Indian Journal of Fibre & Textile Research

Vol. 15, September 1990, pp. 93-99

Effect of swelling agents on unoriented nylon-6 film-Structural changes

N V Bhat, V H Buch & A K Kalkar
Centre of Advanced Studies in Applied Chemistry, Department of Chemical Technology, University of Bombay.
Matunga, Bombay 400 019, India
Received 4 April 1989; revised received 4 April 1990; accepted 20 April 1990

Unoriented nylon-6 films were subjected to aqueous formic acid and benzyl alcohol treatments.
Formic acid was found to be more active in causing structural changes. The highest possible formic
acid concentration that could be used advantageously was found to be 50% owing to heavy shrin-
kage at higher concentrations. Solvent-induced crystallization with respect to time of treatment and
concentration of solvent revealed entirely different trends. These treatments give rise to shrinkage of
films. WAXD and IR spectroscopy revealed that crystallization results in the formation of a large
amount of monoclinic a-crystalline form. Scanning electron micrographs revealed significant changes
in surface morphology due to solvent etching.

Keywords: Crystallinity, Nylon-S, Polyamide, Polycaproamide, Shrinkage, Solubility parameter,

Solvent pretreatment, Spherulites

1 Introduction (thickness, 30 f.J.) supplied by Mis Garware Nyl-

The effect of organic solvent pretreatments on
linear high polymers has been a subject of interest
since last few years. All solvent-induced structu-
ral-morphological changes in the semi-crystalline
polymer matrix arise due to effective lowering of
glass transition temperature in presence of a sol-
vent'. The major implication of solvent-induced
crystallization has been in wet-finishing of textile
materials, either as solvent pretreatment or in car-
rier dyeing+', The possibility of using solvent pre-
treatment as a useful means of imparting favour-
able structural changes has been investigated in
detail earlierv". In all these works, major empha-
sis was on textile properties of fibre-forming po-
lymers like silk, nylon-S and poly( ethylene tereph-
thalate). Similar study on nylon-6(in the form of
film) has also been carried out", Shrinkage is an-
other important swelling-related phenomenon. At-
tempts have been made to get better insight into
it by using several swelling agents9.12• Solubility
parameters, shrinkage and morphology can be
correlated. In this paper, we present some data on
changes in crystallinity, crystal structure, crystal-
lite size, shrinkage and spherulitic structure of un-
oriented nylon-6 films subjected to aqueous for-
mic acid and benzyl alcohol treatments.
ons Ltd was used. The formic acid solutions were
prepared by adding the required amount of 90%
formic acid (AR grade) in distilled water. In all,
five different concentrations in the range 10-50%
were used. Benzyl alcohol and methanol used
were of AR grade.
2.1 Swelling Treatments
The film samples were immersed in 50 ml of
formic acid solutions at room temperature for dif-
ferent durations. This was followed by a wash
with distilled water and subsequent drying in vac-
uum at room temperature. The samples were fi-
nally stored in a desiccator over silica gel.
Benzyl alcohol treatments were given by im-
mersing the samples in 50 ml of benzyl alcohol for
different durations. This was followed by rinsing
the samples with methanol to remove benzyl alco-
hol. Finally, the samples were washed thoroughly
with distilled water and dried at room tempera-
ture under vacuum.
2.2 Measurement of Weight Loss
Film samples were weighed before and after the
treatments using a microbalance. The % loss in
weight was calculated as follows:

2 Materials and Methods 0/

/0
L .
oss m .h
welg WI - W2 x 100
t = ----
Tubularly-extruded translucent nylon-S film ~

