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Online Light Scattering Measurements: A Method To Assess Morphology Development of Polymer Blends in a Twin-Screw Extruder


Laboratoire des Prockdks et Mat&iauxPoZyn-kres Ecok de Chimie PoZydres et Matkriaux 25 rue BecquereZ, F-67087Strasbourg Cedex 2, France
Light scattering has proved itself an efficient technique to determine particle diameters in heterogeneous dilute dispersions in the micrometer range. Extrusion of polymer blends is expected to give rise to very small particles, typically in the range from hundreds of nanometers to tens of micrometers. A light scattering device developed in OUT laboratory has been used to study the morphology of polymer blends obtained in a twin-screw extruder. The main advantage of this technique is the immediate response obtained without any surface or interface modification that can occur during the sample preparation by using more conventional techniques like electron microscopy. To show the possible applications of this light scattering device, preliminary tests have been carried out. First, we present a comparison between experimental measurements and theoretical results for dilute systems. Second, we have investigated the effect of shear flow on the droplet deformation. Finally, we have studied the variations of the light scattering pattern for a reactive blend.


nterest in twin-screw extrusion of polymer blends has been growing in recent years because of the relative ease of producing materials having new properties. As a consequence, many studies concerning the morphology of immiscible polymer blends have been carried out since the 1970s (1-5). Study of morphology evolution along the twin-screw (6, 7) is generally investigated by scanning electron microscopy (SEM) or transmission electronic microscopy (TEM). These methods give a direct picture of the morphology, but they are time-consuming as they require the polymer blend to be quenched rapidly. After that, each sample has to be prepared (curing, ultramicrotome cutting, ...) before observation by microscopy. But morphology can also be studied in the reciprocal space by using the light scattering principle. This technique has been widely used to characterize the morphology of polymer blends under simple shear flow (8-10). Recent papers (11-13) have demonstrated the use of this technique at the exit of an extruder. This paper deals with this technique and the first results obtained with a n original light scattering device that allows online morphological characterization of polymer blends. The instrument has been especially

designed to be connected to high-pressure zones along the &-screw extruder. Consequently, it can be used to study the influence of material and processing parameters. Furthermore, the instrument allows one to monitor the process and its stability.

When the size of a particle is comparable with the wavelength of the light and when the refractive indices of particle and its surrounding are different (Fig. I ) , the light is scattered. Two theories describe physically the phenomenon, the Mie a n d the Rayleigh Debye theories.
2.1. Mie Theory for Spherical Diffuser

The theory of Mie (14, 15)gives a n exact solution of the Maxwell equations governing the problem of the light scattered by a n isotropic sphere of radius a into an isotropic medium. The light, of wavelength A, is assumed to be monochromatic and plane. There is no restriction concerning the respective refractive indices of sphere, 5,and surrounding medium, ns. The amplitude of the scattered light h(0) for a sphere located between two parallel polarizers is given by the following equation:



G. Schlatter, C . Serra, M . Bouquey, R. MuUer, andJ. Terrisse

Incident electric field E(i) Direction of ki propagation


Fig. 1 . Elastic scattering by a sphere.

particle. Using this additivity rule, we have developed a n inverse method to obtain to the particle size distribution from an experimental light scattering pattern. The normalized intensity profile is then given by the following relations ( 17): where the coefficients eBt and "'Bt are built with Riccati and Bessel functions and depend on both refractive indices of the diffuser and the medium, on the number 27ra , and Pfos,) the first order Legendre functions of



degree i?. 2.2. Rayleigh Debye Theory When the polarizability does not occur, the theory of Rayleigh Debye (16) gives a simpler solution of the Maxwell equations under the two following conditions: and:

j= 1



- 1

< <1


Assumption 2 means that one can neglect the anomalous diffraction due to refraction occurring when the indices are too different. Restriction 3 assumes that no phase difference inside the particle occurs. The Rayleigh Debye theory takes advantage of these assumptions to describe scattering phenomena for nonspherical particles. Consequently, the intensity of the scattered light follows the equation:

r(e) = I , k4cos20


where Ii is the incident intensity, k the norm of the wave vector, V the volume of the particle and R(@,the Rayleigh form factor ( 16).
2.3. Intensity of the Light Scattered by a Distribution of Particles

