Comparison Between Five Experimental Methods To Evaluate Interfacial Tension Between Molten Polymers

NICOLE R DEMARQUETIE*, ADRIANA MARTINELLI CATELL1 DE SOUZA, GUILLERMO PALMER, and PAUL0 HENRIQUE PIERIN MACAUBAS

Materials Engineering Department University o f S f m Paul0 Av.ProJ Melo Moraes 3463 05508-900 S h Paul0, Brazil
In this work, an experimental comparison between five different techniques to measure interfacial tension between molten polymers is presented. The five techniques include two equilibrium methods: the pendant drop (PD) and the sessile drop (SD):two dynamic methods: the breaking thread (BT) and imbedded fiber retraction (IF): and a rheological method based on linear viscoelastic measurements of the blend (RM). The polymer pairs studied were polystyrene/polypropylene (PS/PP): and PP/high density polyethylene (PP/HDPE). It was possible to determine the interfacial tension between PP/PS with all the methods tested and the results corroborated within 20%. However, the interfacial tension between PP and HDPE could be evaluated only using rheological methods because of a too-small difference of index of refraction between both polymers. The experimental precision increased in the following order: R M < SD < E5T < IF < PD. The rheological method had the advantage of being simpler and faster than dynamic and equilibrium methods. However, when using the rheological method, care should be taken because the results obtained may depend upon the concentration of the blend used for the measurements. It was observed that the pendant drop and breaking thread methods cannot be used for polymers with high viscosity (above 5 X lo5Pa.s).

INTRODUCTION

hen working with polymer blends, it is important to obtain at least partial compatibility between the components of the product. Polymer compatibility governs the adhesion and the condition of the interface and, therefore, the morphology and mechanical properties of the blend, i.e. the final characteristics of the blend. Interfacial tension is one of the key parameters that govern the compatibility between the components and the morphology of a polymer blend. It is the single most accessible parameter that describes the thermodynamic state and structure of a n interface. Some of the early interfacial tension measurements for polymeric materials were reported in 1 9 6 9 (1). Since then, different measurements techniques have been developed. More details can be found in Wu (2). Among the various methods to measure interfacial tension, only a few are suitable for molten polymers

because of their high viscosity. Most methods are based on a balance between a driving force (gravitational, centrifugal, brownian motion, shearing force) and an interfacial force that tends to minimize the contact area between the phases. In this work, five experimental methods to measure interfacial tension were used and tested for the evaluation of interfacial tension between molten polymers. The experimental methods tested included two equilibrium methods: Pendant Drop (PD) and Neumann Triangle (NT): two dynamic methods: Breaking Thread (BT)and imbedded fiber (IF): and a Rheological Method (RM) based on linear viscoelastic measurements.
MATERIALS

T o whom correspondence should be sent

The pendant drop, Neumann triangle, breaking thread, imbedded fiber and rheological methods were compared a n d evaluated using commercial polypropylene (PP) and polystyrene (PS) at a temperature of 200C and PP and high-density polyethylene (HDPE) at a temperature of 220C.Table 1 shows the charac teristics of the materials used in this study. Two types
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Comparison Between Five Experimental Methods

of PS and three types of PP were used in this work, PP, and PP, were used to evaluate the interfacial tension between PP and PS and PP, was used to measure interfacial tension between PP and HDPE. It was necessary to use different types of PS and PP to evaluate the interfacial tension between PP and PS to satisfy the different rheological restrictions of the different methods tested. The density of the polymers at a temperature of 200C necessary to infer interfacial tension using the pendant drop method were inferred from equation of state (3, 4). The zero shear stress viscosity necessary to infer interfacial tension using the breaking thread and rheological method were inferred by fitting Carreau's model (5)to plots of the complex viscosity against frequency. These data of complex viscosity were obtained using a controlled stress rheometer (model SR-5000 from Rheometric Scientific). Some of the methods tested to evaluate interfacial tension between molten polymers involve long experiment duration during which the polymer is kept at a temperature above its melting point. Therefore, the thermal stability of the polymers was tested by GPC. The samples were kept in an argon atmosphere at a temperature of 200C for 10 hours (maximum duration of the experiments performed in this work). The molar mass of the samples were measured before and after this thermal treatment. It was observed that, within experimental error, neither the number average molecular weight nor the polydispersity were affected by such a treatment (6).
INTERFACIAL TENSION MEASUREMENTS

