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.
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
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 ~
--
.-
.
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
I I 1 I I I L
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).
PEI 0 -62 -136 10.S. Choe, F. E. Karasz, and W. J. MacKnight, Contemp.
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).
15. D. L. Siegfried, D. A. Thomas, a n d L. H. Sperling. J . Appl
Polym Sci.. 26. 177 (1981).
gion (27). However, conclusive evidence for the inter-
16. Z. Hashin and S. Shtrikman, J . Me& Phys. Solids., 11,
molecular interactions in the PEI-nylon 66 blend sys- 127 (1963).
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
a future communication. ( 1994).
18. C. C. Lin, Polym J.,11, 185(1979).
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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