93
 INDIAN J. FIBRE TEXT. RES., SEPTEMBER 1990

where W, is the original weight; and Wz, the final were recorded using a Spectra-Physics He-Ne la-
weight. ser (output power, 5 mW) which gives polarized
light of 632.8 nm wavelength. Sample-to-film dis-
2.3 Measurement of Density tance was 7 ern. Radial intensity distribution at
Floatation technique!' was used to determine 45° azimuth was found by photomctering the
the density of film samples using n-heptane and photographic plates.
CCl.j as inert liquids.
2.8 Scanning Electron Microscopy
2.4 Measurement of Shrinkage Scanning electron micrographs were obtained
The % shrinkage was measured by noting the using an ISI-DS-130 scanning electron micro-
change in the length of film samples before and scope employing an accelerating voltage of 25 kY.
after the treatments. The measurements were car- The samples were coated with thin film of gold to
ried out on samples dried in air" at 25°C for 24 h. avoid the building up of electrostatic charge.
The % shrinkage was calculated as follows:
3 Results and Discussion
I, - 10 3.1 Loss in Weight
'Yc, Shrinkage = - -=- x 100
Fig. I shows the loss in weight of nylon-6 films
II
treated with 50% aqueous formic acid solution
for different durations. It is observed that signifi-
where I, is the length before the treatment; and ./2,
the length after the treatment. cant loss in weight occurs up to 4 h of treatment.
Thereafter, only a nominal loss in weight occurs.
2.5 X-ray Diffractometry
Similar results were obtained for lower concentra-
X-ray diffractograms of nylon-6 films were re- tions. After 8 h of treatment, no significant weight
corded using a General Electric XRD equipment. loss was found. This indicates saturation of disso-
The diffractograms were recorded in symmetrical lution process accompanying solvent action. All
reflection mode in 2 () range of 10° to 35°. Scann- further experiments were performed on samples
ing speed was l°/min. treated up to 8 h. Benzyl alcohol treatments did
a-y conversion was quantitatively estimated us- not cause noticeable change in weight.
ing the method proposed by Mitsuhashi and Kyo-
tani '4. The change in lateral order was followed 3.2 Density Measurements
by measuring the change in resolution of the The values of densities for different pretreated
peaks in the diffractograms using the method of nylon samples are given in Table 1. These values
Manjunath et al.I5 The crystallite sizes were calcu- were used to calculate the crystallinity index. The
lated using Scherrer's formula 10. For this purpose, changes in crystallinity index with respect to con-
the peaks were resolved after the normalization of centration of solution and duration of treatment
the profile. are depicted graphically in Figs 2 and 3 respect-
ively. It is seen that density increases linearly as
2.6 Infrared Spectroscopy
IR spectra of the film samples were recorded 8
using a Perkin-Elmer IR Spectrophotometer 7
(model 397). The IR crystallinity index was deter-
mined using absorbance measurements at 930 cm-I 0:6
~
and 1120 em -1, the latter being the internal
~5
standard 17. w
~4
z
...
Crystallinity index
A930
= --
;(;3
<J)
A1120 g2
where A is the absorbance defined by A= log loll
in which 10 is the incident intensity, and I, the
transmitted intensity at a given wavelength. o 2 4 6 8 10 12 t4 16
DURATION OF PRETREATMENT I h

2.7 Small Angle Light Scattering (SALS) Fig. 1 - Loss in weight of nylon-6 films pretreated witl: 5 (JO;;,
H v SALS patterns of control and treated films formic acid for different durations

94
 BHAT et al: UNORIENTED NYLON -6 FILM

10 ( a) 1h ( a) 2 h
Table 1 - Density and crystallinity of nylon-o films pretreated 09
with formic acid and benzyl alcohol 08
07
Solvent Duration of Cone. of Density Crystallinity 06/~ _~
pretreat- solvent g! cc index 05_- .:
ment % 0-4

h 83
:x
~- J'2
1.139 0.40 Z ~J' ~

Formic acid 1 10 1.158 0.54 :3 a L---<--L----'------'---'

;'!
1 30 1.163 0.57 ~ ,·0
50-9 (c)4h (d)8h
1 50 1.173 0.64 ~ 0·8
8 10 1.160 0.55 ~ 0·7

8 30 1.165 0.59 ~0-6~ __~

o 5 .:
8 50 1.173 0.64 04
03
0-2
Benzyl 1 100 1.141 0.42
0-1
alcohol 8 100 1.150 0.48
o 10 20 ~O 40 50 0 10 20 30 40 50
CONCENTRATION OF FORMIC ACID /1.

Fig. 2 - Effect of formic acid cone. on the crystallinity of

the concentration of formic acid solution in- nylon-6 films treated for different durations
creases for any fixed duration of treatment. On
the other hand, the variation of crystallinity with 0·8
respect to duration of treatment is of different
character. The crystallinity increases rapidly up to 0·7
2 h of treatment for all the concentrations of for- I"

