JOURNAL OF POLYMER SCIENCE: PAllT C

NO. 14, PP. 173-235 (1966)

Analysis of the a, p, and y Relaxations in

Polychlorotrifluoroethylene and Polyethylene:
Dielectric and Mechanical Properties
JOHN D. HOFFMAN, G. WILLIAMS, and E. PASSAGLIA, Pol7pzers
llivision, Institute l o r Materials Research, National Bureau 01 Standads,
Washinglon, D.C. 20234

Synopsis
Theoretical models for the mC and y c relaxat,ion effects found in chain-folded polymer
crystals (single crystal mats and bulk) are presented and compared with the available
dielectric and mechanical loss data for polyethylene and polychlorotrifluoroethylene.
Details of morphology and crystal structure that can be varied by crystallization and
annealing procedures, e.g., roughness of chain-folded surfaces, number of intercrystalline
links and cilia, number of chain-end defects and dislocations, and the existence of the
extended-chain phase, are brought into the discussion. The m C process, which consists
of two overlapping mechanisms, is a result of motions of chain folds and reorientation
(with translation) of chains in the interior. (Chain twisting also occurs for long chains.)
The theory connects the data on the n-paraffins and their polar derivatives (n-ketones,
esters, ethers) with the results on polymers: the common feature is the chain reorientation and twisting process. A new theory of chain twisting is introduced. The y e
relaxation is a result of reorientation of chains in a loose chain-end induced defect,
(a vacancy row) in the polymer crystal. When the effect of chain twisting is included,
the theory successfully predicts the unusually broad and asymmetric loss curve found
in the polymer, and is consistent with the experimental activation energies. The fl
relaxation arising in the amorphous component of PCTFE is analyzed, and its upward
shift in temperature with increasing crystallinity discussed in terms of the Adam-Gibbs
theory of relaxation in the glassy state. The y a amorphous relaxation, and the 6 relaxation which is found at cryogenic temperatures, are also discussed.

I. INTRODUCTION
Considerable scientific and technological interest attaches to the understanding and manipulation of the physical properties of the class of semicrystalline polymers that consist of inherently crystallizable linear flexible
chains. Polychlorotrifluoroethylene (PCTFE) and polyethylene are
typical members of this class. Our principal objective is to describe the
various manifestations of the a, p, and y relaxation processes in these
polymers, and t o discuss the underlying mechanisms. I n the course of
classifying the loss mechanisms, certain very low temperature (or extremely
high frequency) processes were noted which were clearly not associated
with the a, p, or y effects. These effects are called 6 relaxations and are
discussed briefly a t the end of the paper.
173

174

.T. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

We have chosen PCTFE and polyethylene for analysis for a number of

reasons. Both polymers are free of independently rotatable side groups, SO
that, any major relaxat,ion processcs that appear must be associated with
some motion of t,hc main chain. Polyethylene has the distiiict, advantage
that it has been the subject of fairly extensive mechanical relaxation studies,
and has the practically unique feature that considerable data on its shortchain homologs, both polar and nonpolar, are available. Also, mechanical data of high quality are available on polyethylene single crystals of
known thickness, and these will prove to play a key part in the interpretation. However, the dielectric properties of polyethylene are mostly due to
the adventitious occurrence of dipoles introduced through oxidation, so
that the dielectric properties of this material, though useful, are subject to
some uncertainties. Also, polyethylene has a somewhat limited range of
crystallinity. PCTFE has the advantage of having a permanent dipole
moment on each monomer unit, and the dielectric data on the bulk polymer
are as extensive with respect to range of frequency and temperature as are
available for any polymer. PCTFE also has the advantage of exhibiting
a wide range of crystallinity (0.12 to over 0.80) and texture, so that it is
relatively easy to separate the relaxation effects which belong to the crystalline and amorphous phases. lVIechanica1 relaxation data are available for
the bulk polymer, but little information exists on its short-chain homologs.
In the case of both polymers, data and theoretical interpretation on the
crystal morphology and rate of crystallization exist and form a framework
in which the crystal defects leading to some of the relaxation processes can
be identified and understood.
The customary method of studying the a , 0,or y processes in bulk semicrystalline polymers has been to measure the dielectric or mechanical loss
a t a constant frequency. Plots of the loss at constant frequency against
temperature then reveal loss maxima, the highest temperature relaxation
process being called a, the next 0,and so on. The questions that immediately arise are then: ( I ) in which phase does each relaxation process
originate, and (2) what particular molecular motions or defects cause
each relaxation process? Attempting to answer these questions is one of
the main aims of this paper, but it must be immediately emphasized that
the question is not really complete if it is posed in terms of plots of loss
versus temperature a t constant frequency. One of the important points
about the processes underlying the a, p, and y relaxations is that they exhibit a distribution of relaxation times and absorption intensity that is highly
characteristic, and, especially in the -yc process, the nature of the distribution points toward the molecular interpretation. This distribution is
related directly to the shape of loss versus log f plots (wheref is frequency).
We have, in the case of PCTFE, where the required data are available, correlated loss versus T plots (constant frequency) with loss versus log f plots
obtained at various temperatures and then where possible, attempted to
explain the observed effects with a molecular model or other appropriate
represent ation.

a, p,

AND

RELAXATIONS

175

I n both PCTFE and polyethylene, samples with a similar degree of crystallinity can sometimes lead to quite dissimilar experimcntal results. Also,
the magnitude and location of the relaxation processes often depend strongly
on the degree of crystallinity. These effects are especially prominent in
PCTFE. These facts place a premium on giving a full disclosure of the
methods of preparation of the samples. The causes of these effects are
interpreted in terms of recent theories of morphology and molecular chain
folding in the case of those relaxations arising in the crystalline phase or
its surface, and in terms of recent theories of the glassy state in the cast
of relaxations arising in the amorphous component.

11. PREPARATION AND MORPHOLOGY OF PCTFE SPECIMENS

As noted above, dielectric data on bulk P C T F E will occupy a special
place in this paper because of the wide range of frequency employed in the
dielectric measurements and because of the wide crystallinity range obtainable by various crystallization procedures. Discussion of these specimens
also provides an opportunity to relate their properties to recent theories
of morphology and chain folding, which will prove useful in the interpretation.
The dielectric measurements on P C T F E discussed in this paper are
principally those of Scott et a1.l which were published in 1962. The frequency range extended from 0.01 to 10'0 Hz. and the temperature range
extended from -50C. to temperatures above the melting point (TvF =
221C.). Both the dielectric constant e' and the dielectric loss index 6''
were measured. One of the main reasons that measurements were made
a t low frequencies was to facilitate coinparison with mechanical relaxation data, which are commonly taken a t low frequencies. The crystallinity range of the bulk specimens was 0.12-0.80. The dielectric measurements of Scott and co-workers compare favorably, in the range where
a comparison can be made, with the studies of Reynolds et a1.,2Mikhailov
and Sazhin,3 and Hartshorn e t aL4 All specimens used in the investigation of Scott and co-workers were Kel-F 300 polymer, where the numberaverage molecular weight was stated to be approximately 415,000, COPresponding to a number-average chain length of about 9000 A.
Table I gives the method of preparation of the specimens, together with
certain characterization parameters. I n Figure 1, the degree of crystallinity and specific volume of the specimens is shown as a function of temperature. The specific volume data were converted to degree of crystallinity according to the data of Hoffman and Weeks5 (x is the mass fraction
crystallized). The degree of crystallinity scale is believed to be quite
accurate for the lower x values. For the specimen with x = 0.80, the actuaI
mass fraction crystallized is probably nearer to 0.90 or 0.95, because in dilatometric methods small voids are measured as amorphous material in bulk
polymers.G

0.73
up to -200C.

x = 0.80
up to --200"C.

0.73
Specimen 0.44 annealed two
(quench-crystallized
weeks a t 190C
and annealed)

0.80
(isothermally
crystallized)

0.44
up t.o 120C.

0.44
Disk 2 mm. thick heated to
(quench-crystallized) 250C. aiid plunged in ice wat.et

Almost all crystallization took place at 180C.

Heated t,o 250C. Crystallized

1 day at 200"C., 1 day a t
190"C., and 3 days a t
180"C., cooled to room temperature"

0.12
up to -60C.

0.00

Heat any specimeii above 221 "C.

0 . 0 (liquid polymer)

0.12
Film 0.15 mm. thick heated to
(quench-crystallized) 250C. aiid plimged in ice water

Degree of
crystallinity

Method of preparation

Specimen
designation

Type of crystals

Remarks

Subcooled liquid measrurable down to about

190"C, where crystals
begin to form
0.4788 -40
Crystals extremely small; Specimen will crystallize
do not scatter visible
if heated above 60C.
(est.)
light
0.4711
50 Slightly opalescent apCiystallizes further if
pearance; small crysheated above 120C
tals, probably of disordered chain-folded
type
0.4642
59 Slightly opalescent apMelting of crystals bepearance; small crysgins at 200 to 210C
tals, probably of chainfolded type
0.4624
46 Specimen opaque whit>e, Thin lamellae melt out
highly spherulitic; conbeginning a t about
b i n s large fraction of
185C.; largest lamellae melt a t aboiit
typical chain-folded
218C.
lamellae. 30G300 A.
thick

Specific T , ("C.)
volume from
a t 23"C., 7-T
cm.3/g. data.

TABLE I
PCTFE Specimens

a, p,

AND

KELAXATIONS

177

1.0

.8

.6
X.

.4

.2

.O

TEMPERATURE, OC

(6)

Fig. 1. ( a ) Degree of crystallinity (x)and ( b ) specific volume (P) a s a fuiictioii of temperature for PCTFE specimens. (Data of Scott and co-workers.')

Also given in Table I are the glass transformation tenipcratures of tlic

various specirneris as estimated froin p-T curves. The same procedure
was used for all specimens:
data between 0 and 110C. were fitted
with two straight lines and the temperatui*e of intersection noted. This
procedure is somewhat arbitrary, but serves to show that T , as ineasured
dilatoinetrically does vary with the degrce of crystallinity and crystal
texture. The variation of T , with x was iiot stressed in the original paper
by Scott ct a1.l The T , values cited were obtained by a re-cxaiiiination of
the dilatoinetric data on the original dielectric specimens. I n some of the
drawings, T , is given nominally as 50C.

v-5"

178

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

Modern theories of crystallization based on the kinetic nucleation

approach and recent experimental studies combine to give a fairly accurate
picture of the morphology of bulk polymers. The basic picture changes as
the supercooling at which the crystallization takes place is varied and as
the polymer is annealed. It is useful for the purposes of the interpretation
to follow to outline briefly this basic picture for the important crystallization and annealing procedures.

A. Bulk Polymer Isothermally Crystallized at Low to Moderate Supercooling after Cooling from the Melt (Isothermally Crystallized)
PCTFE specimen 0.80 was crystallized in this manner.
Linear polymers consisting of intrinsically crystallizable units usually
form typical lamellar spherulites when crystallized at low to moderate
supercooling. PCTFE is entirely typical in this r e ~ p e c t . ~ Each
J
spherulite starts at a heterogeneity. The spherulite consists of a set of platelike
lamellae that radiate outward from the heterogeneity. As revealed by
electron m i ~ r o s c o p yand
~ ~ ~low-angle x-ray diffraction,6s8the lamellae in
PCTFE are about 300-800 A. thick, depending on the crystallization
temperature and annealing time with higher crystallization temperatures
and longer annealing leading to thicker lamellae. It is now commonly accepted that the lamellae are basically chain-folded structures, with a fairly
high occurrence of regular folds with adjacent re-entry (see Fig. 2). The
general appearance of the lamellae, including their resemblance to single
crystals, can be explained in terms of the chain-fold model6 Thus, the
basic morphological unit in a spherulite of this type is a chain-folded lamella.
However, this description does not, by any means, encompass all that is
important to dielectric and mechanical behavior in such specimens. The
somewhat idealized kinetic theory of chain folding originally given by
Lauritzen and Hoff man6*9s10
is capable of explaining the existence of chainfolded lamellae in bulk and allows the prediction of the growth rate and
initial lamellar thickness, Zg*. Also, the melting behavior can be explained
after lamellar thickening is tasken into account.6pll This theory in essence is an approximation that applies at low supercooling, where chain
folding with adjacent re-entry is predominant and the fold surface relatively smooth.
More recent developments of the kinetic nucleation theory by Frank and
Tosi,12Price,13and especially Lauritzen et al.14clearly show that one must
expect a spectrum of behavior depending on the supercooling. For
crystals formed at low supercooling, the fold surfacc as initially formed is
relatively smooth, a root-mean-square deviation of 8-12 A. being typi~a1.l~
As the crystallization is carried out at higher supercoolings, the surface as
originally laid down becomes substantially rougher, leading to loose or
looplike folds (still with mostly adjacent re-entry). This effect is especially clear from the work of Price13 and Lauritzen et al.14 At a very
high supercooling, in the simplest approximation approaching AT, =
2aTmo/Ahfb0,the fold period becomes ill defined and the crystals produced

AND

a, p,

RELAXATIONS

I A. .QUENCH CRYSTALLIZED
b
,

179

(0.12. 0.44)

'ROW

VACANCIES

\NUMEROUS
AMORPHOUS
LINKING CHAINS

CHAIN-FOLDED
STRAINED

SURFACES

INTERLAMELLAR

EXTENOEO CHAIN PHASE

MAY BE PRESENT

C.

ROW VACANCY

DEFECT^^

ISOTHERMALLY
NEAR T i (0.80)
CRYSTALLIZED

INTERLAMELLAR
/L!NK

CHAIN-FOLDED LAMELLA
REJECTED LOW
M.W. MATERIAL.

Fig. 2. Fine structure of bulk samples of PCTFE prepared under different Grystalliaatioii
conditions (schematic).

will have extremely rough surfaces with loop-type folds (CJ is the lateral
surface free energy, Tm0the equilibrium melting temperature, Ah, the heat
of fusion, and bo the lateral lattice spacing). A t T,, which is Tmo- AT,,
every polymer segment that strikes a surface sticks to it, giving virtually
no regular folds a t all. Here the supercooled liquid simply collapses into a
highly disorganized mass of microcrystallites. The implication that these
microcrystallites are connected to one another on a massive scale by intercrystalline links is clear. When calculated without approximations, the
original theory of Lauritzen and Hoffman gives the nucleation collapse a t
YC.l5 The value of A T , for PCTFE is about 8O"C., i.e., T , is a t about 14OoC.
It is important to bear in mind that the ltinetic nucleation theory of chairifolded growth leads to a wide range of surface roughness and fold regularity
depending on the supercooling.
Returning to the morphology typical of bulk polymer crystallized a t low
to moderate supercooling, it must be noted that recent evidence obtained by
AndersonI6 and Keith and Paddenl7slgmakes it clear that only molecules
exceeding a certain length undergo chain folding: the shorter molecules in

180

J. D. IOFFMAN, G. WILLIAMS, E. PASSAGLIA

the distribution are rejected during the crystallization process. A highly

approximate theory by Hoffman6 shows how the rejection of short chains
might come about. In any case, it is clear that the rejected short chains
can have one of two fates: they may remain in the liquid or supercooled
liquid state, or alternatively they may crystallize in the extended-chain
form (Fig. 2). Anderson has clearly demonstrated the simultaneous existence of chain-folded and extended-chain type crystals in bulk polyethyene. lG
Thus, it must always be borne in mind that when crystallized in the maiiiier
described, a whole polymer may exhibit two classes of crystals: (I)
cxtcnded-chain and (2) chain-folded lainellae.
Some other points are of interest. First, the chain-folded lamellae
tend to thicken even during the isothermal crystallization process, or on
subsequent annealing at a higher temperature. Thickening by a factor of
two to four times is typical and has been observed in polyethyknell and
PCTFE.lg Thickening occurs in both bulk and in single crystals. The
thickening process will be mentioned further in the discussion of the y
relaxation process, since it produces the defects (Fig. 2) believed to lead to
the y c component. Second, interlamellar links (Fig. 2) will occur between
t8heIamellae, the number being greater the higher the supercooling.6 No
detailed theory of interlamellar links has been given, but it is clear that they
can arise from multiple nucleation acts where one long molecule becomes
involved in crystallization of two or more lamellae. Keith, Padden, and
Vadimsky have obtained excellent electron micrographs of such links in
polyethylene. 2o For specimens of very high molecular weight, a considerable fraction of a bulk polymer may be in the form of interlamellar links
because of such multiple nucleation acts, but in whole polymers of moderate
molecular weight such as PCTFE and the usual type of polyethylene, the
number of such links will be lower, allowing the attainment of a high degree
of crystallinity. The tendency of high molecular weight to suppress the
attainment of a high degree of crystallinity (especially in a fraction) may
be seen in the data of Banks et aL21 Annealing tends to remove the interlamellar links. Finally, some cilia (Fig. 2) are to be expected, especially
in freshly crystallized material. These will tend to be lowered in number by
the annealing and thickening process.

B. Bulk Polymer Rapidly Crystallized at High Supercooling by Rapid

Quenching froin the Melt into Bath Held below T, (Quench Crystallized)
PCTFE specimens 0.12 and 0.44fall in this category.
Under these conditions of crystallization, a very large number of nucleation centers become active. lractically every heterogeneity is active
as a nucleation center, and additional ones of homogeneous origin may
occur. (In PCTFE, homogeneous nucleation becomes very pronounced
at and below about 155OC.) The direct result of t,he high injection rate
of nucleation centers is that the crystallites would be very sinall even if
they completed their growth. I n the present case, the optical properties of
PCTFE (Table I) clearly point to the existence of very small crystallites in

a, p,

AND

RELAXATIONS

181

specimens 0.12 and 0.44. Most of the crystallization occurs near thc
growth rate ma.ximum which is usu lly a t about 0.87 Tmo,i.e., roughly
midway between Tmoand T,.6 Sp cimen 0.44 has a higher degree of
crystallinity (and larger crystals) t h n specimen 0.12 because the greater
thickness of specimen 0.44 allowed a longer residence time in the temperature region of maximum growth rate. (The interior of a very thick specimen of P CT FE would resemble specimen 0.80.) I n some polymers, notably polyethylene, the crystallization kinetics are such that it is not possible to obtain specimens of ordinary molecular weight with a crystallinity
as low as 0.12 or 0.44 even by quenching thin films.
According to thc kinetic nucleation theory of chain-folding mentioncd
above, we must expect rather rough surfaces with somewhat looplike folds
in the small crystallites in quenched specimens (Fig. 2). Furthermore,
bccause of multiple nucleation acts, and the large number of crystallites, a
considerable number of the molecules must participate in more than one
crystallite. It is of considerable significance that this picture, which
resembles in one important respect (numerous intercrystalline links) the
classical frin ged-micelle model, is relevant under conditions of very high
supercooling, i.e., crystallization very far from equilibrium conditions,
whereas early attempts to justify this sort of model wcre based on equilibrium theories
The crystalline component in 0.12 and 0.44 samples does not increase
significantly if the specimens are stored near or below T,. Increase in
crystallinity and the formation of larger crystals would require two conditions to bc met: (1) chain motions in the amorphous component would
have to become rapid enough to allow transport to the growing crystal face
and (6)some interchain cntanglcinents in the interlamellar links would have
to bc resolved either by allowing chain motions in the crystallites or by
melting some of the crystallites. These conditions arc met in ICTFE by
annealing a t about 190C. (specimen 0.73).

