Rheologioa Acta

Rheol. Acta 21, 270-279 (1982)

Rheology of polymer blends

Yu. S. Lipatov, V. F. Shumsky, I. P. Getmanchuk, and A. N. Gorbatenko Institute of Macromolecular Chemistry, Ukrainian Academy of Sciences, Kiev (USSR)
Abstract: Rheological properties of blends of amorphous and crystalline polymers were studied for a broad range of compositions and temperatures. It was established that below the melting point Tm the viscoelastic properties of blends of crystalline polymers are similar to those of polymers filled with mineral fillers. In both cases these properties are influenced by the existence, in such systems, of a temporary structural network formed by mineral or polymeric particles and its subsequent breakdown under the action of shear stresses. It was found that an anomalous decrease in the melt viscosity of the main component on addition of a small amount of a second polymer depended on deformation conditions. The comparison of data on viscoelastic properties and thermodynamic interaction between the components in the melt, estimated from the parameter X23of a new Flory theory, shows that the sharp drop of viscosity takes place in the region of microphase separation due to the appearance of an excess free volume in the interphase region. Calculation of the relaxation spectra for various blends also revealed marked changes when various amounts of a second component were added to the main polymer. Key words: Viscoelastic properties, polymeric blend, Vogel equation, filler 1. Introduction

The study of the rheological properties of polymer blends and mixtures is of great theoretical and practical importance [1 - 4 ] . A strong mutual influence of components was found for such systems despite their thermodynamical incompatibility and heterogeneity, the latter being a result of incompatibility. As a result, the properties of mixtures and blends are not additive. The main problem considered here is the description of the phase state of the components and the colloidchemical structure of blends, because the size, shape, concentration and mode of particle distribution have a strong influence on the rheological properties. The interactions in the system influence the properties of continuous media. Treating the dispersed polymer particles as polymeric filler, one must recognise that the size and shape of these particles are dependent on deformation conditions and the composition of the blends. Therefore, it is very interesting to investigate the rheological properties of mixture of crystalline polymers having different melting points. The study of their behaviour above and below the melting point of one of the components allows conclusions to be
750

drawn about the phase composition of the blends and about the changes that accompany the transition of a polymeric filler from a solid to a liquid state. When investigating the properties of polymer blends and the behaviour of multicomponent polymeric system one usually uses the principle of additivity and tries to discover the reasons for any discrepancies that exist. Until the present time, the rheological properties of blends have only been studied for a narrow range of compositions, and little attention has been paid to the region of very small concentrations of one component. It may be supposed that the addition of high molecular weight compounds to the polymer will influence their viscoelastic properties in the same way as low molecular weight compounds do [5], especially if data [1] concerning an anomalous decrease in the viscosity of mixtures for small additions of one polymer to another are taken into account. At present there is no satisfactory explanation for these effects. Therefore, it is important to study the mechanism by which such additions influence the polymer and to determine those compositions in which such effects occur. It is also of interest to relate

Lipatov et al., Rheology of polymer blends these effects to the molecular and thermodynamic characteristics of the polymers. 2. Experimental

271 mixtures was 0.5, 1, 2, 5, 10, 20, 50, 80, 90, 95, 98, 99, 99.5 and 100 wt.%. The viscosities of the mixtures were measured using the capillary viscometer MV-2 [7] at shear stresses of (0.123-2.58) 105 dyne/cm2 with capillaries 0.85, 1.24 and 1.10 mm in diameter and 8.3 mm in length. The real and imaginary parts of the complex shear modulus and the dynamic viscosity were measured in the linear viscoelasticity region using the PIRSP-1M device [8] in the range of circular frequencies from 10-2 to 10 s-1 at temperatures from 180 to 260C. All measurements were performed in an inert gas atmosphere. For some polymers and their mixtures (PEHD and PP) the viscoelastic characteristics were calculated from the value of extrudate swell after annealing. In this way elastic deformations, normal stresses and elastic moduli were calculated according to [9]. Thermodynamic interaction parameters between components were calculated using reverse gas chromatography data [10] from specific retention volumes of sorbate.

