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Polymer Testing 23 (2004) 763–773

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Test Equipment

A miniature extrusion line for small scale processing studies


J.A. Covas , P. Costa
Department of Polymer Engineering, Institute for Polymer Composites, University of Minho, 4800-058 Guimaraes, Portugal
Received 8 March 2004; accepted 12 April 2004

Abstract

A miniature extrusion line using a micro-extruder was developed and used to produce extrudates with a simple
cross-section from a few grams of raw polymer material. Given the difficulty in applying standard design scale-up
rules, the definition of the geometry of the screws was based on the predictions provided by plasticating extrusion
software developed previously by the authors. The aim was to induce thermo-mechanical environments comparable
to those found in bigger machines. Several materials were processed with the device, model predictions were assessed
experimentally and the quality of the dispersive mixing achieved was estimated for two more complex polymer sys-
tems.
# 2004 Elsevier Ltd. All rights reserved.

Keywords: Extrusion; Micro extrusion; Compunding; Mixing; Scale-up

1. Introduction of the most popular solutions uses a small conical, par-


tially intermeshing, twin screw extruder fitted with a
The scientific and technical advances in reactive bypass system that allows for melt recirculation via a
compounding and in the manufacture of a new gener- backflow channel. The same recirculation principle was
ation of materials (e.g., nanoclays, carbon nonotubes) used by Gough et al. [10] to manufacture the ‘‘Bradford
provided the framework for the production of innova- Mini-Recirculation Flow Cell’’, where flow birefrin-
tive polymer systems with improved performance, such gence and particle velocity measurements can be carried
as (immiscible) polymer blends, modified polymers, out through two opposite glass windows, working as
thermovulcanizates and nanocomposites, [1–5]. Very lateral walls of the rectangular recirculation channel.
often, during the development stage of some of these or Internal mixers, or torque rheometers (such as the
other new materials, one has to manipulate minute Rheomix or the Brabender Plasticorder), are also used
quantities, either as a result of the synthesis method, or frequently for mixing relatively small amounts of
due to the high cost of some of the ingredients. One material. In these cases, the manufacture of useful sam-
may wish to mix thoroughly a few grams of compo- ples implies the subsequent use of techniques such as
nents in order to produce a new compound, to process compression moulding or film casting using solvents.
a few grams of material and thus obtain samples with The above mentioned devices operate mainly in
the required geometry for further characterization, or batch mode, i.e., at prescribed time intervals they yield
to estimate the new material’s processability (e.g., ther- samples without a specific regular shape capable of
mal stability, viscosity level, elasticity, melt resistance). being directly used for, e.g., mechanical characteriza-
Several devices aiming predominantly at mixing
tion. Also, the recirculation flow through a channel of
small amount of material (1–10 g) have been developed,
uniform cross-section may allow for filler/fiber re-
some of them being available commercially [6–9]. One
agglomeration or coalescence of the dispersed phase in
the case of composites and polymer blends, respectively

Corresponding author. Tel.: +351-253-510-320; fax: +351- [9]. In fact, most of the existing mixers were designed
253-510-339. with the objective of providing successive melt reorien-
E-mail address: jcovas@dep.uminho.pt (J.A. Covas). tation (i.e., distributive mixing), but do not induce

