JOURNAL OF POLYMER SCIENCE: PART A-1

VOL. 4, 2479-2485 (1966)

Thermal Volatilization Analysis: A New Method for

the Characterization of Polymers and the Study of
Polymer Degradation
I. C. McNEILL, Chemistry Department, University of Glasgow,
Glasgow, Scotland

Synopsis
I n a continuously evacuated system in which volatile products are pasing from a
heated sample to the cold surface of a trap some distance away, a small pressure will
develop which varies with the rate of volatilization of the sample. If this pressure
(measured by Pirani gage) is recorded as the sample temperature i s increased in a linear
manner, a TVA thermogram showing one or more peaks is obtained. TVA thermograms
for a number of polymers and copolymers are presented and briefly discussed. The
technique has some advantages over TGA for characterizing polymers or studying qualitative aspects of polymer degradation.

In recent years the techniques of differential thermal analysis (DTA)

and thermogravimetric analysis (TGA) have been increasingly applied to
problems of polymer characterization and degradation studies. Each
involves the measurement of a convenient variable (in the former a temperature differential, and in the latter the loss in weight of the sample)
during a gradual, linear increase in temperature.
Much useful information could in principle be obtained by combining
linear temperature programming with the measurement of other variables.
One of these is the pressure of volatile products during degradation.
In a continuously evacuated system in which condensable volatile products
are passing from a heated polymer sample to the cold surface of a trap,
some distance away, a small pressure will develop due to the time taken by
the products to travel from the hot to the cold surface. The magnitude
of the pressure developed varies with the rate of volatilization of the sample.
A system can be designed in which the pressure developed during the degradation of a convenient weight of polymer varies within the range 10-LlO-l
torr and is therefore readily measured by means of a Pirani gage. This
technique has been used by Grassie and co-~orkersl-~in isothermal
degradation studies over a number of years. No previous attempt appears
to have been made, however, to apply the method to temperature-programmed experiments.
When the variation in pressure of volatile products is recorded during a
degradation in which the temperature of the polymer sample is increased
2479

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I. C. McNEILL

at a steady rate, the resulting thermogram is of considerable interest. It

is proposed to refer subsequently to this technique as thermal volatilization
analysis (TVA). The purpose of this communicatioq is to illustrate the
potential usefulness of the method by presenting and discussing very briefly
a small selection of examples of TVA thermograms.
The apparatus required for TVA is simple, and since no moving parts
are involved, it is sturdy. A flat-bottomed glass tube containing the
polymer sample as a fine powder or film is inserted into the top of a small
oven, the temperature of which is varied by means of a linear temperature
programming unit. The glass tube is connected first to a trap surrounded
with liquid nitrogen and then to a mercury diffusion pump and rotary
oil pump. Between the tube and the trap is attached a Pirani gage head.
The gage control unit provides an output for a 10-mv. potentiometric
strip chart recorder so that a continuous trace of pressure versus time
(temperature) may be obtained. Polymer samples from 10 to 250 mg. can
conveniently be handled; in the case of materials which give only very
small amounts of volatile products, increased sensitivity is readily obtained
by using a 2.5-mv. recorder range. A fuller description of the apparatus
and details of temperature calibration will be published later.
As with TGA and DTA, each polymer will, in general, give a characteristic thermogram, and detail differences may be observed for samples of a
given polymer, depending on their history. TVA differs from TGA,
however, in that the rate of volatilization is being measured, since the
pressure at any temperature is related to the rate of volatilization at that
temperature. Hence the TVA thermogram for a polymer sample shows
one or more peaks, whereas in the case of TGA what is obtained is a trace
with one or more points of inflection, which has to be differentiated to
obtain a rate plot. For purposes of polymer characterization or qualitative
investigation of the degradation of polymers, the technique of TVA
therefore offers advantages in a convenient form of trace as well as in experimental simplicity. The possibilities for quantitative application of
TVA are being examined.

SELECTED EXAMPLES OF TVA THERMOGRAMS

The thermograms reproduced were all obtained with the use of 25-mg.
samples, a linear heating rate of lO"C./min., and a recorder sensitivity of
10 mv. The ordinate covers a nominal pressure range (based on the dry air
calibration of the gage) from
to 3 X 10-1 torr, the scale being nonlinear and considerably compressed towards the high pressure end. The
nonlinearity of the scale is useful, since smaller peaks, which may be of
considerable interest when detail differences in similar polymer samples
are being examined, are more readily detected.
As in the case of TGA, the trace obtained is somewhat dependent on the
heating rate. In many cases the only difference observed with different
heating rates is a slight shift in the positions of the rate maxima. With

THERMAL VOLATILIZATION ANALYSIS

2481

some polymers, however, the changes can be more profound. A standard

heating rate (10"C./min.) has therefore been adopted in the present work.