Pendant drop method:The pendant drop method involves the determination of the profile of a drop of one denser liquid suspended in a less dense liquid at mechanical equilibrium. The interfacial tension between both liquids can be inferred from the resolution of Bashforth and Adams equation (7) that relates the surface tension to the difference of density between both liquids and the geometrical profile of the drop. More details can be found in the literature (8- 11). In this work, the interfacial tension measurements were made using a pendant drop apparatus that basically consists of three parts (6): an experimental cell

where the pendant drop of the polymer was formed, an optical system to monitor the evolution of the pendant drop and a data acquisition system to infer the interfacial tension from the geometrical profile of the drop. A proportional temperature controller with a precision of kO.5"C was used to maintain the sample at the desired temperature. The experimental cell was maintained in an argon atmosphere in order to avoid degradation. The drop insertion device consisted of a specially designed syringe to avoid problems of necking and capillary effects (9).The drop profile analysis was done using algorithms based on a robust shape comparison between the experimental profile and theoretical profile of the drop (6). More details about the experimental procedures can be found in Demarquette and Kamal (9). Neumann Triangle: The Neumann triangle or sessile drop method is very similar to the pendant drop method, consisting of the study of the profile of a drop of one liquid resting on a flat plate surrounded by another liquid of smaller density (in the case of the determination of interfacial tension) or by a i r (in the case of determination of surface tension) at mechanical equilibrium. The shape of the drop is determined by a balance between gravily (or buoyancy forces) and surface forces. It is possible to infer the value of surface or interfacial tension from the shape of the drop at mechanical equilibrium. However, because of long equilibration times, it is very ditficult to be used in molten polymers. A new variation of the sessile drop method consists of using the Neumann triangle (12,1 3 ) . to evaluate the interfacial tension between two liquids. When a drop of a molten polymer rests on a plate formed by another polymer, two contact angles el and e,, can be measured as shown in Flg. 1. Using the values of these two contact angles and the values of surface tension of both polymers determined by another method it is possible to determine the interfacial tension between both polymers using the following Eq 1 :
= ylz cosez

+ y2 case,

(11

where yl,y , , are the surface tension of both polymers, ylz is the interfacial tension between both polymers, el is the contact angle formed between the horizontal

Table 1. Materials Used in This Work.

PP, pp2
pp3

75.200 76.000 91.200 76.600 44.000 17.000

4.65 4.5 2.5 2 3.2 9.0

PSI ps2 HDPE, HDPE,

1.5 20 8 2.2

4.64 0.11 3.39 1.85 86.40

0.751 0.751 0.970 0.970

1.07 0.850

Polibrasil Polibrasil Polibrasil Estireno do Brasil BASF lpiranga Petroquimica Aldrich

MFI Melt Flow Index, q , , . zero shear stress viscosity, p: density.

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Nicole R. Demarqllette et al.

Hg. 1 . Sessile drop geometry.

line and the &/polymer surface of polymer 1 and 8, is the contact angle formed between the horizontal line and the polymer 1/polymer 2 interface. In this work, drops of polystyrene were formed on a plate of polypropylene at a temperature of 200C. The samples were left in an argon atmosphere until mechanical equilibrium was reached (around 8 hours). The sample was then cooled, encapsulated in acrylic resin, cut with a diamond disc rotary cutter, and observed with a reflected light microscopy. The contact angles could be subsequently measured. Breaking Thread method: The breaking thread method involves the observation of the evolution of the shape of a long fluid thread imbedded in another. Because of Brownian motion, small distortions of arbit r a r y wavelength are generated at the surface of the thread; this leads to a pressure difference between the inside and the outside of the thread, which induces more important deformations caused by the effect of the interfacial tension that tends to reduce the interfacial tension. It is possible to infer interfacial tension between the polymers forming the thread and the matrix from the study of the evolution of the disturbances and the zero shear stress viscosity of the polymers. ' l b o theories have been developed to infer interfacial tension between both polymers from the study of the evolution of the thread the theory of Tomokita (14, 15) and the theory of Tjahjadi et aL (16).More details about the calculation of interfacial tension from the study of the evolution of the thread can be found in Luciani et aL (17)andTjahjadi et aL (16). In this work, based on the melting and glass transition temperatures, PS was chosen to make the films (matrix) and PP to produce fibers. PP fibers were obtained by melt spinning of molten pellets from a hot plate. Fibers diameters varied from 30 p,m to 110 pm. The fibers were annealed during 12 hours at 150C under vacuum to avoid residual stresses. The fibers used were cut in 1.0 cm pieces prior to annealing. The aspect ratio b f / D b f (where and D , are respectively