0142-9418/$ - see front matter # 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2004.04.005
764 J.A. Covas, P. Costa / Polymer Testing 23 (2004) 763–773
v
significant extensional flow, which is known to be more platform. The extruder can operate up to 300 C and
efficient for dispersive mixing purposes [11,12]. A num- the screw speed can be varied continuously in the range
ber of laboratory extrusion lines are also available and 0–100 rpm. A few flights of the screw’s feed zone pro-
capable of manufacturing some of the most important trude from the barrel and are directly exposed to the
types of extrudate, such as tubing, blown and cast film, material deposited in the hopper, thus facilitating
monofilament and electrical wire. However, they material drag downstream (a similar configuration has
require the availability of several hundred grams to a been adopted by an extruder manufacturer [13]). The
few kilograms of raw material. melt is extruded horizontally through a die that is
This paper presents a miniature extrusion line screwed to the barrel. The angular speed of the winding
developed with three main purposes, namely: (i) possi- spool can be varied, in order to adjust to the linear
bility of mixing/processing a few grams of material; (ii) speed of the extrudate, set its cross-section, or induce a
capability of producing continuously an extrudate, certain degree of axial molecular orientation. This ver-
such as a rod or a strip (useful, for example, for mech- tical set-up is convenient for attachment purposes. For
anical characterization purposes), (iii) creation of a example, the device could be coupled to a rotational
thermo-mechanical environment inside the extruder rheometer.
which is as similar as possible to that developed in Due to the small dimensions of the apparatus, the
practical extruders. The layout of the device is pre- raw materials should be in powder (or liquid/melt)
sented and the underlying design method is discussed. form. In order to ensure trouble-free gravity solids flow
The functional response and the mixing capabilities of and smooth drag during the initial screw truns, not
the miniature extruder were studied for a number of only the hopper can be directly cooled by a circulating
materials. fluid, but also the top portion of the barrel can be inde-
pendently cooled/heated. This is important, as local
temperatures influence differently the polymer’s friction
2. Development of the device
coefficient [14,15]. The geometry of the screw, to be dis-
2.1. General layout cussed in greater detail in the next section, comprises
the usual feed, compression, metering (with the event-
The miniature extrusion line presented in Figs. 1 ual presence of mixing devices) stages, plus discharge
and 2 has the main principles and functionalities of and sealing sections.
equivalent industrial lines, although at a much smaller Both the die and the screw can be easily replaced, in
scale, i.e., the line is capable of producing continuously order to change the cross-section of the extrudate, or to
a constant cross-section (typically a rod or a strip) fine-tune the extruder to the processing characteristics
through the usual stages of plastication in the extruder, of the material being processed, respectively. For visua-
pressure melt flow in the die and post-extrusion cool- lization/monitorization purposes (e.g., collecting sam-
ing/drawing. Due to the small dimensions of the equip- ples along the extruder axis, identifying the location
ment steady state is reached rapidly, hence it becomes where the material becomes fully molten, detecting
possible to produce samples with a few (less than 10) eventual processing difficulties such as material block-
grams of material. The line comprises a vertical single age in the screw channel), the screw can be quickly
screw extruder (with an external diameter of 6 mm and ejected from the barrel (and while the screw is rotating)
a length to diameter ratio, L/D of 11.5), a die, a cool- by pressing a lever. Thus, unlike most extruders (where
ing bath and a winding system, all fixed to a common screw extraction requires interrupting its operation,

Fig. 1. Layout of the micro-extrusion layout.


J.A. Covas, P. Costa / Polymer Testing 23 (2004) 763–773 765

[16,17]. Probably, the most widely used in industry


scale-up method [16,19] was developed by Maddock
[20], which stipulates that constant shear rate is main-
tained by increasing the channel depth by the square
root of the diameter ratio, decreasing the screw speed
by the square root of the diameter ratio and increasing
the channel depth by the square root of the diameter
ratio:
Q2 ¼ ðD2 =D1 Þ2 Q1 ð1Þ
0:5
N2 ¼ ðD1 =D2 Þ N1 ð2Þ
0:5
H2 ¼ ðD2 =D1 Þ H1 ð3Þ
where Q, D, N and H represent output, diameter, screw
speed and channel depth, respectively, and the indices 1
and 2 refer to the extruder being scaled to and from,
respectively. The helix angle and the total L/D are kept
constant.
Since shear rate (together with residence time) is a
very important parameter in mixing, this being a major
goal of the new miniature extruder, these rules were
adopted here. However, even when scaling down from
a conventional to a miniature laboratorial scale, the
proposed dimensions make no sense. For example,
assuming D1 ¼ 45 mm, Q1 ¼ 40 kg=h, N1 ¼ 50 rpm
and H1 ¼ 10 mm, for D2 ¼ 5 mm one obtains
Q2 ¼ 0:49 kg=h, N2 ¼ 150 rpm and H2 ¼ 3:3 mm. Not
only is still Q2 far too high, but D2 is physically inco-
Fig. 2. The micro-extruder. herent with the value proposed for H2. Although these
results could eventually improve with the adoption of
another scaling-up rule, the design of miniature screws
removing the die and using some kind of contraption using such an approach would most probably generate
to slide the screw or the barrel) one avoids the rela- solutions with reduced performance, as the validity of
tively long dwell times at high temperatures, when some of the assumptions concerning flow and heat
changes in the location of the screw where the material transfer is jeopardized. For example:
appears to melt and/or alterations in the material’s
characteristics (e.g., filler or fibre re-agglomeration
– Since heat conduction is more efficient for small
when producing composites, or coalescence of the dis-
thicknesses (the time for heat penetration is
perse phase in the case of polymer blends) are possible.
approximately proportional to the square of the
distance [21]), the relative importance of conduc-
2.2. Screw Design tive and dissipative heat during melting will be dif-
ferent for the miniature extruder. For example,
Scale-up rules of single screw extruders have been Rauwendaal [16] computes the Brinkman number
established with a view to extrapolate from laboratory before selecting the correct specific scaling-up rule
to industrial production size machines and vice versa. for melting.
Overviews of the development of scale-up rules and – According to Carley and McKelvey [22] and
respective strategies are available [16–18]. Usually, they Rauwendaal [16], the output and power consump-
are set up after imposing constant global conditions tion in melt conveying increase by the cubic power
(e.g., shear rate), or analysing separately each main of the diameter ratio, if the channel depth and
process parameter (e.g., solids conveying rate, melting width are increased in proportion to the diameter
rate, pumping rate, residence time, total shear strain, ratio and the screw speed remains constant. How-
power consumption and ratio of barrel surface area to ever, as the barrel diameter decreases, the barrel
throughput). Each of these methods has drawbacks surface area to volume ratio increases, so that more
and may result in poor performance with respect to the external heat can be transmitted and less contri-
remaining variables not considered in the analysis bution from viscous dissipation is expected, with
766 J.A. Covas, P. Costa / Polymer Testing 23 (2004) 763–773