C. Bulk Polymer Crystallized by Rapid Quenching From Melt and Annealed near Melting Point (Quench Crystallized and Annealed)
1CTFE specimen 0.73 falls in this category.
The crystallites in this specimen are still small, though thc incrcascd
optical scattering indicates that they arc larger than those in 0.44. Some
of the amorphous material has been incorporatcd in the crystallites, but thc
slowness of the crystallization at 190C. (compared to specimen 0.80 a t the
same temperature) clearly implies that retardations due to chain entanglements in interlanicllar links in the amorphous regions hinder the crystallization. The hypothesis that the annealing process (i.c., conversion of
specimen 0.44 t o 0.73) has caused a number of the interlameIlar links to be
drawn rather tight is advanced. Dielectric data to be given later support
this hypothesis. A fair number of the folds are probably looplike. The
crystallites in specimens of this type melt out if heated above about 200210C., and subsequent isothermal crystallization a t 170-190C. yields
a specimen similar to 0.80.

182

1. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

111. PLOTS OF

VERSUS T AT 1 HZ. AND NOMENCLATURE OF

THE RELAXATION PROCESSES

Figure 3B shows schematically the type of loss peaks that frequently

appear when the dielectric loss index 6 of a semicrystalline right-angle
dipole type polymer in bulk is plotted as a function of reduced temperature
T/T,O a t a fixed frequency of 1 Hz. The relative peak heights are arbitrary. As will be seen shortly, P C T F E exhibits such behavior in the semicrystalline state. As an aid to organizing and understanding much that is
to follow, the behavior of the polymer in the completely (normal) amorphous state (Fig. 3A) and the completely crystalline state (Fig. 3C) is
shown scheinatically. While i t in some respects represents an anticipation
of certain of our conclusions, i t is useful t o remark on the a, p, y, and 6
processes noted in Figure 3 .
The highest temperature peak in semicrystalline P C T F E is denoted 01,
and will subsequently be shown t o result partly from motions involving the
chain folds and partly from reorientation of the interior chains. This
peak does not occur in the amorphous phase. I n some right-angle dipole
type polymers in bulk, the 01, peak has three identifiable components.
Later we will suggest a possible origin for these contributions. The 01,
relaxation was called the high-temperature process by Scott and cow0rkers.l
The p peak in an unbranched polymer is of strictly amorphous phase
origin, and does not occur in the completely crystalline polymer (Fig. 3C).
The relaxation process leading to this peak will be shown to be associated
with the onset of the glass transition a t To. The 0 relaxation process was
called the intermediate-temperature process by Scott and co-workers.
The y peak in semicrystalline P C T F E is complicated, and can definitely
be shown to consist of two components, one arising in the crystalline phase
(y,), and the other originating in the amorphous component ( y a ) . The ye
and ya components have common relaxation times a t moderately high
frequencies, and the magnitude of the y peak in a semicrystalline polymer is
therefore not proportional to either x or 1 - x a t these frequencies. The
y c peak is believed to be associated with crystal defects wherein chains can
reorient over a low barrier. Scott and co-workers called the y effect the
low-temperature process.
The 6, relaxation process has not been observed directly in PCTFE in
a n E versus T plot, and its existence a t low temperatures is inferred from
a high frequency loss peak of high intensity that occurs in an 2 versus log
f plot at 1OO Hz. at 23C. This relaxation was called the high-frequency
crystal polarization by Scott ct al.
The nomenclature used for the corresponding mechanical loss peaks
plotted as the loss decrement n- tan 6 versus T is similar t o that noted in
Figure 3. Plots of J (shear loss compliance) or G (loss modulus) versus
T a t various crystallinities lead to plots with slightly shifted maxima of
quite different intensity compared to the T tan 6 (mechanical), as noted by
Passaglia and ll/Iartin.22 This occurs when the change of modulus AG

a, p ,

AND

RELAXMTONS

183

A. AMORPHOUS STATE

d '

'

0.2
I

'

0.4
I

"

0.6' To

0.8
I

'

'

1.0

B. SEMICRYSTALLINE POLYMER
-HIGH

X, ISOTHERMAL

0.2

0.4

0.6

0.8

!-

8
J

C. SINGLE CRYSTAL MATS

a:

w
n

a,

._...
0

0.2

0.4

0.6

0.8

1.0

REDUCED TEMPERATURE, T / G

Fig. 3. Dielectric or mechanical loss factor a t 1 Hz. versus reduced kmperature T/T,"
for a linear polymer with no independently rotatable side groups (schematic).

associated with the relaxation process is comparable or larger in magnitude

than the static (low-frequency) modulus. This can on occasions lead to
ambiguities regarding which phase is the seat of a certain relaxation
process. The interpretation of E'' versus T and more especially d' versus
log f plots is not ambiguous in this respect.
It is necessary t o bear certain provisos in mind in interpreting E" versus
2' or T tan 6 (mechanical) versus T plots. First, the loss peaks that appear
in such plots represent the onset of the freezing out of molecular motions
associated with a certain relaxation mechanism. In the dielectric case, a
loss peak found with n measuring field of 1 Hz. represents a mean dipole
reorientation frequency of 1 per second; if the measuring frequency is
increased, the temperslture at which the nlaximum occurs will in general
also increase. Thus the loss maxima on a loss versus T plot in no way
generally represent transitions in the thermodynamic sense, and it is misleading to call loss maxima of the type shown in Figure 3 "transitions."
This does not mean, however, that some of the processes, when extrapolated

J. D. IIOFFNPAN, G. WILLIAMS, E. PASSAGLIA

184,
.00

.07

PCTFE

.06

.05
.04

.03
02
.01
0

I.4

DEGREE OF
CRYSTALLINITY

I Hz

100

50

150

2 0

TEMPERATURE , C
(bJ

Fig. 4. ( a ) e versus temperature at 1 IIz. for PCTFE specimens 0.12, 0.44,0.73, and
0 3 0 . (Data of Scott et al.1) ( b ) T Tan 6 versus temperature a t 1 H z . for PCTFE
specimens 0.27, 0.42, and 0.80. (Data of M c C r ~ i r n . ~ ~ )

t o zero frequency, might not be related to equilibrium thermodynamic phase

transitions. The description loss process or relaxation process is t o
be preferred to the term transition in referring to peaks such as those
shown in Figure 3. Second, it must be borne in mind that the structure of
the system is changing in an 2 or r tan 6 versus T plot. A plot of el versus
log j a t a given temperature is in important respects more closely and
simply related to fundamental quantities, e.g., the distribution of relaxation times.
Figure 4 shows a plot of el versus T a t 1 Hz. for PCTFE specimens 0.12,
0.44, 0.73, and 0.80 according to Scott and co-workkers.l The shift of the y
pe.& to higher temperatures with increasing frequency is shown by the data
at 500 1-I.z. Also shown are the mechanical loss data of l K c C r ~ mplotted
,~~
as T tan 6 versus T a t 1 Hz. These data are in general similar to those in
the more extensive study of Crissman and P a ~ s a g l i a . ~ ~

IV. THE

a,

RELAXATION PROCESS

A. Preliminary Considerations
I n PCTFE, the a, process gives a loss peak a t 1 Hz. a t about 150C. or
0.855 Tmo(Fig. 4). It appears in clearly resolved form in the dielectric
data only in specimen 0.80, which contains large chain-folded lamellae in
typical spherulitic structures. Note also that the mechanical loss data of
l \ I ~ C r u mshow
~ ~ a resolved a, peak onlyfor specimen 0.80, and Crissman and
PassagliaZ4indicate a resolved a, peak for their isothermally crystallized
specimen. Dielectric specimen 0.73, which contains only very small and
probably disordered crystals, shows no resolved peak at 150C. (The peak
a t about 125C. in speciinen 0.73 can definitely be shown to belong mostly t o
the 0class since it has a strongly temperature-dependent activation energy.)
While it is evident that the resolved a, peak in PCTFE is associated with
the crystalline phase, i t does not appear to be entirely a property of the
interior of the crystal. It was therefore concluded by Scott and coworkers
that the molecular mechanism leading to the a, peak in PCTFE probably
arose mostly in the chain-folded surfaces of the 1amellae.l
Recently, S i n n ~ t has
t ~ ~convincingly demonstrated in the case of polyethylene single crystals that one of the two main a, mechanical relaxation
processes that appears in such crystals is associated with the chain-folded
surfaces. On annealing, the single crystals irreversibly thicken, with a corresponding decrease in the number of folds. At the same time the intensity
of the a, relaxation process observed by Sinnott falls. Other authors have
also suggested that the a, process involves the crystal surface^.^^^^^ Sinnott has also shown that as the chain-folded lamellae thicken, the teniperature T,,, corresponding to the maximum in a loss versus T plot for the a,
process shifts to higher temperatures. This means that thickening of the
lamellae leads to higher activation energies and increased relaxation times
a t a given temperature. Taliayanagi and co-worliersZ8have shown that
the a, process of single crystals of polyethylene as measured with frequencies near 1 Hz. actually consists of two superposed processes of different activation energy. (The discussion of Wada et aLZ9and Iwanagi
and Nalranc30on bulk polyethylene suggests that two a, processes, called a
and a', are superposed in mechanical dispersion data a t 1Hz.) Accordingly
we have investigated a class of models which will lead to a decreased absorption with increasing thickness, an increase of T,,, with increasing
thickness, and either one or two relaxation processes in the a, region.
It is of interest to show the a, process on an E" versus logfplot for PCTFE
and obtain the activation energy. The a, dielectric process is readily
discerned in PCTFE in specimen 0.80 in a plot of 6' versus logs between 150
and 190C. This is shown in Figure 5 . The intensity of the ac process is
quite low, especially in relation t o the y process. The activation energy
of the a, process may be calculated by identifying the frequency frnax at the
maximum in the 2' versus log j plot and computing the activation energy as

,I. D. HOFFMAN, G. WILLIAMS, E. PASSAGLTA

186

AH*

- R b h fmex/b(l/T)

(1)

The activation energy is 80 h 10 kcal./mole.

A plot of 1ogfmaxversus103/Tfor the a, process is shown in Figure 6. It is
seen from the linearity of the plot in Figure 6 that AH*(a,) is approximately
constant for the a, process over the range where i t was measured. It is
extremely unlikely that the a, relaxation process is a result of premelting.
Practically all of the polymer crystals are unmelted in specimen 0.80 at
both 150

LOG,, FREQUENCY, Hr
Fig. 5 .

as a function of frequency for PCTFE specimen 0.80 at various temperatures

showing ae process. (Data of Scott and co-workers.1)

A number of mechanisms have been suggested t o explain the ac crystal

process. The theories can be divided into two classes: (1) those which
treat the a, process mainly as a property of the interior of the crystal and
(2) those which treat i t mainly as a surface effect. Yamafuji31 treats the
a, dielectric process as arising from torsional vibrations in the body of
the crystal. Later Ishida and YamafujiZ6advanced the suggestion in the
case of oxidized polyethylene that the chain foldq reorient among three
equilibrium sites. The latter treatment is consistent with the finding that
the a, process in P C T F E and polyethylene single crystals is partly a surface effect. However, the fact that the relaxation time increases somewhat
with thickness was not explained, and the model gives only a single effective
relaxation time unless arbitrary distributions are introduced. Meanwhile,
T ~ i j n i n a nadvanced
~~
a theory for long-chain ketones in paraffins which
involves rotation of the chains in the interior of the crystals, with chain
twisting treated in the general manner proposed b y F r O h l i ~ h . ~Again,
~
this approach does not explain those acprocesseswhich relate largelyto some
type of surface effect. I l l e r ~has
~ ~interpreted the CY relaxation in the nparaffins in terms of chain rotation, which implies a bulk effect.
The representation of the a, process by various authors as being a n interior or, alternatively, a surface effect, is not entirely misplaced-it very

a, 6,

AND

RELAXATIONS

187

Fig. 6. Log finax versus 1/2 for various PCTFE specimens. (Data of Scott and coworkers.)

probably involves both. The models that we propose below have this
feature.
We proceed by discussing the high-activation energy modes of motion
possible in a chain-folded single crystal of a polyiner such as polyethylene
or PCTFE. I n the first model considered, a, - A, the chain-fold motion is
coupled to motions within the crystal interior. Next, the high activation
energy process that corresponds t o reorientation of a paraffin molecule in
a defect region in the prerottltor state is given, and extended t o the case
of long chain lengths by using a new theory of chain twisting (model ac - B).
With suitable modification, this model is applicable to the case of extendedchain crystals in a bulk polymer. Finally, in modcl a, - C, it is assumed that
the folds act independently of the crystal interior, leading to the relaxations
in a single crystal being represented by model a, - Cf for the folds and
a, - C, for the chains in the interior.

B. a , - A Model (Chain-Folded Crystal with Folds and Interior Chains

Coupled)
The ac - A model is shown in Figure 7. The methods used to calculate
relaxation times and polarizabilities for site models have been outlined in
several paper^^^-^' and a review. 38 Calculations for the particular models
given in this paper are given in detail by Williams and
A chain fold may turn between two equilibrium orientations, denoted 1
and 2, by surmounting the intervening free energy of activation barrier.
The equilibrium free energy difference between the two sites is V . The
clementary process transition probabilities are

J. D. HOFFMAN, G. WILLlAMS, E. PASSAGLIA

188

;:

and

w~~ = A I e -AQA*(n)/kT

(3)

where A&** and V are taken to be free energies. The dipole moment p i
associated with the fold changes its angle with respect to the x axis from
Of(,) to e,(,, as the dipole jumps from site 1 to site 2. An essential feature
of the model is the assumption that as the fold jumps from site 1 to site 2,
some turning of the chain in the interior of the crystal (accompanied by
some chain translation) is required to attain the activated state. The chain
fold is thus assumed to be coupled to the chains in the interior part of the
crystal. If the fold has extra links in it, the turning of a chain in the interior of the crystal would not be required to allow reorientation of the
fold. If, on the other hand, the fold is a sharp one of minimum contour
length, it will be coupled to the interior. We envision that in turning the
fold to the activated state, the interior chain is translated along the x axis.

SITE I

7
CHAIN FOLD IN
STATE

Fig. 7. Model for process

01 c -

A (chain fold coiipled with crystal interior).

A translation of one C atom in the case of an n-paraffin would cause the

new equilibrium orientation in the interior to be 180" opposed to the previous one, and a barrier making a contribution to A&*(n) would occur between them. The interior chain may either revert to its original position
cp = 0 when the fold is in site 2 , or it may be in a new orientation cp = cpc
when the fold is in site 2.
The relaxation time of this two-site model is given by35s3'j

7-

a,

6, AND

1/[2(W,l

e A Q ~ * ( n/ )k T

RELAXATIONS

w121

/[~A(I

(1/A) e

189

+ e-PkT) J

(4)

AQA*(n)/kT

where 2A = A . Thus, the observed relaxation time mainly reflects the

larger of the two transition probabilities, ~ 2 1 . The symbol n represents the
number of chain units in the fold period exclusive of the folds.
AgA*(n) js a free energy of activation. Therefore we break it up into
the energy AH*(n) and entropy AS*(n) of activation and write r as
r = (l/A)e-

kT

ASA*(n)/keAHA*(n)/

(5)

As a first approximation, we shall treat the chain in the interior as a rigid

rod. I n n subsequent section, the rigid rod approximation will be modificd
Cl,-A,

CI,-B,and

ac - =c
component o f

twisting

C2,-Cc(M)

or chain

/ / component of a;A(M)

or

(0)

(same

rn)

rigid

71I

ac-A,(Yc-Cc

biqh t&

LOG n

(dl
lbl
Fig. 8. Behavior of models aC- A, a - B, and 0 1 ~ - C (schematic).

t o account for the twisting of long chains.