the length and diameter of the fiber) was chosen so that it would be higher than a critical value that depends on the viscosity ratio A = qd/qom (where qofis the zero shear viscosity of the fiber and qom is the zero shear viscosity of the matrix) (16).The fibers had their extremities fixed during annealing to avoid sigmficant distortions of the diameter. The films used in the experiments were obtained by compression molding and had a thickness of 0.25 mm. This thickness was optimized to minimize eventual problems with air bubbles and to promote a melting process fast enough to avoid the fibers distortion to start before complete melting of the film. The width and length of the f i l m were 1.5 cm. These dimensions are much larger than those of the fiber, preventing edge effects to have an influence on the capillary instability (17, 18).The experiments were carried out placing the PP fibers between two PS films. The "sandwich" formed was then placed between two glass sheets and heated in a hot stage (Mettler FP-90). The temperature was raised at a rate of 2OoC/s to 150OC. The system was maintained at 150C until a l l the a i r bubbles were able to escape. Then, the temperature was raised to the temperature at which the experiment was performed (200C).Photos of the breakup process were taken using a CCD camera. More details about the experimental procedures can be found in another work (18). Imbedded Fiber Retraction method. The imbedded fiber retraction method is very similar to the breaking thread method, except that the fiber is shorter. The method involves the observation of the fiber that retracts into a sphere. From the study of the evolution of' the fiber and the knowledge of the zero shear viscosity of both polymers, it is possible to infer the interfacid tension between those both polymers. Two theories have been developed to infer interfacial tension between both polymers from the study of the evolution of the fiber: the theory of Carriere and Cohen (19, 20) and theory of Tjahjadi et al. (16).Both theories were used in this work.

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Comparison Between Five Experimental M e t W s

The experimental procedures to perform an imbedded fiber retraction experiment were similar t o the ones adopted for the breaking thread method except for the length of the fiber which was, in the case of the imbedded fiber method considerably shorter. Rheological methods: A continuous effort h a s been applied in the last fifteen years in order to improve the understanding of the relationship between the viscoelastic properties of polymer blends, their morphology and the interfacial tension between the polymers forming the blend (21-26). in particular, it has been shown that immiscible blends have a higher elasticity, in the low frequency range, than the individual components of the blend. The higher value of elasticity of the blend results in the presence of a secondary plateau in the curve of the storage modulus G versus frequency, w, for low frequencies, that can be used to infer the interfacial tension from the rheological properties of the blend (21, 22). Two emulsion models have been developed to predict the linear viscoelastic behavior of polymer blends: a) Paliemes (21); b) Bousminas (22). Those models correlate the dynamic response of polymer blends to their morphology, composition and interfacial tension between the components. Two types of analysis can be performed to infer interfacial tension from small amplitude oscillatory shear measurements: a) comparison between the complex modulus of the blend measured experimentally to the emulsions models in the plateau region; b) identification of a relaxation time relative to the relaxation of the dispersed phase in the relaxation spectrum of the blend (23, 27). Those two types of analysis were used here to infer interfacial tension between PP and PS and between HDPE and PP polymer. The small amplitude oscillatory shear experiments were carried out using a controlled stress rheometer (model SR-5000 from Rheometric Scientific) under nitrogen atmosphere. A parallel-plate configuration was used. Dynamic frequency sweeps were performed for PP,/PS, blends, HDPE,/PP, blends and pure polymers. Blends of PP,/PS, Blends were prepared in 90/10 concentration and PP,/HDPE, were prepared in six different weight concentrations ranging from 95/5 to 70/30. The blends were prepared in a Werner & Pfleiderer twin-screw extruder, model ZSK-30, with six zones of temperatures, ranging from 170 to 210C along the barrel of the extruder. The morphology of the blend was characterized by scanning Electron Microscopy (SEW using a Cambridge microscope, model Stereoscan 240. The samples were fractured in liquid nitrogen and then covered with gold using a Bakers sputter coater, model SCD-050. The average diameter and volume fraction of the minor phase were calculated using the SEM photomicrographs. About 300 particles were used to calculate these parameters. For the calculation of average size of the minor phase, Saltikovs correction (28) was used. This correction takes into account the polydispersity of the samples and the fact that the fracture in the sample does not
POLYMER ENGINEERINGAND SCIENCE, MARCH 2003, Vol. 4 3 ,No. 3

always occur at the maximum diameter of the dispersed phase droplets.