Poly(methy1 Methacrylate)
TVA thermograms are reproduced in Figure 1 for three samples prepared
by bulk polymerization with azobisisobutyronitrile as initiator a t 60C.
The number-average molecular weights were 820,000,250,000, and approximately 20,000, respectively.
The two stages in the degradation are clearly distinguished. The first
peak above 200C. represents reaction initiated at unsaturated ends formed
in the termination step of the p o l y m e r k a t i ~ n . ~The
~ ~ second, larger peak
corresponds to reaction at higher temperatures, initiated by random scission
of the main chain.6 It is apparent that as the proportion of chain ends in
the sample increases, the size of the first peak increases also. These TVA
thermograms illustrate very clearly the conclusions recently drawn by
MacCallum7 in a general consideration of the mechanism of degradation of
this polymer.
The peaks occurring below 200C. can be attributed to trapped solvent,
precipitant, etc. These show up very clearly, indicating the usefulness
of TVA as a method of testing polymers for freedom from this type of
impurity.

W
l-

a
K

Fig. 1. TVA thermograms (lOC./min.) for samples of poly(methy1 methacrylate) of

various molecular weights: (a) 820,000; ( b ) 250,000; ( c ) approx. 20,000.

Poly(viny1 Acetate) and Poly(viny1 Chloride)

The similarities in the degradation mechanisms of these two polymers
make the TVA thermograms (Fig. 2) of great interest. The lower thermal
stability of PVC shows up strikingly, but the second stage of the degradation of both polymers, corresponding to breakup of a (-CH=CH-).
chain, is clearly similar in both poIymers. The PVC sample was prepared
by bulk polymerization with azobisisobutyronitrile as initiator; the PVA

I. C . McNEILL

2482

Fig. 2. TVA thennograms (lOC./min.) for ( a ) poly(viny1 acetate); ( b ) poly(viny1

chloride).

was a B.D.H. sample. The former shows a large solvent peak due to
trapped solvent (cyclohexanone) ; the latter is almost free of trapped volatile material. A commercial PVC sample (Geon 101) gave a thermogram
similar to Figure 2b, but without the solvent peak.

Polyacrylonitrile and Polymethacrylonitrile

The degradation reactions of these polymers have been fully discu~sed.~~
The former gives only small am0unt.s of volatile material, but the latter

l-

a
K

Fig. 3. TVA thennograms (10"C./min.) for (a)polyacrylonitrile; ( b ) polymethacrylonitrile.

THERMAL VOLATILIZATION ANALYSIS

2483

undergoes a number of reactions, monomer being produced in large quantities (Fig. 3).
The PAN was a Chemstrand polymer. PMAN was prepared at 65C.
with azobisisobutyronitrile as initiator, and had a number-average molecular weight of approximately 12,000.

Polystyrene, Poly-a-methylstyrene, and Poly-a-phenylacrylonitrile

Polystyrene and poly-a-methyl styrene both give thermograms consisting of single peaks (Fig. 4),that for the latter occurring at a very much
lower temperature. Poly-a-phenylacrylonitrileis even less stable: degradation begins below 200"C., and in this case two or more reactions are
clearly involved, because of the double peak.
The polystyrene sample was prepared by bulk polymerization at 60C.
with the use of azobisisobutyronitrile as initiator. Poly-a-methylstyrene
was prepared at -78C. in methylene chloride solution with stannic
chloride as initiator. Poly-a-phenylacrylonitrile was a Chemstrand
sample.

Fig. 4. TVA thermograms (lO"C./min.) for ( a ) polystyrene; ( b ) poly-a-methylstyrene;

( c) poly-a-phenylacrylonitrile.

Polyisobutene, Butyl Rubber, and Chlorobutyl Rubber

The decrease in stability resulting from incorporation of small amounts
of isoprene in a polyisobutene chain is apparent from a comparison of curves
a and b in Figure 5. Conversion of butyl rubber to chlorobutyl rubber
results in a further decrease in thermal stability (Fig. 5c).
Polyisobutene was prepared at - 78C. in methylene chloride solution
with stannic chloride as initiator. Butyl (Enjay MD-501, 3.5 mole-%
unsaturation) and chlorobutyl (Enj ay HT 10-66, 1.5 mole-% unsaturation)
were Esso samples.