The use of the rigid-rod approximation at short and moderate chain lengths will be theoretically justified
in Section IV-D and experimentally justified in Section IV-F.
The rigid-rod approximation leads to

AH,*(n)

AHw*

+nAHm*

(6)

for the heat of activation and

+ nASCH2*

(7 1
for the entropy of activation. This gives a free energy of activation that
is a linear function of n:
ASA*(n)

Asfold*

-1. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

190

AQ,*(n)

(AHmd* - TA&oid*) -k ~ ( A H CH~

TASCH~*) (8)

Thus, from eqs. (4) or (5) and eq. ( 8 ) )we expect that to the degree that
the rigid-rod approximation holds, a plot of log T as a function of n at a
constant temperature should rise linearly with increasing n (Fig. 8a).
Data showing that eqs. (6), (7), and ( 8 ) )which depend on this approximation, are valid up to surprisingly high values of n will be given subsequently.
We now investigate the behavior of T,,, as a function of n, where T,,,
is the temperature a t which a loss peak occurs in a plot of loss versus T
a t a fixed measuring frequency fm, where 2rfinrm = 1. We now have
from eqs. (5-8):

In T,

In (l/A)

(AHfold*

4-nAHcH,*)

- (ASM"

+ nAScH,*)
R

R T,,,

(9)

or

T,,,

TO(OC,
- A ) [(a

+ n ) / ( b+ n)l

(10)

where

To(a, - A )

is the value of T,,, for very long chains (n

AHcH~*/ASCH%*

(11)

a),and

AH~.I~*/AHcH~*

(12)

[R In (AT,) A S r o ~ d * ] / A S ~ ~ z *
(13)
Equation (10) gives a value of T,,, that rises rapidly for small n, and
then levels off to To(a, - A ) as n gets larger (Fig. 8b). This behavior is
a direct result of the assumption that AHA*(n) and AS,*(n) are linear in n,
i.e., the rigid-rod approximation.
If the elementary process is correctly identified, we must expect 2A' = A
to be roughly 10g-1013 events/sec. These estimates are based on the
activated state being (a)a vibrator, with one degree of freedom of vibration
(I/IcT)~" lo9,where 1 is
replaced by one degree of rotation, so that A
the moment of inertia, or ( b ) a vibrator with one degree of vibration being
replaced by translation, giving A
kT/h S
The orientational polarizability (Y is related to the static dielectric
,
the relation
perinittivity, E ~ by
b

es - E ,

E4an(~

(14)

where n is the number of active dipolar units per cubic centimeter and
the high-frequency dielectric permittivity. The quantity [ is

E,

for the Onsager internal field, and may be regarded as essentially constant
for most simple calculations; for E , = 2, [ is 16/9 if es = 2 and 24/9 if

a, p,

AND

RELAXATIONS

191

es = a. For convenience we call the magnitude of the dipolar absorption I,, and define it as the area under a loss peak in an e" versus log .f plot:

I,

J0

e"d l n f

(7r/2)(ts -

em) =

2[7r2na

Thus, the magnitude of the dipolar absorption is for all practical purposes
directly proportional to na, and henceforth we concentrate on calculating
this quantity.
The methods used to calculate na for various types of "site" models have
been detailed elsewhere.37 I n the present case we first quote a simplified
result for the ae - A model that is applicable to dielectric measurements
carried out with the applied electric field in the x direction (Fig. 7). This
corresponds to the manner in which dielectric measurements would often
be carried out on mats of single crystal platelets. The weighted orientatiorial polariaability resolved in the x direction is39

is the dipole moment associated with the fold, p is the density,

the molecular weight of the fold, Nu Avogadro's number, 1 the
thickness of the crystal exclusive of folds, and I , the contour length of a
fold. C1 is the number of dipoles in site 1, C2 is the number in site 2, and
C1 C; = N ; C2 is given by C1 exp { - V / k T ] so CIC2/N2 is '/4 when V =
0. I n the simple case e f ( ] )= 0, e,,,, = 90, V = 0, na, is ( p f 2 / 4 k T )
(pNa/hfw(fold))
[L,/(Z f Z,)].
Notice that for values of 1 substantially
larger than 1, (which is always the case) that naz, and hence I,, varies as
1/Z a t a specified temperature.
For a polycrystalline sample (implying averaging of the applied electric
field over all orientations) one obtains for the particular case 0, = 6',(1) =
ef(2,and 9 2 = (27r - cpl) for the ae - A process

where

p,

Mzu(fold)

where pc is the total resolved component of the dipole moment to a right

angle to the chain of length I , & f w( f old) and M,(,) the molecular weight of
the fold and repeat unit, respectively, and A p the angle that the chain in
the crystal turns as the fold reorients from site 1 to site 2. (The quantity
cp is measured from the x: - x plane.) I n the case A p > 0, the interior of the
crystal contributes to I,, but if the interior chain reverts to its original
position as the fold jumps from site 1 t o site 2, only the folds contribute
j s no longer required for pI to contribute,
to I,. The coiidition fl,(,) #
:IS was the case for na,.

192

J. D. IIOFPMAN, C. WIJ>LIAMS, E. PASSAGLIA

For the case Aip = 0, I,, varies as 1/Z (Fig. 8c) just as does naz. We
note also t hat if the interior chain of length Z contains but one dipolar
unit, then I,, again varies as 1/1 or l/n. The case where each chain unit
has a dipole moment pl leads to pc2 = ( n p ~ )which
~,
givcs a contribution
to I , from the interior that varies as n (not shown). The case for a dipolar
chain with a helical arrangement of dipoles gives I,, a 1/Z when Z is considerably larger than the helix repeat distance.
The behavior of I p with I is shown in Figure 8c. The variation of I,,
with temperature for two extreme cases of V is shown schematically in
Figure 8d.
I n the simple form presented hcre, the ac- A model produces only a single
dielectric relaxation time. The introduction of a distribution of Z values,
representing chain-folded crystals of different thicknesses, would introduce
a distribixtion of T through eq. (4). Similarly, a distribution of relaxation
times arises naturally when a model with three or more equilibrium orientations is ~ o n s i d e r e d . ~ ~However,
-~~
we have chosen not to complicate the
model presented for the ae - A relaxation, especially in view of the fact that
the observed distribution is not particularly broad (see later). The
situation is quite different in the case of the yc process, which exhibits a
very broad and asymmetric loss peak on an E versus log f plot that mci-its
special consideration.
It is of interest to indicate certain factors relating to the magnitude of
the mechanical absorption. In the case where the mechanical absorption
is weak, i.e., the change of modulus small, the magnitude of the loss will
vary as the number of relaxing elements per unit volume times the
ecVliT)
exp { -V/lcT} (see
factor C1C2/N2 = exp { -V/lcT}/(l
Appendix). Thus, the folds will contribute as (C1C2/N2)[lf/(Zf
Z)] and
the interior will contribute as (C1C2/N2)[Z/Zf
1) J C C l C 2 / N 2as depicted in
Figure 8c. If the interior chain reverts to its original position as the fold
jumps from site 1 to site 2, the interior will be mechanically inactive. Also,
if the crystal symmetry is such that XI - Xz = 0 for a particular stress field
acting on a site model, the overall process will be mechanically inactive (see
Appendix). The factor governing the magnitude of the mechanical relaxation given above is to be multiplied by (hl - hz)2/kT as noted in thc
Appendix.

C. The a, - B Model (n-Paraffins and Extended-Chain Crystals)

The ac - B model is shown in Figure 9. A short-chain molecule denoted i
rotates and translates from site 1 over a barrier and comes to rest in site 2,
which is energetically quite similar to site 1, i.e., E is quite small. Meanwhile, the dipole (in the simplest case) has turned on an angle of Aip = 180.
The reverse process 2
1 takes place over the barrier AQB*(TL)
in the same
way. The corresponding process or rotation of a paraffin chain molecule
in the perfect region denoted ii, where translation may be assumed to be
forbidden, or a t least highly difficult, leads to a site 2 of high energy E due to
repulsions (Fig. 9). Similarly, we would expect the A Q B * ( ~ )corresponding

LY,

p, A N D

1XELhXA'rlONS

193

ifi
LL
a
W

SITE

- _ _----

Fig. 9. Modcl for process

aC -

B (r~-para&~sa i d ex,uteiided-ohain cryslds).

to ii to be quite large. This would cause the strength of the relaxation to be

extremely low, T to be extremely long, and T,,, higher than is reasonable.
Accordingly, we confine our attention to molecules of type i, which abound
in extended-chain material, and are doubtless present in some degrcc-often
t o one or two per cent in the absence of extensive purification-in many
n-paraffins and n-paraffin derivatives.
In the most general case, the rotation of a paraffin chain (with translation) in a cage of its neighbors involves a t least four minima, with barriers
between them: the two deepest minima are probably 1SO" opposed as
shown, but subsidiary minima of almost the same energy as the lowest ones
very probably exist.38 Thus, the two-position mode1 with sites 180" opposed used here for illustration is an oversimplification of the physical
situation. For the derivation of the dielectric relaxation time and T,,, as a
function of n, the use of this simple model has no misleading consequences.
However, in the case of the mechanical relaxation time, it may become
necessary to mention the subsidiary minima where Acp # 180" in order to
obtain activity in the mechanical relaxation spectrum, i.e., to achieve the
condition X I # Xz (see Appendix). These subsidiary minima could relate
to chain rotation that corresponds to a chain translation along the x
axis of less than one carbon atom. Also, the multisite niodcl will naturally
introduce a distribution of reIaxation times. 38,38
Retaining the two-position model for the purpose of calculating T(n>and
Tnlax(n),we have for the relaxation time of the i-type molecule
7

1/[2(w,z

021)]

Fs

(l/A)eAQ=*(n)'KT

where we may take A & B * ( ~ )to be a free energy of activation where

A&*(?%)

AHs*(n) - TAXs*(n)

and where for the rigid rod approxiination we have

(19)

194

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

A H B * ( ~ ) = 2AHeg*

and
AS,*(n)

2ASeg*

+ (n - ~ ) A H c H % *

(20)

+ (n - ~ ) A S C H ~ *

(21)
Here AH,,* and AXeg* represent end-group effects. For a given crystal
structure, we anticipate that AHcH,* and ASCH, *for the ac - B mechanism
will be similar to those for the ac - A mechanism.
It is immediately seen that In 7 is a linear function of n at a fixed temperature:

In

7 =

-In A

+ 2[(AH,,*

- TAS,,*)

- (AHcHz* - TASCH,")]
t1 simple calculation then gives
T,,

To(aC- B) [(a'

+ n(AHcHz* - TASCH,")

(22)

+ n)/(b' + n)l

(23)

where

T
a'
6'

~ - (B) ~= AHCH,*/AXCH,*
~

(24)

2(AHeg* - AHCH~*)/AHCH,*

(25)

+ 2(ASeg* - ASCH,*)/ASCH,*

R In (Arm)

(26)

The dominance of the R In A r, term should lead 6 and b' in eqs. (10) and
(23), respectively, to be rather similar. Moreover, the values of To are
identical for a, - A and aC- B. Hence the differenccs that occur arc a
result of differences in AQfo~d*and A&,,*.
The weighted orientational polarizability for the ac - B model for he
case where site 1 and site 2 are 180" opposed is given by

where J4w(r)is the molecular weight of the repeat unit, p, is the total
(resolved) dipole moment associated with a given chain, and x d the mass
fraction of short "defect" chains of the type shown in Figure 9. Herc
C,C2/N2is exp { - E / k T ] / ( I
exp { -E / k T f ) . 2 Theinodelexplicitly implies that the strength of the ac - B relaxation in a single crystal of high
purity would be very small, since X , -+ 0 in such a case. A similar remark
applies to the strength of the mechanical relaxation, the intensity of which
is proportional to (ClC2/N2)Xd,multiplied by the usual factor (A, - Xe)2/lcT
(see Appendix).
The distribution of relaxation times can arise from the distribution in
I and from the presence of more than two orientational sites.

D. Chain Twisting
The rigid-rod approximation cannot remain exact for very long chains.
For sufficiently long chains, one would expect the rotation of one end to
leave the other end unaffected. This will lead log r and T,, to fall

01,

6, AND

RELAXATIONS

195

/RIGID ROD
I

U (0)= SINZ@ MODEL

RIGID ROD

UP

TO

Fig. 10. Departure from rigid rod behavior resulting from chain twisting for sin2 'p
potential (upper curve) and the parabolic potential (lower curve).

below the rigid rod curves a t large values of n or I, and approach an asymptote (Figs. 8a and 8b).
F r O h l i ~ hhas
~ ~given an approximate treatment of chain twisting based
on the assumption that the two potential wells in a two-site model are
parabolic with a cusplike barrier of magnitude AQcH,* between them.
This calculation, when revised to deal with the present situation in model
ac- A and ac- B40leads to AQl*(n) = AQl*
2%AQcH2* tanh (n/2%) where
we regard the AQ% to be free energies of activation. AQl* is 2AQ,,* for
ae - B and &fold* for the ac - A model. a is a chain twisting parameter,
f i = 4 A 2 / A Q o , * (7r/2), where A Zis the chain twisting force constant.33
For values of n considerably less than 2n the rigid-rod approximation is
approached, and when n exceeds 2n, the function 2nAQcH,* tanh (n/2%)
approaches the limiting value Z%AQCH~*(Fig. 10). The model is somewhat
crude, especially in that the barrier between the two sites is a cusp formed
by the intersection of two parabolas (Fig. 10).
A potential barrier of the form U(cp) = Qmax* sin2 cp for a two-position
model seems physically more realistic. Williams and Lauritzen40 have
shown that this leads to
AQ*(n) ==
Z ~ Z A Q ~[ ~
~ E
~ (cos
*I po) - sin2 cp0& (cos p0)] (28a)

Here El (cos cpo) is the complete elliptical integral of the second kind,
&'i (cos po) is the complete elliptical integral of the first kind, defined as
follows:

196

J. D. IIOFFMAnl, G. WILLIAMS, E. PASSAGLIA

I n addition to eq. (28a) we have the condition

n/2m

Ez(cos cpo)

(2W

For convenience, we abbreviate the function [2El(cos 90) - sin2 PO

Ez(cos cpo) as [ ~ ( E&)I.
I,
AQ1* represents AQiold* for ac- A, and 2A&eg* for
aC- B. AQ,,,*
is the barrier height per CH, group, between the maximum
in the function U ( 9 ) = AQmax*sinz
cp, and may be identified with AQcH~*.
I n eqs. (28) the chain-twisting term rtz is given by r ~ z = (A2/AQ~I~,)"Z.
Note m is related to fi of the Frohlich treatment by f i z = f i ( ~ / 2 ) - ~ .
It is emphasized that eqs. (28) are valid only in the region n/2m 2 7r/2.
For n/2m < r / 2 , the chains behave strictly as rigid rods. Thus the WilliamsLauritzen treatment gives the result that chains behave as rigid rods
up to n = 7rm, and longer chains arc twisted an angle cpo at one end and
180" - cpo a t the other. As n increases, cpo tends to a very small value.
This behavior contrasts with the Frohlich cusp barrier model, where
some twisting occurs even for chains much shorter than ~ 7 % . The two
functions arc compared in Figure 10, where [AQ*(n) - AQ,]/2rtzA&~,*
is plotted as a function of n/2m. After investigation of a number of models,
the conclusion was reached that Frohlich's model is unusual in leading to
some twisting at all values of n, and that this result is caused by the unrealistic cusplike barrier between the sites. Models other than the U(p) =
AQcH~* sin2 (o that still resemble it in having a continuous path between
sites 1 and 2 with no discontinuities in the derivative d[U(p)]/dp exhibit
strictly rigid-rod behavior up to a certain length not far from a m and then
begin to exhibit twi~ting.~OAccordingly, we shall use the WilliamsLauritzen model in the discussion.
The theoretical value of m2for the sin2 cp barrier is A 2 / A Q ~ ~ ~ ,where
*,
A2
is the intramolecular twisting energy, which Frohlich suggests is about 5
C.V. or 110 k ~ a l . / m o l e . ~Later
~
it will be shown by independent analysis
is within the factor of two of 150 cal.
that AQcH,* = AHCHz* - TASCH~*
for polyethylene in the ac region. This suggests that m is roughly 20 to 40.
Hence we anticipate strictly rigid-rod behavior for chains up to roughly
60-120 carbon atoms in length, with longer chains beginning to show the
effects of chain twisting (Fig. 10).
The activation energy for ac - A and aC - 13 with the effects of chain
twisting included is of the form
AH*(^)

ARi*

+ 2?12ARcl1,* [ ~ ( E&)I
I,

(29)

where aHl*is AHf,,ld* for ae - A and 2AHe,* for ac - B. The heat of activation increases linearly for values of n up to ~ mand
, then tends to level
off. The limiting value for very large n is
AH,,

*(rL) =

AH,* f ~!???AHcH['

This is to be contrasted with the behavior of A H as given by expressions

such as eq. (20).
The value of T,, implied by eqs. (28) is

a , p,

AND

RELAXATIONS

197

where a = a', b = b', and To are the same as defined for aC- A and ac- B.
Assuming @t is of the order of 20-40, TE",,,,
will increase in accord with the
rigid-rod approximation results up to n = 60-120 and then bend off
with a further increase of n somewhat more rapidly than is predicted by the
rigid-rod approximation (Fig. 8b).
The effect of twisting will be more obvious in plots of I n T against 22,
or in plots of the observed activation energy against n. These plots will
be linear as long as the rigid-rod approximation is valid, but will show a
distinct leveling off when this approximation fails (Fig. 10). Note in
is independent of frL for the rigid-rod approximaFigure 8b that (T,,,),,
tion. However, in the case with chain twisting, (Tmax),+,, depends on
j,n even for a fixed m.

a,- c,

%- c c
Fig. 11. hlotlel for process

aC- C

(slightly rorigh fold surface arid iiidepeiideiiL interior

chain and fold motions).

E. Model a, - C (Chain-FoldedCrystals with Independent Chain Fold and

Interior Chain Relaxations)
Model 0 1 ~- C, (Fold Contribution). If the folds considered in model
a, - A have a number of extra links in them, the fold will be able to turn
from site 1 to site 2 without disturbing the chains in the interior of the
crystal. This leads t o model a, - C (Fig. 11) which has two independent
relaxation processes, one belonging to the folds ( a , - C,), and the other
being a result>of chain rotation and twisting in the interior (ac - C,).
I n the case of thc folds, one has

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

198

where AHc,* and AScf* are the heat and entropy of activation for the wZ1
transition. These quantities are independent of the length of the chain in
the crystal interior. The above expression leads to

T,,,

AHc,*/(R In AT,

+ ASc,*)

(32)

and hence T,,, for this process is independent of n.