RESULTS AND DISCUSSION

The interfacial tension between PP and PS was evaluated using the five different methods studied in this work. It w a s possible to evaluate the interfacial tension between PP and HDPE only using the rheological method; the pendant drop and dynam~c methods tested in this work are based on the visualization of a drop or fiber of one of the two polymers in a matrix formed by the other. For that, both polymers should have a difference of index of refraction high enough to enable the visualization of the profile of the drop. This was not the case for PP and HDPE. The experimental results found using each method tested are reported below. The different experimental techniques are then compared in terms of experiment a l duration, reliability and experimental difficulty.The advantages and limitations of each method are then discussed.

Pendant Drop

Figure 2 shows the interfacial tension calculated from the shape comparison as a function of time of a typical drop of PS, in PP, at a temperature of 200C. It can be seen from Fig. 2 that after 10 hours, the value of interfacial tension is constant. Typically, it takes eight to ten hours for a drop of PS in a matrix of PP to reach equilibrium. The time to reach mechanical equilibrium depends on the viscosity of the samples involved in the measurement, i.e., on the temperature at which the experiment is performed and also on the molecular weight of the sample. The interfacial tension between PP, and PS, at a temperature of 200C was found to be equal to 5.52 2 0.2 mN/m, corroborating the values obtained by other authors (27, 29).
Naumaxu~ Triangle

F@ue 3 shows a typical cut of a sessile drop of PP, on a plate of PS, imbedded in acrylic resin. The contact angles 8, and 8, as well as the values of surface tension of PP, and 5, at a temperature of 200C necessary for the calculation of the interfacial tension between PP, and PS, using Eq I are reported in Table 2. The values of surface tension of PP, and PS, were obtained using the pendant drop method. Using the values reported in Tabte 2, the interfacial tension between PP, and PS, was found to be equal to 6.65 t 1 mN/m. Breaking Thread
In order to determine the interfacial tension between two polymers using the breaking thread method, the fiber should be formed with the material with the lower viscosity (30, 31) and with the highest melting or glass transition temperature. If the fiber is formed by the material with the highest viscosity, phenomena
673

Nicole R. Demarquette e t a l .

200

400

600

800

1000

1200

1400

1600

1800

Time (min)

m.2. Interfacialtension between PSIand PPl at a ternperahre of 200C as a-n

such as end pinching and retraction could occur. If the fiber is formed by a material with the lowest melting or glass temperature, its distortions will start before it is completely imbedded in the matrix and air bubbles will occur at the interface between both polymers (18). If both conditions are not satisfied at the same time, it is possible to use a fiber with a lower melting temperature than the matrix using appropriate thermal treatment during the experiment (18). However, the difference between the melting or glass transition temperatures should not exceed 20C. Therefore, it was not possible to measure the interfacial tension PP. usin@ __ ___ between - - - - ___ - 1 and PS, --I --- - -the - breaking ~ thread -method. In order to test the breaking thread method for polypropylene/polystyrene polymer pair, it was necessary that the zero shear viscosity of the polypropylene be lower than that of polystyrene. Therefore a higher melt index PP, PP,, was used. Similar procedure was necessary for the imbedded fiber experiments. Figure 4 shows a typical evolution of a fiber of PP, imbedded in a matrix of PS, at a temperature of 200C. It can be seen that the fiber is completely imbedded, before any significant growth of instabilities can be observed. Also during the experiments, no matrix thinning was observed. The average values of interfacial tension obtained in this work for PP, and PS, polymer pair using the theories of Tomotika (14, 15) and Tjahjadi et al (16) were respectively 8.28 lr. 0.79 mN/m and 7.83 5 0.57 mN/m showing that both methods lead to a similar result. It was noticed, however, that
0

of time.

the theory of Tjahjadi et at (I6)allowed a better evduation of the dynamic behavior of the maximum and minimum instabilities of the fiber during the breaking phenomenon, facilitating the discarding of bad experiments. Figure 5 shows the time for complete breakup of a fiber of polystyrene (PS,) in polypropylene (PP,). as

Fig. 3. Sessile drop of PPl on PSI.

