3298 Macromolecules 1992,25, 32963300

Overview of Transition Phenomenon in Nylon 6 very difficult: (A) Depending upon the annealing tem-
perature, T, a small endothermic peak attributed to the
Yash P.Khanna +
melting of microcrystals, is observed at about T 20 OC
in the DSC technique.2 (B) Over this broad temperature
Research and Technology, Allied-Signal, Inc., region, the conversion of any y-crystals to the a-form also
Morristown, New Jersey 07962 takes place; this process is detected by X-ray diffraction
(XRD), infrared (IR), and nuclear magnetic resonance
Received November 4, 1991 (NMR) but not by DSC or DMA. (C) If the samples were
not very slowly cooled or annealed, the phenomenon of
Introduction crystal thickening/perfection would occur. DSC or DMA
unlike XRD is not sensitive to this gradual process. (D)
Although nylons have been known since the 19308,new Recently, a Brill transition (crystal-to-crystal) has been
transitions and/or interpretations continue to appear in reported in nylon 6 between 80 and 170 OC on the basis
the recent The purpose of this paper is to of XRD and NMRst~dies.~ DSC and DMA cannot detect
briefly summarize the known information and introduce such a transition at least in the melt-crystallized samples.
yet another transition in nylons. (E)Using an especially high temperature annealed (220
"(360 h) nylon 6, an a'-relaxation at approximately 170
Experimental Section "C has been reported on the basis of DMA,this relaxation
was associatedwith the mobility of interfacial amorphous
Commercially availablefilm grade nylon 6, nylon 66, and nylon phase which requires crystal mobility as a precursor.2
12 resins were used in this study. About 1% powder Laponite New Sub-T,,Transition
, in Nylons. This exothermic
(a commercially available clay material)was added to the nylon transition at about 195 "C in nylon 6 has long been observed
resins, and thin filaments (0.03-in. diameter) were extruded in by use5 Recently we have observed a similar sub-Tm exo-
a capillary rheometer at a shear rate of about 100 s-1 at
approximately 40 "C above the polymer melting temperature. therm in nylon 66 and nylon 12 (Figure 1). The Sub-Tm
Most of the characterization was done on a Du Pont 9900 exotherm is observed to some extent in shock-cooled
differential scanning calorimeter (DSC),and the experimental nylons, but a combinationof mechanicalstressesand rapid
details are given in the figure captions. cooling (e.g., in melt extrudates from a capillary rheom-
eter) enhances the development of this transition. More-
Results and Discussion over, the addition of non-nucleating minerals, such as
Laponite and montmorillonite, further enhances the
First we will briefly summarize the informationon nylon transition.
6 transitions known in the literature. This will be followed Although the Sub-Tm exotherm is clearly seen in the
by our present work leading to the identification of a new DSC thermograms, other techniques have not been able
Sub-Tm transition in nylons. Finally, we will comment on to shed further light. For example, variable-temperature
the anomalous doublet melting behavior of nylons when IR studies over the 175-215 "C temperature region (i.e.,
these are crystallized at moderate cooling rates. covering of the 195 "C transition) have not revealed any
Transitions in Nylon 6. When a nylon 6 sample is specificchangesexcept for a alightbroadeningof the bands.
heated, several relaxations and transitions are observed Solid-state 13C NMR indicated no dramatic changes in
over the temperature range -150 to 250 "C. Following is the 2'1~ and TzCrelaxation times within the Sub-Tm
the discussion of these processes in the order of increasing transition zone. We would have expected major changes
temperature. in the event of a phase transformation. Rather, a steady
A y-relaxation is observed in dynamic mechanical decrease in TI, with increasingtemperature was observed
experiments at about -115 "C and is unaffected by in accordance with the increased mobility but without a
moisture, crystallinity, molecular weight, etc. This is change in mechanism. Using XRD,samples of nylon 6
assigned to the motion of three or more CH2 sequences.' with the 195 "C transition and without the transition (e.g.,
A 8-relaxation is observed in dynamic mechanical by annealing at 200 "C; Figure 1) were characterized at
experiments at about -55 "C.l This has been attributed room temperature. The crystallinity and the a:y-crystal
to the mobility of H-bonded >C=O groups, and its position ratio were found to be quite similar for the two samples.
depends upon the moisture content.' Starkweathel.4has The crystallite size and perfection of the a-crystals were
proposed that water molecules interfere with the H- higher for the 200 "C exposed sample, but that is to be
bonding in the nylons. Our own work has shown that a expected. As shown in Figure 1,the Sub-Tm transition is
well-dried nylon 6 (e.g., 175 "C/17 h) shows a hardly temperature specific for a particular nylon; i.e., it cannot
detectable &peak at about -25 0C.5 In the presence of be eliminated by annealing below it. In addition, the
1%or more moisture, the peak gains intensity and shows heating rate, e.g., 0.1-50 "C/min, does not change this
up at about -55 "C,presumably due to the weakened H- transition. We must mention that a Sub-Tm exotherm
b~nding.~ reported here is associated with nylons and we have not
An a-relaxation with onset at about 45 "C (or damping observed this behavior with other common semicrystal-
maximum at about 65 "C) in dynamic mechanical analysis line polymers.
(DMA)is the same as Tgobserved by DSC and many other On the basis of the above information, we propose that
techniques. The a-peak temperature is lowered by mois- the 195 "C exothermic transition is due to the release of
ture, while crystallinityand orientation reduce its intensity strain energy absorbed during processing. An exotherm
and broaden the transition. in the Tgregion is well documented for polymers frozen
Sufficiently amorphous samples of nylon 6 exhibit a under mechanical stresses.6 These mechanical stresses
cold crystallization peak at about 70 "C in the DSC are frozen-in in the form of high-energy conformations,
technique. The crystalsat that temperature are primarily and the strain energy is released when the polymer
in the y-crystalline form.5 segments acquire mobility at a Tg. Since the Sub-Tm exo-
The temperature range 80-190 "C involves a number of therm is typically associated with the nylons,5 it appears
simultaneous processes, thus making the interpretations that H-bonding might play some role. It is possible that
0024-929719212225-3298$03.00/0 0 1992 American Chemical Society
Macromolecules, Vol. 25,No. 12, 1992 Notee 3299

