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INTRODUCTION
118
Manufacturer
~
MiniMAX (MM)
Capacity
~~
(0.5 g
Haake Instruments,.
Paramus, N.J
-50 g
vertical, conical
twin-screw extruder
DACA Micro
Compounder (DACA)
DACA Instruments,
Santa Barbara, Calif.
(designed by DSM, Netherlands)
1-5 g
16 mm diameter co-rotating
intermeshing twin-screw extruder
Welding Engineers,
Blue Bell, Pa.
up to 5 kglh
(m.
(m.
have different levels of shear or extensional flow. Anticipating that mixing would be most difficult in the
M i n i m , we operated it at its maximum rotattional
rate, hoping to facilitate breakup of the minor phase.
The maximum shear rate in all other mixers was then
matched to the MiniMAX by assuming Couette flow in
the minimum gap between the mixing element and
the wall. Thus, the rotation rates used in the ViafiOuS
mixers were based on matching this shear rate. We
la Original MiniMAX design [MM). b) The MiniMAX with three steel balls (MM-3b). The ball diameters are 3.8 rnrn each The
arrows indicate the possibbflow lines of thefruid around the batls.
Q.
119
EXPERIMENTAL
Materials. The polymers used with their abbreviations and sources are summarized in Table 2. The
amine terminated PS (PS16-NH2)was synthesized by
Cernohous et al. (17).The anhydride functional PDMS
(PDMS43-(AnI2)was produced by a hydrosilation reaction between commercial telechelic Si-H terminated
PDMS (PDMS43-(SiHI2,United Chemical Technologies) and ally1 succinic anhydride (Polysciences) (18).
Reaction between the amine and the anhydride on the
Q. 3. Cross-sectionalview of the DACA conical miniature twin-screw extruder. Qpical sample sizes are 1-5 g . The screw dilwneter
is I4 mm at the entrance and 5.5 mm at the exit. Note the recirculation channel which allowsfor variable mixing times.
TDN
?mar=--
110s-1
gap
At various times, small samples (-20 mgl were taken
from near the cup edge with tweezers and quenched
in liquid nitrogen to freeze the morphology. Mixing
121
mixing. Five grams of polymer was fed into the extruder. Mixing times of 5 and 15 minutes and a screw
rotation rate of 50 rpm were used.
The Haake internal batch mixer (Fg.4) was set to a
rotor speed of 80 rpm with 50 g of polymer. At various
times, the mixer was stopped, the front face plate was
removed, and samples were quickly removed and
quenched in liquid nitrogen. The face plate was then
reattached and mixing commenced. This entire process
took about 15-20 seconds.
The PRISM 16 mm twin-screw extruder (16 mm
TSE) had a clam shell barrel design with a length to
diameter ratio of 25: 1 (Fig. 5). One of our goals was to
test the mixing capability of this small extruder relative to a larger 51 mm diameter extruder (1, 2). The
flow rate was 0.3 kg/h at the screw rotation rate of 27
rpm. This may seem low for an extruder, but the
tighter clearances in such a small extruder can produce relatively high shear rates. The maximum and
minimum gaps in the 16 mm TSE are 0.2 mm and 3.3
mm, respectively. The screw configuration matched
that in a larger 51 mm diameter twin-screw extruder
used elsewhere (1, 2). The extruder was run without a
die since its presence may elongate the dispersed
phase domains (10). Samples were taken at various
locations shown in Fig. 5 after the motor drive was
stopped and the bolts removed. The samples were
then quenched in liquid nitrogen. This process took <
1 minute, which was somewhat longer than the sampling times for the mini-mixers. The results of Sundararaj et aL (2) show that these differences in quenching times will not effect particle size comparisons.
Sample Preparation for Microscopy. As discussed above, all samples were quenched within 20 s
122
of cessation of mixing in liquid nitrogen with the exception of the 16 mm TSE. The PS/PP blend samples
were placed in a vial containing methylene chloride
(CH,Cl,) at a concentration of 10 mg of blend/mL solvent. CH,Cl, selectively dissolved the PS, thus allowing observation of the PP dispersed phase. After 8 h,
the solution was centrifuged for 10 minutes to further
separate the PP from the PS/CH,Cl, solution. A few
drops of the solution were filtered under vacuum
through a polytetrafluoroethylene or poly(propy1ene)
membrane filter (both had pore sizes = 0.10 pm, Millipore). Then, fresh solvent was also filtered to remove
any residual PS particles on the membrane. A section
of the membrane was cut and glued onto a n aluminum stub for observation by scanning electron microscopy (SEM). A similar preparation technique was
used by Luciani and Jarrin (19). The sample was
sputter-coated with 50 A gold-palladium to make the
sample conductive and then viewed with a JEOL 840I1 HRSEM at an accelerating voltage of 10 kV.