I@) is the intensity profile for a particle of diameter di, Niis the number of particles of diameter di, Nclass the number of classes corresponding to the different diameters and (9) the normalized total light intensity. For a given set of Nchs droplet diameters (0.2 km u p to 10 km) and for a given experimental normalized (0). the method consists in comintensity profile puting each N i with a least square method and a nonnegativity constraint. The inverse method has been numerically tested. First, intensity profiles were calculated for different kinds of chosen distributions. The inverse method has then been used to re-calculate these distributions and to compare them with the initial ones. The results show a good correlation between the initial and the re-calculated distributions. Furthermore, Eq 4 shows that the intensity of light scattered by a large particle is much higher than that scattered by a smaller particle. As an example, a ratio of 2 for the radius results in a ratio of 64 for the scattered intensity at 0 = 0". However, if one considers the normalized intensity I(f3)/I(00), small particles scatter light at wider angles (see also Fig. 6).


In the case of a highly dilute system, the light scattering intensity of a distribution of N particles corresponds to the sum of the intensities scattered by each

2.4. Multiple Light Scattering

For highly concentrated systems, multiple light scattering occurs. This means that the intensity scattered


Online Light Scattering Measurements by a particle reaches its neighbors. Therefore, such systems scatter the light at wide angles. In this case, the two previous theories are not applicable anymore. Rusu (17)has proposed the following criteria to evaluate when multiple light scattering can be neglected:

- 5 0.2


where cW1 is the volume fraction of spherical particles and h the thickness of the observed system. As a consequence, the use of a n inverse method will give smaller droplet sizes that one really gets.

3 . 1 . The Light Scattering Device The light scattering device has been especially designed and built for this study. It consists of three different parts (Fig. 2). The light source: It is constituted of three He/Ne red laser beams of which the wavelength is 633 nm. Each laser can be individually translated and rotated in and around two directions to facilitate the alignment with the two other parts. The first laser is in the center of the optical bench, whereas the second and the third lasers are respectively at 35" and 70" in order to observe the scattered light at wide angles. In this study, only the centerline laser has been used. The Light scattering ceU: This part is directly connected to the extruder by means of special connectors: therefore, a small flow of molten polymer is separated from the main flow inside the extruder to the light scattering device. The latter consists of a thermoregulated barrel in which a 10-mm-diameter glass sphere is strictly aligned with the axis of the cell. Into the glass sphere a 0.8-mm hole is drilled to let the polymer blend flow through it. This is the heart of the device since the small volume of blend inside the sphere is illuminated by the laser beam and expected to scatter the light. A set of two distributors leads to a switch between the purge and the analysis mode (m. 3). In the former, the dead volume beneath the sphere

is flushed away and fresh blend is therefore ready for analysis. The latter permits the fresh blend to flow through the sphere and lets evacuate it from the device. Furthermore, one can observe the scattered light when the polymer blend flows or not through the hole of the glass sphere (respectively dynamic or static mode). The ratio of flow through the scattering device to the main flow in the extruder is typically around 1/100 to 1/1000. The opticcrL bench: An aspheric condenser lens, an achromatic doublet lens, and a diaphragm are used to get back the scattered pattern on a semi-transparent plate. The pattern is recorded with a CCD camera (Sony XC ST70). The bench can be translated and rotated in and around two directions for alignment purposes. Furthermore, the achromatic doublet lens and the diaphragm can be independently centered. The CCD camera is linked to a computer for data acquisition (Matrox MeteorLI) and the pictures are processed with a commercial software (MatroxInspector).

3 . 2 . Materials
Two kinds of polymer blends have been used: PSIPP blend: polystyrene is a Styron 6783 from Dow and polypropylene a Stamylan P 48M10 from DSM. The PP is the minor phase whereas the PS is the matrix. They were chosen for their high refractive index contrast. As a consequence, even at low concentration we had sufficient turbidity to give adequate light scattering. At room temperature, the respective refractive indices of PS and PP are nPs = 1.6 and npp = 1.49. Successive masterblends have been prepared in order to analyze a low concentrated blend of 99.2% . 8 % PP in weight. First of a l l , a masterblend PS and 0 of 80% PS and 20% PP in weight is extruded at 200C. A second step consisted in the preparation of a masterblend of 96%/4% in weight obtained at 200C from the 80%/20% blend and PS. The blend of 96?40/4% was analyzed at the same time. In a final step, we extruded and analyzed the 99.2%/0.8% blend obtained at 200C from the 96%/4% and PS. The dependence of the viscosity on the shear rate was determined on a

Fig. 2. Schematic overviau o f the @hi scattering device.



