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Morphology and Dynamic Mechanical

Properties of Nylon 66/Poly(Ether Imide)
Blends
KIL-YEONG CHOI, SUNG-GOO LEE, and JAE HEUNG LEE

Advanced Polymer Division
Korea Research Institute of Chemical Technology
Yusong. Taejon, 305-606,Korea
and
JINGJIANG LIU

C hangchun Ins tit Ute of App lied Chemistry
ChineseAcademy of Sciences
Changchun, 130022,P. R. China

The morphology and dynamic mechanical properties of blends of poldether
imide) (PEI) and nylon 66 over the full composition range have been investigated.
Torque changes during mixing were also measured. Lower torque values than
those calculated by the log-additivity rule were obtained, resulting from the slip at
the interface due to low interaction between the components. The particle size of
the dispersed phase and morphology of the blends were examined by scanning
electron microscopy. The composition of each phase was calculated. The blends of
PEI and nylon 66 showed phase-separated structures with small spherical dc-
-
mains of 0.3 0.7 Fm. The glass transition temperatures (T,s) of the blends were
shifted inward, compared with those of the homopolymers, which implied that the
blends were partially miscible over a range of compositions. T g l ,corresponding to
PEI-rich phase, was less affected by composition than Tg2, corresponding to nylon
66-rich phase. This indicated that the fraction of PEI mixed into nylon 66-rich
phase increased with decreasing PEI content and that nylon 66 was rarely mixed
into the PEI-rich phase. The effect of composition on the secondary relaxations
was examined. Both q,corresponding to the motion of amide groups in nylon 66,
and T,., corresponding to that of ether groups in PEI, were shifted to higher
temperature, probably because of the formation of intermolecular interactions
between the components.

INTRODUCTION of nylon 66 with polyethylene. polypropylene,
poldethylene terephthalate), nylon 6, elastomers, and
ylon plastics are extensively used in the manu-
N facture of automobile parts, engineering prod-
ucts, and textile fibers, because they have many ad-
high performance engineering plastics (1-3).
PEI, (poly(2,2’-bis(3,4-dicarboxyphenoxy) phenyl
propane)-2-phenylene bisimide), belongs to a class of
vantages in properties such as high mechanical and relatively new high performance materials. It is a
impact strength and good processability. However, thermally stable and soluble thermoplastic that has
they reveal relatively low heat deflection temperature excellent high temperature resistance, toughness,
and absorb water easily, which limits uses in struc- good dielectric properties, low flammability, and high
tural parts. Recently, blending nylon 66 with different resistance to radiation and deformation under load a t
polymers h a s generated considerable interest be- elevated temperature. In particular, PEI combines a
cause this is a n easy and economical way of tailoring relatively low production cost with appreciable physi-
nylon 66 to suit specific end uses. Sometimes, blends cal properties (4-6). However, it has some disadvan-
of nylon 66 with novel mechanical performance and tages, such as high melt viscosity and low resistance
excellent processing properties were provided. Nu- to chemicals, owing to its amorphous structure. Some
merous studies have been carried out on the blends basic research on the blends of PEI with thermotropic

POLYMER ENGINEERING AND SCIENCE, OCTOBER 7995, VoI. 35, No. 20 1643
Kil-Yeong Choi, Sung-Goo Lee,Jae Heung Lee, and Jingjiang Liu