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Comparison Between Flue Experimental Methais

Table 2. Interfacial Tension Between PP, and PS, Evaluated Using the Sessile Drop Method. PP, Ips,

yps and ypp, are the surface tension of PS and PP,. y,* is the interfacialtension between PS, and PP,. 0, and O2 are defined in Fig. 6

calculated by Elemans (311, at a temperature of 200C as a function of fiber radius for different viscosity ratios, A. A = 0.059 corresponds to the viscosity ratio of the polymers used in this study. The range of fiber radius studied corresponds to the radiuses used for the different experiments. It can be seen that the time for complete breakup increases with increasing fiber radius and with increasing viscosity ratio, A. However, it can be seen that for A = 0.059 (case studied here) the time for complete breakup is less than three hours, for radiuses ranging from 15 Fm to 55 pm. Therefore, the time to perform a breaking thread experiment is considerably smaller than the time to perform a pendant drop experiment. Figure 6 shows the time for complete breakup of fiber of polystyrene (PS,) in polypropylene (PP,) at a temperature of 200C as a function of matrix viscosity or fiber viscosity. When the value of either the fiber or matrix were varied, the viscosities of the complementary phases were considered as the viscosities reported in Table 1. The values of interfacial tension and fiber diameter taken in the calculation were respectively 6.5 mN/m and 60 pm. Assuming four hours as a reasonable time for an experiment without thermal degradation, it can be seen that the breaking thread suffers limitation as far as viscosity of both the matrix and fiber are concerned. For a diameter of 60 pm and a n interfacial tension of 6.5 mN/m, the viscosity of the matrix should not exceed 69,200 Pa.s (when the zero shear viscosity of the fiber is 1100 Pa.s) and the viscosity of the fiber should not exceed

5590 Pa.s (when the zero shear viscosity of the matrix is 18,583Pa.$. These upper limits of viscosity can be increased to 110,000 Pa.s and 18,583 Pa.s respectively if the diameter of the fiber is reduced to 30 Fm, which the lower limit for a breaking thread experiment (18). These upper limits of viscosity are lower if the interfacial tension between both polymers is lower, which is the case of compatibilized blends.
Imbedded Fiber Retraction Figure 7 presents a typical evolution of a fiber of PP, imbedded in a matrix of PS, at a temperature of 200C. The interfacial tension between PP, and PS, was measured using both the methods of Carriere and Cohen (20, 21) and Tjahjadi (16).According to Carriere and Cohen the evolution of an imbedded fiber as a function of time can be described by:

where, f ( x ) = 1.5Ln{(lt . l- x x2)0'5>

+ 1.5fitan-' (2+x

- 0 . 5~ 4x-2

(3)

where x is an hydrodynamic coefficient, Re is the radius of a sphere having the same volume as the fiber,

FYg. 4. Optical micrographs o f a P P 2 imbedded ~ i n a PS2matrix at 200C.

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Nicole R.Demnrquette et aL
-

14

12 10 -

8A

2 5
13 +

6-

10

20

30

40

50

60

Ro,

(P-0

FQ. 5. Breahng time of ajtber o f PP, i n a matrix of PS, at a temperature o f 200C as afunction offiber radius.

in I W

w I
I
I

T -

8-

6n

n +

4-

4 2-

; ;. /.
7
-C- q ,

1
7
I

/=

-+-

= 18583 Pa.s q, = 1100 Pa.s

0I

1
f

20000

40000

60000

80000

100000

120000

ro (Pa4
Flg. 6. Breaking time of
676

o f PP, i n a matrix o f PS, a t a temperatureo f 200C as afunction o f matrix andfiber viscosity.

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CornparisonBetween Five Experimentai Methods

Fig. 7. Optical micrographs o f a PP,jiber hbedded i n a PS, matrix a t 200C.The UnpertUrlEd radius o ft h e m a, = 26 krn and viscostty ratio p = 0.059. The dimensionless tirnes,frorn the top, are t = 660,840,960,1 1 10 and 1560 s, respectiuely.

Rv is the radius of the fiber as a function of time and

qe is the effective viscosity, which is a function of the viscosities of both polymers, given by:
qom

FTgure 8 shows f

(2) (4)
-f

as a function o f

XTe =

+1 . 7 Tof
2.7

(4)

where qom is the zero shear stress viscosity of the mat r i x and qof is the zero shear stress viscosity of the fiber.

7. It can be seen time for the fiber presented in that the data lead to a straight line from which the interfacial tension can be inferred using Eq 2. Using qe defined by Eq 4 and ROiJ= 32.01 p,m, the interfacial tension was found to be equal to 15.85mN/m. Tjahjadi et aL (16) presented a method to determine the interfacial tension between two Newtonian fluids

6 .

