MORPHOLOGY OF AMORPHOUS POLYMERS AND EFFECTS OF THERMAL AND MECHANICAL TREATMENTS ON THE MORPHOLOGY 0. S. Y. YEH Departments of Chemical Engineering, Materials and Metallurgical Engineering, and The Macromolecular Research Centre The University of Michigan, Ann Arbor, Michigan 48104 ABSTRACT This report covers the experimental evidence of order and structure in three polymers, namely non-crystallizable atactic polystyrene (including amorphous isotactic polystyrene), crystallizable polyethylene terephthalate in its glassy amorphous state, and natural rubber in its near molten state. All the available evidence from diffraction and microscopy studies strongly indicate that there is a liquid-crystal type chain packing order contained within a nodular structure of limited size (— bOA) present in all three polymers. Effects of annealing and orientation give further support to the structure evidenced in the original poly- mer. The kinds of models which have been proposed for the amorphous state of polymers have also been discussed in order to clarify further the meaning of order in amorphous polymers and the presence of truly disordered regions. INTRODUCTION Considerable study of the morphology of crystalline polymers in the past decade or so has led to the development of the chain-folded lamella as a basic structural unit for both the undeformed' and deformed2 polymers. Although there are still numerous questions concerning, e.g., the presence or absence of a truly amorphous phase inbetween the lamellae,3 the regularity of the fold structure,4' and the origin and extent of interlamellar links,8 the recognition of this basic, lamellar structural unit in crystalline polymers has led towards a much better understanding of the physical and mechanical properties of crystal- line polymers. In contrast, little is known concerning the morphology of amorphous polymers or polymers in their amorphous states (glassy, melt or solution). Clearly a better understanding of their morphology should also lead to a better description of the stress—strain behaviour of polymers in their rubbery state; a clearer understanding of ductility, crazing, and yielding behaviour of polymers in their glassy state; as well as possibly answering some of the questions raised earlier concerning the morphology of crystalline polymers. A much more extensive review on the morphology of amorphous polymers has been written and will be published shortly.9 In this report we wish to review experimental evidence of order and structure in three polymers, namely noncry- stallizable atactic polystyrene (APS) (including some results on crystallizable 65 P.A.C—31---I/2-D
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MORPHOLOGY OF AMORPHOUS POLYMERS ANDEFFECTS OF THERMAL AND MECHANICAL
TREATMENTS ON THE MORPHOLOGY
0. S. Y. YEH
Departments of Chemical Engineering, Materials and MetallurgicalEngineering, and The Macromolecular Research Centre
The University of Michigan, Ann Arbor, Michigan 48104
ABSTRACTThis report covers the experimental evidence of order and structure in threepolymers, namely non-crystallizable atactic polystyrene (including amorphousisotactic polystyrene), crystallizable polyethylene terephthalate in its glassyamorphous state, and natural rubber in its near molten state. All the availableevidence from diffraction and microscopy studies strongly indicate that there is aliquid-crystal type chain packing order contained within a nodular structure oflimited size (— bOA) present in all three polymers. Effects of annealing andorientation give further support to the structure evidenced in the original poly-mer. The kinds of models which have been proposed for the amorphous state ofpolymers have also been discussed in order to clarify further the meaning of order
in amorphous polymers and the presence of truly disordered regions.
INTRODUCTION
Considerable study of the morphology of crystalline polymers in the pastdecade or so has led to the development of the chain-folded lamella as a basicstructural unit for both the undeformed' and deformed2 polymers. Althoughthere are still numerous questions concerning, e.g., the presence or absence of atruly amorphous phase inbetween the lamellae,3 the regularity of the foldstructure,4' and the origin and extent of interlamellar links,8 the recognition ofthis basic, lamellar structural unit in crystalline polymers has led towards amuch better understanding of the physical and mechanical properties of crystal-line polymers.