liquid crystalline polymers, PEEK, poly(ether volume fraction of the domains was calculated, with
sulfone),and polybenzimidazole have been carried out the assumption that the dispersed domain was of
(7- 10). spherical shape and each particle had been cut at its
The significant improvement in processing proper- equator.
ties for PEI can be achieved without a consequent Dynamic mechanical measurements were per-
decrease in the mechanical properties by blending it formed in a Rheometrics Dynamic Spectrometer
with nylon 66, which is a semicrystalline material (RDS) in the shear mode operating at a frequency of
with relatively high mechanical properties, low cost, 1 Hz and a constant strain of 0.1%. The dimension
and low melt viscosity. Moreover, the strength and of the testing sample was 40(L) x 12(W)x 2(T) mm.
heat resistance of nylon 66 can be increased remark- Nitrogen gas was circulated in the environmental
ably by adding PEI as a minor component. Blend- chamber to minimize degradation and chemical reac-
ing the two polymers seems to be most attractive tion during testing. The dynamic mechanical proper-
both in terms of processability and performance ties, shear storage modulus, G', shear loss modulus,
improvement. G", and loss factor, tan 6 , were collected at a heating
Blends of nylon 66 and PEI were studied over the rate of 3"C/min over the temperature range of - 150
whole range of composition. Morphology and rheologi- to 300°C. The temperature that corresponds to a
cal and dynamic mechanical properties were exam- maximum in the tan 6 vs. temperature curve was
ined, and the miscibility between two components, considered the glass transition temperature, Tg. for
transition, and relaxation behaviors were described. the homopolymers. For the blends, the higher Tq,
represents the glass transition temperature of the
EXPERIMENTAL PEI-rich phase i d the lower Tq2corresponds to that
of nylon 66-rich phase. Each relaxation temperature
Materials denoted by the peak on tan 6 vs. temperature curves
PEI is commercially available a s Ultem from Gen- was reproduced exactly.
eral Electric Plastics. Ultem 1000 with a density of The melting behavior of the blends was evaluated
1.27 g/cm3 was used in this study. on the DuPont 990 Differential Scanning Calorimeter
Nylon 66, Toplamid 2021, was supplied by (DSC). The calibration in temperature and heat flow
Tongyang Nylon Co. (Korea) in the form of pellets. scales followed standard procedures. The 10 k 2 mg
The density and the melting point are reported a s of sample was heated up to 300°C. held for 5 min to
1.14 g/cm3 and 255°C respectively, by the manu- erase the effect of the previous thermal and mechani-
facturer. cal history, and then cooled at 10"C/min to room
temperature to obtain the crystallization exotherm. A
Mixing dry -nitrogen atmosphere was used. The melting en-
dotherms were obtained in the second heating cycle
Both nylon 66 and PEI are known to absorb mois- at 10"C/min. The melting point, Tm,and crystalliza-
ture easily. Before use they were dried at 90°C for
tion temperature, Tc,were given a s the maxima of the
24 hrs. A n internal mixer (Haake Rheocord 90) was thermal transitions. The degree of crystallinity, Xc,
employed to prepare the blends and determine
for nylon 66 was calculated with equilibrium heat of
their rheological properties during blending. Both
fusion, A H ; , of 188.1 J / g for the 100% crystalline
shear rate and mixing temperature were controlled.
nylon 66 (1 1).
Typically, a 50-g sample was mixed at 60 rpm for
- 10 min at 320°C. Torque and melt temperature
with time were measured. The same processing prc- RESULTS AND DISCUSSION
cedure was followed for the homopolymers. The hot Rheological Behaviors
blends were removed from the mixer, rapidly cooled
Fzgure I shows the typical Haake Rheocord 90 data
to room temperature, and then stored in a desiccator
curves illustrating changes in torque during the mix-
until testing.
ing process at 320°C for the component PEI (PEI 1001,
The weight ratios of PEI and nylon 66 were as
nylon 66 (PEIO), and the blends of PEIlO, PEI50 and
follows: 100/0, 90/10,85/15, 75/25, 50/50, 25/75,
PEI9O. The high loading peaks resulting from the
15/85, 10/90, 5/95, and 0/100, which were coded
as PEI100, PEI90, and so on. melt fracture of cold samples were recorded prior to
complete fusion of the materials. On the torque vs.
time curves for the pure nylon 66 and specimen
Characterization
PEIlO in Fig. 1 , the second small peaks, resulting
The morphology of the blends of PEI and nylon 66 from the melting process of crystallites remained in
was investigated on compression molded samples. the materials, were observed at around 1 min after
Transversal sections of the specimens were obtained the mixing was started. They were accompanied by
by fracturing them in liquid nitrogen, and then the the temperature decrease of the mixtures at the melt-
surface was coated with gold-palladium prior to view-
ing with a JEOL JSM-840A scanning electron micre
-
ing point of nylon 66, 250°C. After the mixing pe-
riod exceeded 5 min, both the torque and tempera-
scope operated at 20 KV. The apparent diameter of ture were leveled off, indicating that an equilibrium
each particle in the field of view was measured. The state was reached.