the resulting higher heat transfer efficiency than general (it was proposed by Lindt et al. [24,25]), but
anticipated [16]. the combined influence of conductive and dissipative
heat is considered. Nevertheless, some limits to the
Also, for smaller extruders maintaining constant L/D usual predictive capacity of the programme are expec-
and H/W ratios will result in progressively weaker ted, because:
screws, which become too long for the resisting cross-
section (and more difficult to machine). Therefore, the – the small channel cross-section and the relatively
practical design of small screws may impose the use of large solids power may not favour uniform drag
lower L/D ratios together with lower helix angles, to solids conveying in a fully filled channel, as
preserve sufficient residence times. assumed by the modified Darnell and Moll theory
Given the above difficulties and the current avail- implemented in the plasticating model [26,27];
ability of sophisticated mathematical models of the glo- – given the highly efficient heat transfer, it is ques-
bal plasticating process, which can predict with tionable whether truly Tadmor-type melting mech-
reasonable accuracy the influence of geometry, operat- anism will develop [28];
ing conditions and polymer properties on the general – flow complexity increases with increasing channel
response of the system (e.g., output, degree of mixing, depth/width ratios, H/W, which puts at risk the
power consumption, melt temperature, melting effi- validity of the local 2D flow assumption.
ciency), these will be used to assist the design of the
miniature screws. The routine used considers the plasti- The response of each tentative screw was examined
cating process from hopper to die, i.e., it includes the in terms of the main process performance parameters
sequential contribution of gravity solids flow in the identified above. The aim was to design screws: (i)
hopper, drag solids conveying, melting, melt conveying ensuring a sufficiently long solids conveying stage,
in the screw and die flow. It has been validated via the guaranteeing stable continuous drag, (ii) promoting
direct comparison between experimental data and the quick and efficient melting, so that a long pumping
corresponding theoretical predictions [23]. Application zone can be used for mixing and (iii) minimizing vis-
to the present situation should be straightforward, cous dissipation. Fig. 3 and Table 1 show some of the
since not only is the melting model implemented quite predictions (melt pressure, melt temperature, average

Fig. 3. Melting, temperature (set and melt values), pressure and shear rate axial profiles for the screw geometry shown (micro-
extruder).
J.A. Covas, P. Costa / Polymer Testing 23 (2004) 763–773 767

