J O U R N A L OF M A T E R I A L S SCIENCE 26 (1991) 5085 5092

Evaluation of the structural behaviour of

annealed nylon 6 fibres from density
measurements
I. M. F O U D A , M. M. E L - T O N S Y , A. M. S H A B A N
Physics Department, Faculty of Science, Mansoura University, Mansoura, Egypt

Nylon 6 fibres were annealed in the temperatures range 8 0 -1 8 5 ~ for times from 1 - 1 0 h, and the
density of the annealed fibres was measured by a system based on the theory of vibrating strings.
The fibre diameter was also determined, using the laser forward diffraction technique. Differential
thermal analysis (DTA) measurements were used to determine the glass transition temperature
and the melting point of nylon 6. Some annealed samples were subjected to X-ray diffraction to
clarify the variation of crystallinity with the annealing conditions. The mechanism of structural
variations for nylon 6 fibres due to the annealing process is discussed, and structural details for
crystalline and non-crystalline phases of a polymer are suggested. The behaviour of the number
of oriented chains, number of crystallized nuclei, relative amount of recrystallized material and
the shrinkage ratio with annealing time is proposed to explain the thermal structural variations.

1. I n t r o d u c t i o n effects of annealing increase drastically with temper-

Recently, polymers have been considered commer- ature, but also depend on the time the sample is held
cially, as one of the most fundamental materials. The at the annealing temperature. To understand anneal-
technical importance of polymers is based on the ing effects, their molecular source must be known
ability to produce polymers with different character- [8, 9].
istics, such as steel hardness, sponge softness, glass In this work, the mechanism of changes in the
transparency, etc. The main polymer feature, for these molecular structure of nylon 6 fibres, due to anneal-
widely different products, is its flexible structure, ing, is discussed, based on density measurements car-
which can be controlled either by chemical construc- ried out for nylon 6 fibres annealed at different tem-
tion or by technical processing. Thus, the most im- peratures for different times. The suggested structural
portant parameters with which to characterize an behaviour is supported by the X-ray diffraction data.
anisotropic property of an oriented, polycrystalline
polymer are the fraction of each phase present, the
intrinsic property of each phase and the orientation
2. Experimental procedure
function of each phase. In general, the fraction of each
2.1. Annealing of samples
phase present in the polymer is determined by density
Long bundles of nylon 6 fibres were loosely folded in
or X-ray diffraction measurements [1].
a cocoon form with free ends. Several samples were
For density determination of the fraction of each
distributed in small glass bottles, and then left in an
phase present, the density of the crystalline and
electric oven and heated at a constant temperature
amorphous phases must be known individually. While
ranging from 80-185 _+ 1 ~ for different annealing
the density of the crystalline phase can be determined
times ranging from 1-10 h. The samples were then left
using X-ray data, the evaluation of the density of the
to cool at room temperature, 28~ Thus for each
amorphous phase is sometimes a very formidable task.
annealing temperature, there was a set of ten samples
This is because only a relatively small number of
annealed at different times.
crystalline polymers can be produced in the amorph-
ous state. For many crystalline polymers the deter-
mination of amorphous phase density is carried out by
extrapolation of the temperature dependence of the 2.2. Differential thermal analysis (DTA)
density of the melt to room temperature [2]. The measurements
density of the polymer sample may be determined by The greatest number of applications of DTA in recent
any of a number of standard experimental methods, years has been in the area of polymeric materials. This
including pycnometry, hydrostatic weighing and the technique is routinely used to measure glass transition
use of a density gradient tube [3]. temperatures, Tg, melting points, Tm, and numerous
The most available technique for changing the poly- other parameters. Several DTA instruments were de-
meric structure is the annealing process [4-7]. The veloped mainly for use in polymer measurements. In
0 0 2 2 - 2 4 6 1 / 9 1 $03.00 + .12 9 1991 Chapman & Hall 5085
the present work, a Shimadzo thermal analyser model whose output signals were supplied to the second
DT-30B was used. channel, CH2, of the CRO. The received wave, on
CH2, thus possesses maximum amplitude only at res-
onant modes of the sample (odd modes were observed
2.3. X-ray diffraction out-of-phase, while even modes were observed in-
The X-ray diffraction technique was used in this work phase with the reference wave) when the vibrator's