1644 POLYMER ENGINEERING AND SCIENCE, OCTOBER 1995, Vol. 35, No. 20
Morphology a n d Properties of Nylon 6 6 / P E I Blends

- PEllOO
_ _ - P E I 90
_.- PEI 50
..-__
10PEI
PEI 0

-----_ -
0 20 40 60
Time,rn I n PEI,w t Yo
Q. 1. Changes in torque as a function of mixing time for Q. 2. Comparison of experimental equilibrium torques for
PEI, nylon 66, and the PEI/ nylon 66 blends. the blends of PEI and nylon 66 with the calculated ualues
with Equation 1.

The torque values at the equilibrium state are plot-
ted as a function of composition in Fig. 2. The torque by the log additivity rule for the polymer blends have
values can be easily converted to absolute viscosity been observed elsewhere (17-20). Reasons for the
via relationships reported elsewhere (12, 13).PEI re- phenomena have been discussed. It is well known
vealed a much higher torque value than nylon 66, that a n incompatible blend, characterized by a sharp
and a s the content of the nylon 66 was increased, the interface and essentially no interaction between the
torque was greatly reduced, because the processabil- two phases, frequently exhibits a n interlayer slip,
ity of the blend was improved with increasing content which gives rise to a reduction in viscosity of the
of nylon 66 with low melt viscosity. blend, and hence the negative deviations of the vis-
Many rheological empirical or semi-empirical equa- cosities from the additivity values have been ob-
tions have been reported and reviewed to describe the served. Figure 2 reveals that the interface slip pre-
relationship between morphology, composition, rheol- dominates the melt viscosity reduction for the blends
ogy, and processing steps in the polymer blends in the middle of the composition range.
(14- 16). Utracki suggested that the log-additivityrule The dependence of miscibility on the composition of
might be used to classify the flow behaviors of the the blends has been observed in PEEK and PEK-C
polymer blends ( 14): blends (2 1). At low blend compositions, miscible
Log F = Wi log F,
blends of PEEK/PEK-C were achieved.
(1)
However, the analysis of the rheological properties
where F and F, are the melt rheological functions, of polymer blends is very complicated. Besides experi-
e.g., shear viscosities of the blends and the compo- mental difficulties in measuring a n average rheologi-
nent, and Wi is a measure of composition, usually cal response of a blend, there are limitations in inter-
expressed as weight or volume fraction of the compe preting the results owing to concentration and stress
nent. The use of Eq 1 makes it possible to distinguish field dependent morphology, as well a s inherent diffi-
a positive deviating blend (PDB), a negative deviating culties in stress orientational effects. Certain im-
blend (NDB), and a positive-negative deviating blend posed morphologies and the viscoelasticity of both
(PNDB) with a sigmoidal dependence. Comparison components by the stress field frequently allow the
between the variations in torque of the blends as a structures to exist long enough to be retained in the
function of the composition measured experimentally cooled specimens. Sometimes, the rheological proper-
and those calculated readily from Eq 1 can provide ties of the blends during mixing could not be in
us with very interesting information about the mor- agreement with those determined at solid states.
phology of blend melts during mixing. As shown in
Morphology
Fig. 2, all the polymer blends of PEI and nylon 66
revealed NDB behaviors. The largest NBD behavior The morphology of the blends in a mixing chamber
was shown in PEI50, in which the amounts of the two can be related to their memory of the rheological
polymers were comparable. When the weight fraction history in addition to the miscibility between the
of nylon 66, Wn, was less than 0.25 or more than 0.8, components. To evaluate the miscibility of the blends
many fewer NBDs were observed, meaning that the in detail, it seems to be suitable to carry out the
miscibility was improved for the blends with low con- morphological investigation on the compression
tent of one component. molded samples for convenience. The scanning elec-
Lower melt viscosities than the calculated values tron micrographs (SEMs) of the fractured surfaces of

