Thain correlations in symmetric binary polymer blends George E. Garas and Marios K. Kosmas (Ghemaery Departmen Cniversey of locamine, 43) 10 Koni, Greece (Received 20 July 1995; accepted 21 September 1095) ‘The many chain problem of two polymers is studied through the summation of the series of the one-loop diagrams between different poly mer chains. The free energy of the polymer blend is found revealing that chain cortlations affect the phase separation behavior of polymer chains of fnite lengths N. The parameter yu; elated with the seattering form factor is found to overestimate the compotion and moecular weight dependence of the Strength ofthe interactions ofthe two differen polymers expressed by the generalized Flory-Hugeis parameter y. The composition dependences Df both parameters ae afecied by the proximity 10 the critical repion i accord with recent neutron scattering experiments and in the manner Morte Carlo simulations indicate. These dependences become stronger us the system comes close 1o the criieal point ether trom the one phse or from the two phase region. The dependence of yap on the molecular weight is not monotonic and is related with the composition of de system. The ercal value of x Is four 10 present a postive deviation of tie onder of V~" from the avean fick! prediction taking the classical value x,=2/N only at the limit of large molecular weights. © 1995 American Inuinwe of Physics. | INTRODUCTION Our present understanding of the thermodynamics Of polymer blends is mzily relied on theories that use the ab- striction of a lice in order to, model posymer chains and the imeractions becween them! Though lace theories were successful in explaining crical aspects of the intricate phase-separation behavior of polymer blends they did. not account properly for the peculiar inhomogeneity arising fom the connectivity of the polymer units and Grom the more o¢ less Gaussian distributions" of the polymer chains. Floy Huggins theory, which served as the starting point for the posterior theories, regards chain cenfigurations a5 unimpor- tant for the mixing fre evergy and. at crucial stops of the evelopment assumes the monomers 10 be distributed at random. This has led to a cather crude formula For the Eve energy of mixing, which cannot for instance iferentate polymer mixtares of linear chains from mixtures of other ‘macromolecales of meve complex archiiectaces * ‘The early Flory-Huggins equation for the free energy of mixing of two polymer species A and B. of chain lengths and volume fractious ,..Ny and gy. gp spectively. reads AG} _ea 0 Fitlg MO* Heineadt Renee. C0 where isthe segment-sepment interaction parameter jn tually considered to depend aly onthe seperate of the system. The basic prediction of Eq. ((-1) that the entical valve of the parameter behaves ike x, ~~! where Wis the chain length of te syramewie system, nas been epro- duced by secemt theories and is experimentally verified for large W.*'* Neverieles, Eq, (11) isan approximation tha eplets fue compressive, diferences in chan achi- 4 Sem. Phys. 109 28), 22 December 1999 pet BOBEN/ION~AVIOTBON/SECO tecture and segment structure, chain self avoidance, self ontet, and what we are interested in, long-range correla. ‘bons along the chain. Later, Flory in order to account for the entropy changes due 10 first neighbor interacts incorpo- fated an entropic ferm to his initially pure enthalpic detini- tion of x which took the form 8 weate, rey where A and # ure constants and the noncombinatorial extra eniropy is embedded in A> ‘The fact that x was found 19 depend on concentration ‘and melecuar weight, combined withthe observation ofthe LEST (ower entieal solution temperature) behavior in polymer-solvent and polymer—poiymer systems essed in 8 number of new theories all of them aiming at a beter understanding ofthe nonideal part of Eq (1.1). The orginal late theory was amended to account for equaion-of-stae effects and for citferences in segmental shape.” Also off- Inti theres appeared accounting forthe effec of density and concentration Bucwaious "2" lnguid state theory, the reference imeroction site model (RISM), has adapted to poly- rmer blends and inially predited a square roct dependence ofthe erteal temperature on polymer molecular eight.” Recently, this theory by means of new molsculer closures was able to predict the commonly accepted linear depen- ence of T, on Wand to be in good terms with recem data brought out by computer simulations and neutron scatering experiments? In the next