A surprisingly low activation energy can lead to T,,,, values that lie in
the ac region at 1 Hz. Taking AHc,* to be 15 lical./mole and A = 1O1O
gives T,,, = 325K. for A&,* = 0 and 270K. for ASc,* = 10 e.u.
The weighted orientational polarizability is

where the symbols have the same meaning as those discussed under eq. (IS).
This gives a contribution to I , for the whole crystal that varies as 1/Z
(Fig. 8c). The mechanical absorption intensity will vary as (C1C2/N2).
[Zf/(Z
Zf)] (XI - X2)2/lcT. The mechanical manifestation of the aC- C j
relaxation will probably be activated by a shearing motion of one chainfolded lamella with respect to another, which thereby biases the equilibrium
distribution of the folds.
Model 01, - C, (Interior Chain Contribution). I n the case where the folds
have extra links in them, the chains in the interior of the crystal should be
able at least to a limited extent to undergo the translation-rotational
motion discussed in model a, - A and ac - B. This gives in the rigid rod
approximation

T,,,

To(o~c,)[(a

+ n)/(b+ n)l

(34)

where TO(CUC,)
= AHcH~*/AXCI~~*,
a = 2(AH,,* - AHcH~*)/AHcH~*and
b = [R In AT,
2 (AXeg* - AXCH~*)]/ASCH,*. Thus, the In r and
I,,, relationships for ac - A, ac - B, and 0 1 ~- C, depend on n in a similar
manner. By extension of arguments given earlier, we expect a % a % a
and b b
b. The activation energy for the rigid rod approximation is
given by an expression analogous to eq. (6), and with chain twisting it is
given by eq. (29).
The dipolar contribution of ac - C, for two sites 180 opposed is

where the symbols have the same meaning as in eq. (27), except that X C ,
is now the mass fraction of interior chains associated with folds that have
extra links on both ends. The absorption intensity of mechanical relaxation will behave in a manner that is essentially independent of I (Fig. 8c),
i.e., the 0 1 ~- C, effect will act as a bulk contribution.

a, P,

AND

RELAXATIONS

199

If the folded surface is rather rough, then X C ,will be high, and a rather
strong absorption may be expected compared to the ac - B relaxation in
relatively pure n-paraffins, where X , will be small.
The essential difference between model ac - A, which has thc folds
intimately connected to the crystal interior, and model ac - C which has
loose folds that are disconnected from the interior, is that olC - A exhibits
one relaxation time, while the model with independent folds leads to two
relaxation effects, a, - C, (independent motion of loose folds) and ac - C,
(independent rotation of chains in interior).
If a single crystal behaves according to ac - A, it will show one 1osb
maximum in the ae region. Two loss effects, ac - C, arid a, - C,, will
- C representation with
appear in single crystals in the ac region if the aYc
loose folds is correct. A bulk polymer with extended-chain and chainfolded crystals will exhibit two loss effects in the ac region ( a c - A and
ac - B) if the chain folds are connected to the crystal interior, and three
loss effects ( a , - C,, aC- C,, and a, - B) if the chain folds are loose.
The ac - B contribution in each case is due to the extended-chain phase.
The differences in models a, - A, aC - B, and ac - C, arise from differences in AH^^* and ASeg* (or nHfold*and Asfold*) in the various cases.

F. Comparison of Theory and Experiment for the a, Relaxation

Long-ChainCompounds ( a ,- B). The a, relaxation appears prominently
in the n - p a r a f f i n ~ n-esters,
,~~
and n - e t h e r ~ ~ lof- ~normal
~
purity. It also
appears in solid solutions of ketones in n-paraffins where the paraffin
molecule has one more carbon atom than the ketone.43 The T,,, valuc
for 1 Hz. for the n-paraffins, as determined by I l l e r ~
using
~ ~ measurements
of the loss modulus G are shown in Figure 12. I n the same figure are
shown estimates of T,,, a t 1 Hz. obtained from the dielectric data of
Meakins on n-esters, ethers, and ketones in n-paraffins. While the T,,,
values for the dielectric data in general tend to be somewhat below those
for the n-paraffins, the trends with increasing chain length are very similar.
The aCprocess appearing in these compounds may be identified as aC- B.
The dielectric data of M e a k i n ~clearly
~ ~ show that chain reorientation
IS involved in the process leading to the loss. In the dielectric case, it
has becn firmly established by Dryden arid Welsh44that impurities in thc
form of chains different from the average cause the dielectric loss in the
prerotator state : for very pure compounds, the dielectric loss corresponding to the aYc
- B absorption becomes very small. This points clearly to
the short-chain defect mechanism shown in Figure 9i. Similarly, recent
mechanical relaxation experiments by Crissman arid Passaglia on highly
purified single crystals of n-C20H42
fail to reveal the a m e ~ h a n i s r n . ~This
~
again points to the chain impurity effect postulated in our aC- B mechanism.
The n-paraffins and their dipolar derivatives often undergo sharp
rotational phase transitions just below the melting p ~ i n t . ~In~ the
,~~
cven-carbon n-paraffins conipounds from n-C,IS,, up through n-C44Hgo ex-

200

J. D. IIOFPMAN, G. WILLIAMS, E. PASSAGLIA

n
3

10

30

100

300

(a,-8)

(CG-Cc)

1000

+ (a5-C,)

u)

20

3
.
0

LOG,, n
Fig. 12. The temperature of maximum loss a t 1 Hz. plotted against log n ( a cprocesses). Mechanical: (h) single crystal mats polyethylenez5; ( X ) bulk linear polyethylene66; (m) n - p a r a f f i n ~ . Dielectric:
~~
(a)Esters43; (As)ethers43; ( 0 )and (A) solidsolutions of ketones and ethers, respectively, in n - ~ a r a f i n s ~(
~9
; solid
) solutions of ethers in
low density p ~ l y e t h y l e n e ~(~6; ) and ( 9 ) oxidized bulk polyethylene and single crystal
mat polyethylene respectively.26 The upper calculated curve (-)
corresponds to the
relation T
, = 342 (0 n]/[14.5 n ] . The dashed lines (R = 40 and R = 30)
falling off this curve correspond to the modification of this rigid-rod approximation to
include chain twisting. Similarly, the lower calculated curve (-.-)
corresponds to
T,,, = 333 [2 n] /[18 n] and the lines 6 = 40 and % = 30 take into account twisting of the chains.

hibit this effect. The hexagonal phasc above the first-order transition is
called the rotator, phase, and the phase below the transition is called the
prerotator p h a ~ e . ~ The
, ~ ~rotational phase transition is an equilibrium
effect in a pure material, just like the melting point. The chain rotation
effects discussed here all refer to the prerotator state, and are connected
with the presence of short-chain impurities as noted. The rotational
transition occurs even in extremely pure materials, and the hindered
molecular rotation in the solid state above the transition temperature is
not dependent on the presence of chain impurities. The relaxation
time in the rotator state is in general much shorter than in the prerotator
state. Short-chain impurities will induce the rotator state in materials
such as n-Cl8HS which would not otherwise exhibit it, but at the low
temperatures where the
process is observed at 1 Hz., there is no possibility for a rotator phase contribution.
The extensive dielectric data of Meakins43 on symmetrical n-ethers,
n esters, and solid solutions of ketones in n-paraffins show that AH* for

01,

p, AND

RELAXATIONS

201

ESTERS

ETHERS

KETONES
(SOLID
SOLUTIONS)

(a1

Pyy/i
0

--

KETONES

SOLUTIONS)

*I 15

a
10

10

20

30

40

( b)

Fig. 13. ( a )Log,, ( 4 / ~ ) AS (n)/2.3R and ( b ) A H * ( n ) versus n, the number of

atoms in the chain, for symmetrical esters, ethers and ketones. (Data of Meakin~.4~)

-C-

the aCprocess increases linearly with n up to n = 37, the longest molecule

investigated. (Highly unsymmetrical esters have different crystal
structures than the more nearly symmetrical ones.) It is also clear from
Mealiins work that the heat of activation A H * and the entropy of activation AS* increase linearly with n, and that AQ* therefore increases linearly
with n at a constant temperature. Therefore, the paraffin chains behave
ns rigid rods as predicted for the case where n < . r r f i (model U(p) = AQcHz
sin2p) where r ~ zwas theoretically estimated to be between 20 and 40.
There is no substantial evidence of chain twisting in the n-ketones, esters,
and ethers up to n = 37. This is in accord with the earlier suggestions of
Hofman and D e ~ l i e rwho
~ ~ gave evidence showing that chain-twisting
has not begun in the 20-40 carbon region in n-paraffins and their polar
derivatives. The detailed data of Meakins effectively contradict assertions found elsewhere, based on much less data, that severe chain twisting
is seen a t such chain lengths. Mealiins data for AH*(n) and AS*(n),
which appear to have been widely overlooked, are summarized in Figure 13.
Data on some esters of low chain length have been omitted because they
have a different crystal structure than the longer esters.
With the work of Meakins justifying the rigid-rod approximation up to a t
least about n = 37, we turn now to an investigation of T,,, a t 1 Hz. for
short chain compounds. We choose to begin by fitting Illers mechanical

202

.T. D. 1-IOFFMAN, G. WILLIAMS, E. PASSAGLIA

data on the n-paraffins. The rigid-rod equation for the ae - B relaxation

becomes

where To = 333, a' = 2 and b' = 18. The fit is shown in Figure 12. The
fit shows again the validity of the rigid-rod approximation at the chain
lengths given (n = 7 to n = 25). A very good fit can also be obtained
with To = 342K.) a' = 0, and b' = 14.5 (Fig. 12).
It is of interest to obtain an estimate of AHCH2*, ASCH,*and A from the
is 700 f 50
data. llleakins' plots of AH* against n indicate that AHcH~*
cal./CH2 for the ketone-paraffin solid solutions, esters, and ethers. This
value should hold approximately-say, within 20 or 30%-for the n-paraffins. Combining this with To = AHcH2*/AScH2*= 333K. for the nparafflns gives ASCH?" = 2.1 e.u./CHn. Then noting that at 1 Hz. that
b = 18 = ( R In A
AS,*)/AScH2* and letting AS,,' = 0 it is found that
A = 2 X lo8 events/sec., which compares favorably with the theoretical
estimates. The experimental value of A from the entropy data is 3 X
109 (Fig. 13). An alternative calculation of AXcH2*may be made from
the experimental result b = 18 by assuming values of A. If A is lo9,
~ S c I T 2is*2.4 e.u./CHz and if A is
AScF12*is 2.9 e.u./CH2. Somewhat
smaller values of ASCH," are found if b = 14.5 is used in the analysis.
The free energy of activation per CH2 group, A&cII~*
= AHcH~*- TAS~H,",
is 280 cal./CHz at 200K. and 70 cal./CHz at 300K. These figures will
be used subsequently to estimate %.
The above estimates of AHcH2*,AScH2*,To,and A must be regarded as
approximate. They are given mainly to give a rough idea of magnitude of
the parameters involved in the ac - B process. The assumptions involved
in comparing dielectric and mechanical loss T,,, data are minimized in the
treatment, but such factors as subtle differences in the crystal structure
of the substances treated could cause errors in the actual values obtained.
Nevertheless, it is clear that the rigid-rod approximation used in a, - B
holds quite well up to at least n
37, and that this approximation is
consistent with the T,, data for chains up to this length. Furthermore,
our assumption that AQ*(n) must be broken up into linear AH*(n) and
AS*(n) terms is justified. The T,,,, data can be fit using this assumption,
but cannot be fit using the concept that AQ*(n) contains a AH*(n) term
linear in n and only a constant AS* term. In any event, the latter assumption is not justified by Meakins' AX*(n) results, and its use leads to a
T,,, value that rises linearly with n, which is contrary to the experimental
results of both Illers and Meakins.
I n a more ideal situation, activation energies of the various short nparafins would be available from mechanical data obtained at various
frequencies so that AHCx2*and AScH2*could be obtained directly for the
paraffin rhain systcm. The different crystal structures of the even-odd
series could be taken into account. Tn the event, we were forced to use

a, p ,

AND

RELAXATIONS

203

dieleclric data on ketones, esters, and ethers to obtain AHcH2*. These data
are internally consistent and imply A H c H ~ *= 700 cal., but some differences
in crystal structure bctwecn these compounds and the n-paraffins are
possiblc, and AHcH~*
for the paraffin chains could be somewhat different
than that applicable to ketones, esters, arid ethers.
Despite the problems caused by gaps in the available data, the conclusion
is drawn that the ac - B model is capable of describing in a t least a general
way the role of impurity chains, and the variation of T,,,, AHcH2*,AXCH**,
and log r with chain length for chains whose length does not exreed IT^.
The distribution of reIaxation times for the ac - B reIaxation is not
large. The half-width OC the dielectric loss peak on an 2 versus log j
plot is about 1.6 decades. (A single relaxation time gives a half-width of
1.1 decades.) The distribution may be attributed partly to the existence of
inore than two orientation s i t e ~ , ~ and
~ - ~partly
*
to a distribution of lengths
of the impurity molecules.
Single Crystals of Polyethylene. The fit of the T,,, data a t 1 He. on
the n-paraffins using the a, - B mechanism results is seen in Figure 12 to
extrapolate up to the vicinity of T,,, for single crystals as observed by
mechanical reIaxation studies. I n singIe crystals, n is taken to be 1/10, i.e.,
it corresponds to the fold period. This extrapolation, which depends on
the rigid-rod approximation, is provisionally valid only so far as n N 60
20 to @z = 40, but a t such chain lengths T,,, values
120, i.e., @z
to n
not far from those observed in polymers have been approached. The
results shown in Figure 12 suggest that the mechanism causing an important part of the ac mechanical relaxation process in single crystals is
closely similar to the aC- B mechanism jn n-paraffins, which is a result of
reorientation of defect chains in the crystal lattice. The link between the
two cases is provided b y a comparison of the T,,, data for n-paraffins
and their polar derivative with the data for single crystal (Fig. 12). When
the fit to the data for the former, in which the mechanism is known to be
a, - B, is extended to higher chain lengths, the fit to the polyethylene
crystal data is reasonably good. This strongly implies that chain rotation
over a barrier (with chain twisting at large values of n) is a principal contributor to the overall
process in chain-folded single crystals. We
had anticipated that a = a = a and b = b = b in the ac - A, and
aC- B and aC- C, models. Also, we had anticipated that To(a, - A)
T0(a,- B) g To(a,- C,] = AHcx2y/AXcH2y. It is difficult to escape the
conclusion that these equalities, which relate ac - A, ac - B, and ac - C,,
are a t least approximately valid. Because the acrelaxation in single crystals
evidently consists of two components (see below), the ae - C, part of
model ac - C is used henceforth for purposes of comparison with thc
ac - B model for paraffin chains.
The T,,, data on single crystals lie in the region where chain twisting is
expected, i.e., n greater than 6&120. Calculation of T,,, using ?n = 30
arid
= 40 with eq. (36) for the cases a = a = 2, 6 = b = lS, and
a = a = 0 and b = b = 14.5 are shown in Figure 12. These calcula-

204

J. D. IIOFFMAN, G. WIlJAAMS. E. PASSAGTJA

tions correspond to a comparison of models ac - B and ac - C,. The

T,,, values for the mechanical loss data of Sinnott on single crystals are
fit best by a" = 0 and b" = 14.5 with an l;;i that is 40-50, or even larger.
There is evidence that the mechanical manifestation of the acmechanism
in single crystals as measured near 1 Hz. consists of two overlapping
components. Takayanagi and co-workersZ8have shown from data on
single crystals prepared from fractions of polyethylene that the ac peak
involves two processes, one with a low activation energy, and one with a
high activation energy. The data of Sinnott25 are consistent with this.
(Wada et aLZ9and Iwanagi and Nakane30 have examined the situation in
bulk polymers over a wide frequency range, and concluded that the high
activation energy process corresponds to about 60 kcal./mole and the low
one to about 15 kcal./mole; these processes overlap in the vicinity of
1 Hz.) Evidently the presence of overlapping loss mechanisms, together
with their diff erent variation of magnitude with lamellar thickness, ob,,,
scures to some extent the exact interpretation of the variation of T
with increasing lamellar thickness.
For the present, it seems reasonable to give the assignment ac - C,
(independent reorientation of chain folds) to the low activation energy ac
process, and ac - C, (reorientation of chains in interior of chain folded
crystal) to the high activation energy ae process in single crystals. The
T,, data of Sinnott are believed to reflect mainly the ae - C, mechanism,
though there is a contribution to the absorption intensity from the low
activation energy ac - C, process (see below).
The T,,, data obtained by dielectric methods for 1 Hx. generally fall
below those found from mechanical relaxation in the short-chain aC - B
region. The difference has an average value of about 10C. (Fig. 12).
I n the present case, the similarity of the dielectric T,,,, data and the
mechanical T,,, data is sufficient to warrant treating them as having the
very similar underlying mechanisms in the ac - B region.
The dielectric data of Ishida and YamafujiZG
on single crystals of polyethylene give a quite low T,, (Fig. 12) and an activation energy of 25
kcal./mole. This arprocess would appear to be ac - C,. This assignment
is consistent with that indicated by Ishida and Yamafuji, who suggested that
the dielectric absorption was a result of reorientation of lceto groups in the
folds. It is possible that the dielectric polarization observed was mainly
connected with the aZ component. Unfortunately, there are no dielectric
data on single crystal mats covering a range of I values.
If the rigid-rod approximation held at large n values, the observed
activation energy would sum up to very high values. For example, for
n = 300 and AHcH%*= 700 cal., AH* would come to 210 kcal./mole.
Chain twisting prevents the attainment of such high AH* values without
causing anything more than a small leveling off of T,,,.
The activation
energy of the aC- C, process has the limiting value of 4mAHc~z.* As an
upper limit, we would choose m = 60 and AH* = 700 cal. to give AH* =
168 kcal./mole, and as a lower limit, we would choose rtt = 30 and

a, p,

AND RELAXATIONS

002
,004
C
. OO06
,008
RECIPROCAL OF LAMELLA THICKNESS, (Ill)

205

Fig. 14. The plot of the area .f G" d ( l / T )for ac process in arbitrary units as a function of reciprocal lamella thickness for single crystal mats of polyethylene. (Data of
Si~inott.~)