For the PS/PDMS blends, quenched samples were
glued onto an aluminum stub and microtomed at
-140C (below the glass transition temperature of
PDMS) using a Reichert Ultramicrotome with a freshly
cut glass knife. The sample was then placed in h e m e
for no more than 5 minutes to selectively remove the
dispersed PDMS phase. The sample was viewed with
S E M after the same coating procedure described
above was applied.
Image Analysis. To better resolve the minor phase
drops from each other and the filter surface (see Fig. 7),
the particles were traced onto a transparency and
scanned at a resolution of 200 dpi. From the scanned
transparency, the areas Ai of R, particles were measured using Ultimage Version 2.6.1 software. The Ai
were converted to an equivalent sphere diameter DP
At least 300 particles were counted from each sample
to ensure reliable statistics. The size of the dispersed
phase was characterized by the number average diameter, (D)n,and the volume to surface average diameter, (D)vs. (D)vsgives the average interfacial area per
unit volume, which can be used in reactive blending
studies to determine how much block copolymer is at
the polymer/polymer interface (18, 20). For the
PS/PDMS blends, Dimay be underestimated as a result of microtoming or freeze fracturing (21). However,
some small particles are also missed during cutting.
These effects tend to nullify each other. Applying
stereological corrections to some of the non-reactive
PS/PDMS blends gave an error of about 10/o in (D),
(21) and less for
Thus the corrections were not
made on the data reported here.
direction
of flow
Details of kneading-.
block element
Q. 5. 7he 16 mm diameter co-rotating twin screw extruder (PRlSM, Welding Engineers). The numbers 1-8 at the top of the e.&ruder
Source
700
poly(propylene) (PP)
340
Cernohous
Cernohous (17)
6.0
nonreactive poly(dimethylsi1oxane)
(PDMS47)
Aldrich
0.82
0.78
poly(styrene) (PS)
anhydride-terminated poly(dimethylsiloxane)
(PDMS43-(An),)
15.3
123
'
'
'
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'
'
'
"""I
' """I
'
' """I
-I
i
rl*
0.1
0.01
0.1
10
100
1000
frequency, (a)(rads)
Fig. 6. Complex viscosity [q*)of polymers versusfrequency [co) at 200C.
Fg. 7. PP morphology after 20 minutes mixing at 200C in the cup and rotor mixers. The PS matrix has been extracted with methylene chloride leaving only PP particles on the$lter membranes. A PP membrane was used in Fg. 7a while polytetrajluoroethylene
membranes were used in Figs. 7b and 7c. Their pore sizes are identical. The samples arefrom a) MinilMAx mixer (MM), b) MiniMAX
with three steel balls (MM-3b)and c) modged MiniMAX (MM-m).
124
Fg. 8. PP morphology at 200C in the DACA mini-extruder: a) after 5 minutes of miwing and b) after 15 minutes mixing. Fg. <3cindicates the PP morphology after I2 minutes mixing in the Haake internal batch mixer. These particle sues are similar to sampZes taken
&om the MM-3b.Fig. 7b. (See Table 3 for comparison of particle sizes.)
(5)
(D, =
%
l
l
(D)" (pm)
MM
MM3b
MM-m
Mixer
20
20
20
5.1
1.1
1.6
10.3
0.6
0.9
45.8
1.8
2.5
DACA
5
15
1.3
1.2
0.6
0.7
1.9
2.0
Haake
12
1.1
0.5
1.7
End-Fed 16 mm TSE
16 mm TSE
-2
-3
1.o
0.7
0.4
1.5
1.2
0.4
125
Efg.9. PP morphology at 200C taken a t various locations [see Fg. 5) along the 16 rnm twin-screw extruder. mefinest dispersion
[(D)us
= 1.2 prn) was achieved in the twin-screw despite the relatively short residence time (-3 minutes).
Figs. 1 1 a-c for the three cup and rotor mixers. More
particles in the sub-micron range were present for the
blends prepared in the MM-3b and MM-m mixers
compared to the MM mixer (Fig. 11). In particular,
(D)uswas much lower after 20 minutes of mixing in
the MM-3b compared to the other mixers, although
(D), was similar for both the MM-3b and MM-m mixers (Table4).