sections we present our approach to polymer blends that is based on a molecular model of iterating ‘Gaussian chains. The canonical ensembie is employed and ‘the partition function of the system of two polymer species is ‘comsiiced. A simple expression for the fee energy of an incompressible binary blend is found up to an inwearal by (© 1695 Amadican insttute of ysisG_E, Geras ant M1 Kosmas: Symmatic hieary pone Barc summing the one-loop diagrams up to all omders of concen ‘ration and imeracion, char 1 a . a ge: Gms These diagrams (see Chart 1 cases D, E, FG) accoun: For the two-body interactions of the segmeat of all possbie combinations of siferen chains a serios configurations permitted by the Gaussian mevel. Thus tey simile the chanicterste long-range comlations oF the poiymer mol- ecules which are due to the fact that every polymer chain dnterets with many other chains, in corirast with te sy tems of small molecales where the numberof the interacting neighbors is much smaller.” This expression for the free nergy leads to algebraic functions fer the generalized Flory- Huggins interaction parameter y and for the parameter ‘er tat isolated tothe structure factor and is measured via Snal-angle novton scatering experimens (SANS). The critical, for the phase separacion, value of x is found «0 present & postive deviaon of the order of 1/VN from the ‘mean field prediction x.~/~' obtaining the classical valve at lange V in accord with experiment and recent theories. '* ‘The dependencies of y and yur on the volume fraction f te one ofthe components ind on polymer chain length N though similar are not found identical They have. both roughly parabolic dependence on ¢ atthe middle of the y~¢ ple while yar presents « downsim atthe “wings” out of the center of the diagram, becoming linear a the extremities of concentration. The bebavirs of {and op ae bo af ore proeches the critical point ether from the one-phase or from the two-phase region. All these tends of xy With ¢ are in ‘accord with resent theories and are observed in SANS oF Monte Carlo experiments" The dependence of ar on te chain legit N is found to be very rich, connected with the disance from the erical point and with the conceata- ‘ions of the polymers. The parameter yg changes from a ‘ecressing function of Vat the center of the xg plane t an ‘increasing one atthe resi part ofthe plane passing from two concentration regions where a “corrsation hole” is found ‘here yg 3 insensitive o variations in chain length |. THE PARTITION FUNCTION ‘We work in whe canonical ensemble with an Edwards configurations! Hamiltonian for a system composed of two chemically different macromoleculer species A and Bin a volume V2" ‘The individial macromolecwles (12y.tai 12mg) ae represenzed by continuous curves ia d dimer sons Whose chain elements at distances 7, and 7 slong the ‘chain contours are atthe spatial points r4(r,) and td) [aradearavars® +23 & [lar feremy Xe) FAlop ey ‘The first term counts for the connectivity ofthe eins while the second stands fr the interactions between nonadacere pans of the chains. The indies and f run over the my and ‘ig macromolecules ofthe syste, the chain lenath param fits Nand N, cake th vals 1, of Nand the ened Volume paranetars wi the the’ valle) way, any ad wan Wen Whe the indices i and j represen. macomol- ecules ofthe species A or B. Expanding the configurations patton function 7=fDir(eapl—H/KGT) wid respect 10 iner-exshaded-voume interactions we tke feoed bythe rsimiy wo be wil pose The depend: ze en of xq on composton becomes stoner he ssem ap wih fe 1 Magy ft Steg, pte a (-} Zoek f eral degmtledre seals 3 Se f are! Mry wyStleulre) r ae nett php \ rare] +E STE Be des fare Maree fteteamot| ):e#8 wen es ‘where the brackets ( ) denote the average eve all positions fof the units with respect the re pa of the Hamiltonian that includes the remaining inv-excuded- volume interactions Each deli function of Eq, (23) brings into comtot segments of diffrent chains and diagrams wall or er of Wau, Wane td way ae produced. Mlusratve dix — _gaers concerning the one species many chain problems have been depicied in Ref. 4. To adjust these diagrams to the 1wo hain species problem the reader should imagine that ever line of these diagrams stands fora chain ether of the species ‘A or B. Open and diseonnecied diagrams do no: contribute to the fre enerey of the sysiem, with the exception of theross-torm diagrams of the fist order in w, that come from the fre nonideal term of Ea. (23) (see &. B.C an