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Thermal analysis of heat set poly(ethylene

terephthalate) fibres
H.-J. Berndt and Adelgund Bossmann
Textilforschung Krefeld, D-4150 Krefeld, Frankenring 2, W. Germany
(Received 16 July 1975,"revised 23 October 1975)

Differential thermal analysis (d.t.a.) has been used for characterization of the thermal history of
poly(ethylene terephthalate) (PET) fibres. The latter were treated under a variety of temperatures
and times in a manner similar to conditions employed in conventional textile processing. The d.t.a.
revealed an endotherm at temperatures below the main melting peak of the fibre polymer, related
directly to temperature and time of thermal treatment, even with yarns that were heat set for less
than 0.2 sec (e.g. false twisting process). The maximum of this low temperature endotherm is a di-
rect measure of the effective temperature (Teff) that has been acquired by the PET fibres during the
thermal processing. In practice, several thermal treatments are often invo4ved in textile processing.
Results of this work imply that PET fibres subjected to a second heat treatment will show an addi-
tional low temperature endotherm on d.t.a, scanning, provided that the structural characteristics for-
med in the first thermal process are not neutralized in the second thermal process and recrystallizable
material is still present in the fibre polymer.

INTRODUCTION Wiesener 4 who investigated thermally treated drawn
In order to attain a PET yarn or fabric with certain proper- PET fibres, also found an increase in temperature of the
low temperature endotherm when the PET fibres were
ties,.the drawn PET filament will be subjected to various
subjected to increasing setting temperatures. However,
processing steps while heat is applied. During these ther-
also in this investigation the PET fibres were treated for 10
mal mechanical processing operations, changes in the state
to 240 rain.
of order in the polymer occur via a decrease in internal
Our concern is to investigate the changes of structure in
stresses and reorganization of polymer segments. A re-
crystallization and an after-crystallization will concurrently PET fibres as brought about under the influence of various
take place. The solid phase transitions in the PET fibre processing operations. For practical significance, time dur-
polymer can be detected by d.t.a, traces 1-4. Mutiple melt- ing the different heat setting processes varies from 0.2 sec
ing peaks during d.t.a, scanning have been reported s-8 for (e.g. false twisting) to 4 h (e.g. heat setting of heavy tech-
annealed PET bulk polymer. The PET samples were heat nical fabrics). The feasibility of d.t.a, to define the ther-
treated for periods varying from several minutes (5 min) to mal prehistory of PET fibres as produced under ordinary
several hours (24 h) at different temperatures to study the commercial thermal processing is, therefore, studied. Good
effect on thermograms in d.t.a. Between the glass transi- understanding of the structural changes as generated in
tion temperature and the main melting peak at about 260°C, PET fibre poly,ner under various conditions would be use-
a low temperature endotherm was observed. The position ful to predict the specific parameters of the heat setting
of this low temperature endotherm is reported to be related process; an aspect which is needed to attain desirable and
to the temperature to which the PET polymer has been ex- reproducible quality.
posed prior to d.t.a, scanning s-7. An increase in time of
treatment during annealing at a constant temperature cau-
ses an increase in the low temperature d.t.a, endotherm s.
Roberts s ascribed this low temperature endotherm to EXPERIMENTAL
melting of chain folded crystals, and the main melting peak
to melting of bundle-like crystals. More recent work by Material
Roberts 9 and Holdsworth and Turner Jones 8 discounted
The materials used in this study are exclusively commer-
this chain folded and bundle-like crystal endotherms hypo-
thesis because of the change in the relative areas of the two cial drawn PET filament yarns of different origins. The
endotherms with change in d.t.a, heating rate. A change in yarns were heat set at temperatures varying from 110 ° to
heating rate from 4 to 64 K/rain 9 causes not only an increase 230°C under simultaneous constant tension (0.0-0.1 N/
in intensity of the low melting endotherm but also an in- tex) during setting. The time of treatment varied from
crease in temperature on the d.t.a, trace. These changes 0.5 sec to 240 sec in hot air and up to 90 rain during a high
are considered to be due to structural changes takin.g9 place temperature dyeing process. In order to meet these setting
during d.t.a, scanning according to the heating rate 8' • demands, special heat setting equipment was developed ~
These studies were mainly carried out on bulky polymer to control the process parameters, temperature, tension and
annealed for a fairly long time (from ~5 rain to several processing time.
False twisted textured yams are also used to study in par
hours).
ticular, the effect of heat setting for very short times on
* Part XVlI of a series on the heat setting of PET14 structural changes in PET fibres.