G . Schlatter, C. Serra, M. Bouqwy, R. Muller, and J. Terrisse

Laser light attered Flow of the molten polymer

Analysis underflow

Analysis w~thout~ow

Purge mode

Upper distributor \ ation

Glass sphere I

/- distributor


\ Arrival of the molten polymer from the


Flg. 3. Schematic views o f 4) the glass sphere and b] Operating modes o f the light scattering ceU.

single-screw extruder equipped with a capillary die. Figure 4 shows the viscosities and the extrapolated viscosity ratio between the PS and the PP at 200C. One can observe that in the range of shear rates from 102 s-l to lo4 s-l,the viscosity ratio ypp/qPs varies only between 0.7 and 1.1. E M F A 6 and R E M P A 6 blends: PA6 is a n Ultramid I35 from BASF. EBA is a copolymer of ethylene and buthyl acrylate (Lotry1 17BAO7 from Elf Atochem) while REBA is the EBA for which 4.6 molecules of

maleic anhydrid (MAH) have been grafted per chain l f Atochem). MAH of the REBA (Lotader AM3410 from E can react with the terminal m i n e function of the PA6 and give rise to a reactive polymer blend. Both blends were extruded at 250C.
3.3. Co-rotating Twin-Screw Extruder

The co-rotating twin-screw extruder (Werner & Pfleiderer ZSK30) has a length to diameter ratio of 40. Figure 5 shows the screw profile used. The optical cell is







z 'd


.e 100
x >



a m

10 100

1000 Shear rate (s-1)

0.6 10000

Flg. 4. Shear r a t e dependence of the viscosity and the extrapolated viscosity ratio o f PP to PS at 200C.PP: ( 0 1 PS: ( 0 1 TlPP/qPs: ( A ] .


Online Light Scattering Measurements

P2a P2b P3a

P3b P4a



Fig, 5. Screw p r o m of the b i n s c r m extruder. ma, P2b, P3a, P3b, P 4 q P 4 b and P 5 a are the dtzwent possible locations o f the light scattering device.he light scattering cell i s mounted on P4b.

located at the point P4b at the end of the mixing zone. For all experiments, the feed throughput was 3 kg.h-' and screw rotational speed was set to 150 RPM.
3.4. Procedures for Light Scattering Experiments

I m a g e processing: The data acquisition needs a statistical treatment to eliminate the noise resulting from variations in the scattered pattern. Therefore, a stream of 400 pictures (x, y patterns, see Figs. 2 and 3 for the x and y axis definition)was recorded at a frequency of 25 pictures per second. These 400 frames were averaged to get an image from which the variation of intensity as a function of the angle was extracted and compared. A statistical study has shown that one has a Gaussian distribution of the scattered intensity for each pixel of the CCD camera. Run o f an experiment: First, a diffraction grating film (140 grooves/mm) was used to correlate scattering angle with the coordinates of each pixel of the CCD camera. Second, the polymer blend was extruded for at least half an hour to reach a steady state after some process parameters were changed. Then, the dead volume beneath the optical glass sphere is flushed away and the fresh blend was allowed to flow through the hole of the glass sphere for measurements. Then, the 400 patterns were recorded and processed in the dynamic or static mode.
3.5. Microscopy
A scanning electron microscope (JEOLJSM 5900 LV) operated at 20 kV was used to take micrographs

