16 Time-Temperature Superposition - A Users Guide John Dealy McGill Unis Menten! Qucbee Canada and Don Plazek nines of Pisburgh, Pemylvni USA Abstract “Time emperature uperpsiton a alse tol for scribing the vicocaste behavior of bnew palyners ‘ver rod range of Uns fequccies by sing thus obained at several peratures toa comes Feleence emperatue.Thisacniqu ales he use Df temperstur-depenat sil factors fort ‘mageteds of measured sss (vere si factor) Sd forine or requeey (hora shift ftar ox Tog-tog pots of material funtion suchas the reaaton ‘dan the storage and los mod, ad the ereep Compliance. The lemeratre- dependent, vera shit Factor by is silly defined so th maples stress ‘iermined temperate ro yield reed sess” thatthe vale at reference tempers” Ta normaly very else wo nity. The temperate dependent Forze sit factor ay mites regency & divides atime to yield a refoced vue equal 64,0 6° ty ime temperate supesposton is oeyed the se DF shit factors Wil yeka "ser cure” showing ‘sceletic behuvir over a mosh grange of imes toe lrquencies han could be suid wing single Fleometer atone emperatre However. 8 Hf fcr ‘alin he plateau aa ermial zones snot expected 0 be applicable in he vansidon zone. And the success of superpasion shoul pote Judged onthe bass Smal fog-tog pat or imprelse ca Inerodution sage rheometer operated at sng temperature an ‘ually provide dats ony over eran of tee our fzcads of requeney or ine nd hiss nacequte © trek visoelestebebavior rom he igh-Fequeey end ‘ofthe psa zoae fot the low-frequeney terial zoe By obi dt at several exerted temporture serpin canbe used to gnezte@ “master eure” showing tbe behavior a2 "Ylereace tempers’ that covers man decades a ne or flequeny. A material to which ths ecnigu is ‘pliable isda be "thermorologiclly spe” In preparing master curves, variables havi {ripen ine) are sajet horizontal shi hile those ving unite of ses (or rial tess) are ‘sujet vera! hi, For example n pcp Compliance "muster curve” the variable pte on the eral xsi Jy, an tha pled on Te horizontal Auisis ty where beth aby are shit Tats that {pend on emperatre ‘Thermorbeoloicalsiplctyobais when at contig earlaon of elation mechanisms ofthe teal have te same ampere dependence and when sess sugitudes at limes oF fequeaces have the same temperature dependence Thi miles hal when ‘scoelstieTustons, suchas the vlaation modales {Gif or he creep compan 1), fe shown ona double logic ple, daa various tomers ean be sled horney by const (ndependeat of tine) stance ete fog) and Yercly by sate ‘ons diataace identified ak by oobi sng tater curve bringing ogee the dla. The maser ure displays data over a wie range of requencies Or Times “educe to eeence tempera, Ty A Thora dnesson of me empertre sperposition ‘abe found inthe book by Fem [Seton T1-C) who vo discuses the siting of at obi a evra presses ‘We ean mii the ove dessin by suing ht 2 str curve ofthe frequeney-dependen sore modus. ted on dt bined at various emperstars Pit ‘obiind by peting DGD vers ony o ‘sng logarithmic sas for oth aes, Whi is at indiwed exp, by nd ay are fuetions of remperatute, hough te by dependence gute weak “The quuny on the ef sale the “Yedued storage ‘modal sometimes given the sybol G while te rele aqueey iy Using these varies the maser ‘carve tpt of G; venus And the temperate dependences ustllyeponed by means of «pot of Toga) venus. Likewise forte me depend srs easton ‘models a maser curve obtained by plating yGAT) versus ay 2 aang logan sae, Tica be wet terms of reduced varables s G; vers J, However, be reader shoul be awe tat an aeraive defini of by has ben wed parca nae earl pablietions af Gresley sd his eolleagbes nin the esa! book by Rog Bn, 782) ty 2008Rubinscio snd Coty (2) In these pubic the redoed modal is (MU) ‘The concept of time-temperature