mic acid, decreases slightly between 2 and 4 h for

lower concentrations and remains constant up to
8 h for higher concentrations (40% and 50%). -'
-'
<
Pretreatments using benzyl alcohol also reveal a I-
~ 0·5
slow increase in the values of density and crystal- a::
u
linity (Table 1). 11-
o
x 0·4 0-10 '/.
w
o A-20'/.
3.3 Shrinkage Z
o -30'/,
Shrinkage is a swelling-related phenomenon 03 e-40'I,
which results from the relaxation of orientational e -50'1,
strain induced in the polymer during the process of
0·2L-L-l_.l....--L---IL..~-+_!:-~...,..!
manufacturing. Attempts have already been made o 1 2 3 4 5 6 7 B 9 10
to acquire better insight into this phenomenon by DURATION OF PRETREATMENT, h
using swelling agents. In case of drawn nylon-66
Fig. 3 - Effect of time of pretreatment on the crystallinity in-
the rate of contraction in aqueous phenol has dex of nylon-6 films at different concentrations of formic acid
been correlated with a series of elementary rate
processes". For nylon-S, it has been suggested!" gave maxima when the solubility parameter of the
that a range of order prevails in the so called dis- solvent approached that of the polymer. The solu-
ordered regions of the polymer and that this may bility parameters of solvent-non solvent mixtures
be the key factor in determining the nature of sol- such as water-formic acid solutions can be calcu-
vent-polymer interaction, especially in the case of lated bya simple method suggested by Froeling
weak swelling agents. et all", In the present study, we have attempted to
Existing Iiterature+!' suggests that solvent-po- correlate the shrinkage behaviour with the solubil-
lymer interaction is maximum when the solubility ity parameters of the aqueous formic acid solu-
parameter of the solvent is close or equal to that tions using solubility parameter as a measure of
of the polymer. In these investigations, the sol- the swelling power of solutions.
vent-polymer interaction has been quantified in Fig. 4 depicts a plot of the % shrinkage of nyl-
terms of solvent-induced crystallinity (SINe), vo- on-o films with the solubility parameter of the
lume swelling and shrinkage. These, when plotted aqueous formic acid solutions. It is seen that with
against the solubility parameter of the solvent, decrease in solubility parameter and increase in

95
 INDIAN 1. FIBRE TEXT. RES., SEPTEMBER 1990

--10'"
11001 ----30-,.
-_·-so·/.

....
>
in
z
w
•...
z
- L_----
..
~-:"~
.-
--

o~~~~--~
30 40 50 60
__70~~~~ __~
eo 90 100
BRAGG ANGLE,2e

SOLUBILITY PARAMETER
Fig. 5 - X-lay diffractograms of nylon-6 films pretreated with
formic acid solution for 8 h
Fig. 4 - Shrinkage of nylon-6 films pretreated with formic
acid of different concentrations
Table 2 - Lateral order (crystallinity) of nylon-6 films pre-
concentration, the shrinkage increases in a fairly treated with formic acid and benzyl alcohol on the basis of
linear manner. This can be understood in terms WAXD and IR spectroscopy
of changes in morphology taking place due to Solvent Duration of Cone. of Amount Crystallinity
swelling action. The mobility of chains increases pretreat- solvent of
ment % yform IR WAXD
and chain folding may take place, leading to sol- h %
vent-induced crystallization. This leads to contrac-
35.5 0.27 0.14
tion of chains and subsequent crystallization. The Formic acid 1 10 33.5 0.27 0.18
values of crystallinity indices obtained from the 1 30 29.1 0.54 0.20
measurement of density and X-ray diffraction are 1 50 0 0.66 0.49
in conformity with this mechanism. 8 10 32.5 0.39 0.20
8 30 28.9 0.63 0.24
8 50 0 0.90 0.50
3.4 X-ray Crystallinity and Crystallite Size
Fig. 5 shows the X-ray diffractograms for nyl- Benzyl 1 100 35.0 0.28 0.18
on-6 films treated with different concentrations of alcohol 8 100 34.5 0.53 0.19
formic acid. The three peaks occur at the Bragg
angles 20S, 21.r and 23.8° out of which the
peak at 21.r corresponds to the y-phase (I) and disappears and the peak corresponding to
the remaining two to the a-phase (I al and I a2)· (002)+(202) doublet shifts by about 1°. It has
These peaks correspond to the reflection from the been observed by previous workers'Y" that the
planes (200) and (002) + (202) corresponding to crystallization of nylon-6 proceeds at different
monoclinic a-form. The middle peak corresponds rates along the different crystallographic direc-
to (100)+(010) reflection from the hexagonal y- tions of the monoclinic a-unit cell. It was ob-
form. By using maxima and minima observed in served that as the crystallinity increases the half-
such diffractograms, the values for the lateral or- width of the (200) reflection (a, peak) reduces,
der were calculated using the method mentioned indicating increased crystallite size in the direction
in 2.6. The values (Table 2) show that the lateral normal to these planes (Table 3); as this direction
order and the amount of a-form increase as the corresponds to the direction of interchain hy-
concentration of formic acid is increased. The drogen bonds forming the n-crystallites it may be
corresponding values for benzyl alcohol show on- concluded that more and more molecular chains
ly slight increase in this parameter. From the dif- tend to align themselves with the crystallite as the
fractograms, it is observed that the relative crystallization proceeds. In other words, more and
changes take place in the several peaks. In parti- more hydrogen bonds are formed. Another inter-
cular, the reflection peak (100)+(010) at 21.r esting feature is that an increase in crystallite size

96
 BHAT et al: UNORIENTEO NYLON-6 FILM

Table 3 - Changes in crystallite sizes in nylon-o films pre- ....

