Beruflich Dokumente
Kultur Dokumente
C. L. Choy
Department of Physics, The Chinese University of Hong Kong, Hong Kong
(Received 29 April 1976; revised 29 March 1977)
In this review we have concentrated on the interpretation of three essential aspects of the thermal
conductivity K of polymers: the temperature dependence, the crystallinity dependence and the
orientation effect. K for all amorphous polymers is approximately equal in magnitude and charac-
terized by a T 2 dependence below 0.5K, a plateau region between 5 and 15K and a slow increase at
yet higher temperatures. While a number of models involving different phonon scattering mechanisms
are capable of explaining these features, further corroborating evidence would be needed to explain
the adhoc assumptions involved. For semicrystalline polymers K shows both strong crystallinity and
temperature dependence, with a distinctive cross-over point at about 10K. These marked features can
now be understood as the result of the interplay between two competing factors: the intrinsically
higher conductivity in the crystalline regions, and the reduction in K due to an additional phonon
scattering mechanism which becomes important at low temperature. This scattering could arise from
either the correlation in the spatial fluctuation of the sound velocity in the polymer or the acoustic
mismatch at the interfaces between the crystallites and the amorphous matrix.
Orientation produces a very large anisotropy in semicrystalline polymers, which however decreases
at low temperature and becomes insignificant below 10K. This feature can again be understood in
terms of the same competing mechanisms if one realizes that the molecular chains in the crystallites
are essentially lined up along the direction of orientation thus offering very little thermal resistance
along this direction. For polyethylene with an extrusion ratio of 25 the thermal conductivity at 100K
along the extrusion direction is 91 mW/cm K, a value extremely high for polymers and close to that of
stainless steel. At this temperature the anisotropy is only about 20, yet because of the different tem-
perature dependence of the thermal conductivity along and perpendicular to the extrusion direction,
we predict an anisotropy as high as 60 at room temperature.
K of PET at 30K and above increases with increasing crystal- (either arising from correlation in sound velocity fluctuation
linity, the values below about 10K show the opposite trend. or boundary resistance) is not expected to be much affected
At 1.5K, K of a 50% crystalline sample is one order of mag- by the orientation of the chains in the crystalline regions so
nitude lower than that of the amorphous material. the orientation effect is much smaller. We will see how these
This unusual behaviour has been explained by considering ideas can be applied to interpret the data of a few oriented
a semicrystalline polymer as a composite consisting of crystal- semicrystalline polymers.
line lamellae embedded in an amorphous matrix. Then the
increase of K with crystallinity at high temperature can be
understood as the reflection of the higher average conduc- AMORPHOUS POLYMERS
tivity of the crystalline regions. However, the cross-over of
the conductivity and the subsequent large decrease for the General considerations
semicrystalline samples reveal an additional scattering In insulating solids heat conduction takes place by means
mechanism which becomes important at low temperatures. of the lattice vibrations. Theoretical effort has been mainly
This strong scattering process has been treated in two sepa- confined to crystalline solids where the lattice vibrations can
rate approaches which are valid in different temperature be resolved into normal modes which can then be quantized
range (i.e. different phonon wavelength range). In the first giving rise to the concept of phonons. These phonons are
treatment the presence of crystallites is assumed to introduce particles obeying Bose-Einstein statistics and the heat cur-
an additional correlation length (~- 100 A) for the fluctuation rent is determined by the phonon distribution which can be
of the sound velocity and the increase in phonon scattering obtained by solving the Boltzmann equation. The thermal
(with the accompanying decrease in conductivity) can be conductivity is then given byaT:
calculated either using the Klemens ls'24 or the Morgan--
Smith models 6'~6. It has been emphasized 16 that this approach
works only when the phonon mean free path is larger than the
correlation length, and this condition holds below about 5K. K(T) : 3 Ci(m)vili(w)dw (1)
The second model 7 assumes that the difference in elastic
i
properties between the amorphous and crystalline regions
gives rise to a thermal boundary resistance R b at the inter-
where C i ( w ) d w is the heat capacity contribution of phonons
face. Direct measurements 2s-27 Of Rb for a number of solids
of polarization i and frequency 60, v i is the phonon velocity
show that it increases with decreasing temperature and be-
and li(co ) is the phonon mean free path. In the Debye ap-
comes proportional to T - n (2 < n < 2.7) below 4K, which
proximation where Ci(~o) is a known function and v i is inde-
is in slight disagreement with Little's 2a theoretical prediction
pendent of 60, K(T) is determined by l(~). Thus the whole
of T -3. Nevertheless, this rapid increase in R b can certainly
problem reduces to the calculation of the phonon mean free
account for the much smaller conductivity of the semicrys-
path l(~o).
talline samples 7. Although there is no simple criterion for
Equation (1) can be considerably simplified by using the
the validity of this treatment it certainly will not be valid
dominant phonon approximation. This follows from the
below 2K where the dominant phonon wavelength is larger
fact that, at any temperature T, the phonons which contri-
than both the crystallite size and the distance between
bute significantly to the integral in equation (I) have fre-
crystallites.