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677

N i c o l e R. Demarquette et al.
from short fiber retraction. The method uses curve-fitted polynomials to describe the decrease in length of the fiber as a function of the viscosity ratio, X, and dimensionless computational time as:

AT^^ is then compared to At- and the interfacial tension can be inferred using Eqs 6 and 7.
Figure 9 presents __ L(7) as a function of time for

K?

=
=

0.03.Using the experimental value of

, , for different viscoswhere the five coefficients, k,- k ity ratios and initial aspect ratios, AR,can be found in the article of Tjahjadi et al. (16),L(T) is the half length of the fiber at time T , and 7 a dimensionless computational time defined as:
7

= t/tclf

(6)

where t is the real time of the experiment and tCiJis a characteristic time for the interfacial tension driven motions in the experiment given by:

where y is the interfacial tension, %ifisinitial the radius of the fiber, -qom is zero shear matrix viscosity. To infer interfacial tension from the retraction of a fiber using Tjahjadi's method, two images of the evolution of the fiber at two different times t, and t, (with At, = t, - tl) are analyzed and the half length of the fiber for both images are measured. Independently, L(T)/R, is plotted using Eq 5 and the coefficient k,,for the appropriate viscosity ratio. Using the graph and the experimental values of L ( t ) / R efor both images, it is possible to determine AT^^^, which corresponds to the theoretical time interval between both images.

Re 540 s and & = 600 s, can be measured from Fig. 9. It was found equal to 0.74. Using Eqs 6 and 7, the value of interfacial tension was found equal to 7.34mN/m. Figures 8 and 9 show that the values of interfacial tension obtained, from the study of the retraction of PS, in a matrix of PP,, using Carriere and Cohen's analysis is considerably larger than the one obtained using Tjahjadi's analysis using the same fibers. The values obtained using Carriere and Cohen's analysis is also considerably larger than the one obtained with the pendant drop or imbedded fiber method. S i m i l a r behavior was observed for all the experiments. These high values may be due to the use of Eq 4 to determine the effective viscosity of the polymer pair. This expression has been derived empirically for polystyrene/polymethyl methacrylate polymer pair and may be not adapted to polypropylene/polystyrenepolymer pair.

YT) for t,

RheologicaI Method

Figures 10 and 1 1 show the storage modulus for PP,/PS, (90/10) blend at a temperature of 200C and for different PP,/HDPE, blends at a temperature of

- 2

10

12

14

16

18

(s)
FYg. 9. Analysis o f a PP, imbeddedjiber in PS, according to "ahjadi's analysis.
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Comparison Between Five Experimental Methods

1000000
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I II

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10000
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Frequency (rad/s)
Q. 1 1 . Storage (G'fw)) moduli of the PP3/HDPE, blendsfor different compositions and o f the pure phases a t 220C. POLYMER ENGINEERING AND SCIENCE, MARCH 2003, Vol. 43, No. 3
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Nicole R. Demarquette et a l .
160000

I i l l l

I I l l .

1 1 1 1 k 1 1

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Rg.12. Weighied relaxation spectrum o f PP, IPS,(901 1 0 )bknd and o f the pure phases a t 200C.

220C respectively as a function of frequency. It can be seen that for PP,/PS, blend, it was not possible to identify a plateau from which the interfacial tension could be determined (21,22).In the case of PP3/HDPEl blend, it can be seen that no well defined secondary plateau can be distinguished in the storage modulus (G(o)) m e , for PP3/HDPE, blends with low dispersed phase concentration (5% and 10% HDPE,). A small shoulder can be observed for PPJHDPE, blends with high dispersed phase concentration (25% and 30% of HDPE,). This behavior corroborates the predictions of Graebling et aL (26),who observed that increasing the dispersed phase concentration increases both G,, value of the storage modulus at the plateau, and the width of the plateau. In order to infer the interfacial tension, the data of the complex modulus of the blend could be fitted to Paliemes or Bousminas model (21, 22).This was tried in the case of both blends and it was observed that varying the interfacial tension from 1 to 20 mN/m (in the case of PP,/PS,) and from 1to 5 mN/m (in the case of PP3/HDPE,) did not result in better fitting of the theoretical model to the experimental curves. In order to evaluate the interfacial tension between two polymers using the linear viscoelastic behavior of the blends, it is also possible to identify a relaxation time in the relaxation spectrum of the blend that corresponds to the relaxation of the shape of the dispersed phase. The value of this relaxation time is directly
680