to examine the crystallinity and the crystalline struc- frequency was increased.
ture of the crystai]ine phase in the anriealed samples. Using such a system allows the determination of the
X-ray diffraction examinations were done with fundamental resonance frequency, fo, of a certain
a Shimadzo X-ray diffraction DX 30 with conven- length, l, of the sample (l is the distance between T and
tional CuK~ (0.1542 nm), at 45 kV and 35 mA. The R) when it is loaded by a mass, M(g). Then the mass
scan-speed was adjusted at 5 deg min- 1. per unit length, m, of the sample under test could be
calculated from Equation 1. An accurate value of
m could be obtained as an average over several modes
2.4. D e n s i t y m e a s u r e m e n t s of resonance.
For the measurement of fibre density, a special From the obtained value of m, the density, P, of the
measuring system was constructed. The apparatus for sample material can be easily calculated. If the sample
this system was based on the concept of vibrating is taken as a bundle of N individual fibres per bundle,
strings. It is well known that when a string is stretched
P = gm/4~Nl2rZf 2 (2)
by a tensional force, T, and put in contact with a vi-
brator which vibrates at right angles to the axis of the where g is the acceleration due to gravity, and r is the
string, a definite length, l, of the string will vibrate radius of an individual fibre.
stationary as the reasonance condition between fre-
quencies of vibrator and string is achieved. Let fo be
the resonance frequency, then 2.5. M e a s u r e m e n t of t h e fibre d i a m e t e r
In this work, the fibre diameter, d, was measured by
fo = (p/21) ( T / m ) 1/2 (1)
the technique of laser beam forward diffraction
where p is the number of resonance modes within the [11-13]. In this technique the following formula was
string's length, l (p = 1 for the fundamental mode) and considered
m is the mass per unit length of the string [10]. The
d = -t- )~L/x (3)
sample was clamped at one end while the other end,
(connected to small scale pan) passed over a small where k = 632.8 nm, the wavelength of the He-Ne
frictionless pulley, Fig. 1. The clamp, C, and pulley, W, laser used, x is the distance from the centre of the
were fixed to an optical bench, B. An electromagnetic obtained diffraction pattern to the first minimum, and
pulse transmitter (vibrator), T, as well as a pisocrystal L is the distance between the fibre and screen on which
transducer, R (receiver) were also fixed tightly to B. the pattern was produced. Each sample was examined
The sample, S, was tightened by mass, M, and left in at several positions and the average value was
contact with T and R. The vibrator, T, was stimulated considered.
by sinusoidal electric pulses from the adjustable fre-
quency pulse generator, G. Pulses from G were also
supplied to the frequency counter, FC, to be counted, 3. Results and discussion
and to the first channel, CH1, of the double-beam The DTA measurement of unannealed nylon 6 fibres
cathode ray oscilloscope, CRO, to be taken as the showed that the glass temperature, Tg, of nylon fibres
reference wave. The frequency of the vibrator, T, was is 47 ~ while the melting point Tm is 210 ~ There-
increased, from zero, up to the resonance frequency, fore, the range of annealing temperatures was selected
fo, at which points on the sample (from T to R) were from 80-185 ~ in order to avoid any phase transition
vibrated with the same frequency, )Co. Thus R receives during the isothermal annealing process, and to keep
pulses with a maximum amplitude. Pulses from samples in their fibrous form throughout the whole
R were magnified using a low-noise pre-amplifier measurements.
The measurements of fibre diameter showed no
observable changes, after annealing at different tem-
C T S R W peratures.
The colour of the nylon 6 fibres was visually ob-
served to change from light yellow to dark brown with
9 ,\,,,j,,,,,N\\\\\, increasing annealing temperature and annealing time,
/
although, as the annealing temperature and time were
T increased, the fibres became more brittle; for these
IN~ / ' r "- reasons it was impossible to measure the density of
I G I samples annealed at 185 ~ for periods longer than
CH1 ] s 6 h, due to the partial production of ash on the sam-
ples.
Figure 1 Schematic diagram for the constructed density measuring Fig. 2a-g show the density variations of seven sets
system. of nylon 6 fibres with annealing times from 1-10 h.
5086
 1.3~.]

1'301

/ 1'261
1.12~ ............. 1.22

1.18

1.1

,eo ~E 1.10

1.20.

m~1.16. ~, 1.20.

t.16. t ",d
1.12,

1.08, lb) 112 ~1 . . . . . . . . . . . . . . . \_

1L-- ..........

'1 X
1 2 3 4 5 6 7 8 9 10
Anneating time (h } 1.12~;f . . . . . . . . . . . . . . . .

1 2 3 4 5 6 7 8 9 10
Annealing time ( h )
Figure 2 Density variations of nylon 6 fibres isothermallyannealed at (a) 80 ~ (b) 100 ~ (c) 120 ~ (d) 140 ~ (e) 160 ~ (f) 170~ and
(g) ~s5 oc.