Diagrams ‘of Chart 1), 1s also foune! that the ring-form diagrams (one-oop stelston type diagrams see D, &. FG in dia grams of Chart 1, play a dominant role in the evaluation of ‘macroscopic properties suc asthe fie enerzy and the a= Imotic pressure while the rest of che snictured (connected) iagrams can be considered a derivative diagrams and theit ‘minor contribution can be estimated and incorporate i ibe solution in a separate step. Equation (2.3) in terme of the ‘one-loop diagrams tks the for 205 kh walt EE KOA wm mgt ingame where he fat (3, nn the Dinca (n, ng? that 18 the teemodynemic nt ff the peck (ny naling rng Weg ing 2g ‘ng-m) sving fot ake manne wats mans can te thosen amas ttm ote" far the de oimtor comes for the Fagor (m1)! tt gies the turner of ferent arangements form chun forma ing divided by m! fom he Taylor stpinon, whic the 2 ames fom the wo ferent ways exh cha ca be placed inva positon ise ring A factor UY" alo pears ecu te mera pefomed in he ume Of he eee FF pat fat oe fa [anes [ara xe oy [a [a x [at [at [ Nan tfXNe~t3 es) Employing the dimensionless varidles f= (1iV, and AP seh erated Hk 28) average of Eg, (2.3) are mt fewer than the imegrations Performed inthe denominator and thi is due tothe fact that sn chains forming ating move in he availabe space together Each individual ring diagram consis of my chains of type A and my chains of type B with my4+mg=me which interact wwity As and interactions f kinds AA, WH, and AB, respectively In Chart we see ning diagrams when special relations between A As my. Mg» ad mold. The dia sams of the cases and E come from the resinctions my=K=m and my-N~m, respectively, They are the only ting agra that Eo. (23) yields when no imeractions be- tween different species exist. The diagrams of the type F some from the restictions ma=my=a2=n/2 and core spond to the case when only interactions between different species of polymers are taken into account “The factor {7p comesponds to te integrations of the general term of Eq (2.3). There ae two indices /) rvnning ‘on ach chain backbone (se diagram G of Chart 1) which ‘means that thers are 2m integrations along the chains A and ‘my integrations along the chains B to be performed. As Edwards have shown! fong poiynier chains in dense sate obey Gaussian statistics. The form of the sing diagrams in the Gaussian model is expat 19 (4/27a)™ "(length of oop)? where is the segment length which for conve- inienc is taken equal for dhe wo species. Upon absorbing the (ai2eray" constnts in ws we get the Form [st cathe.) th) (Mo UME Seok, ates) Se with ¢ a dummy integration variable, each mg. my inegra- tions become equivalent yielding the expression Ab veneer) [ap ett {ener fesinernl™ which by means of the Debye functions sie fasion eI +pyip®, a) J.Cham Pips, Yel. 103 No 26, 22 Okesber 1995 -——---6. £. Caras and M. K: Kosmas: Symmetric binsry polymer bends transforms 10 th =ev-@errcany [an pimiamayme, (29) “The evaluation of the Fing diagrams up to an integril permits the evaluation ofthe skeleton patton funtion ap an integral. Ths evaluation is easy to be done for a number ‘of cases of some special interaction symmetry, ste below. @ ay= n= Wap eF0, AD) a=W UM) x4 = Wa UY) aa= ‘Considering the excluded volume interactions between the same species 0 be negligible in dense systems, we fall ino the case (Ill) where only interactions between chains of ci ferent species are important and only ring. diagrams of the case F of Chan | survive Thus under dhe restriction mF my=W2=m/2 Bq, (2.4) takes the form (wand (marta) ee [NeoPa (a2) » [ap 0 trateln’, 2.10) where the subscript if to denote that we deal with a skel- ton quantity coming ftom the contributions of the one loop iagrams only. ii, THE FREE ENERGY ‘The summation in Eq, (2.10) is trivial: thus we manage to find forthe Gibbs free energy of mixing of the system of two polymers the expression AG __e lee Fea HOt EA) mo) Xe(1-9)+® @.la) with warcann, dp pt Min) +4) (31b) and k=20w/opl ll @)r Nata)" (Be) VaVyt¥p=(ngNa tna pig is the total volume of the system. uy a reference monome: volume, w= Wap. @=V4/V fand 1g-Uq/V’ the volume fractions of the components, N=N, and PN=Ny the chain lengths (nimhers of see- ments) of the polymer chains A and Band J, and Jy the Debye functions defined in Eq, (2.8), The first two lozarith- ‘mic terms correspond to the combinational entropy of the system while the (w/t(g)¢(1—e) term comes from the eval ation of the first order diagram C of Char 1. The new term a s0793 comes from the contributions