PS16-NH2fPDMS43-(An),
Reactive Blends. The
reactive PS 16-NH2/PDMS43-(An), (80/20)blend morphology developed rapidly into small PDMS drops of
(D), -0.5 pm within five minutes mixing (Fig. 12a-e,
Table 4). The much smaller particles relative to the
non-reactive blends ((D)us-10 pm) observed in samples taken from all three mixers suggest reactively
formed block copolymer strongly reduced the interfacial tension and prevented coalescence of the dispersed phase (24-26). Gel permeation chromatography
(GPC) confirmed the formation of block copolymer
as a result of reaction between the PS16-NH, and
PDMS43-(An), and this data is presented elsewhere
Fg. 10. PP morpholcgy at 200C at various locations [seeFg. 5) of the twin-screw extruder. Here, the extruder was operated in the
batch mode with 5 g fed near the end of the extruder. Note that a reversing element was added after kneading section (d)to increase
back-miring.
(18).(D)uswas lowest in the MM-3b for the nonreactive PS/PDMS blends mixed in the MiniMAX type
mixers. However, for the reactive blends (D)uswas
slightly lower in the MM-m. A disadvantage of the
MM-m mixer is the time required [ 15-20 s) to loosen
the clamps and remove the sample. If the reaction
studied is very fast (20) or frequent sampling is required, the MM-3b is preferable. However, if larger
samples are desired and they are to be removed infrequently, the MM-m provides the best dispersion of
PDMS in PS.
The MM mixer was the worst small dispersive mixer
since the shear rate was zero at the center of the cup
and no cross flow existed to re-orient the fluid. The
final drop size is caused by Rayleigh instabilities governed by a critical disturbance such as a deformation
rate change (2, 27). As the dispersed phase morphology develops from sheets into threads, thread disintegration may be facilitated by such oscillations. In both
the MM-3b and MM-m mixers, the flow was periodic
'
127
M i l a n M a r k and Christopher W. M a c o s k o
ACKNOWLEDGMENTS
The authors wish to thank the Dow Coming Corporation for their financial support, Dr. Jeff Cemohous
for donating the PS16-NH2 and PS22, and Mr. Paul
Nowatzki for performing some of the rheological measurements. We also thank Dr. Olivier Martins of the
Monsanto Chemical Co. for the preparation of the
blends mixed in the DACA conical twin-screw extruder.
REFERENCES
1. U. Sundararaj, C. W. Macosko, R. J. Rolando, and H. T.
Chan, Polyrn Eng. Sci., 32,1814 (1992).
2. U. Sundararaj, C. W. Macosko, A. Nakayama, and T.
Inoue, PoLym. Eng. Sci., 35,100 (1995).
3. T.Sakai, Adu. Polyrn Tech, 14, 277 (1995).
4. M. A. Huneault, M. F. Champagne, and A. Luciani,
Polyrn Eng. Sci.,36,1694 (1996).
5. D.Bouny and B. D. Favis, Polymer, 39,1851 (1998).
6. L. Y. Yang, T. G. Smith, and D. Bigio, Int. PoZyrn Proc.,
12,11 (1997).
7. J. K. Kim. S. C. Lee, and H. K. Park, Int. Polyrn Proc.,
10, 19 (1995).
Table 4. PDMS Particle Sizes for Nonreactive and Reactive PSlPDMS Blends in the Cup and Rotor Mixers.
Mixer
IS
Blend
0 ) " (w)
u(l-4
W"*(wm)
MM
MM-3b
MM-m
PS2ZPDMS47
PS22/PDMS47
PS221PDMS47
20
20
20
6.8
2.7
3.5
4.4
1.8
3.1
11.8
5.2
10.9
MM
PS16-NHz/PDMS43-(An),
5
20
0.3
0.2
0.2
0.1
0.6
0.3
MM-3b
PS16-NH2/PDMS43-(An),
5
20
0.2
0.2
0.08
0.08
0.3
0.3
MM-m
PS16-NH2/PDMS43-(An),
5
20
0.2
0.2
0.06
0.05
0.2
0.2
128
5 min.
20 min,
FSg. 12. Comparisonof reactive P S I 6-NH,/PDMS43-(An)2180/20)blend morphology at 200C afer 5 and 20 minutes of mixin,g in the
original MiniMAX l a b ) , MiniMAX plus three balls (MM-3b) (c. d) and the modified MiniMAX (MM-m) (e.8. Finer dispersions qf PDMS
were achieved earlier in blends prepared in the MM-3b and MM-m compared to the MM mixer (see Table 4).
129
130