quency o3 ~- 4kTfli. Thus the frequency dependence of 1
The last topic to be covered in this article is the effect of
can be converted to an equivalent temperature dependence
orientation on the thermal conductivity of semicrystalline
and, after averaging over all polarizations, equation (1)
polymers. Contrary to the case for amorphous polymers
becomes:
where orientation effect above 100K has been investigated
in some detail 1'29- 32, work on semicrystalline polymers has
1
been reported only recentlya'a3-36. On comparing these K ( T ) = - C(T)vl(T) (2)
data, it is clear that semicrystalline polymers show a much 3
larger anisotropy, but this effect diminishes with decreasing
temperature and becomes insignificant below 10K. For in- where Cis the heat capacity per unit volume and v is the
stance, whereas at 100K a high density polyethylene sample average phonon velocity. This is exactly the expression ob-
extruded to 13 times its original length has a thermal con- tained if the kinetic theory of gases is applied to a system of
ductivity in the extrusion direction (K0 equal to 10 times phonons. At sufficiently low temperatures where C ~ T 3, a
the value in the perpendicular direction (K3_),the correspon- frequency dependence o f / ~ w - n will result in K o: T 3 T - n =
ding ratio below 10K is only about 1.5 a4. T 3 - n. Therefore the temperature dependence of K will
These contrasting effects can also be explained by the provide vital information on the dominant scattering mecha-
composite model in the following manner. When a semi- nism at low temperatures.
crystalline polymer is oriented, the spherulitic structure is The temperature dependence of the thermal conductivity
deformed and gradually broker~ up. Even at low extrusion of crystalline solids (see a-quartz in Figure 1) can be under-
ratios such as 4, the chain axes (c-axes) within the crystalline stood qualitatively by means of equation (2). At high tem-
lamellae are mostly aligned along the extrusion direction. peratures where most of the phonons are excited, the proba-
Since the covalent bonds along the chains are much stronger bility of interaction among the phonons through the Umklapp
than the van der Waals bonds across the chains, the thermal processes 37 is proportional to the number of phonons, i.e.
resistance along the c-axis of a crystallite is negligible com- to the temperature. Thus I is proportional to T -1 and since
pared to that in the perpendicular direction. Thus the crys- C-~ constant it follows that K cx T-1. As the temperature is
talline regions in an oriented sample provide almost no resis- reduced fewer phonons are available for interaction and this
tance to heat flow along the extrusion direction, and so at leads to an exponential increase in both l and K. For crys-
high temperatures, Kll will be much larger than/(1. However, talline solids containing defects or impurities this exponential
at low temperatures, the dominant resistive mechanism rise is usually not observed but the net effect is still a rapid
, ,
106
i0 s
d., i ,o ,60
T(K)
Figure 1 Thermal conductivity of crystalline and amorphous SiO2,
amorphous selenium (Se) and poly(methyl methacrylate) (PMMA).
The data for SiO 2 and Se after Zeller and Pohl (ref 14); data for 104
PMMA from refs 3, 5, 11 and 12. A, e-quartz, U c-axis; B, vitreous
A
silica; C, Se; D, PMMA
A
(2rO2M 2 ds' 1 (4)
B f v032 t'q J
2.2
i i i i i i i i I i i
I 0 °l I I0 10 2
T(K)
Figure 3 Thermal conductivity of amorphous polymers. The data
for PMMA, poly(ethylene terephthalate) (PET), polycarbonate (PC), 2.0
polystyrene (PS) and poly(vinyl acetate) (PVAc) are taken from refs
2 t o 1 3 . A, PMMA;B, PET;C, PC;D, PS;E, PVAc
B C
p
/ ---Boo -2 for - - , >> 1 (3a)
6oa
1.6 E F
P
l = constant for , ~< 1 (3b)
03a
\
this mechanism to be boundary scattering, the thermal con-
\ ductivity can be calculated by using a total mean free path
,%
id 2 1-1 = lb-1 + le-1, where 1b denotes the size of the sample
and le is the mean free path due to elastic scattering. The
\ Tronsverse modes
results are shown in Figure 6 (using parameters appropriate
to amorphous Se) for different values ofa. For large values
of a (1000-3000 A)Kcx T n where 2 < n < 3 in the range
t(S31 i
\ i i
lO-i I I0 10 2
qa
Figure 5 The relaxation times from the model of Morgan and
Smith (ref 16). ~ = "rX 1012A 2 vL/aVn, VL = 2vTand Vn = 4 X 103
m/sec, where Vl_ and v T are the longitudinal and transverse velocities
of phonons. The straight line corresponds to the long wavelength
form, for transverse modes, extrapolated to short wavelengths
E
and the spatial correlation function:
f(7) = ~s2)
,f d~s(~)s('~ + 7) (7)
i 0 -2
2q
tO-o'm I I0 IO 2
r - l ( q ) = 6 ( s 2 ) f p 3~D(p)dp (9) T(K)
(a) t.o~<¢o R, l = D ~ - 1 *
io-31 iO-I
i
I
1
Io
* If the expression I ¢~~-1 coth(hw/2kT) is used, then the satura-
tion of the two-level system at high temperatures would lead to un-
realistically long phonon mean free path for the low-frequency
r (K) phonons, and other scattering mechanismswould have to be inclu-
Figure 7 Theoretical fit to the data of amorphous Se. Data from ded s2. Because of the primative state of the model we will not
Morgan and Smith (ref 16) consider this refinement.