ofthe ring diagrams, expresses, the effects of chain correlations and it is negative inrespec~ tively of the allowed values of its variables, This reveals that Ris primary of entropic origin and its negative contribution to the free energy shows that chuin correlations stabilize the system. As the chain lengths increase the absolute value of R increases and this stabilization becomes stronger. This means that chain connectivity and chain interpenetrations impose an ‘equilibrium between iniermolecular segment-segment forces that is more stable when the chein length is larger. This sta~ bilization for finite imensity of interactions is characteristic of the macromolecular systems while for ery short chains oF simple molecules it can only exist at temperatures close 10 the absolute zero, where thermal motion ceases, The evalsa- tion of the integral of Eg. (3.1) can be performed and SG can take an analytic form if we replace J, Jp with the approximants? Taz (Pt2', Tye (prs2y! 2) ‘The approximation Eq, (3.2), reproduces comectly the p-+0 ‘and p> limits of the exact expressions of the Debye func~ tions introducing an error that lies within sbout 3% of the inte values, Thus we get forthe ring term K of Eq (3.1) for the symmetrical case with r=1 the analytic result FPS pe eo ee Re sympa e# BAM Varo)} a where c= dw e(1—@)N™ a4) sand vy is taken to be equal t unity for simplicity, a conven- tion that will be kept throughout this paper Equation (3.3) reveals thatthe R term of AG becomes zero at the limit c= 0, it takes negative values as expected for ¢>0 and it is unde- fined for €>4. AG then of Eq, (3.1) has also a limited do- ‘main of existence lying outside the surface cla= wp @)N7=L es) ‘As we show below [Eqs (44) and (47)] the inverse seater ing stuctue factor vanishes for c= 4 and the line given by Eg, (3.5) behaves as a spinodal though it does not coincide with the familiar mean‘iekd spinodal curve. It crosses the binodal fine around the critical point creating a region where the bimodal does not exist. This region dliinishes as the molecular weight increases in Une same way that has been fbserved in Monte Casio simalaiors." A thing to notice related with the behavior af i that though its absolute alive inereases with X. for constant ¢ it behaves like R—N-® decreasing absoltely with an increasing N. Hence comparing binary systems of diferent species of macromol- ecules close to their spinodals we see that chain corelations fffect more strongly the systems of the smaller molecular ‘weishtsané this because of the enlargement of w under con- stant ¢ Tn cider to study phase equilibria we need the chemical potentials y,=(@MG)/(an,) of the two polymers i=A.B Where #8 the numberof molecules of species ¢ Subsitut ing AG trom bq, (3.1) we get “Chiom, Phys, Vok 108, No. 26, 2 December 1895giaive)+|1-]1-e)+wat =e) so evaesl oor fou~ BH ~elt(L—ie)twrng! stews vata ftp oat 20-1 ! Tall en Fok two aaa jae tr aura ie aaa pn tio ba Oete ein tnt be Gal Por Bele cmevidi= ah Gene seneae +wN(I-29) Lt¢ aia ar (a/2)} 3.8) and applying the approximation Eq, (32) we get { (29 * 2 il 2) sunt nag) ae ai aig [Barer -o, where ¢=4w79(1—g)N?, Equation (3.9) can be solved mu- ‘merially ad yield the binodal curves w(g) As itis already ‘mentioned, for finite N te binodal cune is crossed arcund the critical point by the “spinodal” curve, This region of an undetined binodal tends to diminish asthe chain length in creases and at the limit V2 the two curves coincide at their iowest point which for the symmetrical casei the crit- al point forthe phase separation of the mixture located at #05 and w.=2/N, This can be shown by solving Eq Gd) at the @0.5 limit. We find the expression B9) EOE se tains] al a2 vw I (3.10) ‘This equation shows that w, tends to 2/N for large N but it hhas no solution for finite N’inside the spincdal as expected, ‘We can make though an analytic continuation iato the unde- fined region by replacing y2— J¢ with ~ y/2= Vel thus ob- taining a smooth exteasion of the binodal and alse the criti- cal value of w which to a frst approximation reads (2- By 1 ON en and yields w,=2UN for large N. Equation (3.11) shows that systems of larger molecular weighs must be of smaller w's in onder to be suble. The binary cluser integral w= Sdr{i~exp|—U(ny/Kg1)] fora realistic potential U(r) with a repulsive core anda weak either tractive o repulsive tai takes the form w= a~ O/T where a and b are constants determined from the microscopic parameters of U(R).