-
3000

Figure 1. DSC thermograms at 10 OC/min showing the sub-T,

0 ¶O Id0 130
r.w.r.tur. mi
Id0
Y O1.C

m
Y GO

Figure 3. DSC thermograms at 10 OC/min showing the doublet

-8.0 1 and 8.9 J/g, respectively. The values reported here for
the sub-T,,, exotherm are about the highest we have come
i across for these systems. These values as percentage of
the heat of fusion (i.e., crystallinity measure) are 12, 13,
-85i- ' 50 ' '
100
---7
150
1.WP.P.t"PC l.Cl
----
200
o+-
250
and 19% for nylon 66,nylon 6, and nylon 12,respectively.
Future work might revealwhy nylon 12is the most sensitive
Figure 2. DSC thermograms at 10 "C/min showing the corre- polymer in terms of strain energy absorption.
spondence of the S U b T m exotherm in nylon 6 to the mechanical Doublet Melting in Nylons. Nylon 6 is known to have
history (sample size 9.0 f 0.7 mg). two crystal forms melting at 215 (y-form) and 225 "C (a-
form).8 As a result, when one comes across a doublet
the thermomechanical stresses upon rapid cooling of the melting at 215 + 225 "C,it is likely to be associated with
nylon melts get frozen-in and locked through H-bonding. the two crystal forms. We report that a doublet melting
Considering that such is the case, frozen-in strains might behavior is common to nylons including nylon 66, which
not be released at the T,. It is possible that the strain melts only in one crystal form, doublet melting being a
energy is released in the SUb-Tm region where the polymer characteristic of melts crystallized at moderate cooling
segments have enhanced mobility. The correspondence rates, e.g., 10 OC/min (Figure 3). Note that the crystal-
of the 195 O C exotherm to the strain energy release is linities of nylon 6 or nylon 66 are very similar regardless
reinforced by the results in Figure 2. As a speculation, we of the cooling rate (0.1 or 10 O C / m i n ) , and the nylon 6 is
can point out that the frozen-in stresses might be located predominantly in a-phase (<3 9% y-phase), irrespectiveof
in the interlamellar regions which become mobile at the the cooling rate used (Figure 3).
pre-melt temperatures.2 Our recent work on the process- It appears that at high cooling rates, e.g., quenching,
induced memory effecta in nylons is a further support to the imperfect crystals undergo a continuous thickening/
the role of H-bonding in preserving the melt history.' perfection process in the T8-Tm region and, therefore, melt
Under similar processing history, the heats of SUb-Tm at a higher temperature, e.g., 222 "C for nylon 6. At low
exotherm for nylon 6, nylon 66, and nylon 12 are 6.3,6.7, cooling rates, e.g., 0.1 OC/min, the resulting crystals are
3300 Notes Macromolecules, Vol. 25, No. 12, 1992
quite perfect and, thus, melt at a higher temperature, e.g., References and Notes
222 "C for nylon 6. Apparently at intermediate cooling
rates. e -a .- 10 OC/min, a bimodal cwstallite distribution (1) Murayama, T. Dynamic Mechanical Analysis of Polymer
I
Material; Elsevier: Amsterdam, 1978; p 66.
may occur and result in a doublet melting. We are aware Khanna, Y. P. J. Appl. Polym. Sci. 1990,40, 569.
of the multiple melting characteristics of semicrystalline Murthy, N. S.; Curran, S. A.; Aharoni, S. M.; Minor, H.
polymersg but feel that the doublet melting observed in Macromolecules 1991,24, 3215.
nylon 6 and nylon 66 at moderate cooling rates is not Starkweather, H. W. J. Appl. Polym. Sci. 1959,2, 129.
typically observed in other semicrystalline polymers. Khanna, Y. P. Unpublished data, Allied-Signal, Inc., 1975-
1991.
Acknowledgment. Helpful discussions with Dr. J. P. Prest, W. M. Polyrn. Eng. Sci. 1981,21 (18), 1181.
Khanna, Y. P.; Reimschuessel, A. C.; Banerjie, A.; Altman, C.
Sibilia,Mrs. A. C. Reimschuessel, and Prof. S. Krimm are Polyrn. Eng. Sei. 1988,28 (24), 1600.
highly appreciated. Thanks are due to Dr. S. Curran Illers, K. H.; Haberkorn, H. Macromol. Chem. 1971,142,31.
(NMR),R. Bray (IR), and N. S. Murthy (XRD) for their Khanna, Y. P.; Turi, E. A,; Sibilia, J. P. J.Polym. Sci., Polym.
respective contributions. Phys. Ed. 1874,22, 2175.