proportional to the value of the interfacial tension (23). Figure 12 shows the weighted relaxation spectrum of PP,/PS, (90/10) blend and of PP, and PSI pure phases at a temperature of 200C. The relaxation spectra were calculated using a non linear regression of the storage modulus raw data following the work of Baumgartel and Winter ( 3 2 ) . Three relaxation times can be identified in Rg. 1 2 two correspond to the individual phases of the blend (PP, and PS,), since they are of the same order of magnitude a s the ones of the pure phases, the remaining peak was associated with the contribution of the interface and was used to evaluate the interfacial tension between PP, and PS,. The value obtained was 6.25 2 0.87 mN/m, corroborating the value obtained with other methods. TQble 3 shows the value of interfacial tension between PP3 and HDPE, obtained using the analysis of
Table 3. InterfacialTension Between PP, and HDPE, at 220C.

PP,MDPE, Blend
Composition
9515 90110 85115 a0120 75/25 70130

InterfacialTension (mNm
1.01 2 0.26 1.09 ? 0.24 1.44 2 0.27 1.72 ? 0.31 1.72 5 0.22 2.32 -t 0.26

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Comparison Between Five Experimental Methods

the relaxation spectra of the different blends of PP,/ HDPE,. It can be seen that the values of interfacial tension between PP, and HDPE, vary from 1.01 to 2.32 mN/m at 220C. It can also be seen that for composition range from 85/15 to 75/25, the interfacial tension seems to be constant. These results seem to indicate that there is a range of compositions for which it is possible to use the rheological method to infer interfacial tension between polymers.
Comparison of the Methods

three hours. The experimental precision of the break-

ing thread and imbedded fiber methods is limited because the interfacial tension is directly proportional to the zero shear stress of the polymers involved, a difficult parameter to be determined accurately (5).Moreover, the breaking thread and imbedded fiber experiment need to be done under a precise temperature control, owing to the large variation of viscosity with temperature. Any small variation of the temperature during the experiment could lead to erroneous results of interfacial tension. The interfacial tension, as determined using the Neumann triangle, depends on the values of surface tension of the other polymers evaluated using another method and on the preparation of the samples. At last, the rheological method is the one that involves the largest imprecision in the determination of interfacial tension, as the value obtained depends on a precise characterization of the morphology and on the values of zero shear stress of the polymers involved. The rheological method is the simplest method to be used to measure interfacial tension between molten polymers. The main experimental difficulties encountered when using the pendant drop, breaking thread, imbedded fiber and Neumann triangle methods rely in the preparation of the samples. In the case of the pendant drop method, it is very difficult to form a polymer drop avoiding the necking and capillary effect: lots of care has to be taken in the image analysis to avoid errors such as dependence of interfacial tension with drop volume, which contradicts the Laplace equation (10):the analysis of the pendant drop is relatively complex. The Neumann triangle presents a n intrinsic difficulty since the measurement of the contact angles depends on the abilily of cutting the sample in the middle section of the drop and at the same time perpendicular to the base of the drop (12).In the case of the breaking thread and imbedded fiber methods, the fibers have to be annealed to avoid residual stresses that could affect the breaking or retraction process, the thickness of the film that surrounds the drop should be carefully lailored to avoid problems such as matrix thinning. This matrix thinning squeezes the fiber and affects the dynamic phenomena (18).
CONCLUSIONS

Table 4 shows a comparison of the values of surface tension between PP and PS and between HDPE and PP using the different experimental methods tested in this work. The difference between the highest and the lowest value of interfacial tension between PP and PS is around 20% but is acceptable within experimental error. The higher values obtained with the dynamic methods may be due to the fact that the theories of these methods do not take into consideration the viscoelastic character of the polymers. Also, the values obtained using the dynamic methods are directly proportional to the zero shear stress viscosity of the polymers, which is a parameter that is diffcult to measure with high accuracy. The interfacial tension between PP and HDPE could only be evaluated using RM due to a too small difference of index of refraction between both polymers. Table 4 also shows the duration, experimental error and experimental difficulty for each method. The experimental methods are ranked from 1 to 5 according to those characteristics. Table 5 shows the advantages, limitations for each method tested in this work. It also presents the parameters necessary for the evaluation of interfacial tension. The pendant drop method is the most precise of a l l the methods tested in this work. I t s precision is limited by the precision with which the density of the polymers is determined. Nowadays, this density can be determined with a good precision because of the development of PVT apparatus ( 3 ) . The pendant drop method is, however, limited as f a r as duration of experiment is concerned, as the times to reach mechanical equilibrium of the drop can be up to five times the ones needed for other methods. The time for a pendant drop to reach mechanical equilibrium can reach ten hours whereas the time to perform a rheological experiment does not exceed two hours, an imbedded or breaking thread experiment

In this work, five rqerimental methods were tested a n d compared to evaluate t h e interfacial tension

Table 4. Summary of the Experimental Results. Pendant Drop (P.D.) Neumann Triangle (N.T.) Breaking Thread (B.T.) Imbedded Fiber Retraction (I.F.R.) Rheological Method (R.M.)