superposition canbe ‘expres infers of an equation relating the property at the etree temperature To that measured at temperature Pad then shied oT POT a01) = CiTa0) Gi.) =00.0) However, some authors wie he equity ina ifforeat vey. whic can case confsion, Viscosity, which involves both sues and me, eqs ‘he application of bath sb facta For exaple. mater curve ofthe aol value ofthe complex Viscosity is consti by mean fa double: Toga plot of Peigsry vers ay “ where br} -Ne7EF fo ‘A special ease she zee shear viscosity BA) MCT) = Mo 5) Baye) ° ue vet shit eon taken to Be wit the orzo shi tor cane infeed from te 2eco- Shee cs, =!) Ona) Since vcosiyisthen proportional othe shit fat, the isco ao reve te viscosity Hel gi ‘fen aed ea hrzontal si fo. (One can determine the horizontal sift for without ‘making any assumption abot (7) by plating ssa ‘Andon a Gequaney 3 quantity tht bt alee by Dy sub asthe loss angle ois angen, which equ ie. Conroe sin somerset ted for ‘menses at moderse an igh feqercis, while Cone orgoe (sss iestrumsns ar more useflat Tower quences. However, ota happens that neler silty sear method ean provide data ine eral zone at creep ae cree recovery ate ued to provige ‘he missing information. The combination of daa rom ‘hese we ecniqns to produce single ase curve regules a method for conversion of ene mei fenton, forexample he eeep compliance, ino ans, or sample te Socage modus. One approach his conversion was proposed by He ef (3. porn, ‘oot that while tee ecovery isthe most accurate ‘ald for dtriaing the steady sate compliance. ‘ie cae the steady-state recoverable compliance for (his veaso, i allege la ae-earig Instumens, ‘esa torque prevents the relucon ofthe sess 220 her this mas be eonsced for using a model or 4 api sispension ied place of on i bearing. Ihe ese of erysalabe melt wefal temperate ‘ange extends ony om the crystallization temperate, ‘on below end to he degradation temperate, athe highend, and this is the appleby of sperpsion ‘obese polymers, ‘Tre compilation of dts tained at several tempers Inevitably ae none nto the resling maser eure. Ard ‘deermin the melecalar weight essibton F189 the Sitereion of [4 wires een. ‘Theoretical bass for thnetemperatare superposition ‘esta shor ‘The Husche Roae there fhe nea vical of uneriangled polymer mes and soltions 56] assumes ha sess magni, eg, GU), Ge) and Go), ae proportional the product ofthe density and temperature ‘This imple thatthe vere shi ator bys oem taut o Foc entangled polymer ystems, the molar mode ‘nos widely used are had othe eaey of Dot end. Edward [7]. which preditsthat the magnitude of he ‘elution modulus of an entangled mel proportional {0 efector p that appears inthe Rouse prediction ‘mulled by anew factor tht depends very Weakly on temperate, Thus te vera sb factor i predicted 0 bo slghlyaiarat rm tbe patio, bt dats are acy * ever precise enough o oval ths ifereee Rates than using Eq, 6 he verticals ator is sietines dtenined del rom he vation with ‘enpaate of dsintive value of the mols or oy Bein 782) ty 2008compliance, sch a maxima o inmate oss ‘todos. Th pnts nthe relation mosis GU, te ‘seep compliance J), the strage mous Go) the Storage compliance) isalse sometimes se However, since re patents wth oo slopes en scully ofserveg, te values atthe asseited wax ‘of minima provide more rele bases for y(D. ‘Although peice mearorement poses challeess, he eady state compliance provides reiabi basis or ‘ding ba demonstrated by Resch tl (] and lac (9), Another way to determine the eral (ses) sit itr ta Is lndependen of he ine or ‘Requeny shifts to fod the havin sof ss ngs dia rqued o aban sgerpostinn on la of los angle versus lg IGM, which sealed a Van Gup Paimen plot (10), ‘The vere sit actor is sometines used as a ing parameter for an enire se of