AH^^^* = 500 cal. to givc AH* = 60 kcal./mole. The cxperimental data

on AH* for the high activation energy ae process in thick crystals are
difficult to assess, but a value of 43 kcal./moIe2*has been mentioned for
single crystals, and values of 60 k c a l . / m ~ l eand
~ ~ 168
~~~
lr~al./mole~~
have
been suggested on the basis of data on bulk polyethylene.
While the effect of chain folds is not particularly evident in the mechanical T,,, data for the ac process, their contribution is clearly apparent
in the mechanical absorption intensity data. S i n n ~ t has
t ~ ~plotted the
absorption intensity of the ac relaxation process in single crystals (calculated from areas under G" versus 1/!!' plots) as a function of 1/Z. This
plot is shown in Figure 14. The part that varies as 1/Z may be identified
as being proportional to (C1C2/N2)[Z,/(Zf
Z)] in eq. (33) for the ac - C
model (contribution aYc- C,), and the intercept may be identified as
[Z/(Z,2 )
Z)] in eq. (35) for the ae - C
being proportional to X ~ , , , ( C ~ C 2 / N
model (contribution ac - Cc). Eby and Colsonsl and Crissman and
PassagliaZ7have also suggested that fold reorientation is involved in the
overall aCprocess in bulk polyethylene. Model ac - A leads to similar
results, but we have given model ac - C more weight because it produces
two relaxation processes.
It is concluded that the ac - C model gives a satisfactory representation
of the aCprocesses observed in single crystal mats. The high activation
energy component aC - C, has a T,,, value that appears to be a straightforward extension of the rotation-translation process with twist in long
chains ( a , - B) in the short-chain homologs. To a remarkable degree,
the high activation energy aC component of a single crystal whose fold
period contains n-CHP- units acts like an n-paraffin with a similar number

+
+

206

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

of chain units. The model leads to a semiquantitative explanation of the

variation of T,,.,,, with fold period, and relates this to the properties of short
chains. Moreover, the aC - C modcl leads to a second and lower activation energy relaxation proccss involving the folds, which accords appi-oximately with expcriment. The model leads to a qualitative explanation of
the absorption intensity of the (overlapping) processes as a function of fold
period.
Theoretical studies suggest that single crystaIs have slightly rough
surfaces when they are first formed.l3~l4However, it is entirely possible
that sufficient annealing (or certain crystallization procedures) will lead
to extremely smooth chain-folded surfaces. Experimental evidence based
on the presence of dislocation networks between single crystals in contact
shows that highly regular fold surfaces exist in certain single crystal preparati0ns.5~ Meanwhile, it is well known that many single crystal preparations exhibit densities well below that calculated from the unit cell dimens i o n ~ . ~A
~ t-least
~ ~ some of this could be a result of rough surfaces. Our
point here is that the nature of the surfaces of single crystals niay well
depend on temperature of crystallization, annealing time and temperature,
and other factors, in such a manner as to lead t o variations in the surface
roughness. A smooth surface would lead to model a, - A, while a slightly
rough surface gives model ac - C. Meanwhile, the presence of residual
solvent can enhance fold surface mobility. Accordingly, care should be
taken t o state methods of preparation of single crystal mats. Moreover,
caution must be exercised in interpreting experimental results in view of
the possible effects of various treatments on the nature of the chain-folded
surface.
Bulk Polyethylene. The T,,, value found in mechanical studies for
bulk polyethylene a t 1 Hz. appear to fall in line with those calculated for
To = 333 K., a" = 2, and b" = 18, or even better, To = 342K.) a" = 0, and
b"=14.5 (Fig. 12). In this sense. the dominant a , process observed mechanically in bulk polyethylene seems to be a straightforward extension of
the ac - B model for the n-paraffins. The mechanical studies also imply
that T,,, a t 1 Hz. for a bulk sample of a certain lamellar thickness is
similar t o that of a single crystal of the same thickness. Therefore, we
would propose that the ac - C, component of model a , - C with chain
twisting jn the interior provides the basic explanation for the main aCpeak
that is observed in bulk polyethylene. The ac - C, component of a, - C
overlaps the aC- C, component a t 1 Hz.29p30
Illers' mechanical relaxation data on bulk p ~ l y e t h y l e n eindicates
~~
that
there are actually three closely spaced &,-type peaks. We tentatively
propose that two of the peaks are ae - C, and a? - C, in the chain-folded
lamellae, and that the third peak is a result of an ac - B type mechanism
in the extended-chain phase that is known to occur in bulk specimens of
this polymer.
An interesting and important difference between the mechanical data on
single crystals and bulk polymer occurs on annealing. On annealing,

01,

8, AND

RELAXATIONS

207

single crystals thicken, and Sinnott has shown that absorption intensity of
the ac incchanical relaxation proccss decreasesz5 (Fig. 14). This is preciscly what is predicted by the a , - A 01- ac - C models as has been discussed earlier. Just the reverse occurs in bulk polyethylcne samples:
according to Illcrs, the mechanical absorption of the main ac mechanical
process increases with annealing and thickening, which processes are associated with an increase of density. These results are not necessarily contradictory. I n the case of Sinnotts mechanical data on single crystal
mats, there is of course little change in the degree of crystallinity as the
lamellar thickness is increased. Therefore the decreasing intensity that is
found with increasing fold period in single crystal mats may be regarded as
being without complications. However, there is a small but definite increase of density in bulk polyethylene that clearly correlates with the
increase of G.27*56We would tentatively attribute the increase of density
and hence G in the ac region on annealing in bulk polyethylene largely
to the following factors: (a) removal of cilia by thickening, which improves contact between the lamellae, and (6) tightening of interlamellar
links caused by thickening.
The amorphous component in the type of linear polyethylene samples
usually prepared never becomes separate and distinct enough to lead to a
Iarge and clear-cut p type Ioss peak such as is found in PCTFE. The
reason is that the rapidity of crystallization of polyethylene of the usual
molecular weight precludes retention of any significant amount of clearly
identifiable amorphous phase even with rapid quenching. The crystallization of PCTFE a t a specified supercooling is much slower than that of
polyethylene at a similar s ~ p e r c o o l i n g and
, ~ ~ ~rapid quenching through the
region of rapid growth (which lies about midway between Tm0and T,) is
capable of preserving a considerable amount of amorphous material which
is then metastable below T,. The increase of density on annealing bulk
polyethylene of the type used by Illers is therefore probably not due to
crystalljzation of truly amorphous material, but rather to removal of
voids caused by smoothing of the chain-folded surface, removal of cilia by
thickening, removal of some looplike folds, and tightening of interlamellar
links. I n quench-crystallized PCTFE, definite evidence for the existence
of an amorphous phase appears in the dielectric and mechanical data,
which show a distinct /3 relaxation (see later).
Dielectric studies reveal an ac process in slightly oxidized bulk polyethylenezGp57
that appears to be quite similar to that discussed by Ishida
and Yamafuji2Gin single crystals. We tentatively identify this as a, - Cf.
It is concluded that two of the ae relaxation peaks found in bulk polyethylene correspond in many respects to the ac - C, and a, - Cf relaxations found in uncomplicated form in single crystal mats, and that these
processes are basically described by the CY. - C model with chain folds as
modified to include chain rotation-translation and twisting in the lamellar
interior. The differences between the behavior of single crystals and bulk
polymer arc suggested to be the result of the effects of cilia and inter-

208

J. D. IIOFFMAN, G. WlT,LIAMS, E. PASSAGLIA

lamellar links. It is suggested that a third a, relaxation occurs in the

extended-chain component in the bulk polymer, and corresponds to model
ac - B.
Bulk PCTFE. As notcd earlier, a clearly resolved a, process is seen in
a loss versus T plot only in the isothermally crystallized specimen 0.80,
which contains typical lamellar spherulites (Fig. 4). The a, mechanism
is absent in the quench-crystallized specimen 0.44 and in the quenchcrystallized and annealed specimen 0.73. The implication is that the
intensity of the a, process depends partly on the chain-folded surfaces, as is
true for model a, - A and a, - CI. The virtual absence of a resolved a,
process in specimen 0.73 may be attributed to the fact that the folds in
0.73 are rather irregular and contain enough extra links to allow the fold to
reorient with considerable ease. This would lead the ac - C, component
to have a low activation energy and fall under the p peak, or cause the
occurrence of a broad background. The dielectric data in Figure 4 suggest
that the latter is the case. The ac - C, component may also be broadly
spread out in 0.44 and 0.73 because of the large fold period distribution,
or it may occur under the p process because the average fold period is rather
short. T,,, for aC - C, or aC - A falls rapidly for low n in a lamellar
crystal.
The activation energy of the a, relaxation in PCTFE is 80 f 10 kcal./
mole. Since the lamellae in the specimen 0.80 corresponds approximately
to n = 300, AHcH**would be 270 cal. if the rigid-rod approximation held up
to 300, i.e., f i 1 300/7r = 96. This is a lower limit for AHCx,*, since it is
probable that twisting intervenes before n = 300. If SO kcal. is the limiting
value 4 m ~ H ~ ~then
, * ,AHcx," would be 20 kcal./m, which gives AHcx," =
1 kcal. for m = 20 and AHcx," = 500 cal. for = 40. The true value of
AHcx," for PCTFE for the ac - C, process probably lies in this range.
It is not possible to proceed further without more data, for example activation energies for various samples of known lamellar thickness.
It would be very useful to have mechanical and dielectric relaxation data
on single crystal mats of PCTFE of varying thickness, and on bulk specimens of fractions of varying lamellar thickness in order to mal-\e a more
complete test of the theory.
Conclusions. The a, process in the n-paraffins and their dipolar derivatives seems to be adequately described by model a, - B. The basic relaxation mechanism is the reorientation of a "defect" chain, probably accompanied by a small lengthwise translation. The rigid-rod approximation holds up to at least n=100, but sufficiently long chains twist. The
behavior of the aE mechanism in polyethylene single crystals appears to
be described at least in some respects by model ac - C. The ae - C,
component is very similar in nature to ac - B: the basic motion in the
chain-folded crystal is a chain reorientation with a small lengthwise translation. This leads the aYc- C, component to behave just like an extension
of the ac - B process. The a, - C, component describes the independent
reorientation of the chain folds, and is independent of the fold period.

a, 0,

AND

RELAXATIONS

209

Thus, single crystals with slightly rough fold surfaces can give two a,-type
relaxation effects. Bulk polyethylene exhibits the aC - Cc and ac - C f
relaxations and a third mechanism probably arising from the extendedchain phase. Certain additional differences between the behavior of
single crystals and the corresponding bulk polymer are attributed to
effects due to cilia and interlamellar links. The results on PCTFE indicate
that a clearly resolvable ac process occurs only when the chain-folded
lamellae have a reasonably narrow distribution of thickness, and foIds that
are not too looplike. These findings are consistent with the models
presented.

V. THE p RELAXATION PROCESS

No evidence of a p effect is found in (linear) polyethylene single crystals,
and only a very small p effect is found in linear bulk polyethylene. Highly
branched polyethylene exhibits a peak between the ae and the y re,'vions
that is usually called p, and commonly attributed to the "amorphous"
phase-its true origin is in the opinion of the authors by no means settledbut discussion of this process lies outside the scope of this paper, which is
restricted to processes in linear chains without side groups. Therefore the
discussion of the p process is confined to PCTFE, where the phase in
which it originates can be identified.
The p relaxation effect appears clearly in the dielcctric data' for PCTIW
specimens 0.44, 0.73, but only quite weakly for specimen 0.80 (Fig. 4).
(Specimen 0.12 cannot be measured in the fi region, as it crystaIlizes when
heated above about 60C. The hypothetical p peak estimated for specimen
0.12 is shown in Figure 4 as a dashed line.) The temperature where the
maximum occurs at 1 Hz. depends on x, and the texture of the specimen.
The values of T,,, for 1 He. are given in Table 11.
TABLE I1

a Relaxation Process in PCTFE

Degree of
crystallinity

T , (dilatometric)
( t lo5 see.),
"C.

T , (dielectric)
from WLF
analysis, "C.

0.12
0.44
0.73
0.80

-40
50
59
46

65
87
45

T,,,

at 1 IIz.,

"C.

110
125
92

It is seen in Figure 4 that the intensity of the @ relaxation as observed

from the dielectric data iricreascs M S the crystallinity decreases. The
dielectric data thus indicate that thc relaxation is a property of the
amorphous component of the semicrystalline polymer. On assuming that
the amorphous content of the polymer, 1 - x, is proportional to the estimated area under the peak and using the 0.44 specimen as a guide, it is

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

210

LOG,, FREQUENCY,HZ
Fig. 15.

t"

versus log f at various temperatures for PCTFE specimen 0.73 showing the
p process. (Data of Scott and co-workers1)

estimated that specimen 0.80 actually has only about a 5% amorphous

component, i.e., its true crystallinity is about 0.95. This is expected from
the fact noted previously that the dilatometric method of estimating x for
highly crystalline specimens can lead to low results because voids between
the lamellae are incorrectly counted as amorphous material.
The mechanical loss dataz3shown in Figure 4 also imply that the scat
of the p relaxation is the amorphous component of the polymer. Conclusions of this sort, when based on mechanical IT tan 6 data, must be viewed
with some caution because of the large change of modulus in the ,8 region.
No analogous large dispersion occurs for the dielectric data, which are
superior in this respect, and lead to generally reliable conclusions regarding
the phase in which a relaxation process originates. Nevertheless, in this
case it is clear that the conclusion one would naturally draw from the T tan 6
mechanical data concerning the phase of origin of the ,8 process is correct.
Further information concerning the nature of the p relaxation in the
amorphous component of the semicrystalline polymer can be obtained from
plots of e" versus log J at various temperatures, and the plot of log fmax
versus 1/T that can be constructed from them. Figure 15 shows a typical
plot of e" versus log f that exhibits the relaxation peak in PCTFE in
specimen 0.73. A similar plot1 is obtained for specimen 0.44. The plot of
log fmax versus 1/T obtained from the various e" versus log f plots for the @
process is shown in Figure 6. The apparent activation energy of the p
relaxation process calculated by using eq. (1) is shown in Figure 16 for the
various specimens.
It can be shown by using the activation energy data that the p relaxation
effect is associated with the onset of the glass transition in the amorphous
component of the polymer. The mean dielectric relaxation time of an
amorphous molecular dipolar substance generally follows the form

a, 8,

AND

RELAXATIONS

211

= ceUr*/R(T-T=)

(37)

1,/2..fm

as has been shown by Davidson and Cole a number of years

For the
particular class of liquids studied, the viscosity obeys the similar relation

roe U q * / R ( T - - T m )

(35)

where for a given supercooled liquid U,* and U,* and T, are practically
identical. This temperature dependence of the viscosity was noted by
Vogelsg in 1921. More recently, Williams, Landel, and Ferry60 (WLF)
have assigned the approximate values U,,*
4.12 X lo3 cal./mole and
T , G T, - 51.6 to cover the case of many amorphous polymers. These
quantities may vary considerably from one polymer to another, but the
values cited are still useful for the present purposes. Equations (37) and
(38), while quite probably more fundamental in origin than q or T in the
form C exp { AH*(@/RTf, are still altogether equivalent to stating that
AH*@) is temperature-dependent. The temperature dependence of AH*
that accords with eqs. (37) and (35) is
AH*(p)(cal./mole) G 4.12 X 103T2/(51.6
as may be found by taking AH*
substituting the WLF constants.

+T -

(39)

-Rb lnjm/b(l/Z') with eq. (37) and

j3 PROCESS
TG=87' C

201

I
50

100

I50

200

TEMPERATURE, 'C

Fig. 16. AH* versus temperature for the p process in PCTFE samples. (Data of Scott
and co-workers.') Solid lines calculated using eq. (39) with Tovalues shown.

The solid lines in Figure 16 show A l l * as calculated with eq. (39) for
the I', values shown. The observed temperature dependence of AH* for
specimens 0.73 and 0.50 is approximately accounted for by the WLF expression for AH*, eq. (39). (The temperature range where
could be
located in specimen 0.44 was too short to allow AH*(@) t o be calculated a t
J;r,LX

212

J. D. IIOFFMAN, G. WILLIAMS, E. PASSAGLIA

two widely different temperatures.) We conclude from the above behavior that the relaxation peaks that we have denoted ,8 for specimens
0.80 and 0.73 in Figure 4 are definitely of mostly amorphous phase origin.
Thus, we are correct jn distinguishing the acpeak in specimen 0.80, whose
origin is in the crystaIline phase (surface) and which has an activation
eiiergy that is independent of temperature, from the ,8 peak in specimen
0.73 which originates mostly in the amorphous phase and which has an
activation energy that is highly temperature dependent. There is little
doubt that the ,8 peak in 0.44 is of amorphous origin.
The glass transition temperature evidently depends on the texture and
degree of crystallinity (Table 11). Consider first the set of quenchcrystallized and quench-crystallized and annealed specimens 0.12, 0.44,
and 0.73. T , (dilatometric) increases steadily as x increases. This may bc
attributed to the increasing degree of strain and entanglement found in the
amorphous regions of these specimens (Fig. 2). The amorphous material
in specimen 0.12 is probably only weakly strained, and the T , value must