Table 1 – distributive mixing (computed in terms of the


Predicted response of the micro-extruder Weighted Average Total Strain, WATS [29])
N WATS Q (g/h) Tmelt Pmax Mechanical increases with increasing screw speed, due to the
v
( C) (MPa) Power (W) associated increase in shear rate and stability of
the melt conveying length;
20 163.6 7.6 280.0 7.5 12.9
– mass output increases roughly linearly with screw
40 165.2 15.6 280.1 13.1 44.8
60 171.3 23.1 280.2 15.3 64.3 speed. Moreover, at this screw rotating frequency
range, it seems conceivable to produce samples
with a few grams of material.
shear rate and melting—in terms of the solids to chan-
nel width ratio, X/W, are represented graphically) for
one specific screw geometry and also illustrate the effect
Fig. 4 and Table 2 show the equivalent predictions
of screw speed (20, 40 and 60 rpm) on the behaviour.
for a Leistritz LSM 36 laboratorial single screw
Extrusion of a polycarbonate Lexan 141 from GE at
v extruder (screw diameter 36 mm, L=D ¼ 24) fitted with
280 C (Tb) through a 1 mm die was assumed. The fol-
a general purpose screw, processing the same polymer
lowing features are evident:
under identical operating conditions. As expected,
– melting is essentially instantaneous, (largely) screw melting will be less efficient and screw speed will now
speed independent and triggered by the barrel tem- play a role. Nevertheless, the global predicted thermo-
perature, which confirms the efficiency of heat mechanical environment is comparable to that of the
transfer; miniature extruder in terms of the average shear rate,
– viscous dissipation is minimal (the melt tempera- melt temperature and relative shape of the axial press-
ture is similar to the barrel temperature, and an ure profile. Despite the large differences in L/D
v
increase of only 0.2 C in melt temperature is esti- between the two screws, distributive mixing in the lar-
mated when the screw speed increases from 20 to ger machine is estimated to be 25% on average more
60 rpm); efficient than in the small extruder, but this difference

Fig. 4. Melting, temperature (set and melt values), pressure and shear rate axial profiles for the screw geometry shown (Leistritz
LSM36).
768 J.A. Covas, P. Costa / Polymer Testing 23 (2004) 763–773

Table 2 ance with the inner barrel wall. Upon flow through this
Predicted response of the Leistritz LSM 36 extruder clearance, material will be exposed to the high stresses
N WATS Q (Kg/hr) Tmelt Pmax Mechanical required, for example, to rupture surviving agglomer-
v
( C) (MPa) Power (W) ates of small solid particles. However, since the blister
ring does not produce any positive drag flow, local
20 220.2 5.3 278.6 14.0 558.7
pressure drops are high and the output is reduced (and,
40 196.8 8.7 280.7 17.8 1176.6
more importantly, may become unstable, since the blis-
60 201.8 14.8 283.3 24.9 2663.1
ter ring does not wipe completely the barrel [30,31]).
Alternatively, a fluted mixing section can be used.
will decrease at higher screw speeds, due to the shorter Typically one or various barrier flights are placed along
pumping zones in the case of the bigger machine. the screw, so that the material is forced to pass in the
resulting clearance, where the required high shear stres-
ses and also some degree of elongational stresses are
2.3. Improving mixing
generated [31]. The first device of this type (known as a
As seen in the previous section, the conventional Maddock mixing section) had parallel inlet and outlet
v
general purpose three-zone screw depicted in Fig. 3 will channels, with a barrier helix angle of 90 [32].
induce moderate distributive mixing as, under normal Although uniform dispersive mixing was induced, high
operating conditions, recirculatory flow will develop pressure consumption occurred due to the lack of posi-
along the relatively extensive pumping zone. However, tive drag flow. The latter can be promoted if the bar-
since good dispersive mixing is mandatory for a num- riers run helically. Also, the efficiency of the dispersive
ber of systems, the insertion of a barrier mixing section mixing action can be enhanced by exposing the
seems appropriate. The simplest solution from a material to multiple passes through the barrier [31].
machining point of view is the use of a blister ring The barrier section represented in Fig. 5 bottom fol-
(Fig. 5, top), which consists of a cylindrical shoulder in lows the principles of the ‘‘shear refined (SR) module’’
the screw, perpendicular to its axis, with a small clear- proposed by Hong et al. [33] to study the flow of vari-