The viscoelastic properties of melts were investigated for the following systems: high density polyethylene (PEHD)-polyoxymethylene (POM), low density polyethylene ( P E L D ) - POM, P E H D - isotactic polypropylene (PP), cellulose acetobutyrate ( C A B ) - P O M , copolymer of acrylonitrile (20.7/o) and styrene (63%) obtained in the presence of butyl rubber (ABS) - nylon 6, polystyrene (PS-1)- PELD (PS-1 suspension polymerised), PS-2 (bulk polymerised)-polycarbonate (PC). For some systems (PELD - POM, CAB - POM, PC - PS-2) the change in rheological behaviour was compared with the thermodynamical properties. The choice of some polymers (PS, PC) having glass transition temperatures To in the same temperature region in which their rheological properties were studied enabled the extreme changes of viscoelastic properties to be compared with changes in free volume, as in this temperature region the viscoelasticity is determined by the tem- 3. Results and discussion perature dependence of the fractional free volume [6]. The properties of the polymers that were investigated 3.1. Dependence o f viscoelast& properties o f blends are presented in table 1. on temperature and concentration o f polymeric

filler
Table 1. Properties of polymers Polymer PEHD PELD POM Nylon 6 CAB PS-I PS-2 PC PP Tm [C] 130 120 168 225 140 Tg [Cl - 120 - 120 - 83 50 100 100 140 - 10 P20oc [g/cm3] 0.928 0.866 1.492 M 10-3 The study of the temperature dependence of viscosity for blends of crystalline polymers or polymer mixtures, in which one of the components was in a crystalline and the other in an amorphous state, have shown that at the melting point T m of the higher melting point component a sharp change in the form of this dependence occurs, and the slope increases with the concentration of the component in the solid (nonsoluble) state. Moreover the plot of lg y/ vs. 1 / T is nonqinear at concentrations up to 10% (at higher concentration of the solid component the system was not able to flow). Figure 1 shows, as an example, the temperature dependence of the PEHD-PP mixtures. The morphological study of a similar system [11] has shown that the disperse phase formed by PP particles may be detected at a concentration as low as 2%. During melt extrusion of composition PEHD - 2% PP a deformation of the disperse phase takes place with formation of chain-like structures, formed by aggregates of several structural elements of size 0 . 1 - 0.2 microns. The chain axes are oriented along the extrusion direction on despite their distortion, and contact at some points may be observed on electron

165

1.05 1.20 0.883

48 33

Binary mixtures of the initial compounds were prepared mainly by moulding or by mixing the components in a common solvent, namely chloroform (concentration 5 g/l), using a magnetic stirrer. Films were obtained by solvent evaporation at room temperature for 48 h with subsequent drying at 70C and a pressure of 1 - 2 torr until a constant weight was obtained. Films were used to obtain plates with a thickness of 200 microns at 200C and a pressure of 150 atm. The amount of one of the components in the

272
/ x

Rheologica Acta, Vol. 21, No. 3 (1982) linearity of this dependence is explained by an overlapping of the flow processes and a breakdown of the network formed by the filler particles. The dependence of activation energy on the composition may be explained in accordance with [ 1 2 - 14] by the formation in the system of a structural network of PP particles. The inability of systems with PP concentration above 1070 to flow may be considered to be a confirmation of the structure formation, which cannot be destroyed at a given r and PP concentration. The existence of a structural network of polymeric filler particles and its breakdown under the influence of shear stresses may also explain the concentration dependence of the relative viscosity r/r = r//~/0 (where r/is the effective viscosity of the mixture of the PEHD melt with solid PP particles and r/0 is the viscosity of the P E H D melts) at various r (see fig. 2). It is seen that the shape of the fir(C) curves for PE mixtures depends on shear stress: the lower the value of z is, the stronger the influence of the polymeric filler on the viscosity. Such behaviour is typical for filled systems in a fluid state (see, for example, [12]). The mixtures under investigation in the temperature region below the PP melting point exhibit the behaviour typical of the filled systems. Figure 3 shows the dependence of elastic deformation 7e and elasticity modulus G e of P E H D melt on solid particle content at various shear stresses. The analysis of the data enables the conclusion to be drawn that PP particles 40/