for 2 hours, showed a very stable profile of the scattered light. Theoretical curves were obtained with the Mie model. No mono-disperse distribution was found to fit the experimental profile, whereas a bi-disperse distribution of particle size allows a fair fitting of the experimental curve. The distribution highlights a large number of small particles (90% of the total particle volume, which corresponds to 230 particles of 1.5-pm diameter for only 1 particle of 4.5-pm diameter). The respective intensity profiles for the 1.5-pm and the 4.5-pm diameter are also plotted to demonstrate the importance of each class of diameter. Figure 7 shows a representative SEM micrograph for 99.2%/0.8% PS/PP blend. One observes that PP is dispersed in PS matrix. The micrograph shows that the droplet diameters are in the range from 0.2 pm to 4 p.m, with a mean value around 0.8 pm. This result is in agreement with the size distribution obtained from light scattering if one takes into account the precision of the experimental measurements.
4.2. Study Under Shear Flow

of the blends. The samples were taken at the exit of the light scattering cell and rapidly quenched in water. After that, PS was selectively etched out using THF for PS/PP blends and PA6 was selectively etched out using formic acid for EBA/PA6 and REBA/PA6 blends.
4. RESULTS AND DISCUSSION 4.1. Characterization o f the

Morphology for Diluted Blend

Figure 6 shows experimental and theoretical light scattering profiles in the y direction for the 99.2%/ 0.8% PS/PP blend (see Figs. 2 and 3 for the y axis definition). The experimental y profile was obtained in the static mode. Several measurements, carried out

Figure 8 shows the x,y patterns (averages of 400 recorded frames) respectively in the static ( R g . 8a) and in the dynamic modes (Rg. 8b) for the 96%/4% PS/PP blend. One observes that the scattered light pattern for the dynamic mode is smoother than the one obtained for the static mode. The flow through the glass sphere acts as a filter for the signal by averaging the intensity during time. For the static mode, Fig. 8 a shows an isotropic pattern, while Q. 8b shows a n elliptical pattern corresponding to an ellipsoidal deformation of the droplets inside the glass sphere. Figure 9 shows the x and y intensity profiles obtained for the dynamic mode (flow through the glass sphere) and for the 96%/4% PS/PP blend. It should be noticed that the x profiles are available only u p to an angle of 15". The anisotropy of the light scattering pattern shows that the particles are stretched under the flow during the dynamic mode. In this case, a throughput of 0.3 g.min-' was measured, which leads to a wall shear rate around 140 s-l (radius of the hole 0.4 mm and local power law index for the melt viscosity n = 0.35 (see Fig. 4 ) . If one considers that shear flow leads to a n ellipsoidal shape, Glatter and Hofer (18) have shown that the mean length of ellipsoidal particles can be estimated from the light scattering profile observed in the axial direction x of the flow. We



G. Schlatter, C. S e r a , M. Bouquey, R. Mullet-, and J. Terrisse






10 Angle ( O )



Rg. 6. Horizontal normalized light intensity p r o m I / I ( e = 5 4 1 . Comparison o f experimental results and theoretical calculations based Experiment 8:Theory ( 4= 4.5 prn (10% on the Mie model Blend 99.2%/0.8%, noflow through the g l a s s sphere (static mode). 0: UOL). = 1 . 5 prn (9090 uoLJI: Theory (+ = 1 . 5 prn (100% uoLJ)-A-: Theory ( 4= 4.5 prn (100% ~01.)).

- B e :

Q. 7. SEM o f 99.2%/0.8% PS/PP blend



Online Light Scattering Measurements



Fig. 8. Light scattering patterns. a):Static mode. b):Dynamic mode (Flow through the glass sphere = 0.3 g.miK). PS/PP 96%/4%.





Angle ( O )
Fg. 9. Dynamic mode, anisotropy o f the scattered pattern. PS/PP 96%/4%. Flow through the glass sphere = 0.3 g.rninl (the dvection o f the&w i s xJ.A : y experimental pro@ o f the n o d i z e d intensity : x txperimental pro-: 0 :x theoretical prom (+ = 5.5 pm (22% vol),+ = 2.5 prn (38%voL),$ I = 1 . 5 pm (40% vol)).