In contrast, little is known concerning the morphology of amorphouspolymers or polymers in their amorphous states (glassy, melt or solution).Clearly a better understanding of their morphology should also lead to a betterdescription of the stress—strain behaviour of polymers in their rubbery state; aclearer understanding of ductility, crazing, and yielding behaviour of polymersin their glassy state; as well as possibly answering some of the questions raisedearlier concerning the morphology of crystalline polymers.
A much more extensive review on the morphology of amorphous polymershas been written and will be published shortly.9 In this report we wish to reviewexperimental evidence of order and structure in three polymers, namely noncry-stallizable atactic polystyrene (APS) (including some results on crystallizable
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P.A.C—31---I/2-D
G. S. Y. YEH
isotactic polystyrene (IPS)). crystallizable polyethylene terephthalate in itsglassy amorphous state and natural rubber in its near-molten rubbery state. Theeffects of thermal and mechanical treatment on the original amorphous mor-phology will also be presented to the extent that these effects are directly relatedto the original structure in the amorphous state of the three polymers. A briefreview of the various models suggested so far for the amorphous state ofpolymers will also be included, hopefully to serve as a base for furtherexperimentation and clarification of this controversial subject.
RANDOM COIL MODELUntil recently, the random-coil model has been generally accepted by most
polymer scientists as a fairly accurate description of the conformation ofmacromolecules in their amorphous state. This is schematically represented inFigure 1. In addition to the assumed total absence of order of any kind
(including I- or 2-dimensional), the single-phase model assumes numerouschain entanglements and a great deal of free volume. Being statistical incharacter, the model has been very useful in the original derivation of themolecular theory of rubber elasticity. Although the limited applicability of thistheory is known and has been pointed out from time to time, the questioning ofthis theory has only been taken seriously in recent years. The more successfuland recent molecular theories by Guth'° and BIokland have been developedby taking into consideration the presence of structure in rubber networks. Othersuggestions which indicate the incorrectness of the random-coil model havecome from the effects of solvents on the depolarization of light scattered fromn-alkane solutions,'2 on the strain birefringence of swollen polymernetworks,'3 '4and on the comparison of densities between calculated (based onthe assumed random coil model) and experimental values of various polymersin their amorphous state.'5
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Figure 1. Schematic drawing of the random-coil model35.
MORPHOLOGY OF AMORPHOUS POLYMERS
PRELIMINARY REMARKS ON TECHNIQUES
Evidence of order in amorphous polymers can be derived from analysis ofx-ray or electron diffraction patterns either through the well-known Fourieranalysis of the experimental scattering curves or through comparison betweenthe experimental intensity function and a theoretically derived intensity func-tion based on some assumed model. Indication of possible order may also bederived from semi-quantitative analysis of oriented (and/or thermally treated)and unoriented diffractions of the same amorphous polymer, this being the leasttime-consuming of the three methods of analysis.
A more direct technique capable of detecting order and/or structure in theso-called "amorphous" materials is done in an electron microscope using eitherdark field diffraction contrast or phase contrast microscopy. The Fourieranalysis is then carried out automatically by the lens system, provided that theinstrument has the resolution capable of detecting the size of the ordered regionor the lattice spacing within a given ordered region. Neither the dark field northe phase contrast technique has been used to any great extent to derivestructural information on amorphous polymers, although the use of suchtechniques in studies on carbons has provided very informative data, e.g. ref.
To date most of the electron microscope studies on amorphous polymershave been on shadowed or stained samples. With virgin specimens the contrastis mainly based on thickness contrast principle.
The evidence of order and/or structure in the three polymers which we havechosen for this lecture comes chiefly from our own studies, based primarily onelectron microscopy and electron diffraction, and some on x-ray diffractiontechniques. Whenever appropriate, comparisons with available data by otherson the same or similar polymers will also be made.