POLYMER ENGiNEERiNG AND SCIENCE, OCTOBER 1995, Voi. 35, No. 20 1645
Kil-Yeong Choi,Sung-Goo Lee, J a e Heung Lee,and Jingjiang Liu

Fig. 3. Scanning electron micrographs or the blends of PEI and nylon 66.

the blends are shown in Fig. 3 and the information mains, as shown in PE190 of Fg. 3. From close obser-
listed in Table 1 is a summary of the composition and vation of the domain boundaries, it can be noticed
size of the domains obtained from the SEMs. It is that the adhesion a t the interface region became
seen in the SEMs that the blends of PEI and nylon 66 poorer as the PEI content was increased.
have phase-separated structures with small spheri- The weight fraction of PEI in the blends has
cal domains, less than 1 p m in size, mainly ranging been converted into volume fraction, 4,, as shown in
from 0.3 to 0.7 p m which means the blend systems Table 1. The average diameter of the domains, D,
are partially miscible, probably because of the h y d r e depended significantly on the composition in the
gen-carbonyl interactions between the polymer blends, as shown in Fig. 3 and Table 1. The particle
chains. The nylon 66 with lower melt viscosity formed size distribution of the dispersed phase appeared to
the continuous phase with spherical PEI domains for be polydisperse, but became narrow as the particle
the blends with PEI composition u p to 50%. and size decreased. The largest domain size and the widest
above that composition, the discrete nylon 66 phase distribution of the particle diameter were observed in
was segregated in the PEI matrix as spherical d e PEI50.
Morphology generation during mixing of polymer
components involves a balance between the compet-
Table 1. Morphological Parameters Obtained From the ing processes of fluid drop breakup and coalescence.
Scanning Electron Micrographs.
Taylor studied the deformation and disintegration of
Particle Volume Newtonian fluids (22, 23). Tokita h a s derived a n ex-
Composition Size Fraction of pression for describing the particle size of a dispersed
Code +J+,,* D, wn Domains,+, @d/+i +d/+n
phase in polymer blends (19, 24). At equilibrium,
PEI 5 0,04510.955 0.38 0.0048 0.11 where breakup and coalescence are balanced, the
PEI 10 0.09010.910 0.44 0.025 0.28 equilibrium particle size, D, may be expressed as:
PEI 25 0.2310.77 0.58 0.15 0.65
PEI 50 0.4710.53 0.64 0.32 0.68
PEI 90 0.8910.11 0.49 0.14 1.27 4PrE
(2)
* $ i and 6" correspond to the volume fractions of PEI and nylon 66 in the
blends, respectively.