G. Schlatter, C. Serra, M. Bouquey, R. Muller, and J. Terrisse

have therefore fitted the experimental x scattering profile by a theoretical curve obtained with the inverse method using the Mie model. Calculations show a wide distribution of particle size, from 1.5 pm to 5.5 pm (see Fig. 9). I t should be noticed that the size of 5.5 pm, which is underestimated because of multiple light scattering, is nevertheless higher than the one obtained for the 99.2%/0.8% blend, which also highlights the particle stretching. The flow through the capillary of the glass sphere has been modeled in order to estimate whether droplet breakup is possible in this flow section. A Carreau law has been chosen to characterize the rheological behavior of 96%/4% PS/PP blend. Velocity and shear rate fields have been calculated for a throughput of 0.3 g.rnin-l, a capillary radius of 0.4 mm and a length of 5 mm. Figure 1 0 shows the local residence time and the critical time tb versus radial position in the capillary. Time tb corresponds to the time that a droplet needs to break up under flow corresponding to the critical capillary number C h t given by Grace (19) and Meijer (20). Figure 1 0 shows that only droplets located between r = 0.27 mm and the Capillary wall (r = 0.4 mm) are able to break up. Figure 1 1 shows minimum and maximum radii of the droplets that are broken for r = 0.27 mm up to 0.4 mm. The minimum radius is calculated from the critical capillary number given by Grace (19) and Meijer (20). The maximum radius is calculated for a droplet that breaks u p after a time equal to the local residence time. Rgure 1 1 shows that breakup does not occur at the center of the capillary

(from r = 0 up to 0.27 mm), while it occurs for particle diameters from 0.5 pm up to 3 pm (see the breakup zone in Fig. 11. This phenomenon should lead to a bidisperse distribution of the diameters near the wall of the capillary.
4.3. Nonreactive and Reactive Blends Figure 12 shows the intensity profiles obtained for reactive blend (REBA/PAG 80%/20%) and its corresponding nonreactive blend (EBAIPAG 80%/20%). Such concentrated blends generate of course multiple light scattering. Nevertheless, one can have a correlation between the scattered light and the morphology; see Cielo (21) and Belanger (22). For EBA/PA6 blend, all measurements, which were carried out for more than 2 hours, have shown a high stability of the light scattering intensity profile. These results are in agreement with a previous work of Serra (23). A s a matter of fact, Serra (23)has shown for a similar blend (EBA/ Platamid 80%/2O%) that there is no effect of processing parameters such as feed throughput and screw rotational speed. Nevertheless, one has observed high random fluctuations of the light scattering profiles in the reactive case. F'igure 12 shows the two curves Min l l profiles and Max corresponding to the envelope of a obtained during 2 hours of measurements without variation of processing parameters. These random fluctuations highlight, surprisingly, a non-constant morphology of the reactive REBA/PAG blend. However, the level of the normalized intensity profile (Fig. 12) was always higher for the reactive blend than for

0 .E+OO


2 .E-04
radial position (m)

3 .E-04

4 .E-04

Fig. 1 0 . Comparisono f the local residence time and the breakup time inside the optical sphere. 8:Critical time tbA : h a t residence time.

Online Light Scattering Measurements

2 .OE-06


.. .. . .. . . . .. . . .. .. . . ..

1 SE-06



5 .OE-07


1 .E-04

2 .E-04 radial position (m)

3 .E-04

4 .E-04

Fig. 11. Minimum and mcuciTnum radius o f the droplets that are broken. t: M a x radius (ginen by the local residence time)8: min radius @wenby C%).

c ) . I

. I I


. I

7 0.4 E L




Angle ( O )
Fig. 12. Comparison o f horizontal y normalized light intensity prom I/l(O = 5") (static mode) o f nonreactive blend [ EBA/PA6 80%/2096) and reactive blend [REBA/PAG80%/20%). ?he M a x [O) and M i n (.) profiles correspond to the envelope o f dp m ? s obtained during the experimentsfor REBAIPAG blend



G. Schlatter, C. Serra, M . Bouquey, R. M u l k r , and J. Terrisse

the nonreactive one, which means that PA6 droplets are smaller for the reactive blend. This result was quite expected since the reaction at the interface of the two polymers decreases the surface tension, leading to smaller droplets. Figure 13 shows the SEM pictures respectively for EBA/PA6 (Fig. 13a)and for REBA/PA6 (Fig. 13b) taken at the same scale, where the dark areas represent the PA6 phase. For each case, one observes that PA6 is dispersed in EBA or REBA matrix. The micrographs confirm, without any doubt, that the size of the droplets is much lower for the reactive blend.