F ,
o~
5-

v3

+4 x5

2:0

z',5

103/T(K)
Fig. 1. Temperature dependence of viscosity for PEHD and its blends with PP at r 10 -5 = 0.645 (solid lines) and 2.04 dyne/cm2 (dotted lines). PP content (% by weight): 0(1), 1(2), 2(3), 5(4), 10(5) micrographs. The appearance of well developed aggregate structures of PP particles is related to the high shear stresses at the capillary inlet which initiate the intense deformation of the extrudate components and their breakdown. At the minimum possible melt temperature (140C) the crystalline phase of PP is preserved and its deformation leads to an increase in the required shear stresses. Increasing the temperature to 180C leads to the appearance in the extrudate of some isotropic parts with no texture and the formation of PP inclusions of regular shape, Thus, for PP concentrations in the mixture up to 10070 in the temperature range 140-165 C we are dealing with the flow of solid particles dispersed in a PEHD melt, i.e. the P E H D melt containing PP may be considered to be a heterogeneous system. This statement is verified by the presence of an inflection point on the curves lg r/vs. 1 / T in the vicinity of the PP melting point, which indicates the presence of individual PP particles, as well by the observation of the disperse phase for 2% PP using an electron microscope. It is of interest to discuss the change of the slope of the plot lg r/vs. 1 / T (i. e. activation energy of viscous flow) with PP concentration. It is known [12-14] that at high shear stresses the activation energy of a filled polymeric system does not depend on the filler concentration or the shear stress. At low r the non-

z0lO

ol
e2

~
c,vct*/o

ib

Fig. 2. Dependence of relative viscosity on PP particle content at ~ I0 -5 (dyne/cm2) = 0.645(1), 1.35(2), 2.04(3) at 140C

Lipatov et al., Rheologyof polymer blends

/
ol
* 2

273

,/
/
II

5,5

o3

%
t*1 o x2

2,5

6,0 ~
c,wt./o

Fig. 3. Dependenceof elasticityparameters on PP content at r. 10-5 (dyne/cm2) = 1.35(1), 2.04(2) at 140C at 140-165C play the role of a solid filler which restrains the elastic properties of the PEHD melt, as can be seen from the increase in the modulus with PP concentration. At the same time the elastic modulus increases with increasing r. This is typical for filled system in the case in which the process of stress-orientation of dispersion media chains dominates the process of breakdown of the structure formed by filler particles at small filler concentrations [12]. Thus, the results obtained allow us to Conclude that the development of visco-elastic properties of polymer blends, in which one of the components is in a liquid state and the other one in a solid (crystalline) state are analogous to those properties in usual polymeric systems filled with mineral filler. This means that such polymeric mixtures may be considered as usual filled polymers with all their peculiarities [15]. For some systems ( P E H D - P O M , P E L D - P O M , A B S - n y l o n 6) we have observed an anomalous dependence of the melt viscosity on the solid particles content of the one of the components. As an example figure 4 shows the dependence on concentration of the melt viscosity of ABS at various shear stresses. It is seen that adding a small quantity of solid particles to the ABS leads to a dramatic drop in viscosity and it is only at concentrations above 270 that the blend viscosity again begins to increase. The same effect was observed earlier in polymer melts containing small amounts of minerals fillers [16]. As a rule the transition of the polymeric filler from a solid to a liquid state at T > T m does not eliminate its ability to decrease the blend viscosity. The anomalous decrease in ABS viscosity in the presence of a small quantity of solid particles of nylon 6 and the subsequent increase of viscosity with filler concentration can be explained by the appearence of an additional free volume due to micro separation of the system, this excess free

5,5

;
c,~. */o

10

Fig. 4. Dependence of ABS viscosityon nylon 6 content at 190C and r . 10-5 (dyne/cm2) = 0(1), 0.49(2), 1.02(3), 1.55(4) volume being localized in the interphase region [17], and by the hydrodynamic effect of the solid particles which from intermolecular bonds of the polymerpolymer type. The new effect observed is the dependence of the size of the viscosity drop on the shear stress. So at r = 1.55 105 dyne/cmz the viscosity change of ABS at a nylon 6 concentration of 270 is 15070, whereas as z -~ 0 the zero-shear viscosity is changed by 687o. The greatest drop in viscosity is observed for the case in which the structural networks, formed by polymeric filler particles and by macromolecules of dispersion media are not yet destroyed. Namely, in this case the system is characterized by a maximum Newtonian viscosity. With an increase in the shear stress the deformation and breakdown of the filler structural network take place. The additional free volume is then redistributed in such a way that the dissipation contribution into the flow of such a system becomes predominant even for a small filler content. In this case only a slight decrease in viscosity is observed. 3.2. Viscoelastic and thermodynamic properties of Molten polymer blends in the whole concentration ran#e As was mentioned, the polymer mixing leads to a marked decrease in the melt viscosity with respect to that of the main component. In order to establish