'°t
constant -~ a few A. In order to reduce the number of para-
meters we equate the mean free paths in regions b and c and
so the total contribution from these two regions is:
Ol/T
1 x2e x
/
f r2 = f g(6o)(ex_ 112 dx (11)
/ on/r
/
/ KI where g(6o) is proportional to the density of states of the
/ acoustic modes and 01 = h6ol/k. We note that both equa-
/ tions (10) and (11) derive from equation (1), but as a result
/
/ of the difference in frequency dependence of l(6o) and g(6o)
E I in the two cases the forms of the integrals are not the same.
Jd I For solids with linear chain structure such as the polymers
~= I we are considering, it has been shown s3,s4 that g(6o) follows
] I% a 602 distribution from 0 to a frequency characterized by 0 3
and then becomes constant from 0 3 to the maximum fre-
/
quency 01. The values of 03 and 01 for poly(methyl metha-
/
crylate) (PMMA) have been obtained by Reese 9 so we can
I apply equations (10) and (11) to analyse the thermal con-
I ductivity of this polymer. The results are shown in Figure 9
I
iCY2 and it is clear that there is reasonable agreement throughout
I
/ the whole temperature range of 0.1 to 350K. The values of
I
the parameters used are D = 1.35 x 108 cm/sec, OR = 4.7K
I and vl = 1.31 x 10 -2 cm2/sec. Using v = 1.79 x 105 cm/sec
from the sound velocity measurements49 l is found to be
7.2 h.
In the model we are using, the parameter D is considered
to be a constant characterizing the material and OR is to be
identified with the lower frequency limit of the band of
I0 -I I I0 10 2 localized vibrations. The value of OR is consistent with the
T(K) result of specific heat measurements which show that the
Figure 9 Theoretical fit to the data of PMMA according to equa- excess contribution can be explained by the existence of
tions (10) and (11 ). The points are data from Figure 1 non-acoustic modes at frequencies corresponding to 4.9K
(Oa) and 17.5K (Oh), respectively49. The value of 7.2 A for l
is also quite reasonable since the distance between vibrating
where 6oR is the lower limit of the band of localized vibra- units on neighbouring chains estimated from the density is
tions. Substituting this/(co) into equation (1) the contribu- 7.5 flk9'10.
tion of the phonons in this frequency region is: We have applied the same analysis to the low-temperature
data of other amorphous polymers and the resulting values
OR/T of D and OR are given in Table 1, together with O's obtained
k3D f x3eX from specific heat measurements. It should be noted that
K1- - - T2 - - dx (10) the values of D and OR do not vary considerably from one
2n2~2v 2 (ex - 1) 2
0 polymer to another, the reason being that, at any tempera-
ture, the values of the thermal conductivity of all amorphous
where tl is Planck's constant, k is Boltzmann's constant, polymers lie within a factor of two (see Figures 3 and 4).
OR = l~6oR/k and x = ti6o/kT. Here the Debye spectrum is Furthermore, if we consider only the range above 15K, then
used, i.e. the density of acoustical modes is proportional to the thermal conductivity at any temperature is within 15%
6o2 and the integral includes contributions of both transverse of the average value. We will see that this important result
is very useful when discussing the thermal conductivity of
and longitudinal waves.
semicrystalline polymers in the next section.
In conclusion, while existing models are able to explain
(b) 6oR < 6o <<.6oc
where 6oc is the upper limit of the band of localized vibra- Table I Parameters D and OR obtained from the analysis of the
tions. This is the region where the mean free path is expect- low-temperature thermal conductivity of amorphous polymers.
ed to be small (of the order of interatomic distances) because Please refer to the text for explanation of symbols
of strong phonon scattering by the band of localized vibra- Dxl 0 -7
tions. Polymer (cm/sec) 0R(K) 0a(K) 0b(K)
(c) 6oC< ~ -< 6o1 Poly(methyl methacrylate) 13.5 4.7 4.9 17.5
Polystyrene 6.02 5.2 5.5 16
Polycarbonate 5.61 4.5 5.0 14
where 6ol is the maximum frequency of the acoustic phonon Poly (ethylene terephthalate) 5.43 4.3 -- 15
spectrum. In this region of high frequencies we know from
SEMICRYSTALLINE POLYMERS
crystallite size and the intercrystallite distance, and the understandable because the repeating units of these two
boundary resistance is negligible. Here the conductivity of polymers are more complicated and bulky.
a semicrystalline polymer is expected to depend only on the Now it is easy to understand the temperature dependence
conductivity of the amorphous and crystalline regions, of K above 30K as displayed in Figure I0. For polymers
respectively, the crystallinity X and the shape of the crys- with simple structure such as PE and POM Kc±>>Ka near 30K,
tallites. It is therefore not too surprising that early analyses so equation (13) further reduces to K = Ka(1 + 2X)/(1 - X),
by Eiermann 4 and Sheldon and L a n e 6t of the crystallinity i.e. K is proportional to Ka and thus increases with rising
dependence on the basis of the Maxwell model seem quite temperature. However, above 100K where Kc± and Ka be-
successful since this model considered isotropic spherical come comparable, K will depend on both these quantities.