* A positive 6 gives aw decreasing with the temperature and ‘ccounts for the UCST (upper eitcal solution temperature) behavior while a oegatve & gives a/v increasing with the Jemperture and accounts forthe LCST (lower critical slue tion temperature) eases. Thus fr lange N where w.=2/V [see Bq, (3.11)] the linear dependence of we with the inverse tem- erature, w=a+)/T, yields a linear dependence of T, upon NV forthe UCST case where is small and b>O, while for the LCST case with a>0 and 6<0 the dependence comes ‘out to be much softer yielding a T. decreasing with N tend- ing to be independent of N when N-* For smaller N the R term becomes important increasing the values of w, of Eq (3.11) which has aa enhsncing effect on 7, in the case of LCST betavior and a reducing ove in the case of UCST behavior. Thas chein correlations widen the single phase window for both UCST and LCST systems in accord with their subilzing rol. These results ae consisted with expen- restal research!” Monte Carlo simulations" and re- cent theories." By means ofthe analytic eontinuatien, we an also expand Eq, (3.9) around the ertical point for large N IN) and study the critical exponent fof the relation (ey,)~(T-T,)4 which determines the behav ior of the system close tothe critical point. Omitting con- stanis and retaining only the frst rwo smaller order terms in dw=|w—w.) we obtain for the order parameter Ker pale, te slaion zt 12. u Bape ltwite (N+ aw ‘Then since the product Nir. is a constant at large N, w~ UT ‘and T_~N we get the expression (a2) L cnaite(14 te 6.3 we ty { Wr t) (3.13) in terms of the reduced temperature 1=(T~T.)/T,. As we ‘can see for large molecular weights and for wide ranges of temperature, z*~(—F) and the expected mean-field exponent #=05 prevails” while for smaller molecular weights and ‘narrow ranges of temperature z°~(~1)'7 and the exponent ‘B=0.25 is found. Though this list one dees not agree with the expected Ising value 0.32, ic indicates a non-mean- field behavior near the critical point" The difference 0.07 of B=025 from the Ising value is rather small compared withthe difference of 025 from the mean field value and itis ‘not important for the predicted critical behavior. This small difference is due to the fact that the incorporation to the solution of the rest derivative diagrams of more than one loop has been neglected. As in the case of the one species problem,* such inclusion can be done in a solution around ‘Char. Pry, Vol, 109, No. 24, 22 Decernter 1995 11G. Gas ana Mt Kosmas Syrmetic sary polymer DENS sto FIG. 1 teapot =0.0012, sees vlan fraction ef ecw athe pene oe sme ees ieee cha gas 9 the dimensionality #=4 and in an e=4-d expansion scheme where «is teate as svall parameter, Amended ues of the exponents are expected in thie way for €=1 (d ‘bur an ecxpansion is beyond the scope of the present paper which is aiming tothe prediction of the main features (Of the cxitical behavior. As the comparison of the present results with these fiom experiments and other theories re veals this aim is reached by means of the given solution ‘igh at the physical dimeasionalty d= 3, IV. THE INTERACTION PARAMETERS We can uke the anilytic form of the generalized inter ‘action parameter y=w'+ R/C@(1—@}) substituting R from Fg (33), Ve [32430 Faron ae ON newer (aay with = 447 9(1~piN?, Ba. (34). Equation (41) shows that cain correlations add negative contribution 0 x ané permis ust stay 328-2 function of N. , and g. In Fig. 1 we plot 24884 function of ¢ for various values of N fora constart ‘On increasing N, x decreases and sts dependence on concer uation becomes stronger. Thi behavior is in secord with irate by nie of try eel apie x temary polymer-polymer-solvem synems™ and_ with ‘whats now predicted by theory”'="" and ig sugaested from, ‘SANS eaperimerns*** als forthe case of polymer blends. ‘The slas shaped dependence of x on volume fraction ¢ that is seenin Fig. Is precvtd by theory Fortra ae nary sysenstl ad ie observed. in may SANS? ond ccompuser™?* experimen. From Eg (41) the behavior of ‘special ims can be taken out directly. At dilate compo ‘sons where ¢=( or €—+1. ye obtains is maximum valve as 2 function of Ags W. While For @=015 i presents 2 mini mum The quaniy: Ayfw with AY=Anue—Ynie BES the ‘magnitude of the contributions of chain coreitions (0. 