I. C. McNEILL

2484

I-

a
LT

Fig. 5. TVA thermograms (lOC./min.) for (a) polyisobutene; ( b ) butyl rubber;

(c) chlorobutyl rubber. See text for unsaturation data.

Polystyrene and a Styrene-Butadiene Copolymer

Incorporation of large amounts of butadiene into the polystyrene chain
does not result in lower thermal stability, but it is clear that less volatile
degradation products are obtained in the case of the copolymer (Fig. 6).
This is in agreement with the findings of Madorsky and co-workers.6
The polystyrene sample was the same as mentioned above (Fig. 4).
The copolymer was an I.C.I. product (Butakon S 7001) containing 30%
by weight of Butadiene.

W
I-

Fig. 6. TVA thermograms (lO"C./min.) for (a) polystyrene; ( b ) a styrene-butadiene

copolymer containing 30% butadiene.

CONCLUSION
I n conclusion, from a consideration of the examples of TVA given, the
method would appear to have applications particularly in the following

THERMAL VOLATILIZATION ANALYSIS

2485

fields: (1) characterization of polymer samples; (2) studies of the effect

of structural details on polymer degradation behavior; (3) detection of
volatile impurities in polymer samples; (4) studies of the effect of composition on copolymer stability.
The author is indebted to Dr. N. Grassie, Mr. I. F. McLaren, Mr. J. Pang, Rlr. B.
J. D. Torrance, and the firms mentioned in the text for kindly providing some of the
samples used in this work.

References
1. N. Grassie, The Chemistry of High Polymer Degradation Processes, Butterworths,
London, 1956.
2. N. Grassie and I. C. McNeill, J . Chem. SOC.,1956,3929.
3. D. H. Grant and N. Grassie, Polymer, 1,445 (1960).
4. N. Grassie and H. W. Melville, Proc. Roy. SOC.(London),A199,1(1949).
5. N. Grassie and E. Vance, Trans. Furaday SOC.,49,184 (1953).
6. A. Brockhaus and E. Jenckel, Makromol. Chem., 18/19,262 (1956).
7. J. R. MacCallum, Makromol. Chem., 83,137 (1965).
8 . N. Grarssie and I. C. McNeill, J . Polymer Sci., 27,207 (1958); ibid., 30.37 (1958);
ibid., 33,171 (1958); ibid., 39,211 (1959).
9. S. L. Madorsky, Thermul Degradation of Organic Polymers, Interscience, Kew
York, 1964.

Msum6
Lorsquun produit volatile passe dun Bchantillon Chad6 B une surface refroidie
dune trappe situke A une certaine distance de lkchantillon dans un systkme continuellement BvacuB, une faible pression se dBveloppera; elle variaera avec la vitesse de volatilisation de lkchantillon. Si cette pression (mesurr5e a u moyen dune gauge de Pirani)
est enregistrke, de m6me que la temgrature del6chantillon, e t si elle augmente de f q o n
linbaire, on obtiendra un thermogramme TVA manifestant un ou plusieurs pin. Les
thermogrammes TVA obtenus pour un certain nombre de polymbres e t copolymbres
sont prksentks et discutAs bribvement. La technique prBsente certains avantages sur
lanalyse thermogavimBtrique pour caracteriser les polymbres ou pour Btudier des
aspects qualitatifs de la degradation de polymbres.

Zusammenfassung
I n einem kontinuierlich evakuierten System, in welchem fliichtige Produkte von einer
erhitzten Probe zur kalten Oberflache eines in einem gewissen Abstand befindlichen
Abfangers ubergehen, wird sich ein kleiner Druck einstellen, der von der Verfliichtigungsgeschwindigkeit der Probe abhangt. Bei Aufzeichnung dieses (mit einem Piranimanometer gemessenen) Druckes wahrend der linearen Temperaturerhohung der Probewird ein TVA-Thermogramm mit einem oder rnehqeren Maxima erhalten. TVAThermogramme werden fiir eine Anzahl von Polymeren und Kopolymeren vorgelegt und
kurz diskutiert. Das Verfahren besitzt einige Vorteile gegenuber der TGA zur Charakterisierung von Polymeren und zur Untersuchung der qualitativen Aspekte des Polymerabbaus.

Received JuIy 27, 1965

Revised February 17, 1966
Prod. No. 5099A