data, and he das are hited bo veel and hail in an ater chieve a superpositon that “oaks OK". Tas apical procedure can ep o sis the aire of ‘Seperponon by verogig he discrepancy over the ti requeney cane: Sytemate devitons of by) ‘fomits expected behavior (E46) can so res om eapeimentt eon. Fly fb shi ecard out by iting, either factor ha any psc! sian, Forthene eons, such els re qussonabe Horizontal shit factor ‘Wha o molecular models tll ay sbout the horizontal sin fac? The elataon tines af the Rowse made Se those appearing in tube models or he plateau sot ‘erminal zones ll depend on emer the m= ‘ey they ae proportional othe aio JT, wheres de ‘monomers ton cote he tion eeliient oes no depend on tres deformation, and iis ‘ependence Tee know priv sine bh fast ‘sol be apes rom te ery porn of the ‘tanston zoe dominated by Rouse relaxations into the {earl zone apd oP) could be eae fom theory. However ti abeertion doesnot low the resition ‘tthe shit factor, Heese the monomer riton ‘coofcien iu empiri parameter nthe fel joined ‘han model, ane te ve an nly Be infeed rn ‘heolgial da. Thus, whi al the theoses enone’ abe peli themheolgial simplicity over he ime ‘or frequncy rane of sr aplabiy inthe plate ‘nd emial zones, they do nt ead oa rediion of 4D is imponantto note hatte Rouse Bueche mode or nenanged polymers and ube models or entangled Imbecues ate based on the fells chain ad), iwc the actual nlc replaced by nich lope store tat mes pone o make ola Bul, 792) op 2008 _quanitatv peitions of viscosastcbeavie. This Ptr as bes found work very Wola deseibing [ebavionin te peo al eral zones ad ate Tongerime homestfoqeency) prin of te tansion one. Butt sharers resin modes ivelving Pars of molecules seth the egrets ote Freel -oimedehain come ito play, a hese ae not ‘esrb bythe model scussed above As asl, a ‘ale of a abaine using data the terminal and teas zoes wll nt sere sperpose data cain st Significant shone mes (higher equensies). Pak tnd his coworkers [1-13 have reared exceptionally precise ad accurate crep daa over any decades of lime for sever] amorphous polymers a ave used these to demonsrat th fue of tine erent superposion(ocureee of thermoriclogieal omplesi) when one wieso pce alte dat ona Single master curve usinga single vale of at piven temperate, Sorcines, reasonblesperposion can be ‘sine over very de dimeegucny ranges y ing two or mave horizon si fates [14,15] fo diferent \meltegoeney zones. For polis sampls there is 2 paiva unsion fom one zone eather <0 one ‘must examine the data carcul to delet he Beginnings ff hemoreolgialcompleity asthe reauency {creased Italo inpertnt 6 nte hat shortine ‘elation nani wl some no play longer {ies the empersture lowered One us teefore Seon the set fo complex ne oly tort es (igh regain ut aso low temperatures Sine oy cant be prediced, orzonal siting is ‘aie Ou by shag daa unl he spear superpse onerkamp and Weese (16] have described a proce For dong nn abecive manna. ad soar fer this rose spa af the IIS package (17). How does depend on txnperatie’? Ely observations, ofthe dopendeee of qua seas on teporature od {orhe empincal Aen elatonship Hea be expressed in terms of a5 follows ame (t-2)] o Ad his relationship sheen Found tt tar ina polymers inthe pea and terminal zones a long as the empecatare ‘ell above By analogy with reaction rte Theory, Ue eonstan has come to be elle’ the acuvatin energy for Now. However the tcvation enery concep iofen wed to Sharacterze polymers ven wien reological fa donot superposed his rests in fmbiguty a 10 de meaning of Foeexample, is vometimes reported to vary ‘st roueney ore or mods, Various "pproaches have bee popored for suifying a meaningful setivationenerey ‘when dala d nt superrese. One exam ‘value based on, Sever ways of efi vale ne absnoe af ‘sipeposiion have heen compared by ‘Wood: Ads and Costus [18], abl Kener ral (9) have recenly discussed this ise In cet isclear tn eporing ciation energie or ow, i ese to explain in dtl how these were deterine. ‘And ose must not compare values cbisined in diferent ways. nay event, wea dn do ot superpose, the ue of wn activation ‘energy to characterizes polymer is somes questionable Fortemperaures close to Th atonal cormaite ee volume concep af Doo provided te bass for the WLE (Wilans, Tandel Fer uation (9. 