274 some general rules it is necessary to clarify the influence of the values of the viscosities of both components on this effect. To exclude the influence of the chemical nature of the components it is necessary to investigate a system in which the temperature coefficients of viscosity of the components are very different. For this purpose we have studied the rheological properties of CAB, which has a high activation energy of viscous flow [18], and POM with a low activation energy. The flow curves for CAB, POM and their mixtures were obtained. The CAB viscosity depends on shear stress (or shear rate). On the other hand POM is a Newtonian liquid and its viscosity does not depend on deformation conditions. The character of the flow curves of POM is practically unchanged by the introduction of 50070 CAB, and it is only at higher concentration that the mixture flow curves are similar to the log z vs. log ~, curves for pure CAB. If we approximate some parts of the flow curves for CAB and its mixtures with POM by the well known power equation
= k'~ n ,

Rheologica Acta, Vol. 21, No. 3 (1982)

3,5

s'0
wt.V, P0M

I~0

Fig. 6. Dependence of viscosity (1,2) and parameter 3~23(3,4) on composition in melts of C A B - P O M blend. 1,3 - 180C; 2,4 - 200C

then the dependence of the exponent of the equation on composition passes through a maximum at 10070 POM, and n m > nCABfor POM concentrations up to

30

\
\

\
\ \ \ \ \ \

~- 20

\
\ \ \

10-

5'0 wt.*/o P0M

I00

Fig. 5. Dependence of condition and activation energy of viscous flow on composition for CAB-POM blend

2070 (fig. 5). Further increases in the POM content lead to a decrease in n m to npo M = 1. The dependence of the viscosity on the blend composition (fig. 6) may be divided into two regions: the first one for concentrations of one of the components below 20070, the second one for comparable concentrations. In the first region it is typical that for all r values the addition of quantities of CAB smaller than 20070 to the POM melt lead to a rather large increase in viscosity. For example, the zero-shear (Newtonian) viscosity increases more than two-fold. An increase in z leads to a slower and less pronounced viscosity growth. In the second region the mixture viscosity does not change noticeably for CAB concentrations up to 50070. For higher concentrations of CAB up to 8070 a gradual transition from an increase in viscosity to a decrease takes place, this effect being dependent on temperature. In the first region in which the continuous media is CAB, the viscosity of the mixture drops sharply when small amounts of POM are added and then begins to increase, reaching the value of CAB viscosity (the left part, fig. 6). It is worth noting that in the first region a minimum or maximum in viscosity may be observed, depending on which polymer forms continuous phase. This can be attributed to the fact that the phase separation in this system is observed only at addition of POM to CAB, whereas the addition of CAB to POM does not lead to phase separation. This conclusion follows from the data of thermodynamic study of the system (see below). For the CAB-POM system a gradual increase in flow activation energy is observed for increasing CAB content (fig. 5). Above 20070 CAB the phase separation probably takes place. As noted, POM and CAB have very different activation energies of viscous flow