07a “These contribatons for instance for w'=2/V a value close to the critical region are abou! 10% for.V= 10 snd about 1% for 1000 diminishing as. N00. For w—=0, y of Eq. (4.1) tends © 2ero as expected, Also if w—0 then \y~w)hw-—0, Which means thar the correlation term yw feaches zero faster than w, This means that far fom the critical point the contribution tothe free energy ofthe term R which expresses ‘hain corelations is small und x reaches the value 4'=w a5 it ‘docs inthe ease of extreme compositions, Thus x tikes also the form x~wtb/T which is similar to tht proposed by Flory (Eg (1.2)], This form of is widely used wo explain experimental data either for UCST or for LCST behavior. ‘The ctiical value of x can be obtained if we substitute Ba. (3.11) into Bq, (1). To a fist approximation we obrain the expression an ‘Equation (4.2) for large leat the FloryHuggins resale fr the critical imeraction parameter for the symmetical end y= 2/8 while For five its postive quantity 10 the classical value, consised with Monte Carlo ‘experimen. An almost identical conection to the Flon’~ Huggins binoda values near the citical point can he found by solving together Eq, G9) and Eq. (3.5) for lnrpe N. Pre ions theoretical works employing concentration fiid and integral equition metheds have found both pesitve"" and negative” corrections 10 xc Chain coreatons alest strongly the effective interac: tion parameter toy oF polymer Blends of normal and deuter ated species, esimaied by means of coherent small angle neuen scatering. The zero ange scaring pata structure faci of a bind in egulibeium is given by te inverse of the second derivative with respet Lo volume factions of he fee fener) of mixing” Applying this to Ea. 3.1) ve get PAGIKT 1 1 oF ae «ON (Tern ag? (eC —9)¥/09 +R. 3) (On the other hand, $(4) obeys tbe equation” 1 aoa) 1 -eprwa a) where, DIN.g)=20g°R) +e" ¥— Lig RE and DUPN.9) te Debye finctons with Ry=o(N/6) the radius of pyre ioe of the chain and a the Gaussian eyment Jength. Taking {eto sesount the fact that Debye functions D.N.q) and. D(rW.q) reduce 1o N and rN when 90, we get be 4.5) ra Eel) )4/0,2 8) (as) Sanstuting & from Fi. (3.18) we pet the expressionv9 | * FG. 2 The parameter yg fr W=1.0012, vero volume factn , for symmeicsytems of diferent cats lengths ¥. The dashed ine longs 0 te concentration depenset pa ag wa tw-@ariany [ap pt aftzteine *Ge- en He 1/_ 2-1 \ 2, ee | 0 and applying the approximation Eq, (3.2) we obtain for the ) the expression We [1-2-8] ~ aw Hotta [PH ERS feet | me} 24) ¢ iste ee en ANE a with c= 4791 9IN®, The yer of Eq. (4.7) diverges at ‘except forthe case of =p, =0.5 wher it gives a cusp shaped singularity. Thus Ea. (3.5) gives the line where the Inverse structure factor of Eq. (4.4) vanishes, In Fig. 2 we depict xaq ¥S.¢ for different values of chain length V. The curves have the characteristic concave form, which is pre- dicted by ether theories too!" and is observed in many neutron scatering and computer experiments as wel The effective interaction parameter decreases with an in- creasing N in the center of the diagram but out of the midrange of the composition this tendency reverses and oy tums to be an inereasing function of N. We see also that there are two symmetric concentration regions where the curves of different N cross each otter nearly at the same point. This means that for these concentrations tor it insensitive 10 variations of the chain length, so they determine a “corela- tion hole” of independence from W. This behavior remains 10 be seen with suitable experiments on severl polymer sys- tems of different composition and chain lengths. Ako we observe that at the extremities of yolume fractions the ring tenm contributes positively to xr which becomes larger then FIG, 3, The smeracson parameters (and xa (fr =200 vers vine ction eos a lower the pineal ower and upper carve, repost) Wat the wings. Comparing Fig. 1 with Fig. 2 we see that x and eq though roughly similar in behavior they ae not iden- tical. Tn fac, oq Overestimates the concentration and chain length dependence of the to species interactions as they are expressed by and this can be seen in Fig, 3. a8 well where we plot the two parameters in contrast. The effective inter action parameter eq is more sensitive tothe proximity to the spinodal while far trom this region y and xq become ider- tical ard molecular weight and concentration independent ‘This can be seen in Fig. 4 where we depict x and toy ¥sw for 05, We can also study the behavior of xeq taking the limi, of Eq. (4.7) at extreme and mid compositions. At ¢~0 or el and a! @=0.5 we obtain the extrema of ey With ce- spect 10 g Nnue= Ya = Xo oo ot (43) 49) oar oat6 z & & E 018 oor 0.913 0914 9.018 o.016 9017 Gore 0019 B02 FIG. 4, The