8 acomplee discussion of which abe found in Fer I, Seciors I/-B.C) where and eae empire eons Judging the succes of soperpositon “The degre to wtih mperoston x successful i aely jogged onthe basis of ‘objec terion. And oe shoul oc rely ‘on software ro make this judgment. Mast ‘often one simpy loots a he tied data fd declares that time-temperature Was ‘cual runeooerf This it prcalay wus fra porn fa curve that as slope mud estan aos, whee =| significa alr of borzonal fupepostion ess ina shied dats plat that i elowe othe trod line bs iaculy farfrom where it should be Wood- Aas 1a Coteus [18] proposed the we finest Fater tan logaritri seals to detect ‘complexity. laure | shows da fora ‘melocene polyenes homopolymer ‘with very ow level feng hain ‘ranching: On this og-og pot he data apps to superpose wel, dt the ier pl. Shown i Figure 2shows clearly shat ts ‘acrls oot hemrbesiogcaly simple This example the detection of complexity ww 2 ow ra] > = tne oy Ps ac em en v0 10> 1600 7 ‘0a, (radls) Figs: Mea fn os hay hed mec al ets rs ea A ee o3s zo § os Bow =r ae = 976 a 1900 ° os @ & » % » » 0 (MPa) Figo ures ofatonae ae of be cmp mdi of epee (TP UM er swe wor ton aes Teva abt er ‘See teuigan ester vcey honda eb i a os 2 os 2a a Boos el ° eye a) nodes) igen caf nal comple me fe aby ‘buon cpt (8) Une see rb me Tevet se tae ‘Skee bone te een vy el rl i er holo alti, 782) 20093 P02 M130 kg/mol, PDI=1.13, 10wt%| [M92 kg/mol, PDI=1.02, 90wt% 3 G'br, G"br (kPa) a 3 104 103 107 107 10° 10! 128 10? 10% 10° 108 ca, (rad/s) Fee: Mar curves of tag dos mol politi ind ed en dats bined eat pe ‘are: Tse ds perpse wel (Dato Mishel snd Hee Eo uk meso MeO Unies) ‘simp, a provides evidence of ong hs ranching Figure 3 sows te mse “xtve sig linear sues for a eae ‘iylenefbiene copolyner tat exhibits ‘excl superposiliy. Note thatthe ero- ‘hese vtcsty bas been we the fovizomal shit far. while dhe vets Shi factor keno be uniy. Smet i Slam at data superpsed, bu no pot ' Shown: suc a Stemem us be oidered doubsl A simle an net etnique for desing comply {ethe ue of van Garp Palen plot 10} loss ange ‘eri lop" If be effet of hy om the magne of he complex modulus is eaigibe the dts wil uperpose ‘without shifting ie materia tesmtbenlogilly simple ‘The dere of themerteoogis complexity may sot ‘uve serous consquences i enya general ted sof Aten ein 782) ty 2009 Interest ut when on wisest afer structural fetes fom dats, it becomes very mpi. Fo highly ang polyer molecular truture is reveled by ‘efavor nthe pies and terminal zones, a ain ‘he anon Yon an t even shorter ines ae not of Interest forte application Is ft rheological havior ieroresentvevo the presence of sal quanits of Tange molecules han chromatograph. Hove well does it work? Fete dis master curve of dat bind telat temperate fora bind of se lieu polybutadiene. Each point isan avergeof irr messuremens andthe ‘era shift fetor was alld using Ea 6. Catal Jnepecton revel fe sal dovisons fom superposition but, aking acount the pression ‘otaiable inthis ype of meaner, the supepesiion ‘sdeemed o be acceptable (omnes pgs 30) 230 (eT peroston, atin fom ps 21) ‘A mae wil exhibit emoeeotgil implicit fof ts reatation tines have te same dependence 00 temperate As dermnsrated above pet bes inthe paca a ein zones. Ard is should oni