POLYMER, 1976, Vol 17, March 241
Thermal analysis o f PET: H.-J. Berndt and A. Bossman

I The change on d.t.a, traces due to heating rate can be ex-
plained by the theory of Zachmann and Stuart 1°, who found
t
U
i
I
that only imperfect crystals are formed at low crystalliza-
tion temperatures (180°C, 20 sec). On heating, the perfec-
I
O; I tion of the crystals formed at low temperatures increases
0
owing to partial melting and recrystaUization. At low heat-
X
UJ ing rates a kinetic balance of melting and recrystallization
will occur which is not detectable in the thermogram base-
I line. However, if the heating rate is high enough the faster
melting process exceeds the slower recrystallization process,
producing the increase in the low temperature endotherm.
The increase in the partial melting peak temperature with
increasing heating rate is apparently due to the fact that the
k~
crystals may be heated faster than the melt-crystal inter-
<3
face can progress towards the interior and the crystals melt
at a higher temperature H.

Heat setting temperature
D.t.a. traces of a PET yarn 10tex/36 f'daments isother-
I E
U
mally heat set at various temperatures are shown in Figure
E 2. The yarn samples were treated for 20 sec at zero ten-
t- sion. The thermograms were run at a sensitivity range of
"t0-
AT = 0.2 K/in. They show a distinct partial melting peak
LU prior to the main melting peak at 256vC. The partial melt-
ing peak appears 10°C above the machine temperature of
thermal setting. With increasing machine temperature the
I I I I I
maximum of this peak increases linearly on the d.t.a, tem-
150 250 perature scale. These results suggest that the imperfect
Temperotur¢~ T[~TAPC) crystals in the fibre polymer melt on heating in the d.t.a.
Figure 1 D.t.a. traces of PET fibres heat set at 180°C for 20 sec; at a given heating rate just above the temperature at which
d.t.a, heating rates (K/min): A, 5; B, 10; C, 15; D, 20; E, 25; F, 30 they were formed during heat setting. The maximum of
the partial melting endotherm is directly related to the setting
temperature and is defined as the effective temperature
Differential thermal analysis
Teff.
Samples ( 5 - 6 mg) of PET yarn were accurately weighed If the PET fibre is exposed to a further heat process like
into an aluminium sample pan. The covers of the sample a high temperature dyeing at 130°C for 90 min, an addi-
pans were provided with small holes to allow for evapora-
tion of finishing agent and to maintain atmospheric pres-
sure during d.t.a, scanning. The measurements were made
with the sample in air, since prior tests have demonstrated A
that the heat of reaction is generally not influenced by at-
mospheric oxygen. The thermograms of the PET yarns
t
.u
E
samples were run on a Du Pont Differential Analyser, Type
t-
900 using the d.s.c, cell. A good resolution was needed to
observe the heat of fusion, which did not always appear as LU
C
a peak rather than as a deflection in the slope of the d.t.a.
trace. A heating rate of 30 K/min and a sensitivity range
for AT of 0.1 or 0.2 K/in were chosen.
D
I%
RESULTS AND DISCUSSION <3