POLYSTYRENE
Amorphous polystyrenes (atactie or isotactie) exhibit at least four diffuserings in x-ray or electron diffraction patterns. An example is shown in Figure 2,which is taken of an unoriented pattern. The corresponding Bragg spacings (9,4.78, 2.23 and i.26A) of these four rings are also indicated in the figure. The4.78A ring is the most intense of the four. The next most intense is the 9A ring,followed by the 2.23 and I.26A rings. The 2.23 and l.26A rings can be easilyassumed to result from intramolecular scattering. The distances between the ,-
C3 and C1-C2 within the molecule are about 2.23 and 1.26A. The origins of the9.0 and the 4.78A peaks have been elucidated by Krimm's study of orientedpolystyrene.'7 In the oriented pattern, of which an example is given in Figure 3,Krimm showed that the 9.OA ring and the 4.78A ring split into ares and orientalong the equator and the meridian respectively with essentially no changes ind-spaeings. The split in the 4.78A ring is barely detectable in Figure 3, as inmost eases. Krimm concluded that the 9.OA ring is intermolecular in origin,arising from scattering of atoms in neighbouring chains and that the 4. 78A ringis at least due to two different types of interatomic seatterings: those betweenatoms in alternate phenyl groups in the same chain and those between atoms inphenyl groups and main chain atoms in neighbouring chains.
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Ordered regions as revealed by electron diffraction22First I would like to describe some changes in the diffraction patterns
observed when freshly prepared thin films of atactic (three molecular weights:4800. 5 1 000 and 1 800000) or amorphous isotactic polystyrenes were irra-diated with increasing amounts of 80 kV electrons. Figure 4 gives an example
Figure 4. Densitometer tracings showing the changes in the 4.78 and 223A maxima as afunction of increasing crosslinking from bottom to top22.
of such changes in densitometer tracings. The major changes occur in the4.7 8A ring; changes in the 9A ring were not monitored because of its closenessto the main beam and because of its much weaker intensity to begin with. Notonly does the location of the 4.78A ring change, corresponding to an apparentincrease in d-spacing from 4.78 to 6.38A with increasing time of exposure tothe electrons (increasing degree of crosslinking), but there is also evidence ofincreasing line broadening as well as a decrease in intensity (after correction forthe background scattering). These changes appeared permanent upon reexa-mination. No detectable changes, either in intensity, d-spacing, or line profilewere observed in either the 2.23A or l.26A rings.
The observed effects of electron irradiation clearly indicate that the 4.78Aring arises from some kind of liquid-crystalline chain packing existing inamorphous polystyrenes. The ordered chain packing can be disturbed uponcrosslinking by electron irradiation. The increase in disordering of the paracry-stalline lattice results in the expected broadening of the peak, the expected shiftof the peak position towards the main beam, as well as the expected decrease inpeak intensity. Such changes are not expected to occur if the diffuse ring is due
70
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MORPHOLOGY OF AMORPHOUS POLYMERS
below or above T9. This was expected since the polymer is noncrystallizable.Consequently isotactic polystyrene was used. Unlike polyethyleneterephthalate26 or polycarbonate27'28 which showed a tendency for the nodularstructures to aggregate or grow in size, isotactic polystyrene showed hardly anyvisible changes when annealed below Tg. On the other hand, distinct changeswere detected when IPS was annealed above T9. An example is given in Figure9. The various stages of transformation from a nodular to a spherulitic textureare clearly discernible in this micrograph. Other results showed that thenucleation of a spherulite appears to begin with the crystallization of a liquid-crystal like nodule, or a group of nodules merging together to form a few fibrils,which eventually fan out from the nucleus by additional incorporation ofmaturing nodules.
POLYETHYLENE TEREPHTHALATE (PETP)The major publications concerning the presence of order and/or structure in
the amorphous state of this polymer are by Yeh and Geil26 on the glassy state ofPETP and by Ermolina et al.29 on the molten state of PETP.
I wish to summarize their findings in the following.
Order as revealed by electron diffraction29
Ermolina et al. analysed the electron diffraction patterns of PETP that wereobtained at temperatures above and below the melting point of the polymer bymeans of Fourier analysis. They found that the experimental radial distributioncurves are similar, each containing several maxima. The one at 4.45A found inboth crystalline and melt specimens was assigned as intermolecular in origin,due to scattering between atoms in neighbouring molecules which they suggestedhave a parallel packing arrangement. The size of the ordered region was notmentioned, nor could it be determined from their data. The disordered regionwas not mentioned either; but presumably it belonged to the boundary regionsurrounding the clusters of parallel molecules.