inclusions randomly distributed in a matrix and treated the At high crystallinity (X ~> 0.7) its temperature dependence
mutual interaction among them in an average manner. How- is dominated by that of Kc±,so it will decrease with increas-
ever, the model is not strictly valid for polymers since the ing temperature. Therefore, starting from 30K, K first in-
large difference between the intrachain covalent bonding creases, reaches a maximum near 80K and then decreases
and the interchain van der Waals interaction is expected to with temperature. On the other hand, the temperature de-
give rise to large anisotropy in the intrinsic thermal conduc- pendence of K of low-crystallinity (X ~< 0.4) samples.is in-
tivity of the crystallites. In fact, theoretical estimate 6 shows fluenced more by Ka so it will increase with temperature up
that the conductivity along the chain direction of a crystallite to about 200K where it exhibits a very shallow maximum
(Kcll) is more than 50 times larger than that of the amorphous (Figure 14). For polymers with more complicated structure
region (Ka) which is in turn comparable to the conductivity (e.g. PET and PP) Kc±is nearly temperature-independent so
perpendicular to the chain direction (Kc±). This is also experi- K has similar temperature dependence as Ka.
mentally confirmed as we shall see in later sections where Since Kc±is expected to either increase or remain con-
oriented polymers are considered. stant as the temperature decreases equation (13) predicts an
The Maxwell model has recently been generalized to the increase of K with crystallinity even at low temperatures, in
case where the inclusions are thermally anisotropic and this contradiction to the observed behaviour below about 10K.
provides not only a more realistic description of the crystal- Two models have been proposed to account for this unusual
linity dependence but also an explanation for the orientation behaviour and we will discuss them in the following sections.
effect62. For the moment let us concentrate on isotropic
polymer the conductivity of which is given by the model as62: Low temperature behaviour
Correlation in sound velocity fluctuation. The first ap-
K - K a [2 k±- 1 1 ku-l] proach to this problem assumes that the presence of crystal-
(12) lites introduces a correlation length for the sound velocity
K- +- 2Ka - X k±+2 +3 ~1+2]
fluctuation of the order of the size of the crystallites (100 h).
where k± = KcaJKa and kll = K j K a. Equation (12) will of This leads to additional phonon scattering and the accom-
course reduce to the Maxwell expression when the crystallites panying decrease in conductivity. Morgan and Smith 16 have
emphasized that this treatment is strictly valid only when the
are isotropic, i.e. k± = ku. For polymers, however, k n >> 1 and
mean free path is larger than the correlation length, so taking
equation (12) becomes:
amorphous PET as an example and using equation (2), the
range of validity is found to be below 5K. Because of its
K - Ka ~_X - - - + (13)
K + 2Ka 3 kl + 2
12
It is seen from equation (13) that K is almost
independent of Kctl. Moreover, if amorphous samples A ii
are available (as in the cases of PET and PP) K a can also be
~0 I
directly measured. In any case, Ka for all amorphous poly-
mers above 30K are so similar (see Figures 3 and 4) that it I
can be easily estimated to within 15%. Therefore the only I
remaining parameter in equation (13) is Kc±which can be 8 /
obtained by the fitting of data. Figure 12 gives an example I
of such fits for PE at two different temperatures and the re-
sults are quite satisf/~ctory. The resulting Kc±values for four // •
polymers, shown as functions of temperature in Figure 13, E
fall into two distinct groups with the values for PE and POM
decreasing with rising temperature while those for PET and
4
PP being approximately temperature-independent within
the accuracy of the analysis. Furthermore, Kc±of PE follows
approximately a T -1 dependence, which is characteristic of
three-phonon Umklapp scattering processes37'4°. Its magni-
tude throughout the whole temperature range is about the
same as the thermal conductivity of molecular crystals such
as benzene (C6H6)63 which probably possesses van der
O 0'2 0'4 O'6 O'.8 JO
Waals interaction of similar strength. The much lower Kcl X
values for PET and PP are partly the result of weaker inter- Figure 12 The crystallinitv dependence of the thermal conductivity
chain van der Waals interactions but the only possible ex- of isotropic PE at 100 and 300K. 30OK: e, data (from ref 4); - - -
planation for the gentle temperature dependence seems to theoretical. 100K: A, data (from ref 4); - -- --, theoretical. The
be phonon scattering by defects in the crystallites. This is theoretical curves are calculated according to equation (13)
[~)e(qd)] a
Ks(T ) - - - Ka(T ) (14)
[#Pe(qd) ] s
where the subscripts a and s refer to the amorphous and
A
semicrystalline samples, respectively. Therefore, with
(~e(q) already determined from low-angle X-ray data,
Ks(T ) can be calculated in terms of Ka(T) and the results
are shown in Figure 15. It is clear that the main features of
the experimental curves, namely, the large decrease o f K s
with increasing X, can be reproduced by this model in spite
of the crude approximations.
Similar arguments have been employed by Burgess and
Greig 6 to explain the data above 2K of both isotropic and
E
extruded PE. It is again assumed that phonons are scattered
as they pass through regions of varying sound velocity, i.e.