Polymer Pair

PP,/PS, (200C) PPJPS, (200C) HDPE,/PP, (220C) Duration Error Experimentaldifficulty

5.52 2 0.2 5.06 % 0.4

lmpossible 4 1

5 4
3

6.65 L 1
Not tested

7.83% 0.57
lmpossible

Impossible

7.82 % 0.43
lmpossible

Impossible

6.252 0.87

5
1

3 3
4

2 2
4

1.63 % 0.16 1

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Nicole R. Demarquette et a l .

PO

Very good accuracy Theory developed for all types of fluids Requires little amount of material (10 mg for the drop and 3 g for the other) Can be used of LCP Simple experimental set-up and analysis Requires small amount of material (10 mg for the drop and 3 g for the other) Theory developed for all types of fluids

The difference of index of refraction of the two

-

NT

of the three polymer pairs

BT

Short time duration of experiment Requires very small amount of both polymers (< 20 mg of each) Simple experimental apparatus

Theory developed for Newtonian fluids Polymer matrix (with higher viscosity) must be transparent The difference of melting or glass transition temperature between both polymers should exceed 10C The viscosity of the polymers involved should not exceed an upper value that depends on viscosity ratio and interfacial tension

Zero shear viscosity of both polymers

~~

IFR

Same as breaking thread

Theory developed for Newtonian fluids Theories are polymer pair dependent Polymer matrix (with higher viscosity) must be transparent The difference of melting or glass transition temperature between both polymers should exceed 10C The difference of index of refraction of the two materials should be more than 0.1 Cannot be used for liquid crystal polymers
RHEOLOGICAL METHODS

Zero shear viscosity of both polymers

RM

Theory developed for viscoelastic fluids Can be used for polymers having a small difference of index of regraction Can be used for polymers having high viscosities Can be used for polymers having a small difference of melting or glass transition temperature Can be used for opaque polymers

Difficulty in the visualization of the plateau necessary for interfacial tension evaluation Difficulty in the determinationof relaxation spectrum Experimental results may depend on blend concentration Simple version of theory cannot be used for cornpatibilized polymers

Quantitative morphology of blend Zero shear viscosity of both polymers

between polypropylene and polystyrene and between high density polyethylene and polypropylene. The following conclusions could be drawn from this study:
1) The error for determining the interfacial tension between molten polymers, when using the experimental methods, increases in the following

in the following order: Rheological method

<

Imbedded fiber < Breaking thread < Pendant drop < Neuman triangle.

order: Pendant drop < Breaking thread < Imbedded fiber < Neumann triangle < Rheological method.
2 ) The time duration for determining interfacial

3) The experimental difficulties of the different methods increase in the following order: Rheological method < Pendant drop < Neuman triangle < Imbedded fiber < Breaking thread.
4) The pendant drop, sessile drop and Neuman

tension, using the different methods, increases

triangle methods are the only ones that do not make any restriction regarding the rheological nature of the polymer tested.
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Comparison Between Five Experimental Methods

5) The pendant drop and dynamic methods rely on the visualization of one phase into another
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a n d therefore can be used only for polymer pairs presenting a large difference of refractive indexes of their components; the methods cannot be used either the polymer forming the mat r i x (lower density in the case of pendant drop method and higher viscosity in the case of dynamic methods) are opaque in the molten state. 6) The pendant drop method requires the knowledge of the density of the polymer in the molten state, a difficult parameter that can now be obtained using PVT apparatus (3).the dynamic and rheological methods require the knowledge of zero shear stress viscosity of the polymers, a difficult parameter to be determined accurately (5)the rheological method requires an accurate quantitative determination of the morphology of the blends formed by the two polymers.

i m 7) The static and breaking thread methods are l ited to low-medium range viscosities of the polymers (< lo5 Pa.s).

ACKNOWLEDGMENTS
The authors would like to thank FAPESP for financial support grants 94/033051-2, 97/06071-2, 00/ 02744-7.

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