Heating rate
The change of d.t.a, traces on increasing heating rate is
shown in Figure 1. A PET yarn sample was isothermally u
treated at 180°C for 20 sec at zero tension and d.t.a, traces
obtained at various heating rates. An increase in the par- t-
tial melting peak temperature and a change in the low tem- "6
perature endotherm are observed with increasing instru- t-
LU
ment heating rate. On running the fibre sample at a low
heating rate (5 K/min), a small fusion endotherm with a
poorly resolved maximum at 183°C is found, whereas a I
heating rate of 30 K/min leads to a fusion endotherm over o ' ' 'J o' '
a broad temperature range with its maximum at 190°C. Temperoture ,To.T.A.PC}
This change in the endotherm and peak temperature is in- Figure 2 D.t.a. traces of PET fibres heat sat for 20 sec at the
dicative of a reorganization taking place during scanning 8. various temperatures (°C): A, 110; B, 150; C, 190; D, 230

242 POLYMER, 1976, Vol 17, March
Thermal analysis of PET: H. .I. Berndt and A. Bossman

machine temperature. That is, with such a short time of
treatment the PET yams do not adopt the machine tem-
perature. Further prolongation of time caused a linear in-
crease in the effective temperature with log time, owing to
after-crystallization.
The dependence of the effective temperature on the
heat setting temperature, dwell time and high temperature
dyeing is shown in Figure 5. The heat setting temperature
reveals a linear relation with Teff. A change in dwell time
causes a parallel shift on the ordinate indicating that a de-
D crease in dwell time decreases Teff. The effective tempera-
T i I i i ture due to a high temperature dyeing process at 130°C is
6b' 9b" ',~o . . . ,7o
. . 2;o' ' '2~o' drawn as a horizontal line at 170°C. This indicates that
Temperature, TDZA(oc) this process wipes out any structural features of the fibre
Figure 3 D.t.a. traces of PET fibres after heat setting at the polymer which are due to thermal treatments with effec-
various temperatures (°C): A, 110; B, 150; C, 190; D, 230. High
temperature-dyeing at 130°C for 90 min
tive temperatures below that of the high temperature dye-
ing. It follows from this that the intensity of a thermal
treatment should not be characterized by machine data
20~ but rather by its effective temperature which indicates
changes in the state of order in the polymer brought about
by thermal treatment.
~1~ 18(
E /'11 -2 -I
Tension during heat setting
e //i~/-~----~= 14OWm K To study the effect of tension during heat setting, PET
g 16c filament yarn was treated at different specific tensions
E
varied from 0.0 N/tex to 0.1 N/tex. The setting tempera-
>
~ 140 / ture (200°C) and time (20 sec) were kept constant. The
thermograms of these samples are shown in Figure 6a. It
t.u is observed that the tension during heat setting influences
12C I I I

O.I I I0 I00 IOOO the partial melting peak. An increase from zero tension to
Dwell time (see) 0.02 N/tex causes a decrease in temperature of the partial
Figure 4 Effective temperature of PET fibres as a function of melting peak. The result leads to the assumption that the
dwell time of heat setting at 180°C and zero tension. Standard stresses developed in the non-crystalline regions during heat
type (X); chemical modification S-type (D); physical modification
S-type (A) setting cause a less uniform crystal size distribution in the
PET polymer, thereby lowering the partial melting peak
tional low temperature endotherm in the d.t.a, trace is ob- temperature.
served at a constant temperature of 170°C (Figure 3). The If the same material is subjected to a high temperature
increase in temperature of 40°C on the d.t.a, temperature dyeing process an additional partial melting peak at 170°C
scale above the dyeing temperature is caused by the hydro- is observed as shown in Figure 6b. In this case the premelt-
ing peak, at 170°C increases slightly on the d.t.a, tempera-
thermal treatment. Schefer 12 found that a hydrothermal
treatment causes a higher heat setting effect on PET than
hot air does. The d.t.a, traces indicate that the partial melt- a"
ing peak due to the first thermal process, vanishes in cases sS
f
where the Teff of the succeeding process exceeds the Teff
of the first process. Only PET yams which have adopted a 230
Teff in the first thermal process sufficiently above Teff of B
the second thermal process (so as not to be masked by an fs*

