Crystallization of Polyamides

H Nylon 6 and Nylon 66

J. H. MAGILL

A comparison is" made between the rates of spherulitic growth in Nylon 6

and Nylon 66 polymers. Theoretical equations describing the growth rates are
presented using the concept of molecular chain [olding within the fibrils or
lamellae comprising the spherulites. These equations adequately describe the
rate o[ spherulite growth in these two polyamides, which occurs by a coherent
two-dimensional mechan&m. Crystal sur[ace free energies are given.

NYLON 6 and Nylon 66 crystallize spherulitically when cooled from the

molten state ~. Both polymers form positively birefringent spherulites at
supercoolings ( A T ' 0 in excess of 20°C below their respective thermodynamic
melting points (T~,~). At comparable A T " for similar molecular weights,
Nylon 66 spherulites grow many times faster than Nylon 6 spherulites ~':'.
The purpose of this communication is to examine the crystallization kinetics
of these two similar polyamides in the light of recently developed concepts
of crystallization "''~.

RESULTS AND DISCUSSION

T a b l e 1 contains some isothermal spherulite growth rates -~ obtained on a
~,, = 2 4 700 Nylon 6 sample which was fused (prior to crystallization) at
270°C for half an hour. It is assumed that molecular chain folding occurs
in the growing fibrils or lamellae comprising the spherulites. Growth can

Table 1. Spherulitic crystallization rates (G) for Nylon 6

Temperature (°K) 363 368 374 380 390 397"5 408 414 421
G (f~/min) 22-5 3 6 . 6 38'4 6 6 . 5 94"3 116'0 146.3 146"3 1263
Temperature (°K) ~ 445 457 457-5
G (pt/min) 107.4 59"0 18"3 14-4

be perpetuated by either coherent or non-coherent nucleation mechanisms

around a central nucleus. Spherulite growth (G) can be described by an
equation of the form

G = G,, exp ( - A F * / R T ) exp ( - A G * / R T ) (1)

where Go may be considered a constant. A G * is the free energy of crystal

formation and A F * expresses the temperature dependence of the segmental
jump rate from potential wells in the liquid side to the growing crystal
front.
An analysis of these Nylon 6 results (in a manner similar to that used
for polychlorotrifluorethylene0 clearly indicates that a ,--~T--1 (two-
dimensional surface nucleation) law is preferred to a A T -2 (three-
367
 J. H. MAGILL

I07/T2 AT
06 07 08 09 10 1I

~ _

4"

60 i
2"0 3"0 4'0 5"0 6"0 7"0
1012/T3AT 2
Figure /--Determination of the AT law for Nylon 6 (radial
growth rate data) with T,,~---227°C

dimensional surface nucleation as illustrated in Figure 1). The plot of

[log G+AH*/2.3RT] is linear for the A T -1 plot, but distinct curvature
is apparent in the A T -2 plot, using the G values to the right of the maximum
of Figure 2. For the purpose of this analysis, A F * was replaced by A H *
taken to be 10'8 kcal per mole of repeat units of Nylon 66. It is necessary
to include the temperature dependence of this term, in the manner indicated,
to establish the exact nature of the growth mechanism. F r o m the slope of
the linear A T - ~ plot (Figure 1) it was deduced that the product of the
lateral surface free energy (o-) and chain end fold surface free energy (o-e)
was about 480 erg2/cm 4 for crystal growth.
2°°/
o o

~100F

6ot~
I
~i-" 40
Figure 2--Spherulite growth rates
for Nylon 6, M,=24700 and
calculated curve corresponding to
these experimental points
~ 20
¢-

ffl

lO
8
i [ r I
350 390 430 470
Temperature, °K
368
 CRYSTALLIZATION OF POLYAMIDES 1I

A n alternative approach utilizes all the experimental results on both sides

of the maximum. The best curve is fitted by computer to an equation of
the form
G = Go exp ( - £xF* / R T) exp ( - BT'2,,/T 2AT) (2)
or
G=G~, exp ( - A F * / R T ) exp ( B ' T , , , / T ~ T ) (3)

Equation (3) is a less exact form derived from (2). The first exponential
term of equations (2) or (3) can be expressed 7 as e x p [ - A / R ( T - T , , ) ]
which utilizes a reference temperature To ~ T,, rather than 0 ° K as
employed in equations (2) and (3); whence (2) and (3) become
G~-G,, exp [ - A I R ( T - T,,)] exp [-BT'-',,,/T2AT] (4)
and
G = G o exp [ - A ' / R (r- To) ] exp [--B'T,,,/TAT] (5)
The values in Table 1 were least squared with equations (4) and (5) using
T,,,=500°K and T , , = 5 0 3 ° K . The significant molecular parameters are
presented in Table 2.