Each set was annealed at a selected temperature: words, the oriented macromolecular structure may
(a) 80 ~ (b) 100 ~ (c) 120 ~ (d) 140 ~ (e) 160 ~ not be the most compact non-crystalline structure.
(f) 170~ and (g)at 185~ The interpretation of When a polymer is annealed, its structural behavi-
physical variations associated with isothermal anneal- our is due to accumulation of several structural pro-
ing of metals was, in general, fulfilled, but the inter- cesses. These processes may be summarized as:
pretation of similar variations is somewhat problem- (a) disorientation, (b)recrystallization by nucleation,
atical when a polymer undergoes isothermal anneal- (c) recrystallization by growth, (d) shrinkage, and
ing. These difficulties are due to the anisotropic fea- (e) crystal decomposition. They are natural responses
tures of the polymer. for both annealing temperature and time [1, 8,
Most studies, which involve variations of physical 14-16]. To give an acceptable explanation for all
properties, considered polymers as an anisotropic variations in Fig. 2, we have to estimate, individually,
polycrystalline medium, i.e. consisting of crystalline the weight of each structural process during an iso-
regions suspended in an amorphous medium which is thermal annealing treatment at different temperatures.
partially oriented. Thus the polymeric molecular
chains were classified into only three structural
classes: crystalline, oriented amorphous and dis- 3.1. D i s o r i e n t a t i o n
ordered amorphous structures. These three structural The amount of disorientation of the non-crystalline
classes are insufficient, from our point of view, to chains depends on the annealing temperature and
explain the results obtained, Fig. 2. We suggest further time. The greater the annealing temperature for
sub-classifications for the interphase distribution of a given time in a given medium, the greater would be
polymer molecular chains and the proposed classifica- the expected disorientation rl]. Therefore, one may
tion is shown schematically in Fig. 3. deduce that the disorientation process is a conse-
In order to explain the widely different variations quence of the thermal energy transferred to the me-
shown in Fig. 2a-g, it was essential to take the follow- dium. Thus, it is expected that the degree of disorien-
ing assumptions into account. tation may be directly proportional to the amount of
1. All thermally structural variations may be con- energy given to the polymer. Because the thermal
sidered irreversible, at temperatures higher than the energy gained is the resultant of temperature and time
glass transition temperature. of heating, a certain degree of disorientation at a given
2. The most compact non-crystalline structure is temperature and time can be again observed at higher
not 'essentially the ordered structure or, in other temperature but shorter time. Also, because a given

5087
 Regularly
distributed

Crystolline

Randomly
distributed Compactstructure

Polymer
chainstructure Loose structure
Oriented
Randomcompactness

Non-crystQIline

~ Compact structure
Unoriented

Figure 3 Schematic representation of the suggested details of the polymer macromolecular chain structures.

polymer sample contains a finite number of ordered tation process is limited by the number of ordered
chains, the disorientation process should end after chains present, the decrease in density should show
a certain energy value which depends on the initial a stability after a certain annealing time, depending on
orientation, as well as the nature of the medium. the annealing temperature, Fig. 4b. The density may
Therefore, we suggest Fig. 4a to show the change of not show any variation when the initial orientation
disorientation process during the isothermal anneal- and the final disoriented structures were of random
ing treatment. compactness.
In order to estimate the density variations asso-
ciated with the disorientation process, the suggested
details of the oriented polymer phase in Fig. 3 should
be considered. The density response to the disorienta- 3.2. Recrystallization by nucleation
tion depends on the initial compactness of the As the time of isothermal annealing increases, the rate
oriented chains. It may be considered that the given of nucleation first increases and then decreases [16].
mobilizing thermal energy causes chains to displace as This means that the number of thermally produced
well as to rotate about some axis perpendicular to the nuclei is rapidly increased up to a fixed value after
chain backbone at a point which may be taken as the a certain given thermal energy. This fixed value de-
chain's centre of mass. So, if the initial oriented struc- pends on the initial structure of the non-crystalline
ture was compact, it will disorient to a loose structure part as well as on the annealing temperature. There-
and hence, the density decreases. Because the disorien- fore, the authors suggested that Fig. 5a represents the

u~

a Unanneated sample density

(,_
o

r~

E
r5 ~ r~
5
(a) Annealing time (b) Annealing time

Figure 4 Diagrammatic representation of the deduced behaviour of (a) the number of oriented chains, and (b) the density of a polymeric
medium undergoing thermal disorientation at different temperatures (T1 < T2 9 ' 9 < Ts).

5088
 1-5 r4
~l_l Ts r4 9 - . . . . . . . . . . . . . . 7"3 . . . .