1646 POLYMER ENGINEERING AND SCIENCE, OCTOBER 1995, Vol. 35, No. 20
Morphology a n d Properties of Nylon 66/ PEI Blends

where v12,v , E. and P, refer to stress field, interfa- fraction of PEI in the blends when PEI forms the
cial tension, bulk breaking energy. and probability dispersed phase, which implies that the miscibility
that a collision will result in coalescence, respectively. between PEI and nylon 66 increases with a decrease
Equation 2 predicts that the equilibrium particle size in content of PEI in the blends when PEI was the
decreases when the stress field becomes larger, the minor component. These results are associated with
interfacial tension becomes smaller, and the volume the dynamic mechanical properties of the blends,
fraction of the dispersed phase is smaller (23). A s which is discussed in the next part in this paper.
represented inTable 1 and Fig. 3, the average domain For PEISO, the ratio of the volume fraction of the
size increased from about 0.38 p m to 0.64 p m with dispersed nylon phase, qbd, to the volume fraction of
a n increase in the PEI weight fraction in these blends the nylon component, $,,. is 127%. It can be con-
u p to 50%. which was in agreement with the trends cluded that the dispersed domains consist of the
predicted in Eq. 2. homogeneous mixture of PEI and nylon 66 with a PEI
For the blends with higher PEI content, PEI was content of a t least 27%.
found to form the continuous phase with domains of
nylon 66, as revealed in PEISO blend. A domain size of Dynamic Mechanical and Transitional Behaviors
0.49 p m was observed in the SEM for PEISO, while
particles about 0.44 p m in diameter were distin- Figure 4 shows the temperature dependence of the
guishable for PEI 10. Moreover, much wider particle loss factor (tan 6 ) for the blends. Clearly, three well-
size distributions of the dispersed phase were re- defined relaxation peaks were observed for pure PEI
vealed in PEISO than in PEI10, even though the vol- and nylon 66, respectively. The mechanism of the
ume fractions of the minor component were approxt relaxations resulting from the molecular motion has
mate amounts in the two blends. PEISO represented a been investigated by a number of workers. For pure
significant departure from PEI 10 series of blends, nylon 66, three mechanical loss peaks, denoted as a ,
because the matrix viscosity, qm, and hence at the p , and y , are shown in Fig. 4. The maximum in tan 6,
same strain rate, the shear stress, (r12,were much a relaxation, associated with Tg occurs a t -80°C.
higher for PEISO than those for PEI10. In addition, while the p and y relaxations are found near -50
the interaction between the components in PEIlO and - 120"C, respectively, which are related to the
seems to be different from the case of PEISO. As mobility of the polar groups (-CONH-) and the
shown in Fig. 3, the sharp interface was observed in excitation of cooperative motions in the methylene
PEISO, whereas a n improved adhesion between the groups (-CH,-) in the main chain, respectively (2,
dispersed phase and the continuous phase was rec- 25). For pure PEI, three dynamic damping peaks are
ognizable in PEI10. The interactions between the assigned as a ' , p ' , and 7'. The sharp a' peak at
component polymers serve to diminish the interfacial about 230°C is due to the glass transition of the PEI.
tension, and hence the motion of dispersed particle The broad 0' peak near 80°C may correspond to a
within the matrix phase. As pointed out in the litera- local motion of the main chain, which h a s been o b
ture (19). the differences of the particle size between served around 127°C in polyimides based on ben-
the various polymer blends at constant composition zophenone tetracarboxylic acid (26). The y ' peak near
are due primarily to changes in the interfacial ten- - 100°C appears in all polyimides in which the rigid

sion and viscosity ratio. The morphology of immisci- phenyl groups consist of rigid backbone molecules
ble or partially miscible blends appears to be con- spaced with flexible groups such as methylene, and
trolled by a hierarchy of effects, such as : interfacial ether (26).
tension > viscosity ratio > shear stress (23). The for- The dynamic mechanical spectrum h a s become a
mer predominated the morphological difference be- classic method of determining miscibility because the
tween PEI 10 and PEISO. height and position of the mechanical damping peaks
The volume fractions of the PEI component, 4,, and are affected remarkably by miscibility, intermolecular
of the nylon 66 component, 4". are related to the interaction, interface feature, and morphology. The
actual composition of the blends because they are dynamic mechanical properties of the blends are also
converted from the density and weight fraction, as affected by the composition, with particular emphasis
shown in Table 1. On the other hand, the volume on the amount of the minor component. In the blends
fraction of the dispersed domains, I $ ~ can , be ob- of PEI containing a small amount of nylon 66, i.e.,
tained from the SEM. Provided the domains consist of PEISO, the absence of a n u peak is noteworthy. On
pure PEI in PEI5, PEI10, PEI25, and PEI50, the ratios the other hand, when PEI is the minor component
of the volume fraction of dispersed phase, 4d, to 4, and its content is more than 10 wt%, double Tgs, a
represent the relative contents of PEI composing the and a ' , are clearly visible in the blends.
domains. For example, 11% of PEI forms the dis- The phase structure of a blend is inferred from the
persed phase and 89% of PEI is mixed with the ma- number of glass transition temperatures observed in
trix, nylon 66, to form a homogeneous continuous the thermograms; that is, the appearance of two glass
phase in the case of PEI5, as shown in Table 1. The transitions is a clear indication of phase separation;
information presented in Table 1 documents the trend that of a single glass transition at a temperature
of a decrease in the relative amount of PEI in the intermediate between those of the pure components
continuous phase with an increase in the weight indicates miscibility.