be the ase a we move nt the ston zone, a fog selva spoversed hy Rouse odes Hower, iis nt posible fo ty inadvunce ovr whit Portion a the aston zone dts wil saperpose. Molecalr modes sed the ely jointed cui pice ‘nos i or processes involving partons of te cin Stale than the imaginary "subunit hat rakes wp this ‘un. And ante complain t igh frequencies {short ines) shat as tbe enropyseing odes ate famed te glassy mods of eaxation become ‘omirare (20), We expect hen ht shi Taos based ‘1 Gain the platen ad emia nes wil always all some poi not far beyond (higher frequencies or Sore ss) he plata zone Nonlinear properties Gresley (2, p. 239] provides a discussion of he application of time-temperature superposition to rear ropetes and we provi here nl aio Suramar Te viscosity Function hes ben reported wo obey time-lempeatue superposition. Ihe veil sit 2 the horizontal sift factor to obtain a master curve by ‘ltine a7) versus 17 ao a7 1 ‘Te ae vscometi nesions can ao berated in this mime. Bet iseomtrcfnstion ae inctions| fies what soa tine dependent properties? {Conta uations for met aeatoniverally build ‘nie sume specs of relation ines are wed 1 ‘esrb isa violet. This imps tht ime ‘emer superposition bring ner dts ogee. shoul alo wor for online propnies sing the same sit tore, The fanéamentl nso shat the ‘elation times ar independent af the sate of res. Torexample temperate svaraot representation of ‘heshear ses prow coefficient is bse onthe following relat: Pep Ulapshan Tan AT) 0) Malle nd roc (2) spied tie temperate ‘sperpocton extensional sgt daa ‘Structural features contributing to complexity “The mos sesesfl demonstrations of sperposition ‘save involved near homopolymers and complet is ‘olen assed nth eae moe compl moles. Yariaon inthe Ine! micosractor of iear polybotadienes ean from hyogenation ovr {extents wee found nao eit in deviations rm ‘Simplicity [23], and al te polyers produced in that ‘uly wer found wo have the seme horizontal shift factor ‘hen the reference temperture was T, +507. As we ‘ight have expected, hese shit atts dd na upepose ‘ats btn at rogues wel above the plate elon [Pibecause of he prominene of seinen elakations Tats exon ‘Wood. Adan and Coseus [18] found that he very shot ‘ranches in eslene-octee copolyners dd ot esata ‘hemarheological comple The effec offoagehala ‘brnching depends ona comblauion of cain eemsy snd molecule wchitectre. Mtallocenepolyeslenes oniaining iow levels of angen branching have been Turd tobe thamvtcolgially comple (18,25) Polysopone stars have the sane shit facto se ne poly (26 Kepaso [27] studied a series ‘of polybutdines having slike backbones wit red branches and pte ht he hl factors ware {he sane fora te seucares tar they tse. Moco, these were the sme us actors epotd peeviouly Telia and comb polybutadiene On the oe and at for tdrogeated polyouaine sas Were not, Superposale [8], sllmugh thiranydrogenated precursors exhibited simpebekavor 29) This Somaios ber has een examined by Gresley {Bor and heoretcl explanation hasbeen propos (31) Low-density polyethylene has conpexsructre hat fnvolve bth ong sn shoct bah an i ac fo te themrheclgialy compl, Acknovtedgements ‘Te ators teefited fam ng sessions wih W. \W, Gresley and comments ona lof the manuscript fiom Ute Keine ofthe University of range. However, ant to be infeed that those nase re fgreement with every sotement made in te pape. Michelle Lon Hee Ean Park worked for sever! weeks {0 obtain he data shown io Fig. and provided the ple Sen Shueng Tang ea the “ial” manwsrit¥y carefely and fund muny ways to improve ho ein, 782) by 2089Reterenees 1.1. Feay, Viscoelastic Properties o Polymers, ed, John Witey i Sons. N'Y. 1980, 2.M. Rustin and RH. Coby, Polsmer Ply, (Oxf Uv Press, Oxford, 2003, S.C He, P-Wood-Adams snd 1M, Deal, “Broad Teoquency ange characterization of moon polymers" Rho, 48, 711-724 2009. 