Lipatov et al., Rheology of polymer blends

( g p o M = 8.5 a n d E C A B = 32 kcal/mole). Therefore,

275 increases in the PC concentration then decrease the viscosity and at 10% PC the viscosity-composition curve shows its second minimum. In the composition range 1 0 - 50% PC the viscosity increases at different rates. At 9 0 - 95 C a sharp increase in viscosity may be observed once more and finally at 98 - 99% a drastic drop. For a PS content of 0.5% the third minimum on the diagram appears. It is important that in the whole composition range the viscosity of the mixture is lower than the additive values. Thus the maxima and minima of the viscosity function are observed at definite concentrations of one polymer in the other. Let us now compare the viscosity data with the thermodynamic interaction parameters for various compositions. Figure 6 shows that the decrease in thermodynamic stability of the CAB-POM system (positive values of thermodynamic interaction parameter Z23 of the new Flory theory) leads to a sharp decrease in viscosity. The greatest thermodynamic stability (negative values Z23) corresponds to increasing viscosity, which becomes higher than the additive value. The region of maximum thermodynamic stability of the system corresponds to the 5% CAB. In this composition range a sharp increase in the viscosity of the mixture takes place. Increasing the CAB content further leads to a decrease in the thermodynamic stability. The most unstable system occurs at 9 0 - 9 5 % CAB. Increasing the temperature increases the thermodynamic stability (values Z23 diminish), this being accompanied by the greatest positive deviation of viscosity from the additive values. Therefore, in this case there is, for all compositions, a clear correlation between the viscosity of the blends and the thermodynamic state of the system. For the PS-PC blends, despite a more complicated concentration dependence for the viscosity, in the range of small concentrations of PC in PS (fig. 7) the smaller values of X23 correspond to increasing viscosity and vice versa, i.e. in this case the increasing stability of the systems increases the viscosity, whereas the decrease in the thermodynamic stability diminishes the viscosity of the system. However, in the range of small concentration of PS in PC (right part, fig. 7) the behaviour of the systems is very different from that of the CAB-POM mixtures. In this case the smaller viscosities correspond to greater stability, and vice versa, which is typical for usual polymer-solvent systems. Such different dependencies of viscosity on the thermodynamic state of the system can probably be related to the various mechanisms of microphase separation of the systems at small and large concentrations of one of the components [19].

even in a very narrow temperature range such as 170 to 200C the ratio of component viscosities changes very markedly. It may be supposed that the sharp decrease in viscosity in the narrow concentration range in determined by the phase separation. Experimental data, obtained at different temperatures, show that the decrease in viscosity is essentially independent of the ratio of the viscosities of the components. The activation energy of viscous flow in the region of phase separation, supposedly passes through a minimum.
// / / J A

o~ c~

j /

f .f

/ I"

-6
7 J J ~

o ~

P4

wt.%PC

Fig. 7. Dependence of viscosity (1,2) and parameter X23(3,4) on composition for melt of P S - PC blend. 1 - 180C, 3 190C; 2,4 - 200C A more complicated concentration dependence of the viscosity was observed for the system PS-PC (fig. 7). As is seen from curves of the maximum Newtonian viscosity r/0 = lira r/' as a function of composition,
to~0

introducing 1% PC into the PS melt leads to a marked decrease in the viscosity, this decrease being dependent on the frequency and only slightly dependent on temperature. For example, in this case r/0 decreases 13-fold, whereas the dynamic viscosity decreases only 3-fold at log 09 = 0.6. Increasing the PC content to 57o leads to an intense growth in viscosity, although it does not reach the additive value. Further

276 The measurements of viscosity in the range of intermediate compositions have shown that the general picture of its variations depends only slightly on temperature. This is in a good agreement with the temperature dependence of the thermodynamic interaction parameter. The calculation of these dependencies for .~23 shows that at 180-220C OX.E3/OT is very close to zero, this verifies the absence of a change in the thermodynamical stability of the system. Thus, the extreme changes in the rheological properties of polymer blends are the result of variation of the thermodynamic parameters and are determined by the thermodynamic compatibility or non-compatibility at definite compositions. As the viscosity is only one of the integral characteristics of relaxation properties of polymers, it may be supposed that adding a small amount of one polymer to another should lead to changes not only in viscosity, but also in the viscoelastic properties of the blends. Figure 8 shows the concentration dependence of the reduced elasticity and loss moduli for the logarithm of the reduced frequency equal to - 1 . A complete analogy between the changes in dynamic moduli and viscosity with variations in blend composition can be seen. However, the magnitude of the changes in the viscoelastic characteristics at various frequencies is different for different compositions. The greatest drop was observed for the dynamic mod-

RheologicaActa, Vol. 21, No. 3 (1982)