Ordered region as revealed by electron microscopy26Yeh carried out experiments on unshadowed thin films of glassy PETP (MW
15000) at room temperature using bright field and dark field techniques. Anexample of a pair of bright field and dark field electron micrographs taken of thesame area is shown in Figure 10. Regions of fair contrast of about bOA whichindicate the presence of order and/or structure can be seen in both micrographs.The dark field micrograph was obtained by using a portion of the innermost,which is also the most intense, diffuse ring with a Bragg spacing of 4.5 A. Thediffracting regions are suggested to have a paracrystalline packing of alignedchain segments with a constant chain-to-chain distance of about 4.5A.
In a shadowed specimen a distinct nodular texture was detected (Figure 11),the average size of the nodules being about 75A. These structures are present inboth bulk and thin films, and have been confirmed in a separate study byKlement.3° The nodules have a fairly distinct boundary, indicating the majority
75
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NATURAL RUBBERNext to polyethylene, natural rubber is probably the second most inve-
stigated polymer. Yet very little is known concerning its morphology at roomtemperature in its most employed state.
Because of its high molecular weight (in the millions), it remains strongwithout crosslinking iii its near-molten state at room temperature (Tm of naturalrubber is about 25 to 28°C). Consequently structural studies can be conveni-ently carried out at room temperature in its amorphous molten state.
Structural order as revealed by diffraction techniques33Most of the x-ray diffraction studies on natural rubber have been on
stretched, crystallized samples. Simard and Warren33 are probably the onlyones to have analysed in detail the x ray diffraction of unstretched naturalrubber obtained at room temperature by the radial distribution method. Theyshowed that the corrected experimental intensity curve contained one veryintense peak at sin 0/).—0.104 and two other much less intense peaks (at sin0/). 0.22 and 0.41 respectively); the latter two are generally accounted forby intramolecular scattering of the carbon atoms. C1-C2 and C-C3. Theintensity of the innermost one was about 7 to 10 times the outer two. (Theorigin of this peak is still considered to be unknown; its intensity, however.generally decreases with increase in orientation and finally disappears altoge-ther upon further cooling in 'fully' crystallized stretched natural rubber.34 Themeasured crystallinity for a 'fully' crystallized natural rubber is, however,seldom more than 30 to 35 percent).
In the radial distribution curve obtained by Simard and Warren, at least fourpeaks at r - 1.52, 2.68, 4.0 and s.oA were observed. The first three wereattributed to the first, second and third neighbour carbon atom distances. Thelocation of the fourth peak was explained by its high intensity (concentration)due to an atom's nearest carbon neighbours in other chains, i.e., the distance froma carbon atom in one molecule to the first concentration of carbon atoms inneighbouring molecules which is about 5A. This high concentration of scatter-ing, as pointed out by them, is responsible for the very strong peak at sin 0/).0.104 in the experimental intensity curve. They did not explain, however, howthat high concentration could arise if neighbouring molecules were not packedwith any order. However, such concentration could arise if the neighbouringchain segments assumed a near-parallel alignment to one another.
Ordered regions as revealed by dark field microscopy3As we have indicated above, the most intense diffuse ring may be caused by
intermolecular scattering of atoms between neighbouring chains that are more orless parallel to one another. This was proved by high resolution dark field electronmicroscopy using a portion of the innermost ring with a Bragg spacing of 4.5A(Figure 17). A similar image was reportedly obtained by Ban3' in thin sections ofcrossl inked natural rubber. The interpretation ofthis dark field image is the sameas for the ones obtained in polystyrene and polyethylene terephathalate. The sizeof the ordered regions averaged about 30A, which represents a time and space
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STRUCTURAL MODELS OF AMORPHOUS POLYMERSVarious structural models have been proposed ever since the first suggestion
of order in amorphous polymers by Katz in 1927. Some are based on structuralstudies while others are deduced indirectly. Some are also more specific thanothers.