POLYMER ENGINEERING AND SCIENCE, OCTOBER 7995, Vol. 35, No. 20 1647
Kil-Yeong Choi, Sung-Goo Lee, Jae Heung Lee, and Jingjiang Liu

1-
- PEIIOO
_ _ PEI 90
0- PEI 50
- - _ _ _PEI I 0
0
-
4:-1- Y

-3 -
I I I I I I I 1 I

-150 -60 30 120 21 0 0
Tempera ture,'C
Fig. 4. Tan6 us. temperature curvesfor PEI, nylon 66, and the PEI/ nylon 66 blends.

While the miscibility of the blends can be specu-
lated from the number of Tgs, the composition of the
phases can be calculated adequately according to the
Fox equation, with the Tg shift values for the partially
miscible blends, which is:

The subscripts 1 and 2 refer to the pure compo-
nents, and W refers to the weight fraction. According
to the Tgcriterion for miscibility, the polymer blends
of PEI and nylon 66 appeared to be partially miscible
because two Tgs, which were shifted inwardly com-
pared with Tgs of their respective pure component
polymers, were detected in the composition range of
nylon from 0.15 to 0.90. For the polymer blends with
extremely high or low nylon compositions, the detec- 340' I I I I I
0 20 40 60 80 100
tion of the single Tg might result from the small PE I , w t %
amount of the minor component.
Assuming that the Fox relation holds for the Tg Fig. 5. Changes in glass transition temperature as a-function
dependence on composition in the blends and that
,
of PEI content for the PEI/ nylon 66 blends. ( 0 ) Tg : ( - ) T y 2 :
(--I Fox equation.
the system has attained thermodynamic equilibrium
unaffected by both the fast cooling to room tempera-
ture and the mixing dynamics, that is, the quenched
two phases are at equilibrium: the PEI-rich phase were much higher, -4-9 wt%, depending on the
with higher Tg that corresponds to the nylon 66-plas composition in the blends.
ticized PEI phase and the nylon 66-rich phase with In addition to the above, there were a few other
lower Tg that corresponds to the PEI-reinforced nylon differences worthy of note on the storage shear modu-
66 phase, the composition of each phase can be lus, G', vs. temperature plots, as shown in Fig. 6. G'
calculated by the Fox equation. A summary of the decreased with increasing content of nylon 66 in the
experimental investigation on the Tg shift and calcu- blends at the temperature range from about 50°C to
lated phase composition is represented in Fig. 5 and 230°C, i.e., from Tg2 to Tyl,owing to the low modulus
Table 2. A slight decrease in the Tg of the PEI-rich of the rubbery amorphous phase of nylon 66. In
phase was recognizable, showing that a plasticizing contrast to the temperature region between the T,s of
role of nylon 66 took place for the PEI, and the the component polymers, G' increased with increas-
content of nylon 66 mixed into the PEI phase was ing content of nylon 66 and in addition exhibited
very low. The PEI-rich phases consisted of 99% PEI rubber-like plateau behaviors in the temperature
and 1% nylon 66 over a wide composition range of range from 230°C to 255°C. probably because of the
the blends investigated. On the other hand, the physical crosslinks resulting from the crystallites in
amounts of PEI contained in nylon 66-rich phases nylon 66. The crosslinks enable the plateau region to

1648 POLYMER ENGINEERING AND SCIENCE, OCTOBER 1995, Yo/. 35, No. 20
Morphology and Properties of Nylon 66/ PEI Blends
Table 2. Phase Compositions of the Blends of PEI and Table 3. Thermal Transition Parameters of the Blends of
Nylon 66. PEI and Nylon 66.
Nylon 66-rich phase PEl-rich phase Code T,,,'C TmPloC T,,C AH,J/g X,
- ~~