== ~ r3
rz

Unanneoted sampte density

(a) Annealing time (b) Annealing time

Figure 5 Diagrammatic representation of the deduced behaviour of (a) the recrystallized nuclei and (b) the density of a polymeric medium
undergoing thermal recrystallization by the nucleation process at different temperatures (T1 < T2 < 9 "" < T~).

number of nuclei as a function of annealing time at where G is the rate of crystal growth and Qg is the
different annealing temperatures. effective activation energy of growth.
The density variations due to the nucleation process The expression is strictly valid only in temperature
are expected as in Fig. 5b, where the density of nuclei ranges where Qg and the pre-exponential factor, Go,
was considered higher than both oriented and un- are constants. However, because Qg decreases with
oriented non-crystalline phases. increasing temperature, this also increases growth
rate.
Therefore, from the time and temperature depend--
3.3. Recrystallization by g r o w t h of nuclei ence of the recrystallized volume by growth, given in
A number of relationships were proposed to describe Equations 4 and 5, one may expect the change of X,
the kinetics of isothermal recrystallization. The most during an isothermal annealing process and at differ-
generalized of them was that proposed by Avrami ent temperatures, to be as shown in Fig. 6a. Then the
[16] density response for the recrystaltization by growth
can be estimated as in Fig. 6b, where new nuclei ap-
X = 1 - e x p ( - Bt k) (4)
pear and grow after a definite incubation period, to,
where X is the relative amount of recrystallized mater- which is shorter at higher annealing temperatures.
ial, B and k are the coefficients depending, respect-
ively, on the temperature and the nature of nucleation
3.4. Shrinkage
as well as on the growth of nuclei, and t is the anneal-
Because shrinkage means a volume contraction, and
ing time. For a one-dimensional process (as fibres),
due to the conservation of mass, an increase in the
1 ~< k ~< 2. On the other hand, the growth of recrystal-
medium density is expected to be associated with the
lized nuclei is a thermally activated process. For
shrinkage process.
a given time, the effect of temperature on the process is
Studies carried out by Samuels [1], showed that the
described by the Arrhenius equation
ratio of shrinkage is related to the disorientation oc-
G = G o e x p ( - Q,/RT) (5) curring during thermal annealing. He found also that

7"5 r4
r3 re
x ....... Ts__ . . . . . . .

T1
r3 r2

rl

Unonnealed sample density

(el to (b)
Anneoting time Annealing time

Figure 6 Diagrammatic representation of the deduced behaviour of (a) the recrystallized volume and (b) the density of a polymeric medium
undergoing thermal recrystallization by the growth of nuclei at different temperatures ( T 1 < T 2 < 9 .. < Ts).

5089
 the shrinkage ratio increases as the annealing temper-
ature increases. Hence, it is estimated that on shrink-
age, theordered structure is destroyed into a compact
disordered structure.
Fig. 7 shows the deduced density response due to
the shrinkage process.
r2
q
E3

3.5. Crystal d e c o m p o s i t i o n
UnQnneuled sample density
Fig. 8 shows the observed decrystallization of nylon
6 fibres when annealed for 6 h at different temper-
atures, where the X-ray diffraction intensity was re-
duced as the annealing temperature increased for the
Annealing time same period. Fig. 9 shows the X-ray diffraction inten-
Figure 7 The expected behaviour of polymer density due to shrink-
sity of nylon 6 fibres annealed at 140 ~ for different
age associated with isothermal annealing at different temperatures annealing periods. It is clear from Fig. 9 that increas-
( T 1 < 7 ' 2 " ' " <Ts)- ing annealing time also causes crystal decomposition

=
c::

j / ;
25 20 25 20 25 20 f0
(o) 28 (deg) (b) 28 (deg) (c) 28 (deu) (d) 28 (deg)
Figure8 X-ray diffraction patterns of nylon 6 fibres annealed for 6 h at (a) 120~ (b) 140~ (c) 160~ and (d) 170~

>.,,

(b3

s
- Y
J
28 L 20 1~- 1'6 28 24 20 16
(o) 2e (deg) (b) 2e (deg) (c) 2e (deg)

Figure 9 X-ray diffraction patterns of nylon 6 fibres annealed at 140 ~ for (a) 6 h, (b) 8 h and (c) 10 h.