Moreover, the use of the second and third laser will improve the sensitivity to polymer blends having very small particles by analysis at wide angles. Finally, this device could be probably used as a control process apparatus to follow the stability of the process and the quality of the product.

The authors wish to thank Christophe Melart and Patrice Simon for their help in running the experiments and designing the apparatus.

We have developed a new apparatus for the purpose of following the morphology of polymer blends along an extruder by online light scattering measurements. The frst tests have shown the capabilities of this device to assess the development of polymer blend morphology during their extrusion. These preliminary results suggest: For dilute blends, deconvolution of the intensity profile gives access to the droplet size distribution and makes it possible to study the influence of processing parameters such as feed throughput, FWM, screw profile, temperature, ...
The anisotropy of the light scattering pattern induced during the shear flow through the optical cell can be used to analyze the relaxation of the stretched droplets when the shear flow is suddenly stopped.
1. C. D. Han and T. C. Yu, Polym Erg. Sci., 12. 81 (1972). 2. B. D. Favis a n d D. Themen, Polymer, 32,1474 (1991). 3. N . Chapleau a n d B. D. Favis, J. Mat. Sci., 30, 142 ( 1995). 4. D. B o u n y and B. D. Favis, Polymer, 39,1851 (1998). 5. J. K. Lee a n d C. D. Han, Polymer. 40, 6277 (1999). 6. L. Delamare, Ph.D. Thesis, Ecole des Mines d e Paris (1995). 7. J. K. Lee a n d C. D. Han, Polymer, 41, 1799 (2000). 8. S. Kim, J. W. Yu, a n d C. C. H a n , Reu. Sci Inst., 67, 3940 (1996). 9. N. G. Remediakis, R. A Weiss, a n d M. T. Shaw, Rubber Chemistry andTechnology, 70, 71 (1997). 10. S. Kim, E. K. Hobbie, J. W. Yu, a n d C. C. Han, Macromle&s, 30, 8245 (1997). 11. E. K. Hobbie, K. B. Migler, C. C. Han, and E. J. Amis. Ad. inPolym Tech., 17, 307 (1998). 12. S . L i , K. B. Migler, E. K. Hobbie, H. Kramer, C. C. Han, and E. J. Amis, J . Polym Sci.: Part B: Polyym Phys., SS, 2935 (1997). 13. K. B. Migler, E. K. Hobbie, and F. Qiao, Polym Eng. .%A, 39, 2282 (1999). 14. H. C. van de Hulst, Light Scattering by Small Particles, Wiley, New York (1964). f Optics, Pergamon 15. M. Born a n d E. Wolf, Principles o Press, London (1975). f Complex Fluids, Ox16. G. G. Fuller, Optical Rheometry o ford University Press, New York (1995). 17. Rusu, Ph.D. Thesis, Ecole des Mines de Paris (1997). 18. 0. Glatter and M. Hofer, J . Cobid Interfae Sci, 122, 484 (1988).

The important difference in terms of light scattering intensity profile between reactive and nonreactive blends will provide deeper insight into how the morphology is affected by the functionality (number of reactive functions per chain) and the processing parameters.



Fig. 1 3 . d:SEM o f the nonreactiue blend (EBA/PAG 8@%/20%). b): SEM o f the reactiue blend [REBA/PAG 80%/20%].


Online Light Scattering Measurements

19. H. P. Grace. C h e m Eng. C o r n , 14, 225 (1982). 20. H. E. H. Meijer and J. M. H. Janssen, in I. Manas-Zloczower and Z . Tadrnor. eds., Mixing and C o m p o d i n g Theory and Practical Progress, Vol. 4 i n Progress i n Polymer Process Series, Hanser Verlag, Munich (1993). 21. P. Cielo, B. D. Favis, and X . Maldague, PoZym Eng. Sci, 27, 1601 (1987). 22. C. Belanger, P. Cielo. B. D. Favis. and W. I. Patterson, Polym Eng. M,30, 1094 (1990). 23. C. Serra, G. Schlatter, M. Bouquey, R. Muller, and J. Terrisse, t h e 17th Annual Polymer Processing Society Meeting, Montreal (May 2001).