bc close to that of the completely noncrystalline state. For the reasons
cited earlier, the amorphous material in 0.73 must be in a strained state.
The increased strain in the intercrystalline links decrease the number of
configurations per unit length, and thereby increases T , (see below).
The same trend may be seen in T, (dielectric) in specimens 0.44 and 0.73.
[The shift of T owith x in specimens 0.12, 0.44, and 0.73 is quantitatively
somewhat different depending on whether one uses T o (dilatometric) or
T , (dielectric). The error probably lies mainly in T , (dielectric), which
depends on the validity of the constants in the WLF equation, and is also
doubtless affected somewhat by some mixing with the ar process with
loose folds. Howcver, the trends are similar enough to establish that the
upward shift of the ,8 peak with increasing x is largely a result of a real
increasc in T,. J The increase of T , with increasing x in these specimens is
also reflected as an increase in T,,, (Table 11). Poly(ethy1ene terephthalate) exhibits a similar increase of T , as the crystallinity is raised
from low to moderate values by annealing.6I
The plots of a tan 6 do not reveal an upward shift of T , (Fig. 4). This
shift is however seen in plots of G versus T given by Crissman and Passaglia.24
The situation in specimen 0.SO is entirely different than in 0.44 or 0.73.
In 030, both T, (dilatometric) and T , (dielectric) arc much lower than
they are in 0.44 or 0.73. The explanation of the low T , in specimeii 030 is
possibly as follows. In a specimen crystallized in the manner described for
0.80, the crystals grow slowly in an amorphous medium, and the process
may be quenched at any desired time. The result is a two-phase sample
comprising a normal crystalline and a separate unstrained amorphous
phase, where the amorphous phase has a normal T,. This is in direct
contrast to the quench or quench-annealcd specimens 0.12, 0.44, and 0.73
in which the amorphous phase is highly strained (see Fig. 2). The only
source of high T , amorphous material would be the small fraction of the

a,

0,AN13

RISLAXA'I'IONS

213

0.80 specimen that is in the form of stmined interlamellar links. Evidently this fraction is either so low or so dielectrically inactive that thc
high T , is not seen. Poly(ethy1ene tercphthalate) exhibits a similar drop
in T , for high crystallinities for specimcns that have been isothermally
crystallized.61
The foregoing analysis definitely relates the /3 relaxation process to thc
onset of the glass transition at T , in the amorphous phase. The variation
of T , with x in the quench-crystallized and quench-crystallized and annealed specimens 0.12, 0.44, and 0.73 is due to the varying degree of strain
experienced by the amorphous chains in these materials. T,,, for the
p process at 1 He. is the temperature at which the mean dielectric relaxation
time of the molecular motions involved is 1 per second; T , (dilatometric) is
simply thc temperature where thc mean dipolc reorientation timc is on the
order of magnitude of perhaps lo5 or lo6 sec.
Two basically different approaches have been employed to explain cquations such as eqs. (37) or (38), which are the principal relations governing
the temperature dependence of the 0 process. One approach62assumes
that the change of free volume, vf, is the principal cause of the temperature
dcpcndcnce of 7, and presumably T (dielectric), i.e.,

The quantity vf is defined as the actual volume V minus the "occupied))

volume vo. The value of of is supposed to increase markedly above 7',
mainly because of the increase of V , thus causing 7 to fall. Equation (40)
can indeed be recast, assuming a linear dependence of vo and V (and hencc
of vf) with temperature, into the form of eq. (37) or (3S), but this does not
necessarily imply this is the true origin of eqs. (37)-(39).
In the particular case of amorphous polymers, one serious objection to
the free volume concept arises. Williams has shown in dielectric studies
that the p relaxations in both poly(rnethy1 acrylate)e3 and poly(propy1ene
oxide)64 behave quite similarly under constant pressure and constant
volume conditions. The observed activation energies at various temperatures at constant volume are uniformly only about 20% lower than the ones
at constant pressure. The activation energy increases with falling tcmpersture in a manner similar to the PCTFE specimens (Fig. 16). This is
difficult to reconcile with the concept that the change of free volume causes
most of change of 11 or T. A strongly negative coefficient of expansion for
vo mould have to be invoked to retain the free volume approach. Accordingly, we regard the more trenchant empirical expressions governing T and
to be eq. (37), (3s))and (39). A complete treatment of this problem
would doubtlrss include the ef7cc-t of chilngr of free volume, but tlic fact
remains that cqs. (87)-(39) hold surprisingly well under hoth (mistm i
pressure and constant volunic conditions. The change in volume appears
t o act as a perturbation on eqs. (37) and (38), rather than an overall
representation of thc observed effects.

214

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

A derivation of eqs. (37) or (38), that provides %nalternative to the free

volume explanation for the temperature dependence of 17 or T has been
advanced. Gibbs and D i M a r ~ i ohave
~ ~ shown by a statistical mechanical
treatment of polymer chains with inherent stiffness that at a critical temperature Tz, which lies well below T , (dilatometric), the molar configurational entropy S , of the supercooled liquid polymer reaches a minimal
value. The transition at T2 is a true equilibrium second-order transition.
Recently, Adam and Gibbs@ have investigated the relaxation behavior
above T2 and succeeded in deriving
= A l e z * ( 4 d / k T = A l e N a s , * ( ~ d / S c k TN A 1,(4s)sc*/k(Acd (T- Tz)
(41)
where Ap is essentially the potential energy hindering rearrangement per
monomer segment, sc* is the critical configurational entropy of the smallest
subsystem that can perform a cooperative rearrangement to another configuration, both taken to be approximately independent of temperature, and
AC, is the difference in specific heat between the supercooled liquid and the
glass at T,. The right-hand equality in eq. (41) depends further on the
assumption that AC, is constant between T , and T2. The quantity x* is
the size of the cooperative region, which is given by Nas,*/S,, where N u is
Avogadros number. Equation (41) is of the same form as eqs. (37) and
(38), and leads directly to the form of eq. (39), the quantity T2taking the
place of T,, with T,, in one approximation, being T , - 51.6O.
The reason that T rapidly approaches infinity at the finite temperaturc
T 2 is that x* varies as 1/Sr, where X, falls rapidly to zero at TZ. The
cooperative region of critical size x* becomes infinite at T2, causing T to
become infinite at the same temperature. Thus, the basic physical reason
for the behavior of T near and above T , is that the equilibrium configurational entropy of the supercooled liquid approaches zero (or a very low
value) at T2 in line with the Gibbs-DiMarzio equilibrium theory. The
transition at T2 is an equilibrium second-order transition in the Ehrenfest
sense. Above the temperature T , or T2, the glass transition manifests
itself mostly by its associated kinetic effects, the behavior of T, fmax, or
AH*(@)according to eqs. (37), (38), and (39) being typical examples.
Equation (41) may be used to give a qualitative explanation of thc
increase of T , (dielectric) or T,,, with increasing crystallinity. It has
already been indicated that in specimens 0.12, 0.44, and 0.73 that the strain
on the chains is increasing. Tension on the chains will decrease AS,, since
chains undcr tension will have a lower configuration entropy. Hence T
will increase, which will raise T,,,, T , (dielectric), and T , (dilatometric).
A small decrease in AX, can lead to a rather large change of T because the
exponent s,*/k(AC,)(T - T2) is a large number.
The Adam-Cibbs t!heory appears to provide a rcasoiithle explanation ol
thc variation of the mean value of T for the /3 process wilh tenipcrature, but
no theory yet advanced gives a completely satisfactory account of the
distribution of relaxation times a d its variation with temperature for the /3
process in right-angle dipole amorphous polymers. I n the @ process

a, 6 ,

AND y RELAXATlONS

215

region, an t versus log f plot exhibits an asymmetric loss peak with a high
~~
frequency tail which is fit quite closely by the D a v i d s o n - C ~ l eempirical
representation. The distribution narrows somewhat with increasing
temperature. It would be of considerable interest to determine if the basic
chain model used by Gibbs and DilliIarzio, modified to include rigid dipoles
on each monomer unit, led to the appropriate distribution, but this involves
extreme mathematical difficulties in the right-angle dipole polymer case.
Zimm67has calculated the distribution of relaxation times for the casc
where the dipole moment is colinear with the chain, and a loss process
rather closely matching the empirical Davidson-Cole function is produced.
With a suitable choice of the form of the friction cocfficient in Zimms
theory, the infinite relaxation time at T, or T , is reproduced.
Note that a correct model of the relaxation processes in an amorphous
polymer with dipoles attached a t a right angle to the main chain is required
t o produce two separable relaxation processes active in principle in both the
mechanical and the dielectric relaxation spectrum: ( 1 ) the P relaxation
where T varies according to eqs. (37) and (38), and which freezes out a t
1 Haz. a t about O.76Tm0,which is well above T , (dilatometric)
0.63 to
0.67Tm0(see Fig. 2) and (2) the y a relaxation which has a low and temperature-independent activation energy that freezes out a t 1 Hz. near
0.50Tm0(Fig. 2).
The fact that relaxation effects due to the simplest liinking type motions are seen at 1 Hz. well below TZ in the glassy state in the y a amorphous
phase process (see following section) implies that the smallest cooperativc
subsystem associated with x* jn the p relaxation process is substantially
larger than that associated with the simplest noncooperative configurational
change. The simplest possible noncooperative configurational change is
the localized kinking motion that causes the high frequency part of ya.

VI. THE y RELAXATION PROCESS

A. Separation of y Process into ya and ycContributions in PCTFE

The y relaxation process in PCTFE is by a considerable margin the most

intense in the dielectric relaxation speclrum. This is implied by the t
versus T plot a t 1He. shown in Figure 4, and is clearly apparent from the 6
versus log f plots shown in Figures 5 and 15. The behavior of the y peak a t
various temperatures in PCTFE in specimen 0.80 is shown in the t versus
log f plot shown in Figure 17.
The y process is active in the mechanical relaxation spectrum (see
Figure 4, and also the mechanical loss data of Crissman and PassagliaZ4).
Plots of logj,,, versus 1/T for the various P C T F E specimens are shown in
Figure 6.
Figure 18 shows E versus log j for specimens 0.12, 0.44, 0.73, and 0.SO a t
23C. in the y relaxation region. After consideration of the curves in
Figure 18, it is difficult to escape the conclusions that the pure amorphous
supercooled phase (X --t 0) would show a y-type process, and that the

J. D. LIOFFMAN, G. WILLIAMS, E. PASSAGLlA

216
011
0 10

0 09

SPECIMEN 0 8 0

0.08
0.07

0.06

6
Q05

004

003
0.02

0 01
0
I

LOG,, FREQUENCY,

10

Hz

Fig;. 17. 2 versus log f at various temperatures for PCTFE specimen 0.80 sliowing
prominent y process. (Data of Scott and co-worlters.1)

conipletely crystalline material (x 1) would also exhibit a y-type process.

We call these contributions ya and yo respectively.
The intensity of the pure yc process at 23C. is about one-half that of the
pure ya process at the same temperature as measured by the area under the
d versus log f curves in Figure 18.
An important feature of the ya and yc components is that they have
common relaxation times on the high frequency side of the 6 versus log J
inaximum between lo4 and lo5 He. I n this region, all the loss data for all
the specimens are practically identical and independent of x. A similar
separation of the -ya and y. processes can be effected at other temperatures.
The half-width of the ya relaxation is 4.3 decades, and the half-width of
the yc relaxation is 3.2 decades (Fig. 18). The t versus log f peak for y a
appears to be nearly symmetrical. The ye peak on an el versus log f plot
is decidedly asymmetrical, the asymmetry being caused by a distinctive
high-frequency tail. The breadth and asymmetry of the distribution of
dielectric relrwration times for y. will be rationalized in terms of a simple
model to be proposed shortly.
Both the mechanical and dielectric relaxation data reveal the common
high-frequency relaxation times when plotted as loss versus T at some fixed
frequency. The mechanical manifestation of this phenomenon on a a tan 6
(mechanical) or G versus T plot for the y process is that the data for all
specimens coincide on the low-temperature side of the peak. This effect is
seen in the T tan 6 versus T plot in Figure 4 and is especially clear in the G
versus T data at 1 Hz. of Crissman and P a s ~ a g l i a . ~The
~ same phenoinenon appears in the dielectric data at 500 Hz. (Fig. 4). The situation
described above is depicted schematically in Figure 3. The fact that n
process in the amorphous phase and a related one in the crystalline phaw
have common relaxation times and similar intensities does not of course
vitiate the two-phase model of a semicrystalline polymer.

01,

0, AND

RELAXATIONS
I

217
r

.07

06
.Q 5

.O4
E

.o 3
.Q 2
.01

01

-I

4
5
6
LOG,, FREQUENCY, H r

10

Fig. 18. Resolution of the yC and ya processes on a plot of d versus log f a t 23C. for
PCTFE. (Data of Scott and co-workers.)

Our conclusion that the pure amorphous phase exhibits a ya relaxation

quite distinct from the /3 relaxation is supported by mechanical relaxation
data on linear polymers with no independently rotatable side groups that
are in an essentially completely noncrystalline state.61 Further, our conclusion that the completely chain-folded crystalline state (closely approximated by specimen 0.80) exhibits a yc relaxation is supported by the
mechanical relaxation data of Sinnott on single crystal mats of polyethylene.25 These mats exhibit the ac - C, and ac - Cfrelaxations a t high
temperatures as discussed previously, and a yc type relaxation peak a t
lower temperatures (cf. Fig. 2C). There is no hint of a P relaxation jn the
single crystal mats.
TABLE I11
y Relaxation Process in PCFTE

P,,, at 1 Hz., C.
X

0.00 (extrap.)
0.12
0.27M
0.42M

0.44
0.73
0.80and0.80M
1.00 (extrap.)

AH* (dielectric), kcwl./mole

Dielectric

- 10
-1.3.5
-30
-

-41
-50 (-45)

- 18

-30
-

-40
-

17 1 = A H * ( y a )
10.7
15 8
15.7
14.6
14 0 (14 3) = A H * (re)

From T tan 6 data of McCrmn.23

Omitted from extrapolations of AH* Lo x -+1 and x -,0 values.
Calculated on basis that dielectric specimen 0.80 is actually OOo/, crystalline.

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLlA

2111

The activation energies of the pure y a and y. processes can be estimated

from the activation cnergjes for the various PCTFE specimens calculntcd
by using AH* = -Ed I n finzx/d(l/7') with the data given in Figurc 6.
The results are shown in Table 111. Extrapolation to x = 1 gives A H *
(yc) = 14.0 kcal./mole.
[If specimen 0.80 has a true degree of crystallinity of 0.90, AH*(y,) would be about 14.3 kcal./mole.] The value of
AH*(y,) is in any case slightly lower than that of AH*(y,). The yopeak
a t 1 Hz. therefore occurs at a lower temperature than the ya peak on an E"
versus T plot (see Table I11 and also the mechanical T tan 6 data in Fig. 4).
At 1 Hz., the resolved yc peak occurs at -50C. or 0.450Tm0,and the
resolved yn peak appears at - 10C. or 0.533Tm0.

B. Model

ye

-A

(Relaxation at Chain-End Induced Row Vacancies in

Chain-folded Crystals)

Before giving the yc - A model, certain salient facts concerning the y.

mechanical process in polyethylene single crystal mats will be mentioned,
since these facts, together with those deduced from the data on PCTFE,
form an important guide for introducing certain features of the model.
SinnottZ5has demonstrated in mechanical studies that the y relaxation
in polyethylene single crystal mats, which we identify straightaway as
yc - A, increases markedly in absorption intensity with annealing time.
The annealing is known in these specimens to lead to an irreversible thickening of the chain-folded platelets. Thus the yc - A intensity increases
strongly with increasing thickness. This is consistent with neither the
hypothesis that the ye - A process is a surface effect, nor the hypothesis
that is a bulk property of the crystal interior. Furthermore, the value of
T,,, at a fixed frequency increases and then tends to level off as the crystals
thicken. The above phenomena, together with the wide and asymmetrical
distribution of relaxation times, must be explained by the model.
We introduce the concept that the defects that are continuously introduced into the chain-folded crystals by the thickening process are the
source of the yc - A relaxation. In the thickening process in chain-folded
crystals, chain ends must continuously be introduced into the crystal
interior to allow the proccss to proceed.6,11Jj8This is depicted in Figure 19
for the hypothetical case where the initial crystals of thickness I," have
cilia amounting to a small fraction of the total mass emerging from the
surface. The cilia shown in Figure 19A can arise when a new molecule
interrupts the substrate completion process during the formation of a chainfolded crystal. Stage 1 thickening, which involves pulling the cilia into
the crystal surface, plus the formation of some defects (which are vacancy
rows) occurs a t a rate of approximately6*

z = z,*

+ B1 log C(t - t n ) / t o l

(42)

B1

2.303 1 : 7 ' / ( 2 9 ~ ~ / a , )

(43)

wlicrc
=

a, p ,

AND

RELAXATIONS

219

STAGE I

STAGE 2

fcJ

I
LOG

fdl

le I

Fig. 19. (a,b,c) Schematic diagram for the thickening process of a chain-folded
crystal, indicating a mechanism for the injection of chain ends creating a row of vacancies
into the lamella; ( d ) rate of thickening (schematic); (e) edge dislocation a t vicinity of
chain end (schematic).

and t - to is the age of the crystal, and g = 2.54 X lo-* cm. for the carbon
skeleton polymers. Stage 2 thickening, which involves a high rate of
injection of vacancy row defects, proceeds a t the slower rate (Figure 19C)
where B1in eq. (42) is replaced by6s68

Bz

2.303 kT/(2ga2/a,

+ Ello)

(44)

where lo is 1.27 X lop8 em. for the carbon skeleton polymer and E is the
energy required to form a row vacancy per -Cunit. Bulk polyethylene
is known t o thicken in the two-stage rnanne~-ll*~~
depicted in Figure 19D.
Up to the present time, only the second stage has been seen in single crystal