Fig. 5. Screws with blister ring (top) and multi-pass barrier (bottom).
J.A. Covas, P. Costa / Polymer Testing 23 (2004) 763–773 769

ous polymer melts having different viscoelastic proper- All materials were milled in a Retsch mill at 14000 rpm
ties through barrier clearances. While the SR module immediately after immersion in liquid nitrogen in
contains multiple barrier flights located between one order to produce powders with an average size of
inlet and one outlet, slot, all features being parallel to approximately 0.5 mm. This is of course an impor-
the screw axis, all channels of the barrier section tant practical requirement of the micro-extruder.
developed in this work run helically. The barrier sec-
tion is 1D long and contains three barriers, each being
v
6 mm wide, making an helix angle of 60 and producing 4. Results and Discussion
a clearance of 0.1 mm.
4.1. General functional response
These geometric features obey the following design
rules proposed by Rauwendaal [31]: Fig. 6 presents the practical response of the micro-
pDNsinh extruder to changes in screw velocity, die resistance and
Wclearance > tmin ð4Þ screw design, when processing polystyrene. The top
120
  graph (conventional three-zone screw) shows an essen-
pDN k 1=n tially linear relationship between output and screw
dclearance < ð5Þ
60 smin speed, with the usual sensitivity to changes in barrel
where w, d, h are the length, thickness and helix angle
of the clearance, respectively, D is the device’s diam-
eter, N is the rotation speed, k and n are the constants
of the power law equation and tmin and smin are the
minimum exposure time and stress level required for
dispersion, respectively. The values of 0.2 s and 60 kPa,
suggested in the literature for carbon black dispersion
[31], were used in the calculations.

3. Materials

The flexibility of the micro-extruder was tested by


using a wide range of thermoplastics. This included
high density polyethylene, HDPE (Alcudia TR-135,
from Repsol), polycarbonate, PC (Lexan 141R, from
GE Plastics), polystyrene, PS (Edistir N2560, from Eni-
chem), a 50/50% w/w blend of starch with ethylene
vinyl alcohol, SEVA-C (Mater-BI 1128 RR, from
Novamont) and a 30/70% w/w blend of starch with
polycaprolactone, SPCL (Mater-BI ZI01U, from
Novamont). Table 3 shows the corresponding MFI
values at the processing temperatures tested.
The mixing capacity of the device was estimated
from the observation of extrudates of PS incorporating
10% w/w of a calcium carbonate filler (Carbocal LA
with 2.5 lm average size) and of immiscible blends of
polyamide (PA-6 Beatle 6 from BIP Chemicals) with
10% w/w EPDM (Kelton 740 from DSM).

Table 3
Characteristics of the materials tested

Material Density MFI (49 N) Processing Temp-


(g/cm3)
v
erature ( C)
v v v v
PS 1.04 10.11 (200 C) 200 /220 /240
v
PC 1.19 9.78 250
v
HDPE 0.94 0.69 160
v
SEVA-C 1.27 0.89 150
v Fig. 6. Processing PS in the micro-extruder: general
SPCL 1.22 2.57 110
response.
770 J.A. Covas, P. Costa / Polymer Testing 23 (2004) 763–773

temperature (which are due to the combined conflicting cross the extruder, at high speeds that value can
effect of a decrease in die resistance and in conveying decrease to well below 1 min. Finally, the graph at the
capacity of the screw caused by a decrease in viscosity). bottom compares the performance (in terms of output
When the screw rotates at 40 rpm, the output is about capacity) of the three-zone screw of Fig. 3 with that of
17 g per hour. Outputs as small as 3 g per hour are Fig. 5 bottom, i.e., with a built-in barrier mixing sec-
possible at the lowest speed range. The second from tion. Despite the helix arrangement, the presence of
top graph illustrates the dependence of output on the four barriers consumes a significant portion of the
die resistance at constant temperature. Switching from pressure generated, with the consequent decrease in
a 2 mm to a 1 mm diameter capillary die will cause a output. Nevertheless, the melt temperature at the die
reduction in output of circa 10%. Dies with radius (R) exit remained unaffected. Given the purpose of the
bigger than 1 mm and L=R < 4 will create too little micro-extruder and the anticipated increase in mixing
resistance and promote output fluctuations. A decrease performance, this is in fact an advantage (for example,
in screw speed will obviously cause a decrease in output at 40 rpm, the output is now 12 g/h).
and an increase in residence time, as seen in the third A comparison between computer predictions and
from top graph of Fig. 6. Here, the y-axis represents experimental data using the three-zone screw is made in
the initial residence time which, given the usual pulse- Fig. 7. Real outputs are always higher than the pre-
shape of residence time distribution curves, can provide dicted values, but differences are usually within 15%.
an (easy to measure) indication of the average resi- These are encouraging results, given the anticipated
dence time behaviour. Thus, while at the low screw limitations of the modeling routine discussed in the
speed range the material can take more than 6 min to previous section. Experiments also confirmed that melt-