Code W" w, WilW, W" w, PEI 0 252.5 262.1 234.4 69.9 0.37
PEI 10 252.0 262.8 233.7 59.5 0.35
PEI 0 1 .o 0 - ~ -
- - PEI 25 252.6 263.6 232.8 47.3 0.34
PEI 5 0.96 0.04 0.80
PEI 10 0.94 PEI 50 252.0 262.7 232.0 33.4 0.36
0.06 0.60 0.01 0.99
PEI 15 0.93 PEI 75 - 259.5 - 16.2 0.34
0.07 0.47 0.01 0.99
PEI 90 ~

257.7 - 5.33 0.28
PEI 25 0.91 0.09 0.36 0.01 0.99
PEI 50 0.91 0.09 0.18 0.01 0.99
PEI 85 - ~ - 0.01 0.99
PEI 90 - -
~

0.01 0.99 order to understand how the PEI component with
PEI 100 - - - - 1.o high viscosity influences the crystallization behaviors
* W,and W, are PEI wt% and nylon 66 wt% in the phase, respectively. W , is of the blends, a detailed investigation on isothermal
PEI wtQ in the blends.
crystallization from the melt is being performed, and
the results will be reported elsewhere.
extend the higher temperatures ( T > Tql) until the Difficulties in detection of crystalline melting be-
crystallites in nylon 66 are melted at about 255°C. haviors in the G' vs. temperature curves for PEISO, as
In the crystallizable blends, there are many small shown in Fig. 6, might result from both the low
crystallites that act a s crosslinks, and hence the crystallinity in nylon 66, due to the restriction of
viscoelastic properties of the blends are related crystal formation of nylon 66 by the PEI component
strongly to the content of crystallites. In PEI/nylon with high viscosity, and the low sensitivity of RDS for
66 blends, the degree of crystallinity of nylon 66 is detecting the crystalline melting process for blends of
believed to affect strongly the dynamic mechanical low degrees of crystallinity. DSC is more frequently
properties in the temperature region from the glass used to investigate the thermal transition properties
temperature of PEI to the nylon melting temperature. for the polymer materials.
From the results mentioned above, it has been im- The DSC thermograms of the blends are shown in
plicitly concluded that nylon 66 should improve the Fig. 7 and the transition parameters are summarized
rigidity of PEI at temperatures > 230°C. inTable 3. Double melting endotherms of nylon 66
The degree of crystallinity of nylon 66 is strongly (Tml,Tm2)due to the transformation of crystalline
dependent on the mobility of the polymer chains de- structures were observed. The degree of crystallinity
termined mainly by the temperature. The crystalliza- for nylon 66 was calculated with the heat of fusion
tion temperatures (T,) of nylon 66 were observed near 188.1 J / g for 100% crystalline nylon 66. The crys-
the T,s of PEI where the mobility of the polymer tallinity was decreased with a n increase in PEI con-
chains changes abruptly, as shown in Table 3. In tent from 0.37 for pure nylon 66 to 0.28 for the PEISO

--
.-
.

I

1
1 I 1 I I
61
50 100
150 200 250
Tempera ture,"C
Q. 6. Shear storage modulus (GI) curuesJor PEI, nylon 66, a n d the PEI/ nylon 66 blends.

POLYMER ENGlNEERlNG AND SCIENCE, OCTOBER 1995, Vol. 35, No. 20 1649
Kil-Yeong Choi, Sung-Goo Lee, J a e Heung Lee, a n d Jingjiang Liu