E 3
lamellae and amorphous regions, but the Morgan-Smith
model 16 is used to obtain a quantitative fit. For heat con-
duction along the extruded direction the total mean free
path can be written as:
C .---"
/ - l ( q ) = lb-i + lL-l(q) + (1 -- X ) l s - l ( q ) (15)
where IL(q) and Is(q) denote the mean free paths for long-
range and short-range correlations, respectively, which can
be obtained from the universal curves in Figure 5. The values
D ofaL and as used are 100 and 8 A, respectively, and the con-
f stant lb, which is the boundary dimension, is taken to be
E 1 cm. The lL - 1 term accounts for the scattering of phonons
arising from velocity fluctuation in alternate regions of amor-
0 I I i i i
/
J // direction in which K is measured, then equation (15) must
be modified to:
/
lO-i l - l ( q ) = Ib-1 + lL-l(q) + (1 - X)ls-l(q) + X l u - l ( q ) (16)
v
u
where lu(q) is the mean free path arising from Umklapp scat-
E
tering of phonons in the crystallites perpendicular to the c-
axis. Although satisfactory fit 6 to the high temperature data
~ 5
can be obtained by employing an appropriate expression for
/u(q) the above assumption on the arrangement of crystal-
lites is not very realistic, and the treatment given in the earlier
section on 'High temperature behaviour' seems more
appropriate.
D
Heat flow linear heat flow through this parallel arrangement of amor-
phous region and amorphous-crystalline stacks, it is easily
shown that:
K (1 _ f ) 2
///////i -- =
Ka 2XKa(Rb/d ) + (1 - f - X)
+f (17)
Table 2 Parameters obtained from the analysis of the low-temperature thermal conductivity of semicrystalline polymers, d = (2) 1/2 X average
lamella thickness. For the samples of PE1 and nylon-66 the lamella thickness given are the measured values 22 while the rest are just typical values
obtained from literature ss. Refer to the text for explanation of other symbols
EFFECT OF ORIENTATION G
0
Amorphous polymers
When an amorphous polymer is uniaxially drawn the
chain molecules will tend to align along the draw direction.
Since the covalent bonds along the chains are much stronger
than the interchain van der Waals forces we would expect
the thermal conductivity along the draw direction (Ke) to
be higher than that in the perpendicular direction (Ka).
This anisotropy has been investigated 29-a2 for a number of 0.5 i i I
; i
;
polymers at room temperature and for PMMA between 90 Draw ratio
and 300K, the results of which are summarized in Figure 20.
Since these data have already been discussed in detail in Figure 20 Thermal conductivity of amorphous polymers as a func-
tion of draw ratio. -- -- --, Data at 100K. All other data are at room
previous reviews 1 we will concentrate only on those aspects temperature. (Data from ref 1 ). A, PVC; B, PMMA; C, PMMA
which have bearing on our future discussion on semicrystal- (100K); D, PS; E, PS; F, PMMA (100K); G, PMMA; H, PVC; I, PC
line polymers.
Figure 20 shows that the anisotropy of the thermal con-
ductivity of oriented amorphous polymers in the range of
draw ratio (1 to 5) studied is rather small for PS and PMMA
but somewhat larger for PVC. This may be related to the gate would be aligned with the units themselves remaining
fact that PVC normally contains a small fraction (-~ 10%) of unchanged. The thermal conductivities of the partially
crystalline regions 8'66 which provide very little thermal resis- oriented polymer can be obtained either by using the series
tance along the draw direction once the chains are aligned. or the parallel model. The series model assumes uniform heat
Two models have been proposed to explain the effect of flux throughout the aggregate, which implies a summation of
orientation. In the first model 3~ an unoriented polymer is re- thermal resistivities, while the parallel model assumes uniform
garded as a random aggregate of axially symmetric units temperature gradient thus leading to a summation of thermal
whose thermal conductivities were those of the fully oriented conductivities. Using the series model the thermal conducti-
materials. When the polymer is drawn the units of the aggre- vities are given by31:
_ _ i
(20)
io -J Kl
Although equations (19a) and (20) are very different in form
it has been shown t that they do not predict very different
numerical results within the bounds where experimental
data are available.
Semicrystalline polymers
' ' IO
" ' ' 10
' 2
T(K) We have seen that the orientation effect on amorphous
polymers is not very strong, which is at least partly due to
Figure 21 Thermal conductivity of extruded PE. The starting the relatively low draw ratio attainable. However, the pic-
material is Rigidex 50 (X = 0.8). K#: A, h = 20: B, h = 13; C, h = 9,
D, h = 5,4; E, isotropic sample; F, K± (~ = 5.4). K± for other samples
ture changes considerably for the semicrystalline polymers,
of ~, > 5.4 follow the same curve as F. Data from ref 34 the structure of which leads to very spectacular changes in
both the magnitude and temperature dependence of the
thermal conductivity for the highly oriented samples, as
could be readily seen in Figures 21 and 22.