Fig. 7. Processing PS in the micro-extruder: predicted vs. measured outputs and melting profiles.
J.A. Covas, P. Costa / Polymer Testing 23 (2004) 763–773 771

Fig. 8. Processing various polymers in the micro-extruder: screw speed vs. output correlations.

ing is almost instantaneous, i.e., it is mainly due to the valid for the polymer blends, the lack of coherence
very efficient heat transfer between the hot barrel and between the two families of values being probably
the thin solid bed and, consequently, is little affected by related to the distinct non-Newtonian behaviour of the
screw speed and barrel temperature (it is delayed by blends.
increasing screw speeds and lower barrel temperatures).
4.2. Mixing
This also facilitates good correlation between experi-
mental and predicted data. The dispersive action of the micro-extruder was
Finally, Fig. 8 demonstrates that the micro-extruder ascertained through the comparison of the morpholo-
can be used successfully to process a variety of materi- gies of cross-sections of extrudates produced with the
als. In all cases, output varies almost linearly with conventional and with the mixing screw under identical
screw speed. There is also good correlation between the operating conditions.
MFI values of the homopolymers (see Table 3) and the Fig. 9 shows the results obtained for PS filled with
relative output (the volumetric output is represented, to 10% w/w calcium carbonate extruded at 40 rpm and
v
account for the differences in density). The same is 220 C through a 2 mm die. The gain in homogeneity

Fig. 9. Cross-sections of PS/CaCO3 processed with the conventional (a) and mixing (b) screws (optical microscopy).
772 J.A. Covas, P. Costa / Polymer Testing 23 (2004) 763–773

in Fig. 10(b) is very similar to that present in the


second mixing zone of the same twin screw extruder,
i.e., the dispersive action of the micro-extruder seems
equivalent to that induced by a kneading block with
v
discs staggered at 90 [34].
Finally, it is worth nothing that the morphologies
illustrated in Figs. 8 and 9 show well distributed struc-
tures in the corresponding polymer matrix, i.e., the dis-
tributive mixing capacity of the micro-extruder is
satisfactory.

5. Conclusion

The micro-extrusion line presented in this paper is


capable of processing a wide variety of thermoplastics
and of producing a simple extrudate with only a few
grams of material in powder form. The thermo-mech-
anical stresses developed during processing are antici-
pated to be of the same order of magnitude of those
developed in bigger machines. Designing the small
screw used by the micro-extruder was hindered by the
difficulty in using scale-up factors, as some of the
assumptions concerning flow and heat transfer are jeo-
pardized at these small dimensions. Instead, the use of
plasticating models yielded good results.
Since a conventional three-zone screw was only able
to guarantee good distributive mixing, a multi-pass
barrier section was designed and inserted in the screw.
Experiments showed that the dispersive mixing
capacity of the new screw became similar to that of a
co-rotating twin screw extruder with a relatively short
kneading block, which is considered as quite satisfac-
tory for a small extruder.

Acknowledgements
Fig. 10. Cross-sections of PA6/EPDM processed with the The authors would like to thank to Dr. Gaspar-Cunha
conventional (a) and mixing (b) screws (scanning electron
for the motivating discussions on single screw
microscopy).
extrusion modeling. The present work was done
under the framework of the Portuguese–Hungarian
provided by the barrier section seems significant. The Bilateral Intergovernmental S&T Cooperation Pro-
presence of some relatively large agglomerates could be gramme (TeT-GRICES). Thanks are also due to the
due to re-agglomeration during the last screw turns, Foundation for Science and Technology, for financing
although it must be noticed that the gap of the barrier the research reported herein through the IPC–Institute
is 50 lm thick, i.e., bigger than these structures. Fig. 10 for Polymers and Composites at Minho University.
reports similar data for an immiscible polyamide/rub-
ber blend. Again, the improvement in mixing provided
by the barrier section is important, the surviving rubber References
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