parameters y (—) ad ug (~) for N= 100 and 60.5 versus ‘ie moleclariteracion farameet On approaching the spinodal 0:2) the two parameters Seva Chom. Phys. Vo. 105, No. 24 22 December 1995i ese GE. Garas and MK. Kosmas: Symmetc binary polymer blends For the case of dilute systems [Eq, (48)] we see thatthe ring term coninibutes positively 10 4 while for midrange com- positions [Eq. (4.9)] the opposite is true, The contributions of the chun correlations to Yep can also be seen vie the quantity Axel with Aga Xow Ani 8 it 38 already done. inthis section, forthe ease of x. These contributions also close to the entical point at w= 2/N are about $0%, 17%, and 6%. for N=10, 100, and 1000. respectively, while AxgAx~6 “These values show clearly that ye OVerestimates the concen- tration dependence of the free energy interaction parameter by a factor of about 6 near the spinodal an overestimation that does not become smaller far ftom the critical region where the R part of the 2g faints away in a similar way as the R pan of y does, Taking into account that atypical seg- ment for instance of a polyolefin consists of about six monomers,» chain correlations are significant for the xp of polyolefins with polymerization indexes up to 6.000 while for x this number is smaller than 1000. \V. COMPARISON WITH EXPERIMENTS The dependence of yg 00 N. predicted also by oer theones,**""7 ig observed in SANS experiments in many hhomopolymerftomopolymer, copolymerfhomepolymer and stur-copolymer systems. It is observed, for example, at mixtures of parally deuterted and normal poly(vinylethyl- tne) and mixtures of partially deuterated and normal poly (ethylethylene) where one can see a tendency for the Xe) curves of different N to cross each other as the concentration of one of the two components tends to diminish.* very simi- lar to what the graphs of Fig. 2 show. A similar dependence of xa on the chain length N with that predicted by Ba. (4.7) and demonstrated in Fig. 2 has also been observed at recent investigation on binary blends of saturated hydrocarbon polymers An increasing yg with increasing N is found for the case of blends of head-to-head polypropylene (hh) ‘with eltemating ethylene-propylene (PEP), Of interes isthe different behavior of these mixtures compared 10 the ofher samples of the investigation. They present small postive ef- fective interaction parameters agg that depend on N and the dependence of their gq 00 1/7 was found not linear which imply a substantial contribution of the chain correlations of the R term of Eq. (31). The contribution of chain corre tions car ako explain the difference which was found be- tween er and x estimated by the solubility method. This difference that was found to decrease with 7, corresponds to the contribution of the R term to x.y and indicates approsch- ing to the critical region as one can see in Fig. 3, The ap- pearance of ths difference on decreasing the temperature suggests « UCST behavior that was indeed found for this system, In the same figure we see tha this difference can be either postive or negative ¢ fact that was also observed in the same investigation. However, it must be stressed up that this “ext interaction” does no really affect the equilibrium bichavior of the system that is governed by the fe caersy interaction parameter x t0 which chain correlations give al ways negative coneritutions 1s Fig. $ ygq is ploted versus ¢ for # small chain length N=32 in onder to be compared with Monte Carlo results In the homogeneous repion, far from the spinodal, the R term of 2088 kev 08s ous 9G. 5, Parameter oq for spmunetk ses of» ual al eg 32 fran cee 16 the etal rele, a le two pane and a the one Phase repo the free energy is negligible so xg is practically independent fof ccmposition. When epproaching the two phase region the R term becomes important and the dependence of xy on composition becomes stronger especially a! the middle ofthe ‘xar-@ plane where the critical point of the symmetric system lies. Tis gives a concave shape 10 the Ya) curves with an ‘upcum atthe wings, which is connected with polymer blends that lack strong specific interactions As the system comes near to the spinodal this shape becomes more obvious and the difference between the extreme and the midrange com- position values of eq increases. (see also Fig. 6). This ‘radval transformation of the xeq(¢) curve 1 seen in com puter simulations for dense symmetric binary polymer sys- tems and chain lengths up wo 32° Comparing the curves of Fig. 5 with those