mats, so that these crystals may be formed initially with the chain ends

220

J. D. ITOFFMAN, G. WII,LIAMS, E. PASSAGTJA

DEFBT
REGIONS
&-A

Fig. 20. Model for. the yc - A process in chain-folded rrystals.

near the surfaces (Pig. 19B). Either way, extcnsivc thickening cannol
occur in chain-folded single crystals or chain-folded lamellae in a bulk
polymer without injection of the type of defects illustrated in Figure 19C.
Evidence also exists that bulk PCTFE thickens markedly on annealing.lg
The transport of chain ends through the chain-folded crystal by the thickening process has been predicted to be accompanied by the formation of
edge dislocations of the type shown in Figure 19E.6 These dislocations
have been observed by Holland'O in polyethylene single crystals. Importantly, the number of them increases greatly with annealing. This
partially supports our contention that defects involving rows of vacancies
are injected into chain-folded crystals as they are annealed. The increase
of concentration of these vacancy rows will be used to explain the increase
of intensity of the y c - A process on annealing.
The model for y. - A is shown in Figure 20. A chain in the defect
region is subject to a greatly reduced barrier to reorientation from site 1 to
site 2 (Fig. 20) because of lowered repulsion. Any of the chains adjacent
to the defect can undergo turning, or turning and twisting, motions. It is
assumed for simplicity that the barrier system is such that the chain has
two sites 180" opposed (site 1 and 2 ) . We assume further that a simple
kink, similar perhaps to a Reneker
with an activation energy
AWd* allows an anguIar displacement of 180" to take place. The rest of
the chain then rotates, or attempts to turn, each -CHZunit adding a
free energy of activation barrier AWCH2* in the rigid-rod approximation.
The case for the rigid-rod
We consider first the calculation of T,,,.
approximation is given first. The free energy barrier resistling reorientntion between site 1 and site 2 is given by
AW,*(n)

AWd* -I- n A W c a 2 *

(45)

where AWd* is the free energy of activation associated with the kink
defect, and A T V ~ H ~is* the free energy of activation per -CHzgroup.
Breaking the free energy of activation into its entropy and enthalpy contributions gives

AJI,(A)*(~) = aBd*$- ~AIICH,,,"

(46)

4-nA8cH20,*

(47)

and
A s , , ~ ) * ( n ) = A&"

a, p,

AND

RETAAXATIONS

221

The relaxation time is in general given by

= (i/~)&w~*(n)/kT

where T refers to the w21 transition.

This leads directly to

where rm is the characteristic time of the measuring frequency, 1/27i;f,.

The quantity AHcH~(~,*/AXCH~(~,*
may be designated To(yc - A), which
is the convergence tcmperature for the ye - A process a t large n. Thercfore we may write eq. (49) as
Tmax(yc- A)

- A) [(c

+ n)/(d + n)I

(50)
The above equation is similar in form to those obtained for aC - A,
ac - B, and ae - C, in the rigid-rod approximation, but somewhat different
values of TOare to be expected, and in general c # a and d # b. Because
of the looseness of the hole in which the chain reorients in the yc process
compared t o the ace, we must expect AHcH2(,)*to be considerably less than
aHCHz*
for the ac process.
The corrections for chain twisting can easily be made using the WilliamsLauritzen model. The heat of activation becomes
= To(yc

AHyC(,,*(n)= AHd"

+ A ~ c r r 2 ~ , ,[S(E,,Ez)
*2~
I

(51)

and has a t large n thc limiting value:

AHd*

+~~AHcH~(~)*

Twisting begins at am.

The value of m will be substantially larger for the y. process than for the
aeprocess. This can be seen by recalling that m = (A2/AW~~,")"2,
where
A 2 is estimated to be 5 e.v., and noting tkak AWCH~"
is quite certain to be
considerably less than AQcHz*. Values of @z between 50 and 100 are considered reasonable for the y process. Chain twisting will intervene and
cause AH* to level off a t large values of n in a noticeable manner. Consider a crystal where n = 500. Assuming that rtz = 50, AHCH~(~,*
= 70
cal., and AHd* = 2000, we find AH,"
= 16 lical./mole for AH,,*.
On the other hand, if the rigid-rod approximation held, a crystal n = 500
thick would have exhibited an activation energy of 70 X 500 or 35 kcal./
mole, which already is considerably larger than one would expect for a y
mechanism.
The intensity of the yc - A relaxation is given by

where nd is the number of defects per cubic centimeter, n, the number of

units in the fold period, y the number of chains adjacent to the row of

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

222

vacaiicies, and ( p c ) the resolved dipole moment of the chain (or chains) of
length Zd in the defect region. The factor l/n, acting alone would cause
T,
na t o fall with increasing lamellar thickness, but the increase in ?%a
caused by injection of chain ends leading to vacancy rows should for a
time be the dominant effect, leading I , to increase with increasing lamellar
thickness. (HollandO has found that the number of dislocations in polyethylene single crystals increases by 103 on annealing.) This is consistent
with our suggestion that I , will increase with isothermal annealing.

- X-A
-.-

y-A

( r i g i d rod)
(rod w i t h

twist)

E
I-

/low

f,

LOG n

LOG f/f,,,

Fig. 21. Behavior of model ye-A (schematic).

Note that we have not predicted that thick lamellae will always have a
larger yc effect than thin lamellae. Our prediction specifically applies to
new lamellae that have begun to thicken, where the original lamellae were
all produced under the same crystallization conditions. If lamellae of
different thicknesses are prepared by varying the crystallization conditions,
the behavior of the y c absorption with respect to thickness might be quite
different. Note also that after sufficient thickening that nd will tend to
level off, possibly allowing the l/?zc term t o predominate.
The mechanical absorption will vary approximately as (C1Cz/N2)nd,
with Cz = C1 exp { -AW,/lcT}, where AWd is the equilibrium energy
difference associated with the kink-type chain defect, Equation (52)
assumes for simplicity that the two sites associated with the intermolecular
forces for the chain itself have equivalent equilibrium energies.
Perhaps the most striking feature of the y c process is the broad and
asymmetric distribution of relaxation times that it exhibits. This can be
explained directly from the model shown for ye - A in Figure 20. Some
defects will contain short chains such as nl in Figure 20, and others will
contain larger ones such as nz. T o a, good approximation, the active part
of the chains in the defects will possess lengths that vary uniformly between
zero and n,. This gives
(53)

LY,

p, AND

RELAXArIONS

223

where

T(n) =

Toe

AWA*(?L)/~T

(54)

and

AWA*(n) = AWd*

+ ~~TZAWCH,,,,*[J(E~,EZ)I

(55)

The integration cannot be carried out in closed form except for n = a3

in the rigid rod approximation. Equation (53) is derived on the somewhat
crude assumption that all processes corresponding to rotations consistent
with lengths 721, nz, . . . n, make equal contributions to the dielectric constant.
I n thc region where the rigid-rod approximation is valid, i.e., a t crystal
thicknesses less than ~ m eq.
, (55) reduces to AW**(n) = AW,*
nAWCH,,y,*,and eq. (53) leads to a broad and symmetrical loss curve on
err versus log j plot (Fig. 21). For crystals thicker than ~ mthe
, effect of
chain twisting enters, and the loss peak becomes asymmetrical (Fig. 21).
The asymmetry is a result of an accumulation of long relaxation times
arising from chains in the region where twisting occurs.
The y c relaxation can only become active in the case where there are
enough chain units in the loose chain in the defect t o allow a kinli type
defect to occur. Probably the required number of chain units is around
four or five. The integration in eq. (53) should actually be carried out
taking this to account, but little error is caused in most cases by omitting
any correction due to this cause, since in general n, >> 5. A chain that
cannot form a kink-type chain defect of relatively low activation energy
that in turn allows rotation of the rest of the chain through a large angle
should suppress the yc - A relaxation process in chain-folded crystals.

C. Discussion of y Relaxation in %-Paraffinsand Their Polar Derivatives

A process apparently related to the yc process seen in mats of solutiongrown polymer crystals appears in mechanical studies on dispersions of
n-paraffins in p o l y ~ t y r e n e . ~The
~ process is of appreciable magnitude in
this system. One can conceive of chains in loose regions such as might
occur a t grain boundarics and vacancies in these crystals. Clearly, such
chains would lead to a relaxation mechanism similar to that discussed
above as y c - A. It is, however, somewhat difficult t o understand how
the concentration of such defect regions would be sufficient to cause an
effect of the observed magnitude. The distribution of relaxation times
would, unlike y. - A, be quite narrow. It is of interest to note that
1\4eakins data on symmetrical esters reveal no evidence for a y-type process
in bulk samples (see M e a k i n ~Figure
, ~ ~ 24).
I n the case of the a, relaxation, the T,,, results for the mechanical data
on the n-paraffins and the dielectric data on their dipolar derivatives rather
closely parallel one another leading to reasonable certainty concerning the
basic mechanical loss mechanism because the interpretation of the dielectric
studies is well established. However, in the absence of corroborating

224

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

dielectric data for the y process in long-chain dipolar compounds, the

basic nature of the y mechanism in the n-paraffins would appear to be
somewhat obscure. The ye relaxation in polymers is in our view of
fairly certain origin as noted carlicr; we do not suppose that the y rclaxation observcd by Tllers in the n-paraffins is necessarily closely related to
the y c process in polymers. Accordingly we emphasize analysis of polymer
data in what follows.
It has been noted above that there exists a theoretical difficuIty in predicting a strong y,-type absorption in fairly pure n-paraffins because of the
absence of large numbers of row vacancies of significant length. However,
such a process may be predicted to appear in extended-chain crystals consisting of very long chains of different lengths provided that the structure
contains the required concentration of row vacancies.
Before discussing the applications of the yc - A model, it is of interest
to emphasize several points. The yc relaxation in all cases is in our view
dependent on the presence of defects, and highly perfect crystals should
show a practically negligible yc effect. The yc - A relaxation model is
highly unusual in one respect. Annealing ordinarily removes defects, but
in the case of the y o - A model, annealing actually increases the number of
chain end defects in the crystal. The annealing process in a chain-folded
crystal consists of a lamellar thickening which reduces the number of high
energy folds and thereby lowers the free energy of the crystal, but this is
done a t the expense of injecting chain ends and hence rows of vacancics
into the crystal. A double row vacancy could occur if a chain fold were
pulled into the crystal interior.

D. Application of yc-A Model

Polyethylene Single Crystals and Bulk Polyethylene. The T,,, valucs
of S i n n ~ t for
t ~ ~mechanical relaxation a t 1 Hz. for solution-grown polyethylene single crystals of polyethylene are shown in Figure 22. Shown
on the same graph are the results of I l l e r for
~ ~the
~ n-paraffins.
Thc equation

Trnax(7)=

160[(25

+ n>/(50 + n)J

(56)

is seen to provide a good fit of both sets of results. I n the n-paraffins, n

is the number of -Catoms in the chain, and in the single crystals, it is
taken to be the number of -Catoms in the fold period (filled circles,
Fig. 22). SinnottZ5showed that the experimental data in Figure 22 could
be fitted to the relation T,,, = 173(48
n)/(93
n). A comparison of
this relation with eq. (56) shows that there is a degree of flexibility associated with the values which can be chosen for c and d, but Tois a less
sensitive variable.
The value To= 160K. in eq. (56) is inadmissible, since it would imply
that, in the rigid-rod approximation for n >> 50, TrnaX(y)
would be 160K.
a t all frequencies of measurement. However it is known from various
relaxation studies on linear polyethylene that the yc relaxation may
reasonably be expected to persist up to at least T,,, = 300K. for high

a, p,

AND

RELAXATIONS

n-PARAFFINS

tn-PARAFFINS

LOG,,

225

POLYMERS +

t-

POLYMERS +

(SEQUENCE
2n

LENGTH)

3
.
0

(b)
Fig. 22. The temperature T,, of maximum mechanical loss for the y o process i n
single crystal mats of p0lyethylene.~5 Data for low temperature process observed for
%-paraffinsin polystyrene matrix39shown for comparison: (a)T,, versus loglo n where
n is taken to be the number of -Catoms for the n-paraffins, and the number of
-Catoms in a fold period for the single crystals; ( b ) T,,, versus loglo (sequence
number). The sequence number is taken to be n for the n-paraffins and (n / 2 ) for the
single crystals. Dashed line on nght-hand side shows effect of cham twlstmg for case
% = 50.

frequencies. Also, chain-twisting effects should bc tahen into account at

large n. Consequently, in Figure 22 a plot of the function

T,,,,,

300 [55

+ 2@J(Ei,E2)I/ [200 + 27?~J"(Bi,h"Z)

I

(37)

is shown.
I n eq. (57) the effect of twisting is taken into account as was clone in
eq. (30), and f i was taken to be 50. It is seen in Figure 22 that eq. (57)
gives a satisfactory fit t o the paraffin data, but a discrepancy exists hctween the calculated and the experimental curve for the polymers. This
discrepancy is readily explained in terms of the modcl for the y c - A
process in which a distribution of active chain lengths is considered. The
effective ialue of n in the rigid rod approximation is (n/2), whcrc n is
the number of -Catoms in the fold period. Therefore, the polyiner
data in Figiirc 22 should be shifted 0.3 decades of log 7% t o the left, and

226

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

inspection of Figure 22 shows that if this is done (filled squares, Fig. 22b),
the polymer data fall satisfactorily on the calculated curve. An important
will depend upon
fcature of eq. (57) is that it predicts that [lim (Tmax)]n-+a
the frequency of measurement in the manner prescribed by the experiments. For example, for very high frequencies (In ArTnN 0), eq. (57)
becomes in the limit of large chain lengths
lim (T,,,),,,

300(255/200)

380K.

(58)

It is interesting that Starkweatherso has in the case of low-density polyethylene arrived at a value of about 380K. as the maximum tempcrature
at which the. y relaxation in polyethylene can be observed.
A further feature of eq. (57) is that the quantity ASCH,~,,* may be
obtained both from TOand from the constant d = 200 in eq. (57). For
AH,* = 12 kcal./mole from the mechanical studies50, AHcH~,,,* = 60
cnl./mole for m = 40, and AScHao,* = 60/300 = 0.20 e.u. from To =
300K. Alternatively, taking log A = 12 then ASCE,,~,* = 4.6 log A/d =
0.27 e.u. The agreement between the AXCH~,,,* values is satisfactory.
Therefore we conclude that the fit of the calculated curve [eq. (56)] is
probably fortuitous and that eq. (57) gives a more satisfactory account of
the yc relaxation in the single crystal mats of polyethylene. The fit of
eq. (57) to the paraffin data is also quite satisfactory. This implies that
the mechanism operative in the polymer crystals is related to that in the
n-paraffins, but, as previously noted, it is difficult to see how any appropriate variant of our y c - A model can account for the y process in the
n-paraffins. Final acceptance of the connection between the paraffin data
and polymer data implied by the fit obtained with eq. (57) must be delayed
until a satisfactory model for the y process in paraffins is advanced, and
until methods other than the mechanical veriiy and give information on
this process in the paraffins.
We turn now to a further consideration of the mechanical relaxation data
on polyethylene single crystal mats. I n Sinnotts data, the absorption
intensity of the yc peak definitely begins to increase as soon as the lamellae
start to thicken. The yc - A model predicts this result. Sinnotts
data also imply a broad distribution of relaxation times: the G versus T
peak at 1 Ha. is quite broad. These observations are consistent with the
yG - A model.
Ishida et al.72have clearly demonstrated the existence of a yc process
in single crystal mats of poly(ethy1ene oxide) by dielectric studies. The
observed activation energy is 9 kcal./mole. The yc loss peaks on an E
versus log j plot has a half-width of approximately 3.5 decades, which is
consistent with the large distribution of relaxation times produced by
model yc - A (see below).
The y c process appears prominently in bulk polyethylene. Some of this
effcct is a result of chain-end induced defects of the type proposed in model
yc - A, since T,,, appears in the same tcmperature region as it does in
single crystal mats. An extended-chain component giving a low-tempera-

a, p,

AND

RELAXATIONS

227

ture yc - type process at the unmatched chain ends is also probably

present. Annealing will cause T,,, for yc - A to increase, but the T,,,
for the extended-chain component should remain more nearly k e d with
annealing. Data on bulk samples made from fractions would be required
to resolve the yc - A and extended-chain y contributions in the bulk
polymer. Bulk polyethylene (linear) should exhibit practically no y a
effect a t all.
PCTFE. I n PCTFE, no dielectric or mechanical relaxation studies
capable of showing an increase of absorption 011 isothermal annealing of
thin lamellae analogous to thosc given by Sinnott on polyethylene have
becn carried out. However, the magnitude of the yc absorption in the
annealed PCTFE speciniens 0.73 and 0.80 is large, and is consistent with
the presence of numerous chain-end defects in the crystal. The ycprocess
seen in PCTFE is probably mostly the y c - A which rclates to chain-folded
lamellae, but a component arising from the extended-chain phase is also
probably present.
The unusually large y e dielectric loss peak in the chain-folded lamellae
in bulk PCTFE may be attributed partly t o a reinforcement of dipole
moments in the helical chain for chains whose lengths are not integral
multiples of the helix repeat distance of 40 A., leading to a large effective
value of pcr and to the presence of a large fraction of chain-end induced
defects of the type sbown in Figure 20, each row of vacancies giving y
active chains.
The dielectric data on PCTFE afford an excellent opportunity to check
whether the proposed y c - A model gives anything approaching the
correct line shape on an e versus log j plot. The y c peak on ail dversus
log j plot in PCTFE is characterized by a large half-width and a strong
asymmetry (Fig. 18, x
1).