5090
which is associated with a decrease in the density of
the medium, where the density of the crystalline por-
tion, Pc, was considered to be the highest density in the
polymer.
The reduction in the X-ray diffraction intensity, I,
does not essentially mean a decrease in crystallinity,
because 11/2 ~- p~ - P,m, where Pam is the density of
the amorphous region [17]. Thus I may be reduced
due to an increase in Pam by annealing. In most poly-
mers, Pc is higher than Par, by about 10%, but in the
present data (Fig. 8) it is clear that I is reduced by

Y
a much higher percentage, which ensures the occur-
rence of crystal decomposition by annealing at high
temperatures.
From the previous review of the most of the struc-
tural processes associated with the isothermal anneal- 28 24 20 16 28 24 20 16
(a) 26 (de(J) (b) 2e (deq)
ing treatment, it is clear that two processes (disorienta-
tion and crystal decomposition) cause a fall in the Figure 10 X-ray diffractionpatterns for nylon 6 samples annealed
density of a polymer medium, while the other three at 160 ~ for (a) 3 h and (b) 7 h.
structural processes cause an increase in the density.
Thus, the complex variations in density of nylon
6 polymer when isothermally annealed (Fig. 2a g), 4. Conclusions
could be explained on the basis of a combination of 1. The constructed density measuring system (as
the structural processes previously discussed. For a resonance technique) is an accurate (expected error
example, in Fig. 2e, the fast increase in nylon 6 density is below + 1%), easy, quick and non-destructive tech-
with annealing time in the range 0 < t < 3 h is due to nique. Moreover, this technique can equally well be
the recrystallization by nucleation and the growth of used to measure the mass per unit length of any yarns
nuclei with a weight much greater than the density fall or textile long ribbons.
due to disorientation of the non-crystalline portion 2. The fine-density measuring system, used in this
which occurred simultaneously in that annealing work, is recommended as a non-destructive technique
range. The peak point at t = 3 h represents the max- for the determination of the linear density of indi-
imum crystallinity of nylon 6 when annealed at 160 ~ vidual fibre specimens. Although not very suitable for
The fall in density in the time interval 3 h ~< t ~< 6 h is measurements on, for example, cotton fibres because
due to the decomposition of some crystals while most of the within-specimen variability, it has been used,
of oriented non-crystalline part was disordered. It is extensively, in work on man-made fibres.
clear that the point at t = 6 h did not reach the density 3. The macromolecular structure of nylon 6 fibres is
of unannealed sample due to the effect of shrinkage, strongly affected by the isothermal annealing treat-
which may cause a remarkable increase in the density ment.
after 6 h annealing at 160 ~ The second increase in 4. The density of nylon 6 depends, critically, on the
density within the interval 6 h ~< t ~< 7.5 h may be due annealing conditions.
to the end of the disorientation process while the 5. The suggested details of polymeric chain distri-
shrinkage process produces a greater effect. The sec- butions (Fig. 3), are sufficient for interpretation of the
ond peak at t = 7.5 h is due to the most compact thermal, or mechanical structural variations.
unoriented chain structure but, of course, not to 6. From the X-rays diffraction measurements, it
higher crystallinity. Fig. 10a and b show that the was found that the type of crystal in nylon 6 was not
amount of crystal at the second peak (t -~ 7 h) is lower affected by the annealing conditions used.
than that at the first peak (t = 3 h). The fall in density 7. The annealing process affects other physical
during annealing for longer than 7.5 h is due to crystal properties (electrical, mechanical, colour, optical,
decomposition, which is the most dominant structural 9 etc.). Further studies can be carried out in order
process at high temperatures and long annealing to detect which properties are improved by annealing.
times. We conclude that the density measurement offers
This explanation of Fig. 2e can be applied to the valuable information on the structure and structure
other components of Fig. 2. The behaviour of nylon variations of a polymer when it is subjected to external
6 density, which still needs additional explanation, energy. The non-destructive feature of the presented
was represented by points lower than the density of density measuring technique is promising. The density
the unannealed sample. If these points were produced measurement is an important parameter not only as
at low annealing temperatures, they would indicate a quality test for the final polymeric products, but also
that the disorientation structural process is the pre- as an estimation base for the polymer's variations due
dominant process at their positions, while, at high to the applied physical and chemical effects.
temperatures, these lower density points would mean
decomposition of most crystals, including those ini-
tially present in the samples during the fabrication Acknowledgements
process. The authors thank the director and the staff, Monofia

5091
University Center laboratory, for their cooperation H. E. JOHN, R. M. THOMAS and B. E. RICHARD, J.
and for use of the facilities there. Polym. Sci. XXI (1956) 189.
10. N. SUBRAHMANYAM and BRIJ LAL, "A Textbook of
Sound", 2nd Edn (Vikas, New Delhi, 1979) p. 143.
11. S. M. CURRY and A. L. SCHAWLOW, Amer. J. Phys. 42
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(Mir, Moscow, 1981) p. 42. Mater. Sci. 25 (1990) 1416.
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5092