1,5-

"6 V
0,5

Fig. 9. Dependence of ratio of reduced elasticity and loss moduli of reduced frequency in PS and blends with 1% PC ulus G', this drop being frequency-dependent. Figure 9 shows the variation of dynamic moduli with frequency for the system PS (99o/0) : PC (1 070). It is seen that the reduced loss modulus decreases 12.5-fold at log Ogred = --2, and 1.7-fold at log (..Ore d 1.6, whereas the elasticity modulus decreases 35- and 2.9fold respectively. The use of reduced values to construct figure 8 demonstrateds that the variations are independent of temperature at small concentrations. It is clear that the most important changes in the viscoelastic properties of blends are observed in the range of small concentrations of one component in another, and these take place at low frequencies. That means that the structural elements with higher relaxation times present in the melt are subject to more pronounced changes by the addition of another component. Therefore, we consider now the most fundamental characteristics of viscoelastic properties of blends their relaxation spectra H(O). The spectra were calculated by computer from the dependences Gre,a = f(~red) using the well known method of Ninomiya and Ferry [20]. Figure 10 shows spectral characteristics of melts of PS, PC and their blends. It can be seen that there are very marked differences between the spectra. The introduction of small amounts of PC (0.5, 1 and 1007o) into PS, or PS (0.57o) into PC melt lead to a sharp cut-off of slow relaxation processes. Such a large difference between the relaxation spectra
=

5'

/./1 J/t ~'~J /./" /'''/ ./ // "/t/ //

N'-

-3

PSlOO
0

5'o
50

100 PC

Fig. 8. Dependence of reduced elasticity and loss moduli on PS- PC blend composition at log a~re d= - 1

Lipatov et al., Rheology of polymer blends

6 7
5 8 10

277

~ o
5 17

logOisec) 4

Fig. 10. Relaxation spectra in PC-PS blends for various PC content (wt.%): 0(1), 0.5 and 1(2), 2(3), 5(4), 10(5), 20(6), 50(7), 80(8), 98(9), 99.5(10), 100(11) of pure polymers and their blends results in a variation in their viscoelastic properties. This difference manifests itself markedly in the region of low frequencies and becomes smaller at higher frequencies. Let us now compare the change in relaxation properties with changes in free volume in the system. To obtain the necessary values the temperature dependences of the m a x i m u m Newtonian viscosity of initial polymers and their blends (fig. 11) were described using the V o g e l - T a m m a n n equation [21]: B r/o=A + - - ,

Io3/TI*K)
Fig. 11. Temperature dependence of maximum Newtonian viscosity in PS, PC and their blends. PC content (wt.070): 0(1), 0.5(2), 5(3), 10(4), 99.5(5), 100(6) where A, B and TO are the empirical constants of the substance. In the framework of a free volume concept, TO represents some "critical" temperature at which free volume vanishes. As is seen figure 11, the

T-To

Table 2. Parameters of Vogel equation, Tg, fg, fr, Er for PS-1, PS-2, PC and their blends System

B [K]
1703 1877 1464 954 1347 1258 1292 970 1163 616 625

TO [K]
313 309 355 342 331 333 327 341 336 371 395

Tg [K]
372 373 407 379 380 379 375 376 378 394 421

fg

f r* )

E r* ) [kcal/mole]
44 31 47 43 48 47 43 25 27 26 45

PS- 1 PS-2 PC PS-1-PELD (99: 1) (98" 2) (95 : 5) (90" 10) PS-2-PC (99.5 : 0.5) (95 : 5) (90 : 10) (0.5" 99.5)

1.031 0.737 2.011 4.279 2.224 2.689 2.757 2.278 2.266 3.704 5.598

0.035 0.034 0.035 0.039 0.036 0.037 0.037 0.036 0.036 0.037 0.042

0.070 0.087 0.081 0.095 0.076 0.079 0.082 0.136 0.118 0.166 0.125

*) f r and E r for PS-1 and its mixtures with PELD were determined at 160C, whereas for PS-2, PC and their blends at 200C
19

278 temperature dependence of viscosity for PS-PC blend is nonlinear in the temperature range 453 - 533 K, and is described adequately by the Vogel-Tammann equation. The calculated values of the Vogel equation parameters for PS-PC and PELD-PS blends are given in table 2. In accordance with the Tammann criterion, liquid turns into a glass-like state at the temperature where the viscosity becomes equal to 1013 poise. From the Vogel equation we have calculated "Viscosity" glass transition temperatures, using parameters given in table 2. This table also contains the values of fractional free volume at T0 and at the temperature of the experiment, which were calculated as [21]:
fT-T o

RheologicaActa, Vol. 21, No. 3 (1982) are similar to those for polymers filled with disperse mineral fillers. Therefore, the blends of crystallizable non-compatible polymers may be treated as usual filled systems with all their peculiarities. An anomalous decrease in the viscosity of molten polymer mixtures was also observed for small concentrations of solidified particles of another polymer, the maximum Newtonian viscosity being changed here more markedly. The transition of polymeric filler from solid to liquid state at T > Tm does not influence its ability to promote viscosity decrease. The sharp decrease in viscosity takes place in the region of microphase separation due to thermodynamic incompatibility of the polymers, which is related to the appearance of an excess free volume. The more profound changes in the viscoelastic properties of a polymer caused by the addition of small amounts of another polymer take place at low frequencies of mechanical action and consist of a sharp cut-off of slow relaxation processes.