Before any attempt at an explanation of these results it is
--=- +--- - (cos20) (18a) important to have an understanding of the morphological
Kj. 2 rl" K~" structure of these oriented polymers. It is now generally
accepted 7°'7t that when a semicrystaUine polymer is drawn
the spherulite is deformed and gradually broken up. Even
KI u K±U K±U at draw ratio as low as 4, wide-angle X-ray diffraction indi-
cates quite a high degree of crystallite orientation with the
where KI u and K±u are the thermal conductivities of the basic chain axes aligned in the draw direction whereas low-angle
unit along and perpendicular to the symmetry axis, 0 is the X-ray diffraction gives either a four-point pattern or an arc
angle between the symmetry axis and the draw direction and with maximum intensity on the meridian. These results are
(cos20) is the average of cos20 for the aggregate. Since consistent with a roof-top structure in which the lamellae
(cos20) is equal to 1/3 for the isotropic state it follows from are tilted at some angle to the draw direction while the chains
equation (18) that: in the lamellae are aligned in the draw direction. As the
polymer is further deformed the tie molecules between the
3 2 1 lamellae become highly extended and blocks of crystals are
- = -- + -- (19a) then pulled out. Finally, at a draw ratio of about 8, these
K K± Kt blocks, which are still attached to each other by the tie
molecules, become aligned along the draw axis giving rise to
2 1 a fibrillar structure, and further drawing will only increase
+ - (19b)
g~ u Ksu the number of taut tie molecules with the structure itself re-
maining unaltered. The above description is based largely
where K is the thermal conductivity of the isotropic material. on studies of PE but the main features are expected to be
With the aid of the pseudo.affine deformation scheme 3t'67 similar for other polymers ~'Ta. The structure of hydrostati-
(cos20) was calculated as a function of draw ratio X and cally extruded polymers is not well understood, but presu-
K -G
K± + 2Ka
8( [k.L--1 I+(COS20) kll - 1 1 ]
=X - - x +--x (sin20)
k± + 2 2 kll + 2
[
X [lcl-+--2
cos20,
] ,, , 2 ~" (sin20) (22a)
60
E
U
gll - ga
E KIL + 2K a
40
= x [ k i ~ - 1 (sin20) + kn - 1
x x (cos20) ]
ku + 2 kll + 2 J
k'-I
- - x (sin20) + (cos20)
] (22b)
20 ku + 2
where 0 is the angle between the chain axis and the draw IO
direction and ( ) denotes the average over all crystallites.
Wide-angle X-ray diffraction rfieasurements 74-76 have shown
that fc for a number of polymers of widely different crystal-
i i t i i i i i i
linity (e.g. PVC, high and low density PE) have similar ?,- O 0-2 0"4 0"6 0"8 I'O
dependence, that is, fc increases very fast at low ~. and fC
reaches about 0.9 at ;k ~- 4. On the other hand, the amor-
phous orientation is rather low, with fa less than 0.3 for ;k x
< 577'7a. Therefore, if we take into consideration this result Figure 23 The thermal conductivity of oriented PE at 323K against
and the small orientation effect on amorphous polymers dis- the crystalline orientation function f~ Data from ref 33. The hori-
zontal error bar is due to the uncertainty in fc since the measure
cussed previously it seems reasonable to describe the amor- ments of the orientation function and thermal conductivity were
phous region by an isotropic conductivity Ka. Then using made on different sets of samples. The theoretical curves/('l ( )
the modified Maxwell model the thermal conductivities Kil and K j_ ( - -- -- ) are calculated from equation (22)
X
Figure 24 The thermal conductivity of extruded PP at IOOK against
the crystalline orientation function fc. K#(@) a n d / ( 1 (O) data from 15
ref 8. The theoretical curves for K# ( ) and K± ( - - - ) are cal-
culated according to equation (22). X = 0 . 7 9 for the sample at h =
10.5 while X ~ 0 . 6 2 for the rest, so t w o sets of theoretical curves are
given. A, X = 0.79; B, X = 0.62; C, X = 0.62; D, X = 0.79
of K, Kit and K±. The temperature dependence of K of PE 0 0"2 0'4 0"6 0'8 I'0
has already been discussed so we will now consider Kit and 'c
K±.
k
It follows from equation (22b) that when fc = l(perfect
orientation) KII = Ka(1 + 2X)/(1 - X), i.e. Kit is proportional Figure 25 The anisotropy in the thermal conductivity of drawn PE
to Ka and thus increases monotonically with temperature. at room temperature against the crystalline orientation function.
• , data (X = 0.74); v , data (X = 0.45) from ref 35. The theoretical
However, we have seen that the thermal conductivity for iso- curves are calculated according to equation (221. A, X = 0.74;
tropic PE (re = 0) decreases with rising temperature between B, X = 0.45
Extrusion direction analysis. We note that in terms of the model the amorphous
fraction is given by 1 - X = a(1 - b), which, together with
M equation (25), give the values of a and b. It was found a4 that
-,---7--7--7,--i i
1--7-] b increases from 0.02 to 0.09 as ;~ increases from 5.4 to 25
while ~ remains almost unchanged at 0.25. This small value
for b at ~ = 5.4 justifies the neglect of the effect of tie mole-
Jrl iiIji cules in our previous analysis of samples of lower draw ratio.
I-a
d @ We further note that the approximations used to obtain
equation (25) and the equivalent expression for Ell are fairly
well justified since they would lead to at most 25% error in
I , I the worst case, i.e. the sample with the lowest extrusion ratio.