Secondary Relaxations and
Intermolecular Interactions
Four secondary relaxations, denoted as p , y . p '
and y ' , were measured on the dynamic mechanical
spectra for the blends. The mechanical loss peaks for
PEI, nylon 66, and PEI/nylon 66 blends are shown in
Fig. 8, and the relaxation temperatures defined by
the loss peaks are summarized in Table 4.
The y ' relaxations for the PEI phase were shifted to
higher temperatures and the height of the loss peak
was reduced as the content of nylon 66 was in-
creased in the blends. The increase in T,. and a
decrease in tan 6 might result from the interaction
between the polar groups of amide and ether, and
hence the hindrance of the rotation along the PEI
main chain.
The intermolecular interactions for the blends in
which nylon 66 forms the continuous phase may be
further verified by the results shown in Table 4 . The
%is shifted to higher temperatures with increasing
PEI content in the blends. It is possible that some
-PEI100 portion of PEI migrates from the dispersed phase into
the matrix nylon 66 and mixed with nylon 66, thereby
I I I hindering the motion of amide groups. However, even
150 200 250 300 3 I if all the PEI in the nylon 66-rich phase does so, the
Ternperature,"C total amount is relatively small (for example, 9 wt% of
Fig. 7. DSC heating thermograms for PEl, nylon 66, a n d the PEI in the nylon 66-rich phase for PEI50, as shown in
PEI/ nylon 66 blends. Table Z ) , and thus the changes in PEI composition
due to the migration would not seem enough to ex-
plain the Tp increases observed. Further evidence for
blend, probably because of the dilution effect of PEL the interaction between nylon 66 and PEI might be
These results are intuitively confirmed by the mor- the observed T, relaxations that appeared as a shoul-
phology in PEISO, in which a dispersed phase of der overlapped on the a ' dispersion, as shown in
nylon 66 is visible. A detailed study on the thermody- Fig. 8 and Table 4. T, is located about 213°C regard-
namics and the reorganization on heating in the less of PEI content in the blends. It is inferred from
blends will be published elsewhere. the relaxation of polymer chains at the interface re-

---:PEI 100 _ - - - PEI 10
__ PEI 90 ----.PEI 0

I I 1 I I I L

-1 50 -60 30 120 210 300
Temperature P C
Fig. 8. Shear Zoss modulus ( G I curves for PEL nylon 66, and the PEI/ nylon 66 blends. T,is indicated a t right.

1650 POLYMER ENGlNEERlNG AND SCIENCE, OCTOBER 1995, Vol. 35, No. 20
Morphology and Properties of Nylon 6 6 / P E I Blends
Table 4. Secondary RelaxationTemperatures of the Blends 8. G. Grevecoeur and G. Groeninckx, Macromolecules, 24.
and Homopolymersof PEI and Nylon 66. 1190 (1991).
Code rp,"c T,, "c ri,"c r,;,"c T;, "c 9. K. Liang. J. Grebowirz, E. Valles. F. E. Karasz. and W. J.
MacKnight. J . Polym Sci.. Polym Phys., 30.465 (1992).
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PEI 5 -56 -130 Top. Polym Sci., 6.493 (1989).
PEI 10 -54 -130 213 11. M. Dole and B. Wunderlich, Makrornol Chem, 34, 29
PEI 15 -53 -133 213 (1959).
PEI 25 -52 -132 213 12. J . E. Goodrich a n d R. S. Porter, Polym Eng. Sci.. 7 . 45
PEI 50 -51 -134 213 (1967).
PEI 85 76 - 75
PEI 90 79 - 78
13. G. C. N. Lee and J. R. Purdan, Polym Eng. Sci., 9,360
( 1969).
PEI 100 81 -101
14. L. A. Utracki, Polym Eng. Sci., 28,1401 (1988).
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Polym Sci.. 26. 177 (1981).
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16. Z. Hashin and S. Shtrikman, J . Me& Phys. Solids., 11,
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tems will be sought by using Fourier-transform 17. I. Manas-Zloczower and Z . Tadmor. Mixing a n d Corn
infrared (FTIR) and ultraviolet (W)spectroscopies in pounding of Polymers, Hanser Publishers, New York
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ACKNOWLEDGMENT 19. I,. A. Utracki. in Current Topics in Polymer Sciences. Vol.
11, K. M. Ottenbrite. L. A. Utracki, and S. Inoue, eds..
We would like to thank the Ministry of Sciences Hanser h b l i s h e r s . Munich (1987).
and Technology of Korea for supporting this research 20. E3. D. Favis and J. M. Willis. J . Polym Sci., Polym Phys.,
under Grant No. of KRICT JG-2043. 28.2259 (1990).
21. G. C. Alfonso, V. Chiappa. J. Liu. and E. R. Sadiku, Eur.
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