Kargin proposed a bundle (or cluster) theory in 1957 based partly on x-raystudies of polymer melts showing high intensity of intermolecular scattering;and partly on bright field electron microscopy observations, showing spheru-litic fibrils which remain undestroyed after destruction of crystallinity as well asfibrils that formed upon mechanical orientation.35 Although the interpretationof such data, especially the electron microscope observations, may be some-what questionable, the idea of parallel alignment of long chain macromoleculesin the amorphous solid state appears reasonable and analogous to the swarmtheory proposed originally by Bose in l907, and promoted later byOrnstein.4° According to the swarm theory the interior of a nematic liquid iscomposed of clusters of molecules (10 to 106 molecules) with definiteboundaries.4'
In Kargin's bundle theory the parallel alignment of chain molecules is theessential feature; the size of the aligned region can fluctuate from a few segmentlengths to lengths greater than fully extended chain molecules. The order isstrictly intermolecular. The disorder is primarily in the boundaries between thebundles.
Hosemann42 suggested another model for the molten state of polymers(mainly polyethylene and polyethylene oxide). It is a one-phase paracrystallinemodel, based primarily on x-ray findings of disorder within lamellar crystals.With increasing temperature the disorder within the crystal is increased untilfinally at the melting point the lattice no longer has a 3-dimensional crystallinelattice; the chain segments, however, remain essentially parallel to one another.The folds originally present in the crystal are also suggested to remain in themelt. He pictured the melt as consisting of highly disordered crystals (seeFigure 16 in ref. 42).
Yeh35 proposed a two-phase folded-chain--fringed-micellar-grain model forthe amorphous state in general, glassy or molten. The mode! was based onstructural evidence from electron diffraction and dark field microscopy studiesof crystallizable and non-crystallizable polymers. The model contains twomajor elements as depicted in Figure 23. One element, which he called the grain(--30—100A), consists of an ordered domain of parallel chain segmentsbrought about primarily by intramolecular folding of parts of a long chainmolecule. The grains are generally connected to one another as in a string ofbeads especially for those molecules that are longer than can be containedwithin a single grain. Surrounding the grains are the second phase (-. l0—50A)consisting primarily of molecular chain segments in a truly disordered state,which may include low molecular weight molecules, chain ends or segments ofmolecules going from one grain to another.
A natural consequence of this model is the concentration of excess freevolume in the matrix phase. A detailed description of this model and its possiblerelation to lamellar crystallization, rubber elasticity, viscosity, etc. have beencovered in the same article.
86
MORPHOLOGY OF AMORPHOUS POLYMERS
Figure 23. Schematic representation of the fold-chain fringed-micellar grain model showing theordered domain (O.D.) the grain boundary layer (GB.) and the intergraio region (1G.)35.
Another "two-phase" model which needs to be mentioned is the one beingdeveloped by Pechhold.43 Starting with a nondefective (all trans conformations)bundle of molecules, by the introduction of more and more molecular defects(e.g. gauche conformations) into the system, Pechhold calculated from a simplethermodynamic treatment the mean radius of a meander curvature (disorderedregion). This radius came out to be about 50A. His model is reproduced in Figure24.
Figure 24. Pechhold's model for the amorphous molten state of polymers43.
87
G. S. Y. YEH
All four models have one major structural property in common. Themolecules or segments of molecules tend to assume approximate parallelalignment over large regions compared to repeat units. Another commonfeature is that in none of the four models is there any extended region (> 2—3) ofcrystalline-type trans conformations remaining in the amorphous state. In twoof the four (namely by Yeh and Pechhold) some definite regions of more highlydisordered chain segments are included; while in three of the four (namelyHosemann. Yeh and Pechhold) some folded regions are also suggested.
We hope that the presentation and a brief discussion of these models here (allof which. we are sure, will be modified to a certain extent when more experimen-tal evidence presents itself) may help to clarify the meaning of order (and/orstructure) in the amorphous state of polymers. This may be of particularimportance to those who wish to extend or improve these various models bycalculations or experiments.