4. PWood-Adams and 1, eal, “Use of theological ‘measremens oeimat the molecular weight ‘Esbacon a ner pyehylne" J Rho, 761- 778 1095. 5.1. Ronse, “A theory ofthe liner vseoolasi Properiesof diate soatons of cling polymers” J {Chom Py, 2 1272-1280 (1953). 5. F- Bosch, "Viscosity sl-fsion and aed eect insolid polyrrs J Chem Pips, 20, 1959-1968 (198). LM, Dol apd SP, Elnard, The Theory 2fPomer names, Caren Pes OXTord, 198, Chap 7 BJA. ese F3, Sadler. 1. Kashi and H. Mase, “Temperanre dependence ofthe sedy state recoverabl conics o near and long-caie branched polyethylene.” Macromol press 2009 9:4, Plaek and A. Chek, Ir, "Tempest pendence ofthe seedy sate recovers complance of Smmphow polymer” Per 1815-18 (199), superposition for polyerc Ben," Reo! Bll. 61), p54 Published by the Sec of Rhea) (1998), 11. DJ. Phzek. "The erpertaedepeadeace of the ‘vscolaste behavior of oly viny sexta)" Pan J 1245.33 (1980) 12°K.L. NgalundD.J.Pazek, “A quate explanation ofthe fren aims dependences othe ‘sceelsti softening and emia dispersions a Ene mops polymer” J Pal Se B, Poln Pe, 28, 610-68 986) 13. DJ. Plzk, "105 Bingham Meda ress: Ob, ‘hermodteaogial simply, wherein a tou? ‘Rio, 40,987-1014 1996), CG Roberton and CM, Rademacher, “Coupling ‘nde terpreain of termocheoogiea complexity i olybutaiens with varied microsite,” Macronol 57, 10000-10017 200 15. DJ, Phaek, “The temperature dependence of be sce sheng and terminal ispesions a Fear ‘morphs polyrers” Pat Se, Ps E20, 723 742 (1982 16. J. Honertamp and. Weese,“A oie on etimiting usiecure” Rhea! Act, 32 37-64 (1993) TT IRIS volar is described at helo rip.com. 1 P, Wola p85. Contour, "Thenno- ‘heolgial behavior of polyecien: Elects of 2) 2009 microstructure along chain branch 6281-8290 2000), 19, U, Keber J. Kase and H Munstdt, “Determination of mo ivaran’etvaon energies ‘flong-huin branched low-density plgetyene” J hot in pes. 208. 20. CL. Nasi and DJ. Phzek, densification of diferent ‘nodes of molecular ation apse chat cause ‘hermorieaogia complesi.” Rubber Chen Tec, 6, 316-134 1938). 21.W.W. Gresley, Poel Ligas & Nenvors Dynamics and Rheology, Caran Science, Landen. NY. one 2. Maer snd D. Frolic, “New etensonsl ‘comer or elangtonl viscid ow Diretngonce: Some esl 0 peltyeese ml,” Pater 6477-1482 (1985). 23.JM Carll, W.W. Gracey and LJ. Fees, fees of esi mierosractare om th vicotatic proper fina polymer mst Polyotaiene nd Ijdrogentad polybuadianes" Moron 17, 2775-2786 (ioe 24. C.G, Roberson and CM. Ragensher, “Coxplng ‘node iterpetion of termoreogies sorplext in pobuladenes woh aed meres” Mocroma. 57, noe. 10017 (200). 35.74. Stadler} Kascha and H, Mons, “Thermorhelopcl behavior of varias long-chain ‘branched polytiyenes” Macromol 4, 328-1333 (2008). 126.1. Foes, AD. Kiss, DS, Pearson, GF. Quack and F.. Vion, "Rheological behavior of stacshped polymers” Macromol, 26, 67-654 (1993) Fr.M. KapisosG, Koutls,N: Haji, Rovers Di, Laie aD, Viesopole, "Liat ‘theology of comb plynes with stare backbones: Mel ar solutions” het Aca, 4, 273.286 (200) 28. VR Raju Rachapody and W.W. Gracey. “Properies of amorphous and erystlizble hydrocarion pofyners. IV. Mel rheology of linear and star bance hygrogented polybutadiene" J Polym Se, Py E17, Tasi235 (97). 20, WE Rochefort, .G, Smith, H.Rechupudy VR, Raju, and W.W. Grassley, "Properies of amorphous snd cysallabie hydrocarbon payers. I Rhslogy of Linear and Star SvateedPolybtaien."J Polym St Phys 7, 179-1310 197), 30. W.W. Gresley. "Et of tng ranches onthe ‘emperatie dependence of wscoelste proper polymece malty” Macromol 18, 1164-1167 (98D), 51. AU. Levine dnd $7, Miner “Sar polymers ad the Tale of ne epee superposition” Macro 3, Se25.8697 (198)ametfiom Pubiteadtion of ihe Sostaty of TR