of Ref, 19 we see that they are in quaiia- tive agreement while the relative magnitudes of the spreads oftheir wings given by 2(Xnar™ Xan” Aas Nn) 7 almost in quanitative agreement at least near to the critical region ‘where these values are large and their comparizon possible. A similar transition from a concentration depended parameter ‘Xa 10 an independent one by means of increasing. tempera- wt FIG. Aiea el) fr N= 1000 vers w fore and die oe alee Sg Te teens Ag boca s toed ie of ‘low othe spinal wes o> 6ture fer UCST systems has been observed recently in neutron scattering experiments for binary biends of polyolefins and their partially deuterated homologs.” In Fig. $ we see that at the two phise region xy increases in the center ofthe dia gram and finally diverges on the spinodal curve, The difer- ence between the values of Yay at extreme compositions and At midrange compositions is decreasing as the system goes deeper 10 the two phase region which is also seen in the above mentioned simulational work: In Fig, 6 ve plot this difference Yer= Yuk 1) Kel) for 0 and several vale wes of gp. For the e=y=05 case a Ayo that increases ‘monotonically with w is found while for cases of €)7 6A tug changes behavior near the spinodal becoming a decreasing function of w. Thus the way Yay Dehaves asthe system is approaching the spinodal curve is related with is compost tion and the leeation of the catical point, This can explain Why this behavior of Akay studied on mixtures of different ineractions and chain length fractions, which means differ cent critical temperatures and compositions. and measured at cerain volume fractions g and ye wa aot found universal." The linear behavior of (9) atthe extremes of @ is also seen in recent SANS experiments with very dilute polymer blends of dewerated polystyrene in a matrix of ‘normal polystyrene and of deuterated polystyrene in a matrix of poly(vinylethylethere)." This tendency is also seen in the data of the dilute compositions of an earlier work on the same macromolecular system Where one can also see a honlinear dependence of Yq ong a the nondhlute compositions.“ \VL CONCLUDING REMARKS: In this paper we presented a molecular theory of poly= mer blends, eating polymers as Gaussian interacting chains. We found an enalytic expression for the free energy of a symmetric binary polymer system summing up the ring-form rams. The interaction parameter y and the effective in teraction parameter Yay Were found as two different functions of the variables of the syssem a fact thar permitted ws to study them in detail. Both parameters depend on composition and molecular weight and these dependences become stron- ger close to the critical region. These two dependences ‘hough roughly similar are by no means the same, Our result that Yup overestimates in a large scale the concentration de- pendence of the free energy interaction density explains the unphysical large concentration dependences of this param- eter measured in SANS experiments." Aiso xy is found to be richer in betuvior than y presenting regions of relaive independence from the chain length 2, ‘The position ofthe critical point is found to depart from the mean-field prediction as the molecular weight decreases in accord with other theories and experiment. Chain correla tions conibute with nonlinear terms of T~! to the tempera- ture dependences of and x,y but they do not seem to affect the kind of the phase separation behavior (LCST or UCST) of the system. This tehavior comes primarily from the w term of and is determined by the local properties of the system in accord with equation of state theories,” However {for systems of no equation of state effects the dependences ‘on and 1V and a nonlinear dependence on T~! ral expected co manifest cogetter, In conclusion, we have presented a theory for symmetri- cal binary polymer blends which despite its simplicity is in accord with recent findings of experimextal work also pre- dieting certain poines that are worth future investigation. The ‘most interesting One is that related with the concentration dependence of tay on N which, probed with some sensitive experimental technique could be the touchsione for the ve- racity of this theory. are in pen ACKNOWLEDGMENT ‘We thank the Greek General Sseretary of Research and Technology for paral support of this work "1, Pipi. the Molecuer Theor of Polsmer Saute Nort oad, Anserdam, 1957, 2. Fen. Prncipes of Polymer Chemis (Corel Universe. 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