The fact that there is little deviation from linearity in Figure
,1!1
The data of Kii also give us some information on the tem-
perature dependence ofgcl I. It follows from equation (25)
I I that Kctl is proportional to K, which varies roughly linearly
with temperature between 50 and 100K (Figure 21). If the
above analysis is repeated for this temperature range then
the Kcll values (which varies from 150 to 310 mW/cm K)
obtained can be substituted into equation (2) to give a rough
estimate of the phonon mean free path along the chain direc-
tion of the crystallites. However, in this one-dimensional
I- I
-b =.~ b---~ situation, the factor 1/3 should be replaced by 1 since this
Figure 26 Schematic model of extruded PE showing the inter- factor is actually the average of the square of the cosine of
crystalline fraction, & containing the intercrystalline bridges b the angle between the mean free path and the transport
direction. Moreover, the heat capacity term C(T) should
include only the contribution of the acoustical vibrations
along the chains while the sound velocity v is an appropriate
line bridges with increasing ~,. This kind of model has often
average of the longitudinal and transverse velocities of these
been used in the analysis of the mechanical properties of
vibrations. Fortunately, in the temperature range under
oriented polymers (known in the mechanical case as the
Takayanagi model 79) and our modified version is shown
schematically in Figure 26. If we assume that the inter-
crystalline bridges have the same thermal conductivity and IOO
modulus as the crystallites, then we can obtain the follow-
ing expressions for KII and Ell:
1 l-a
- + (23) 8O
K, Kcll bKc, + (1 - b ) K a
1 1 ~
- +
(24)
Ell Ecil bEc, + (1 - b )Ea
KII 4o
b [b(1 - a) + a] -1 (25)
Kc,
Ktl(T) ~ E,(200K)
- - (26)
Kcll (T) k~, II
Since K,(T)/EII (200K) is known experimentally (Figure 2 7) o ' ' 4'o ' go
and as Ec, -~ 240 GN/m 2 so,81, equation (26) can be used to E. o t 2OOK(GN/m 2)
obtain an estimate ofKcll(T ). The result at 100K is 310
mW/cm K, which is about 200 times the value of Ka and this Figure 27 Variation of thermal conductivity along the extrusion
direction at 100K with the Young's modulus in that direction
justifies the assumption of Kc, >>Ka employed in earlier measured at 200K
Kl = Kc±(1 - ~) +
b/Kcj. + (1 - b ) / r a the sample at X = 0.45 to 26 at X = 0.74, i.e. A u is
crystallinity-dependent.
"~ (1 - ; ) r c ± + aK a (27) The application of the aggregate model to the analysis of
the moduli of semicrystalline polymers have received much
so that K± is roughly independent of k, which is indeed the greater attention a2'83 and the limitations of this model, which
behaviour observed~ (Figure 22). Taking K a = 1.8 mW/cm K, have been discussed in detail, apply equally to our case. In
we obtain Kcj. -~ 6 mW]cm K, in agreement with the value the following, we will give the main arguments and our own
obtained previously from the modified Maxwell model thoughts along the same lines. First, the assumption of un-
(Figure 13). We have already seen that K c i has a different altered basic units implies that there are no changes during
temperature dependence, varying roughly as T - ] . The mean the orientation process and this is certainly not true for
free path in this direction is smaller than lcu and is limited crystalline polymers. Secondly, one would only expect the
by Umklapp processes in our temperature range. parallel and the series models to give the upper and lower
bounds for the thermal conductivity of the aggregates, the
Aggregate model. The aggregate model, which is essen- correct value lying between these extremes. Therefore it is
tially a one-phase model, has also been applied to analyse the hard to justify the use of equation (28) (which is derived
anisotropy of PE at room temperature as. It was emphasized from the series model) to obtain a quantitative fit. Thirdly,
that neighbouring crystalline lamellae have a definite orien- since the orientation in the crystalline and amorphous regions
tation correlation and they form clusters within which the differ by such a large extent (e.g. fc ~- 0.9 and fa < 0.3 for
amorphous and crystalline regions are strongly coupled. PE at X = 4) it is rather uncertain whether one should use fc
These clusters can then be taken as the basic units of the or an appropriate average offc and fa to describe the orien-
aggregate and equations (18a) and (18b) can be combined tation of the units. However, since equation (28) is able to
to give: predict the correct trend it seems that there is a definite cor-
A =-
,[
2 IAU - ( ~ C 1 3 <cos20>
- 1
] (28)
relation v~ith fc. Finally, in view of the large difference bet-
ween Kcu and Ks, a two-phase model seems more appropriate
and we have already shown that these data can be adequately
described by the modified Maxwell model.
where A u = K uU/K±u is the anisotropy of the basic unit. If we
assume that the orientation of these units is adequately des-
cribed by the crystalline orientation function fc, then A can CONCLUSIONS
be calculated in terms of the adjustable parameter A u
Figure 28 shows the results for three samples of PE of dif- We have seen that, at low temperature, orientation has little
ferent crystallinity and we can see that there is good agree- effect on the thermal conductivity of semicrystalline poly-
ment between theory and experiment. We note that the re- mers and this could probably be due to the relative insensi-
suiting value of the intrinsic anisotropy A u varies from 7 for tivity of the dominant phonon scattering mechanism (whether
arising from the correlation in the spatial fluctuation in sound Wiley, New York, 1960, p 508; Klemens, P. G. 'Physics of Non-
velocity or acoustic mismatch at amorphous-crystalline inter- crystalline Solids', (Ed. J. A. Prins), North Holland, Amsterdam,
faces) to orientation. In contrast, the thermal conductivity 1965, p 162
16 Morgan,G. J. and Smith, D, J. Phys. (CJ 1974, 7, 649
above 30K exhibits much larger anisotropy. At low draw 17 Anderson, P. W., Halperin and Varma, C. M. Phil. Mag. 1972,
ratio, this anisotropy is well described by the modified 25, 1
Maxwell model which takes into account the orientation of 18 Phillips, W. A. J. Low Temp. Phys. 1972, 7, 351
the chains in the crystallites. Since the chains are already 19 Dreyfus,B., Fernandes, N. C. and Maynard, R. Phys. Lett.
