blend
with nano clay at 20.2 min (Fig. 11) shows the evolution of water
(m/z 18) due to the water desorption. It appears that the evolution
of CO2 (m/z 44), alkenes (m/z 41, 55, 69, 83) and alkanes (m/z 29,
43, 57) may be due to the organic impurities of the clay [20]. The
same seems to apply in the case of PVC/NBR blends with china clay.
4. Conclusions
In conclusion, TG–MS seems to be a useful tool for the interpre-
tation of thermal degradation of polymer blends such as NBR/PVC
and the action of the various additives on the blends. It enabled
the monitoring of the evolved products at each degradation step,
facilitating the comparison of different blends. It appears that the
thermal decomposition of NBR/PVC blend consists of two profiles;
that of PVC and that of NBR. The mass spectra of the polymer blends
with inorganic additives did not reveal any significant changes to
the type of decomposition products of the polymers, compared
with that of NBR/PVC blend without additives. The most remark-
able change is the absence of HCl from decomposition products in
the presence of the Mg(OH)2 additive.
Acknowledgement
The research leading to these results has received funding from
the European Community’s Seventh Framework Program (FP7-
SME-2007-1) under grant agreement No. 222152: “FIRELI-Fire
Retardant Hoses Lines for Forestry Fire-Fighting Applications”.
References
[1] S. Knappe, C. Urso, Applications of thermal analysis in rubber industry, Ther-
mochim. Acta 227 (1993) 35–42.
[2] W.M. Groenewoud, Characterization of Polymers by Thermal Analysis, 1st ed.,
Elsevier Science, Amsterdam, 2001.
[3] K.G.H. Raemakers, J.C.J. Bart, Applications of simultaneous
thermogravimetry–mass spectrometry in polymer analysis, Thermochim.
Acta 295 (1997) 1–58.
110 A. Pappa et al. / Journal of Analytical and Applied Pyrolysis 92 (2011) 106–110
[4] M.C.S. Perera, U.S. Ishiaku, Z.A.M. Ishak, Thermal degradation of PVC/NBR and
PVC/ENR 50 binary blends and PVC/ENR 50/NBR ternary blends studied by DMA
and solid state NMR, Polym. Degrad. Stabil. 68 (2000) 393–402.
[5] R. Knümann, H. Bockhorn, Investigation of the kinetics of pyrolysis of PVC by
TG–MS-analysis, Combust. Sci. Technol. 101 (1994) 285–299.
[6] Q.L. Sun, X.G. Shi, Y.L. Lin, H. Zhu, X. Wang, C.G. Cheng, J.H. Liu,
Thermogravimetric–mass spectrometric study of the pyrolysis behavior of PVC,
J. China Univ. Mining Technol. 17 (2007) 242–245.
[7] F. Pruneda, J.J. Suñol, F. Andreu-Mateu, X. Colom, Thermal characterization of
nitrile butadiene rubber (NBR)/PVC blends, J. Therm. Anal. Calorim. 80 (2005)
187–190.
[8] M. Statheropoulos, K. Mikedi, N. Tzamtzis, A. Pappa, Application of factor analy-
sis for resolving thermogravimetric–mass spectrometric analysis spectra, Anal.
Chim. Acta 461 (2002) 215–227.
[9] A. Pappa, K. Mikedi, N. Tzamtzis, M. Statheropoulos, TG–MS analysis for study-
ing the effects of fire retardants on the pyrolysis of Pinus halepensis needles
and their components, J. Therm. Anal. Calorim. 84 (2006) 655–661.
[10] A. Pappa, S. Kyriakou, K. Mikedi, N. Tzamtzis, M. Statheropoulos, Design consid-
erations and an example of application of an in-house made TG–MS interface,
J. Therm. Anal. Calorim. 78 (2004) 415–426.
[11] A. Pappa, K. Mikedi, N. Tzamtzis, M. Statheropoulos, Chemometric meth-
ods for studying the effects of chemicals on cellulose pyrolysis by
thermogravimetry–mass spectrometry, J. Anal. Appl. Pyrol. 67 (2003) 221–235.
[12] M. Statheropoulos, S. Kyriakou, N. Tzamtzis, Performance evaluation of a TG/MS
system, Thermochim. Acta 322 (1998) 167–173.
[13] M. Statheropoulos, S. Kyriakou, A. Pappa, Repetitive pulsed sampling interface
for combined thermogravimetry mass spectrometry, Thermochim. Acta 329
(1999) 83–88.
[14] H.M. Zhu, X.G. Jiang, J.H. Yan, Y. Chi, K.F. Cen, TG-FTIR analysis of PVC thermal
degradation and HCl removal, J. Anal. Appl. Pyrol. 82 (2008) 1–9.
[15] A. Jiménez, V. Berenguer, J. López, A. Sánchez, Thermal degradation study of
poly (vinyl chloride): kinetic analysis of thermogravimetric data, J. Appl. Polym.
Sci. 50 (1993) 1565–1573.
[16] M. Statheropoulos, Study of the isothermal degradation of poly (vinyl chloride)
by direct inlet mass spectrometry, J. Anal. Appl. Pyrol. 10 (1986) 89–98.
[17] J.A. Hiltz, Pyrolysis gas chromatography/mass spectrometry identification of
poly (butadiene–acrylonitrile) rubbers, J. Anal. Appl. Pyrol. 55 (2000) 135–150.
[18] T. Xu, X. Huang, A TG-FTIR investigation into smoke suppression mechanism of
magnesium hydroxide in asphalt combustion process, J. Anal. Appl. Pyrol. 87
(2010) 217–223.
[19] L. Guangming, M. Peihua, W. Zhiming, L. Mingzhen, C. Minxong, Investiga-
tion of thermal decomposition of MgCl2 hexammoniate and MgCl2 biglycollate
biammoniate by DTA–TG, XRD and chemical analysis, Thermochim. Acta 412
(2004) 149–153.
[20] J.Y. Lee, H.K. Lee, Characterization of organobentonite used for polymer
nanocomposites, Mater. Chem. Phys. 85 (2004) 410–415.