overlapping effect) show a partial melting peak from the
first thermal process and a second one from high tempera-
ture dyeing.
Repetitive measurements on replicate samples showed
good agreement. The mean deviation from 3 or 4 values E ~
did not exceed +-I°C. Results proved also to be instrument s JJ
independent. Measurements carried out in other labora- I
I
,s
tories on different instruments were in good agreement
J
and reproducible to -+I°C. ~-~ f
¢,
Time of treatment I10
Commercial drawn PET yarns of different origin were
heat set for various times (0.5 to 240 sec) at a constant IIC) ' ' ',-so ' ',9o' ' ' ' 2"o'a '
temperature (180°C) using zero tension. The observed par- Heat-setting ~mpcratur¢ (oc)
tial melting peaks (Teff) are plotted as a function of log
Figure 5 Influence of heat setting temperature, time of treat-
time in Figure 4. The results indicate that increasing the ment and high temperature dyeing on the effective temperature.
time of treatment from 0.5 to 5 sec is accompanied by a A, heat setting 20 sec in hot air (El); B, heat setting 0.2 sec in hot
large difference between the effective temperature and the air (O); C, high temperature dyeing at 130°C, 90 min ( . . . . . . )

POLYMER, 1976, Vol 17, March 243
Thermal analysis of PET: H.~I. Berndt and A. Bossman

a length (t.m.a.) 2 or thermal shrinkage force 13 to characteriz~
the state of structural order.

I D
Application old. t.a. to fault analysis
Two further examples indicate the feasibility of fault
analysis by the d.t.a, method.
Figure 7 shows d.t.a, traces of false twisted yarns heat
set at the indicated temperatures for 0.2 sec. A less distin-
guished but still well detectable partial melting peak is ob-
served at about 25°C below the machine temperature. A
b following steam setting process intensifies an endotherm
<3 at 170°C, in cases where the yam was exposed to machine
temperatures less than 2 IO°C, whereas yarns false twisted
at higher temperatures (220 ° or 230°C) show two separate
partial melting peaks in the d.t.a, thermogram. While the
C first peak at 170°C reflects the effect of steaming, the sec-
I- ond one could be associated with the false twisting pro-
d cess itself. In Figure 8 d.t.a, thermograms are shown of
*6
textured yarns from a streaky dyed fabric. The first d.t.a.
hl
I i trace demonstrates the behaviour of the lightly dyed mate-
rial and the second one of the deeper dyed material. Com-
I i I I I I
paring the two traces one can suppose that the lightly dyed
80 1610 240 material has a less broadened endothermal peak, indicating
Temperature,TDXA!°C) that during false twisting the yam adopted a Teff which is
comparable with that of the high temperature dyeing. On
Figure 6 (a) D.t.a. traces of PET fibres heat set (hot air, 20 see,
200°C) at the various indicated tensions (N/tex): A, original; B, the other hand the deeper dyed yarn adopted a Teff during
0.00; C, 0.01; D, 0.02; E, 0.05; F, 0.10. (b) As (a) and high tem- false twisting which is about 15°C higher. The difference
perature dyed (90 rain, 130°C). Tensions (N/tex): A', original; in Teff could be traced back to differences in heat transfer
B', 0.00; C', 0.01; D', 0.02; E', 0.05; F', 0.10 and/or differences in temperature of heating.
In another case difficulties were encountered when a
heavy technical PET fabric were placed on a cylinder
thermosetting machine. During thermal treatment the fab-
ric began to drag. D.t.a. measurements made on the mate-
¢- \ rial showed (Figure 9) that the fabric did not adopt the
.6 A
X
same temperature throughout the whole width. As a re-
ILl
sult different shrinkage forces were developed in the various
\ B regions of the fabric and led to dragging. Checking the
<3 r

\ temperature distribution in the machine by direct measure-
\ C ments confirmed the d.t.a, results.
._u
E
¢- CONCLUSION
.6
~O
e-
The results of this work illustrate the feasibility of using
tel
d.t.a, measurements as an aid to determine the temperature
I i i I I I I I effect which influences the properties of a PET product.
IOO 150 200 250 IOO 150 200 250
Temperature, TD3TA.(°C)
Figure 7 D.t.a. traces of PET yarns false twisted at the various
indicated temperatures: (a) before steam setting, temperatures (°C):
A, 200; B, 210; C, 220; D, 230 (b) after steam setting, temperatures
1
U