REFERENCESP. H. Geil. Polymer Single Crystals, lnterscience, New York (1963).
2 A. Peterlin. J. Polymer Sci. 9. 61(1965).E. W. Fischer and R. Lorenz. Kolloid-Z. 189. 97 (1963).J. B. Jackson. P. J. Flory and R. Chiang. Trans. Faraday Soc. 59. 1906 (1963).T. Kawai and A. Keller. Phil. Mag. 8. 203 (1963).M. Takayanagi. K. Imada. A. Nagai. T. Tasumi and T. Matsuo. J. Polymer Sc!. C 16. 867(1967).T. Tasumi.T. Fukashima. K. Imada and M. Takayanagi.J. Macromol. Sc!. B1.459 (1967).
8 01-1. D. Keith, F. J. Padden. Jr.. and R. G. Vadimsky. Science. 150. 1026 (1965). "1-1. D.Keith. F. J. Padden.Jr.and R. G. Vadimsky.J. Polymer Sci. Al 267(1966). '1-1. D. Keith, F.J.Padden. Jr. and R. G. Vadimsky. J. Appl. Phvs. 37. 4027 (1966).G. S. Y. Yeh. Morphology ofAmorphous Polymers, to he published in CRC Critical Review inMacromolecular Science.
0 E. Guth. J. Polymer Sci. C 12, 89 (1966).° R. Blokland. Ph.D. Thesis, University of Rotterdam (1968).2 K. Nagai.J. Chem. P/is's. 47. 4690 (1967).
K. Nagai. J. Chem. Ph;'s. 49. 4212 (1968).A. N. Gent. Macromol. 2. 262 (1969).' R. E. Robertson. J. Pkvs. Chem. 69. 1575 (1965).
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(1962).22 G. S. Y. Yeh. Order in amorphous polystyrenes as revealed by electron diffraction and
diffraction microscopy. J. Macromol. Sc!. B. In press.21 s L. Lambert. Ph.D. Thesis, University of Michigan (1970).24 T. G. F. Schoon. Brit. Polymer J. 2, 86 (1970).2 G. S. Y. Yeh and S. L. Lambert. Mechanism of spherulitic crystallization as deduced from
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21, G. S. Y. Yeh and P. H. Geil. J. Macromol. Sci. B 1(2). 235 (1967).27 5• Carr, P. H. Geil and E. Baer. J. Macromol. Sc!. B2(1), 13 (1968).28 A. Siegmann and P. H. Geil. J. Macromol. Sc!. B4(2). 239 (1970).29 A. Ermolina. G. Markova and V. A. Kargin. Study of structural changes in polyethylene
terephihalale and polychlorotr(fluorethylene over a range of melting temperatures of crystals,AllUnion Symposium on Electronography. Moscow (1957).
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MORPHOLOGY OF AMORPHOUS POLYMERS° J. J. Kiement. Ph.D. Thesis, Case Western Reserve University (1969).
W. Frank, H. Goddar and H. A. Stuart. J. Polymer Sci. B5, 711, (1967).32 G. S. Y. Yeh and P. H. Geil. J. Macromol. Sci. B1(2), 251 (1967).
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G. S. Y. Yeh. A structural model for the amorphous state of polymers:folded chain fringedmicellar grain model, J. Macromol. Set. B. In press.
36 L. L. Ban. Private communication.aJ R. Katz. Z. Physik. Chem. (Leipzig), A125, 321 (1927). bJ R. Katz. Trans. FaradaySoc., 32, 77 (1936).
38 V. A. Kargin, A. I. Kitaigorodskii and G. L. Slonimskii. Kolloidn. Zh. 19, 131(1957).a Bose. Physik. Z. 8, 513 (1907). "E. Bose. Physik.Z. 10, 230 (1909).° L. S. Ornstein. Z. Krist. 79, 10 (1931).
41 L. S. Ornstein and W. Kast. Trans. Faraday Soc. 29, 881 (1933).42 R. Hosemann. J. Polymer Set. C20, 1 (1967).U w Pechhold. IUPAC Preprints, 789 (1971).