The lainellae in specimen 0.80 are taken to be 380 A. thick, corresponding
to n, = 300 in eq. (53). The observed activation encrgy of the ycprocess
for x
1 is 14.0 kcal./mole, and the shift of the theoretically derived loss
peak with temperature must produce an activation energy close to this.
Furthermore, the free activation energy must be consistent with eq. (55)
or AW,*(n), and the shapc of the loss curve must be matched within thew
boundary conditions.
The limiting value of AWn+,*(n) is ~&AWCEI~,,,*
and f i = ( A 2 /
AWckIn,,,*). Combination of these relations gives A W ~ H
* ~ =~ ~ ,
[AW,,*(n)12/16A2
and rii = 4A2/AWn,,*(n).
Thus AWcHl0,* and f i
can be calculated if A 2 and AW*(n) are known. We assumed A2 is about
5 e.v. or 110 lical./mole, and estimated AW*(n) in the following way.
Extrapolating the plot log Sinaxagainst (l/T) (Fig. 6) t o l / T = 0 gave an
intercept log
= 16.0. Assuming that this is rclatcd t o (l/A) exp
{ -A&,,*(n)/R],
with log A = 12, A&,,*(n)
was evaluated as 18.4
e.u. Wc fuither assumed that AN,,*(n)
= 15 ltcal./mole a t 300K.,
which is near the value for AH*(-y,) shown in Figure 6 for PCTPE. For
these values for AX,,
*(n) and AH,,
*(n),the value of AW,,,
*(n)

--f

228

.I.D. HOFFMAN, G. WILLIAMS, E. PASSAGLlA

I

AHX[%) = 14.0 kcal/mole

.06

LOG,,f
I

12.2 k c d /mole

AH (y, )

yc

EXPERIMENTAL
I

10

(Hz)
I

50

THEORETICAL
I

(CALC)

-6

LOGlo

-2

-4

y,
I

wr.

Fig. 23. Experimental and calculated plots of the dielectric loss factor for the yc
process as a function of frequency a t two temperatures for PCTFE. (Experimental
data of Scott' as aiialyzed in Fig. 18.)

was calculated at 300 and 400K. and the corresponding values for
AWCH*(~)*
and m were evaluated as outIined above. These values are
indicated in Figure 23, together with A H C X ~ ( and
~ ) * AXCX~,,,*.
Figure 23 shows the plots of 'E against log W T O calculated numerically by
using eq. (53) together with the A W C H ~ (and
~ , * in values derived above.
It is seen that the calculated curves have the required shape, and lead t o a
shift of E" (max) with temperature that come reasonably close to reproducing the experimental activation energy. The comparison between
theory and experiment seems satisfactory.
The above analysis implies a To of about 800K. Because of the error in
the estimate of ASCxz,,,*, this value is undoubtedly no closer than 200 or
300K. to the true value. However, it can be shown that experimental
value of TO is quite high, and not inconsistent with the theoretical value.
In Figure 17, it is seen that the y process-the data shown are largely yGpersists up t o at least 200C. or 473K. The actual value of 7'0 is therefore probably near or above TTm"
= 494K.
The absorption intensity of the y e process as observed in dielectric
measurements evidently increases as the temperature is increased (Fig. 17).

a,

0,AND

RELAXATIONS

229

Some of the increase of el (max) is duc to the predicted sharpening of the

distribution with rising temperature, but thc area under the curves, and
hence I,, definitely increascs. This is characteristic of relaxation processes where li
AWd > 0.
The distribution of rclaxation timcs predicted for the dielectric properties
for PCTFE is entirely sufficient to explain the breadth of the ye process
mcchanical peak as plotted as 7r tan 6 or G versus T.23r24
Conclusions. Although the evidence is not as completc as one might
wish, the proposed ye - A model appears to shed light on some aspects of
the yc process as it is observed experimentally. First, the yc - A model for
chain-folded crystals is such that the increase of absorption with thickening
is explained a t the outset. Second, the chain-end defects that are introduced
by thickening lead in a natural way, when considered together with the
twisting of very long chains, to the very broad and asymmetrical loss
curves that are observed. Third, the low activation energy observed for
the yc process is related to the low values of the activation energy per chain
unit in the loose region in the crystal, and chain twisting. The model is
consistent with a high To. Another conclusion must be that there is an
unfortunate paucity of accurate activation encrgy data, especially for
mechanical data. Finally, while the T,,, data for the n-paraffins and
polyethylene solution-grown crystals imply a siinilarity of mechanism, the
actual resolution of the mechanism in the n-paraffins must await more
experimental data on these compounds and their polar derivatives.

E. The ya Relaxation in PCTFE

Thc ya relaxation is strictly an amorphous phase property, but its rcsemblance to the ye crystal process is quite striking. The activation
energies are similar, the one for ya being only slightly higher (Table 111).
However, there are important differences. The half-width of y a is higher,
and the high-frequency tail is practically absent (Fig. IS). Also ya is
considerably more intense than yc (Fig. IS).
While we will not attempt to give a model for y,, there are certain features of the nature of the process that can be explained in a qualitative
manner.
The similarity in thc activation encrgies of ya and y G probably has as its
origin a molecular motion that is quite similar in the two cases. I n the yc
process, the molecular motion was identified as a kinking of the chain of
activation energy Awd*, followed by the reorientation of a chain in a fairly
loose region of the crystal caused by a chain-end defect. A similar effect
can occur for chains in the glassy state. A kink can appear in a section of
chain in the glassy state, causing reorientation modified by twist to propagate a certain distance along the chain. Then if AW,*(yc)
AW,*(y,)
and AWcx,*(ye) AWcx,*(y,), the observed activation energies AH*(?,)
arid AH*(y,) would be quite similar. S h a t ~ k i has
~ proposed some specific
chain ma tions, e.g., thc L~ranli~haft
model, for what we have more
gcnerally refcrred to as kinks. The suggested similarity in the nature of

230

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

the motions is proposed as the basic cause for the observed overlapping of
the ya and yeprocesses shown in Figure 18.
The value of AH*(ya) slightly exceeds AH*(y,), and this point requirw
comment. Both AWd* and AWCX,,,,* involve intermolecular and intramolecular contributions. We would expect the intramolecular contributions to AWd* and AWcxP,,* in the y a and y G relaxations t o be rather
similar. However, the intermolecular forces will be somewhat different
because the packing of the molecules is different in the glassy state and in
the vicinity of a chain end defect in a crystal. One measure of this effect
is the local specific volume. I n the glassy state, this is about 0.475 ~ m . ~ / g .
in the temperature range of the y relaxation (Fig. 1). The free chain in an
idealized hole in an hexagonal lattice in PCTFE has associatcd with it a
local specific volume of 0.453 X (6/5) or 0.543 ~ m . ~ / g .Thus, a chain in a
defect such as that shown in Figure 20 could on the average meet less
resistance from neighbors as it forms a kink and reorients than would be
encountered by a similar motion in the glassy state. This would lead to
the observed fact that AH*(yc) is slightly less than A H * ( y J .
The distribution of relaxation times exhibited by the -ya process is extremely large, and exceeds that of the y c process (half-width of 4.3 decades
compared to 3.2 at 23C.). Considerations based on the properties of
kinks and related simple and localized chain distortions do not ordinarily
lead to such broad distributions, and it is believed that propagation of
twist over various lengths of chain, and correlations of movement along
the chain, are probably involved in addition to the simple motions.

VII. THE 6 RELAXATION

The 6 relaxation process appears in PCTFE specimen 0.80 at very high
frequencies in an E" versus log f plot, as shown in Figures 17 and 18. It
was also observed by Hartshorn et al.3 The corresponding effect has not
been observed in an E" versus T plot at 1 Hz. because measurements were
not made at sufficiently low temperatures.
A highly approximate estimate of the apparent free energy of activation
may be made using the relation
T

1 / ( 2 ' 1 ~ f ~=
~ , )(h/kT)e*"*'"'

(59)

Taking fmax to be loToHe., it is found that AF* is about 2.8 Itcal./mole.

The relaxation time becomes 1 see. when T
60K. If fmex is loll Ha.,
then A F X is 1.4 lical./mole and T,,, at 1 Hz. is at 30K. Thus, the manifestation of the 6 relaxation process on an E" versus T plot at 1 Hz. is
expected to appear at cryogenic temperatures. The intensity of the 6
process decreases with decreasing temperature, so that it may be quite
difficult to observe at low temperatures in an E" versus T experiment.
Crissman et al.74have observed relaxation peaks 011 mechanical loss vcrsus T plots at lo4 Hz. in poly(viny1 chloride) (PVC), poly-4-methylpentene-1, and isotactic polypropylene at cryogenic temperature. These loss

a, p,

AND

RELAXATIONS

231

peaks are possibly to be identified with the one we have called 6 in the E
versus log f plot in Figures 17 and 18. At least in the case of PVC, it is
clear that the 6 process cannot be due t o rotatable side groups. The same
is true of PCTFE. Nevertheless, the possibility that the 6 relaxation is in
some polymers associated with the rotation of side groups cannot be discounted.
The 6 relaxation in P C T F E evidently is a property associated with the
crystalline phase, as is apparent from Figure 17. I n previous discussions,l
the contribution Aecrystal of the 6 relaxation process (then called the highfrequency crystal relaxation) to the dielectric increment tS - E, was
estimated on the basis that the y relaxation process had a symmetrical loss
curve 011 an E versus log f plot. Actually, the y c process has a large highfrequency tail, and the intensity of the 6 process as estimated by using a
symmetrical y c process is probably high by a factor of perhaps two or three.
Thus, the 6 relaxation is not as intense as was originally proposed by
Scott et al.
With few exceptions, the 6 relaxation appears to be most active in chains
that exhibit a helical conformation. For instance, PCTFE, PVC, poly-4methylpentene-1, and isotactic polypropylene exhibit a 6 relaxation, while
polyethylene and nylon 66 do not.

VIII. APPENDIX : SITE MODEL FOR MECHANICAL RELAXATION

Hoffman and c o - ~ v o r k e r s ~evaluated
~-~~
the dielectric behavior of site
model systems, and compared the theory with experiment for special
cases.38*75W a ~ h t m a napplied
~ ~ , ~ the
~ general theory of site models to the
case of mechanical relaxation in crystalline solids. The subject of mechanical relaxation has been reviewed by Nowick and hell^.^^ I n order t o
emphasize the features of Wachtmans theory, the simple two-site model
(see Fig. 7) is considered here.
We assume the barrier system of Figure 7, and evaluate the response
of the system to an applied stress u. The stress causes a linear shift in
the energy a t site 1 and site 2 :

I-lencc 6U

6U1 =

A10

6U2 =

X2W

(XI - Xz)a.

The elementary transition probabilities

the applied stress are given by
~

w120

=
2

~ 1 2 ~ [ l

w12

(6Cil/kil)] =

arid

wl

~ 1 2 [ 1-

in the presence of
(Xia/kT)]

(61)

is the transition probability in the absence of the stress. Similarly,

w21

WZlO[l

(Xaa/kT)]

The rate equation for sites 1 and 2 are given by76

(62)

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

232

where

N 1 = NP

+ rb

Nz =

-n

N20

= N10

N2O

N10and Nzo are the occupation numbers in sites 1 and 2 respectively in the
absence of the stress, and N1 and N2 are the corresponding quantities in the
presence of the applied stress. Substitution of eqs. (61), (62), and (64)
into eq. (63), with ( W ~ ~ ~ / W ~=~ ON2/N10,
)
and retaining linear terms, gives
dn/dl

n(w1z0

W Z I ' ) = Niow12O[(X1 -

XZ)/ICT]U

(65)

Now let

Combining eq. (66) with eq. (65) and writing

= N1~120(X1
- ~ 2 ) ( u o / ~ cwe
T ) , have
no(e+">(iw

0') =

a' = (wrio

and

~ 2 1 ~ )

(67)

Since A is real, from eq. (67) we have

tan#

= w/w'

(68)

CJT

Insertion of eq. (68) into the real part of eq. (67) gives
=

ATei("t-$.)/(l+ w 2 T 2 ) ' / 2

Amiwt/(l i w ~ )

and n are rclatcd accordiiig to

(69)

which niay be written as

Assuming that the strain

Y,

+ en

(7 1)

where ymis the instantaneous (elastic) deformation and c is a proportionality constant, the complex compliance J * = ( y / u ) is given by
J*

Here J ,

= y m / u , and

(-10Since

Jm)

(uYL"/u~IO)

J,

+ [(Jo - Jm)/(l+

iWT)I

( J o - Jm)
is given by

CAT/,, = [ C N I ~ U ~ ~ ~~2 1/O() ]W

[ ( X~
1~ X2)/kT]
~

(72)

(N20/N10)= exp { - V / k T ) , we obtain

(73)

a, p,

AND y RELAXATIONS

233

W a ~ h t m a nhas
? ~ shown that c 0: (XI - X2)/v, where v is the volugne containing N relaxing species. Hence,

where n is the number of species per unit volume. For two-position

models, the corresponding dielectric quantity, E , - E , , is generally of the
form%-38
(E, -

E,)

r 4 ~ n a= 4 T

number-active species
cm.3

(76)
7

where peffis the effective dipole moment per chain unit.

In order for a mechanism to be active mechanically, the energy difference
between the two sites must be changed by the application of the applied
stress. For example, if the energy difference is zero in the absence of
stress, an energy difference must appear in the stressed state if mechanical
relaxation is to occur. In lattices of high symmetry, the application of
stress is sometimes unable t o induce the required energy difference, giving
XI - X2 = 0. I n such cases, gradients of stress can often activate the
mechanical relaxation process.
The authors wish to thank Dr. J. I. Lauritzen, Jr., of the Bureau for numerous extremely helpful discussions, particularly on the subject of chain twisting. They are
also grateful to Dr. K. Sinnott of the Grace Chemical Company for making his work on
solutiori-grown polyethylene single crystals freely available to them prior to publication,
and for a considerable number of stimulating discussions. Special thanks are also due
Dr. D. W. McCall of the Bell Telephone Laboratories for making his highly useful
compendium of relaxation data on polymers accessible to them. The assistance of
Dr. J. B. Wachtman of the Bllreau in formulating the material in the appendix is gratef d i y acknowledged.

References
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44. J. S. Dryden and H. K. Welsh, Trans. Faraday SOC.,
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45. J. M. Crissman and E. Passaglia, unpublished manuscript.
46. M. G. Broadhurst, J . Res. Natl. Bur. Std., 66A, 241 (1962).
47. J. D. Hoffman, J . Chew Phys., 20, 541 (1952).
48. J. D. Hoffman and C. P. Smyth, J . Am. Chem. Soc., 72, 171 (1950).
49. J. D. Hoffman and B. F. Decker, J . Phys. Chem., 57, 520 (1953).
50. H. W. Starkweather, Jr., private communication.
51. R. K. Eby and J. P. Colson, J . Acoust. Soe. Am., 39, 506 (1966).
52. V. F. Holland and P. H. Lindenmeyer, J . A p p l . Phys., 36, 3049 (1965).
53. E. W. Fischer and R. Lorenz, Kolloid-Z., 189, 97 (1963).
59,1906 (1963).
54. J. B. Jackson, P. J . Flory, and R. Chiang, Trans. Faraday SOC.,
55. G. M. Martin and E. Passaglia, J . Res. Natl. Bur. Std., 70A, 221 (1966).
56. K. II. Illers, Rheol. Acta., 3, 202 (1964).
57. C. A. F. Tuijnman, Polymer, 4, 259 (1963).
58. D. W. Davidson and R. H. Cole, J . Chem. Phys., 19, 1484 (1951).
59. H. Vogel, Physik. Z., 22, 645 (1921).
60. M. L. Williams, R. F. Landel, and J. D. Ferry, J . Am. Chem. Soc., 77,3701 (1955).
61. K. H. Illers and H. Breuer, J . Colloid Sci., 18, 1 (1963).

234,

J. D. HOFFMAN, G. WILLIAMS, E. PASSAGLIA

12. F. C. Frank and M. Tosi, Proc. Roy. SOC.(London),A263, 323 (1961).

13. F. P. Price, J . Chem. Phys., 35, 1884 (1961).
14. J . I. Laurit,zen, Jr., E. A. DiMarzio, and E. Passaglia, submitted t,oJ . Chem. Phys.
15. F. Gorniclr and J. I). Hoffman, Ind. Eng. Chem., 58,41 (1966).
16. F. R. Anderson, J. Appl. Phys., 35, 64 (1964).
17. H. I). Keith and F. J. Padden, Jr., J . A p p l . Phys., 34, 2409 (1963).
18. H. I). Keith and F. J. Padden, Jr., J . A p p l . Phys., 35, 1270 (1964).
19. J. D. Hoffman and J. J . Weeks, J . Res. Natl. Bur. Std., 66A, 13 (1962).
20. H. D. Keith, F. J. Padden, Jr., and R. G. Vadimsky, J . Polymer Sci. A-2, 4, 267
(1966).
21. W. Banks, M. Gordon, R. J. Roe, and A. Sharples, Polymer, 4, 61 (1963).
22. E. Passaglia and G. M. Martin, J . Rcs. Natl. Bur. Std., 68A, 519 (1064).
23. N. G. McCrum, J . Polgmer Sci., 60, 53 (1962).
24. ,J. M. Crissman arid E. Passaglia, see this volume.
25. K. M. Sinnott, J . A p p l . Phys., 37, 3385 (1966).
26. Y. Ishida and K. Yamafuji, Kolloid- Z., 202, 26 (1965).
27. J. M. Crissman and E. Passaglia, J . Res. Natl. Bur. Std., 70A, 225 (1966).
28. T. Aramaki, S. Minami, F. Nagatoshi, and M. Talrayanagi, Repts. Progr. Polymer
Phys. (Japan),7, 237 (1964).
29. Y. Wada, H. Enjoji, and H. Terada, Repts. Progr. Polymer Phys. (Japan), 5 ,
131 (1962).
30. S. Iwanagi and H. Nakane, Repts. Progr. Polymer Phys. (Japan), 7, 179 (1964).
31. K. Yamafuji, Kolloid-Z., 195, 111 (1964).
32. C. A. F. Tuijnman, Polymer, 4, 315 (1963).
33. H. Frohlich, Proc. Phys. Soc. (London),54, 422 (1942).
34. K. H. Illers, Rheol. Acta., 3, 194 (1964).
35. J. D. Hoffman and H. G. Pfeiffer, J . Chem. Phys., 22, 132 (19.54).
36. J. D. Hoffman, J . Chem. Phys., 23, 1331 (1955).
37. J. D. Hoffman and B. M. Axilrod, J . Res. Natl. Bur. Std., 54, 357 (1955).
38. J. D. Hoffman, Molecular Relaxation Processes, Chem. Soc. (London), Special
Publication No. 20, Academic Press, London, 1966.
39. G. Williams and J. D. Hoffman, manuscript in preparation.
40. G. Williams and J. I. Lauritzen, Jr., manuscript in preparation.
41. R. J. Meakins, Australian J . Res., 2A, 405 (1949).
42. R. J. Meakins, Trans. Faraday Soc., 55, 1701 (1959).
43. R. J . Meakins, Progress in Dielectrics, Vol. 3, Heywood, London, 1961, p. 153.
44. J. S. Dryden and H. K. Welsh, Trans. Faraday SOC.,
60,2135 (1964).
45. J. M. Crissman and E. Passaglia, unpublished manuscript.
46. M. G. Broadhurst, J . Res. Natl. Bur. Std., 66A, 241 (1962).
47. J. D. Hoffman, J . Chew Phys., 20, 541 (1952).
48. J. D. Hoffman and C. P. Smyth, J . Am. Chem. Soc., 72, 171 (1950).
49. J. D. Hoffman and B. F. Decker, J . Phys. Chem., 57, 520 (1953).
50. H. W. Starkweather, Jr., private communication.
51. R. K. Eby and J. P. Colson, J . Acoust. Soe. Am., 39, 506 (1966).
52. V. F. Holland and P. H. Lindenmeyer, J . A p p l . Phys., 36, 3049 (1965).
53. E. W. Fischer and R. Lorenz, Kolloid-Z., 189, 97 (1963).
59,1906 (1963).
54. J. B. Jackson, P. J . Flory, and R. Chiang, Trans. Faraday SOC.,
55. G. M. Martin and E. Passaglia, J . Res. Natl. Bur. Std., 70A, 221 (1966).
56. K. II. Illers, Rheol. Acta., 3, 202 (1964).
57. C. A. F. Tuijnman, Polymer, 4, 259 (1963).
58. D. W. Davidson and R. H. Cole, J . Chem. Phys., 19, 1484 (1951).
59. H. Vogel, Physik. Z., 22, 645 (1921).
60. M. L. Williams, R. F. Landel, and J. D. Ferry, J . Am. Chem. Soc., 77,3701 (1955).
61. K. H. Illers and H. Breuer, J . Colloid Sci., 18, 1 (1963).

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