III

treated with formic acid and benzyl alcohol z

~
Solvent Duration of Cone. of Crystallite size, A :>
pretreat- solvent a:
<t
ment % 0200 0002 + 0202 a:
....
h coa:
34.5 36.1 <t
Formic acid I 10 37.4 41.0 z
I 30 49.6 30.1 W
u
I 50 74.8 34.7 Z
<t
8 10 35.9 29.3 ....
....
8 30 59.9 39.3
~
8 50 81.6 47.5 III
Z
<t
27.4
a:
....
Benzyl I 100 34.5
alcohol 8 100 35.9 28.2
1200 1000 800 600 400
WAVENUMBER,cm-1
Fig. 6 - IR absorption spectra of nylon-o films treated with
along a-axis is accompanied by a shift in the ref-
formic acid and benzyl alcohol for 8 h [(a) control, (b) 10%
lection corresponding to (002)+(202) planes. formic acid. (c) 50% formic acid, and (d) benzyl alcohol]
This reflection also results from a-crystallites.
With reference to the monoclinic a-unit cell of
nylon-6 these planes correspond to the plane of
hydrogen-bonded molecular sheets and the dia-
gonal plane respectively'". Since an increase in the
diffraction angle of (002) + (202) planes indicates
a denser packing of the crystallites, a better crys-
tallite perfection is achieved in addition to crystal-
lization. Fig. 5 shows that for samples treated
with 10% formic acid, (200) reflection occurs at
20.6° and (002) + (202) doublet occurs at 23.7~
However. when the concentration of formic acid
is increased to 30% the peak position is shifted to
2 B> 23.9° and when it is further increased to
50°/,), the a, peak shifts further 24.4°. These ob-
servations indicate that thermally-induced or sol-
vent-induced crystallization leads to the same re-
sult.
Benzyl alcohol treatments did not give rise to
any of above effects owing to very small increase
in crystallinity.
Fig. 7 - H, SALS patterns of nylon-o films treated with for-
3.5 IR Spectroscopy mic acid and benzyl alcohol [(a) control, (b) 10% formic acid,
The infrared absorption spectra for control and (c) 50% formic acid. and (d) benzyl alcohol]
treated nylon-6 samples are shown in Fig. 6. The
calculated values of crystallinity index for samples in crystallinity. It is observed that, in general, the
treated with different concentrations of formic ac- crystallinity index calculated from IR spectra gives
id for different durations are given in Table 2. It higher values.
is seen that the crystallinity index increases with
3.6 Spherulitic Structure ofNylon-6 Films
the concentration of solvent as well as with the
The H, patterns for the control and treated nyl-
duration of treatment. However, the effect of con-
on-6 film samples are shown in Fig. 7. The pat-
centration is more prominent.
terns are typical of undeformed spherulites. It is
The crystallinity index values for samples treat- observed from the figure that solvent pretreat-
ed with benzyl alcohol show only slight increase ment does not affect bulk spherulitic morphology

97
 INDIAN J. FIBRE TEXT. RES., SEPTEMBER 1990

To gain better insight into the mechanism of

solvent-induced interactions, it was decided to
study the surface morphology using SEM. The
scanning electron micrographs of the control sam-
ple as well as of the samples treated with formic
acid are shown in Fig. 8. It is seen that the con-
trol film possesses well-developed spherulites, the
spherulitic nuclei and fibrillar detail being clearly
visible. However, the films treated with formic ac-
id show sufficient destruction of surface morphol-
ogy due to solvent etching. For the film treated
with 50% formic acid, any of the surface features
typical of spherulitic crystallization are barely re-
cognizable. The average size of spherulite was 8.6
fl for the control sample.

4 Conclusion
Solvent-induced crystallization of nylon-6 by
formic acid and benzyl alcohol results in the for-
mation of a-crystallites. Formic acid is more ac-
tive than benzyl alcohol in causing structural
changes. Solvent-induced crystallization is also ac-
companied by surface etching.

Acknowledgement
The authors are thankful to Mis Garware Nyl-
ons Ltd for supplying the nylon films. They are
also indebted to the Surface Science Laboratory,
University of Western Ontario, Canada, for per-
mitting the use of facilities. One of the authors
(NVB) is grateful to the Centre for Chemical Phy-
sics, University of Western Ontario, Canada, for
the award of a senior visiting fellowship.
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 BHAT et al.: UNORIENTED NYLON-6 FILM

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99