1968, 12, 647
aligned at ?~ = 5 further increase in K~ with k can only be ex- 20 Anderson, A. C., Reese, W. and Wheatley, J. C. Rev. Sci. Instrum.
plained in terms of the increasing number of tie molecules, 1963, 34, 1386
and the application of the Takayanagi model has put this 21 Reese,W. and Tucker, J. E. J. Chem. Phys. 1965, 43, 105
analysis on a more quantitative basis. The aggregate model 22 Kolouch, R. J. and Brown, R. G. J. Appl. Phys. 1968, 39, 3999
also seems to give encouraging results but we have seen that 23 Scott, T. A., de Bruin, J., Giles, M. M. and Terry, C. J. Appl.
Phys. 1973, 44, 1212
there are a few limitations. More work should be done to 24 Assfalg,A. J. Phys. Chem. Solids 1975, 36, 1389
determine the conditions for the applicability of this model. 25 Neeper,D. A. and Dillinger, J. R. Phys. Rev. 1964, 135, 1028
It is unfortunate that investigations of the thermal con- 26 Garret, K. W. and Rosenberg, H. M. J. Phys. (D) 1974, 7, 1247
ductivity have been confined mainly to polyethylene and 27 Schmidt, C. Cryogenics 1975, 15, 17
28 Little, W. A. Can. J. Phys. 1959, 37, 334
only within limited draw ratio and temperature ranges 29 Eiermann, K. Kolloid-Z 1964, 199, 125
(either at room temperature or below 100K), so that some 30 HeUwege,K. H., Hennig, J. and Knappe, W, Kolloid-Z 1963,
aspects of these models have not been adequately tested. 188, 121
For example, we have mentioned that the modified Maxwell 31 Hennig, J. J. Polym. Sci {C) 1967, 16, 2751
model predicts a change of temperature dependence of Kit 32 M/iller,F. H. J. Polym. Sci. IC) 1967, 20, 61
33 Hansen, D. and Bernier, G. A. Polyrn. Sci. Eng. 1972, 12, 204
of polyethylene with orientation and this can easily be 34 Gibson, A. G., Greig, D,, Sahota, M., Ward, I. M. and Choy,
checked by measurements on samples with k between 1 and C. L.J. Polym. Sci. {Polym. Lett. Edn) 1977, 15,183
5. Moreover, measurements on highly drawn or extruded 35 Kilian, H. G. and Pietralla, M. Polymer submitted for publication
polyethylene should be extended to room temperature since 36 Novichyonok, L. N. Prog. Heat Mass Transfer 1973, 5, 293
it may be of considerable technological importance to check 37 Klemens, P. G. Solid State Phys. 1958, 7, 1
38 Kittel, C. Phys. Rev. 1949, 75. 972
our expectation that Ktl and the anisotropy A could reach 39 Klemens, P.G. Proc. Roy. Soc. (A) 1951,208,108
180 mW/cm K and 60, respectively. This Ktt value is close to 40 Ziman, J. M. 'Electrons and Phonons', Oxford University
the thermal conductivity of stainless steel and is thus excep- Press, London, 1968, p 248
tionally high for polymers. Finally, data on a large variety 41 Knappe, W., Lohe, P. and Wutschig, R. Angew. Makromol.
Chem. 1969, 7, 181
of polymers in the widest possible draw ratio and tempera-
42 Hunklinger, S., Arnold, W. and Stein, S. Phys. Lett. {A) 1973,
ture ranges would be most valuable. 45,311
43 Arnold, W., Hunklinger, S., Stein, S. and Dransfeld, K. J. Non-
Cryst. Solids 1974, 14, 192
ACKNOWLEDGEMENTS 44 Piche,L., Maynard, R., Hunklinger, S. and Jackle, J. Phys.
Rev. Lett. 1974, 32, 1428
The author is grateful to Professor I. M. Ward and Dr D. Greig 45 White,G. K. Phys. Rev. Lett. 1975, 34, 204
46 Flubacher, P., Leadbetter, A. J., Morrison, J. A. and Stoicheff,
of the University of Leeds, and Dr F. C. Chen and Dr K. Young J. Phys. Chem. Solids 1959, 12, 53
of the Chinese University of Hong Kong for their critical 47 Antoniou, A. A. and Morrison, J. A. J. Appl. Phys. 1965, 36, 1873
readings of this article and for giving valuable comments and 48 Leadbetter, A. J. Physics Chem. Glasses 1968, 9, 1
suggestions. Thanks are also due to Dr H. G. Killian and Dr 49 Choy, C. L., Hunt, R. G. and Salinger, G. L. J. Chem. Phys.
M. Pietralla for sending us a preprint of their article. 1970, 52, 3629
50 Choy, C. L., Huq, M. and Moody, D. E.Phys. Lett. (A) 1975,
54, 375
5l Rosenstock, H. B. J. Phys. Chem. Solids 1962, 23,659
52 Zaitlin, M. P. and Anderson, A. C. Phys. Rev. Lett. 1974, 33,
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