The last column of table 2 contains the values of apparent (temperature-dependent) activation energy E r which relates to parameters B and TO as follows [21, 22]
E r = RB

T.S

r0)
References 1. Kuleznev, V. N., J. V. Konjukh, G. V. Vinogradov et al., Koll. Zh. 27, 540 (1965). 2. Vinogradov, G. V., A. J. Malkin, V. N. Kuleznev,Koll. Zh. 28, 809 (1966). 3. Han, C. D., T. C. Yu, J. Appl. Polym. Sci. 15, 1163 (1971); Polymer Engn. Sci. 12, 81 (1972). 4. Tsebrenko, M. V., T. J. Albasova, G. V. Vinogradov, A. V. Yudin, Vysokomol. soed. A18, 420 (1976). 5. Andrianova, G. P., A. J. Isaev, Vysokomol. soed. A15, 1852 (1973). 6. Vinogradov, G. V., A. J. Malkin, Rheology of Polymers (Moscow 1977). 7. Konjukh, J. V., G. V. Vinogradov, A. A. Konstantinov, Plast Massy NI0, 45 (1963). 8. Vinogradov, G. V., A. J. Malkin et al., Vysokomol. soed. A20, 226 (1978). 9. Mendelson, R. A., E. B. Bagley, F. L. Finger, J. Polym. Sci. C35, 177 (1971). 10. Nesterov, A. E., Yu. S. Lipatov, Inverse Gas Chromatography in Polymer Thermodynamics, Kiev, Naukova Dumka 1976. 11. Shumsky, V. F., E. V. Lebedev, Yu. S. Lipatov, Vysokomol. soed. A21, 992 (1979). 12. Vinogradov, G. V. et al., in" "Problems of heat and mass transfer", p. 222, Minsk, Energiya (1970). 13. Malkin, A. J., in: "Composite Polymeric Materials", p. 60, Kiev, Naukova Dumka (1975). 14. Shumsky, V. F., Yu, S. Lipatov et al., Vysokomol. soed. A18, 2248 (1976).

(R is the gas constant). As is seen from the data presented in table 2, introduction into PS or PC of a small amount of another component leads to the marked changes in the parameters of the Vogel equation, fractional free volume and activation energy. The calculations show that the experimentally observed decrease in the viscosity of the main component for small addition of another is connected with the increasing free volume fraction of the system. This increase promotes the relaxation processes. It is worth noting that calculation indicates the appearance of an excess free volume in the systems under investigation which is in a good accordance with results obtained earlier [16]. Some increase in glass temperature transition for blends as compared with Tg of pure PS and PC is evidently connected with changes in conditions for relaxation, these changes being preserved in the glass-like state as well.

4. Conclusions The rheological study of binary mixtures of various polymers shows the existence of some general trends in the viscoelastic properties of crystalline polymer blends in the temperature range below the melting point of the component with higher T,,. These trends

Lipatov et al., Rheology of polymer blends 15. Lipatov, Yu. S., Physical Chemistry of Filled Polymers. British Library (1979). 16. Prokopenko, V. V. et al., Dokl. AN SSSR 214, 389 (1974). 17. Lipatov, Yu. S., V. P. Vilensky, Vysokomol. soed. A17, 2069 (1975). 18. Semjonov, V., Adv. Polym. Sci. 5, 387 (1968). 19. Lipatov, Yu. S. et al., Vysokomol. soed. (to be printed). 20. Ninomiya, K., J. D. Ferry, J. Colloid Sci. 14, 36 (1959).

279 21. Berry, G. C., T. G. Fox, Adv. Polym. Sci. 5, 261 (1968). 22. Miller, A. A., Adv. Polym. Sci. A2, 1095 (1964). (Received November 30, 1981) Authors' address: Yu. S. Lipatov Institute of Macromolecular Chemistry Ukrainian Academy of Sciences 252160 Kiev (USSR)

19"