(°C): A', 200; B', 210; C', 220; D', 230
¢-

UJ

ture scale with increasing tension. The slight increase in A I \
temperature of the endotherm leads one to speculate that
the thermodynamically less stable lower melting structures
brought about by thermo-setting under tension, melt and .u_
recrystallize under the conditions of the dyeing process, E
as a consequence they cause an improved crystal size dis- l-

tribution and increased molecular orientation in the non- .6
"10
¢..
dyed fibre. tlJ

This example illustrates that the d.t.a, method should l I I I I I
not be used exclusively for identification of fault analysis 0 IOO 200
to explain the cause of the structural changes of PET fibres. Temperature, TD.T.A!OC)
The results of d.t.a, measurements should be rather support- Figure 8 D.t.a. traces of false twisted dyed PET yarn. A, light
ed by other methods e.g. temperature dependent change of shade; B, deep shade

244 POLYMER, 1976, Vol 17, March
Thermal analysis of PET: H.-J. Berndt and A. Bossman

The effective temperature acquired by the PET material

t
U
is not necessarily equal to the machine temperature since it
relies on many different factors such as transfer of heat,
medium, and dwell time.
IN
e-
However it cannot be said that d.t.a, should be used in-
A
dependently of other techniques to analyse the state o f
order of PET or to optimize the process technology.
B
ACKNOWLEDGEMENTS

C This project is part of the programme of the process tech-
nology research group at the textile research centre at
._u Krefeld. The authors acknowledge the experimental assis-
e tance by members of the group and are grateful to Profes-
¢-
sor Dr G. Valk and Dr G. Heidemann for valuable discus-
sions.
c-

REFERENCES
1 I I I
O I00 150 200 250 1 Berndt, H.-J. Dissertation TH Aachen (1971)
Temperat ur% TDXA.(°C) 2 Berndt, H.-J. and Heidemann, G. Dtsch. Fizrberkal. 1972,
76,408
Figure 9 Effect of a temperature distribution in a cylinder 3 Heidemann, G. and Berndt, H.-J. Chemiefasern Textilind.
thermo-setting machine on the d.t.a, traces of a PET technical fab- 1974, 24(76), 46
ric; heat set at a machine temperature of 220°C. Curve A, original 4 Wiesener, E. Faserforsch. Textiltech. 1968, 19, 301
material; B, right side of treated fabric; C, left side of treated fabric; 5 Roberts, R. C. Polymer 1969, 10, 117
D, middle of treated fabric 6 Lawton, E. L. and Cates, D. M. Polym. Prepr. 1968,9,851
7 Ikeda, M. Chen~ High Polym. 1968, 25, 87
A partial melting peak prior to the main melting peak was 8 Holdsworth, P. J. and Turner Jones, A. Polymer 1971, 12,
195
observed on commercial PET fibres which were heat set at 9 Roberts, R.C.J. Polym. Sci. 1970, 8, 381
various temperatures and times, even if the latter were frac- 10 Zachmann, H. G. and Stuart, H. A. MakromoL Chem. 1960,
tions o f a second, as in a false twisting process. The posi- 41,131
tion o f the partial melting peak on the d.t.a, temperature 11 Wrasidlo, W. Adv. Polym. Sci. 1974, 13
scale determines the effective temperature (Teff) o f the PET 12 Schefer, W. Textilveredlung 1971,6, 69
13 Berndt, H.-J. and Heidemann, G. Melliand Textilber. 1974,
fibre. This effective temperature corresponds to a struc- 55,548
tural feature which is generated b y a thermal treatment of 14 Valk, G., Heidemann, G., Berndt, H.-J. and Bossmann, A.
the material. Lenzinger Ber. 1975,38, 172 (Part XV1)

POLYMER, 1976, Vol 17, March :P45