Table 2. Parameters governing the crystallization of Nylon 6 spherulites by a

secondary, two dimensional nucleation mechanism
Equation (4) Equation (5)
T,,,
500°K 503°K 500°K 503°K
A × 10 -:~ 1.29 1"50 1'56 1"84
B × 10- z 2"98 3"40 2.96 3 38
Go× 10-~ 2.43 6"92 2.14 633
T0 °K 276 269 270 263
,r(r,. 465 520 465 520

G . is expressed above in u / m i n and ~r~ in erg2/cm '. The calculated

curve is shown with the experimental points in Figure 2.
Using the somewhat empirical relationship ~
,~ / 2xhlb~, - ~ (constant) (6)
where Aht is the heat of fusion and b0 the interplanar spacing of the crystal
monolayers, a reasonable estimate can be made for ~ taking ~ = 0 ' 1 . F o r
N y l o n 6, this lateral surface free energy is about 8 e r g / c m :, whence ,~,. is
60 to 65 e r g / c m 2 approximately. These values are of similar magnitude to
those found for other polymers. Interesting, too, is the correspondence of
Go values a m o n g these polymers. Nylon 6, polyethylene '~ and polychloro-
trifluorethylene '~ all have values around 10 '~ cm/sec.

Table 3
Equation (4) Equation (5)
A x 10 ~ 0'76 1-67
B× 10 -.2 2"07 2.04
Go× 10 -a 3.42 257
To °K 334 318
~ro-~ 325 320
369
 J. H. MAGILL

For Nylon 66 the results are somewhat different. An analysis of spherulite

growth rates 8 through the maximum, using equations (5) and (6), gave (for
a Tm=545°K) the following values (Table 3). A heat of fusion s of 48 cal/g
was used in the calculation of o-o-e. From equation (6) o- was derived to be
8-0 to 8 5 erg/cm 2, whence ,o-~ must be 40 erg/cm 2 approximately. A
similar result follows from an analysis of McLaren's spherulitic growth
rates 9 for this polymer. From the slope of [logG+AH*/2"3RT] versus
[I/TeAT], o-o-eis found to be about 360 erg2/cm 4. This corresponds to a o-
of about 8"5 erg/cm ~, and a ~-~ of 40 to 45 erg/cm 2 in good agreement with
the results of Table 3.
Earlier 2, it was suggested that the faster rate of crystallization of Nylon 66
over Nylon 6 might arise because of some configurational differences
between these two polymer molecules. Nylon 66 molecules, being sym-
metrical, can be accommodated in the crystal lattice with greater ease than
Nylon 6 which must pack in antiparallel arrays to favour complete hydrogen
bonding. A definitive explanation still cannot be given for this difference
in rate. However, it is worth noting that a lower Go (1"55 x 10~ cm/sec) is
found for Nylon 66 than for Nylon 6. Furthermore the work of chain
folding, q, which reflects the molecular chain stiffness of the polymer has
been expressed as
q = 2A oo-~ (7)

where A 0 is the molecular cross section of the polymer chain. From Bunn's
unit cell structures 1°' 11, A0 for Nylon 6 was calculated to be 17-7 A 2 and
for Nylon 66 as 17'6 A 2. Since o-,. for Nylon 66 is less than o-e for Nylon 6,
then, using equation (7), the q values for these polymers must be in the
same order. Initial moduli measurements have not been made on lactam-free
dry polymers at equal supercoolings to bear comparison with these results.
Although the theoretical modulus of Nylon 66 has been calculated 12, that
for Nylon 6 would be comparable in such a derivation because of the
assumptions and procedures involved. The melt viscosity a3 and apparent
activation energy for viscous flow of lactam-free Nylon 6 is found to be
greater than that of Nylon 66 of similar molecular weight and molecular
weight distribution at corresponding temperatures above their respective
melting points. This experimental result bears comparison with the results
above.
Clearly further experimental work is necessary to provide alternative
derivations of ~,- and o-e values. In particular, the analysis of dilatometric
measurements of homogeneous nucleation experiments 14 using dispersed
polymer droplets (and long period X-ray measurements on isothermally
crystallized bulk polymers or single crystals) should yield, in conjunction
with the present rate data, consistent and reliable values of o- and o-~ and
so permit a definitive solution to the problem of rate difference in these
two polymers. For the present, however, it is clear that a coherent two-
dimensional secondary nucleation mechanism with chain folding adequately
describes the rate of spherulite growth in these two polyamides.
In all instances the derived To values are approximately equal to, or less
than, the observed glass temperatures for these two polymers. For Nylon 66,
using equation (4), To is found to equal T o but this close agreement is
370
 CRYSTALLIZATION OF POLYAMIDES II

believed to be fortuitous. N o t e w o r t h y too is the fact that the N y l o n 6 rate

curve reaches a m a x i m u m (T ..... ) a b o u t 138°C, while N y l o n 66 peaks a b o u t
141°C giving the ratio T .... /T,~ for N y l o n 6 a b o u t 0"82 a n d for N y l o n 66
a r o u n d 0 7 6 in fair agreement with the values a~ o b t a i n e d for N y l o n 5.6
(0.85) a n d N y l o n 9.6 (0-87).

This work was supported in part by the U.S. O]fice of Naval Research
under Contract N u m b e r N o n r 2693 (00). Gratitude is also expressed to
M r B. Hazlett [or least square calculations.

Mellon Institute,
4400 Fifth A v e n u e , Pittsburgh 13,
Pennsylvania, U.S.A.
(Received N o v e m b e r 1964)

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