158 Tadokoro, et al.

Macromolecules

Molecular Vibrations of Three Crystal Forms of

Poly(vinylidene fluoride)
Masamichi Kobayashi, Kohji Tashiro, and Hiroyuki Tadokoro*
Department of Polymer Science, Faculty of Science, Osaka University,
Toyonaka, Osaka, 560 Japan. Received October 8,1974

ABSTRACT: Infrared and Raman spectra in the region from 4000 to 30 cm-1 of three crystal forms, namely, I, II,
and III, of poly(vinylidene fluoride) (-CF2CH2-),, have been measured. The optically active librational lattice vi-
bration appears at 70, 53, and 84 cm-1 in the far-infrared spectra of forms I, II, and III, respectively. The normal
frequencies have been calculated for the crystal lattices with the space groups Cm2m (for form I), P2i/c (form II),
and C121 (form III), by assuming valence force field intramolecular forces along with van der Waals and electro-
static intermolecular forces. The calculated frequencies of the lattice modes as well as the molecular modes are in
good agreement with the observed data. The difference in vibrational spectrum between crystal forms I and III,
both consisting of the essentially planar zigzag chains, was interpreted reasonably by the difference in relative
height of the chains in the unit cell, as proposed by the previous X-ray work, and, therefore, form III was confirmed
as the third crystal phase different from form I. In the spectra of forms I and III there appear many weak bands
and band splittings on cooling to liquid nitrogen temperature, which are not associated with the optically active
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fundamentals of the regular crystal lattices of these forms. Most of them correspond well to the positions of the
peaks in the frequency distribution functions computed for forms I and III, and are ascribed to the statistically dis-
ordered crystal structures consisting of slightly deflected chains. Some of the weak bands were assigned to the
head-to-head linkages incorporated in the sample on the basis of the vibrational analysis made on the alternating
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copolymer of ethylene and tetrafluoroethylene, a typical model compound of the head-to-head structure. Infrared
and Raman spectra of form II, throughout the whole frequency range, have been found to be consistent with the
space group P2\!c proposed by the previous X-ray work.

In a previous paper1 the authors reported that poly(vi- shed light on the problems the crystal structures of PVDF
nylidene fluoride) (PVDF) crystallizes into three crystal are investigated from the viewpoint of vibrational spectros-
forms, namely, I, II, and III, depending upon the crystalli- copy in the present paper.
zation conditions. The crystal structures of the three forms Infrared and Raman spectra of PVDF have been studied
have been determined in this laboratory by means of X-ray by Cortili and Zerbi,5 Enomoto, et al.,9 and Boerio and
analysis,2 the crystallographic data being reproduced in Koenig.10 However, the previous workers have been con-
Table I. In forms I and III the molecule assumes an essen- cerned with the molecular modes and the molecular struc-
tially planar zigzag conformation, and in form II it has a tures but have ignored the intermolecular interactions
TGTG conformation. which are essentially important in order to solve the prob-
The crystal lattice of form I determined by the authors, lems of molecular packings. In the present work the vibra-
somewhat different from the regular orthorhombic lattice tional analyses are made on the three-dimensional crystal
proposed by Lando, et al.,3 includes a statistically disor- lattices of three forms of PVDF taking into account both
dered packing of slightly deflected molecular chains. the intra- and intermolecular forces. On the basis of group
As for form III which has been first found as the third theoretical considerations as well as the results of the nor-
crystal phase by Natta, et al.,4 Cortili and Zerbi5 suggested mal coordinate treatment, the packing structures of the
from the infrared spectroscopic data that this phase con- molecules in the crystal lattices are investigated.
sisted of disordered planar zigzag chains. The crystal phase Besides the normal frequencies of the optically active
has been referred to phase I' by Doll and Lando.6 This factor group modes, the frequency distribution functions
phase was regarded by the present authors1-2 as a new crys- including all the normal modes in the first Brillouin zone of
tal modification with a monoclinic unit cell consisting of es- forms I and III are calculated. Based on the results, the ef-
sentially planar zigzag chains with slight statistical deflec- fects of the defects involved on the vibrational spectra are
tion. The X-ray analysis of form III, however, has been per- discussed.
formed by using diffraction data from a powder photo-
graph, since form III was not obtained in a highly oriented
Samples and Spectral Measurements
form because of simultaneous change to form I during the The samples of PVDF used were of a commercial source,
orientation procedure. The proposed crystal structure Kynar 201, obtained from Pennwalt Chemical Company.
would, therefore, be less accurate compared with the other They included the head-to-head linkages of about 10% as
two modifications. Moreover, a close similarity in X-ray estimated by 19F nmr spectrum. The melting point was
diffraction pattern as well as in infrared spectrum of forms measured as about 172° with a Perkin-Elmer DSC-1B dif-
I and III makes it obscure to decide whether form III ferential scanning calorimeter and also with a polarizing
should be regarded as the third crystal phase or not. microscope.
As for form II, Doll and Lando7 have proposed two possi- The specimens for spectral measurements, consisting of
ble unit cell structures with the space groups P2i and PI, pure respective crystal form, were prepared as follows.
both being different from that proposed by the present au- Form I. Oriented film specimens of form I were obtained
thors (P2i/c). The discrepancy was thought, according to either (1) by stretching melt-crystallized specimens (form
Farmer, et al.,8 to be attributed to the difference in the II) about six times their original lengths at room tempera-
amount of head-to-head linkages involved in the samples ture, or (2) by rolling film specimens cast from dimethyl-
used in the two schools. acetamide solution (form III). Unoriented film specimens
Thus, there are many problems, which are of much inter- of form I were found to be prepared by casting films from
est but remain unsettled, about packing structure of the hexamethylphosphoramide solution at room temperature.
PVDF molecules in three crystal modifications. In order to Powder samples of form I were obtained by grinding com-
 Vol. 8, No. 2, March-April 1975 Molecular Vibrations of Poly(vinylidene fluoride) 159

Table I
Crystallographic Data of Three Forms of
Poly(vinylidene fluoride)2
Form I Form n Form HI

Crystal Orthorhombic Monoclinic Monoclinic

system
Space Cm2m-<CiJi P2t/c-C2h5 C121-C23
group
Lattice a = 8.58 A a = 4.96 A a 8.66 A
=

constants b = 4.91 A b = 9.64 A b= 4.93 A

c(f.a.)° =
c(f.a.) =
c{f.a.) =
Figure 1. Fiber diagram of the alternating copolymer of ethylene
2.56 A 4.62 A 2.58 A and tetrafluoroethylene.
0 = 90° 8 = 97°
° f.a. = fiber axis.

mercial powder samples (almost form II) for several hours

at room temperature.
Form II. Unoriented specimens of form II were prepared
either (1) by cooling the melt slowly to room temperature,
or (2) by casting films from acetone solution at about 50°.
Oriented film specimens of form II were obtained by
stretching or rolling unoriented specimens of form II about
four times the original lengths at the temperature immedi-
ately below the melting point.
Form III. Unoriented specimens of form III were pre-
pared by casting films from dimethylacetamide solution at
about 65°. Slow evaporation of the solvent increased the
purity of form III.11 Preparation of oriented specimens of
form III is very difficult because this crystal form changes
very rapidly to form I by mechanical deformation. A speci-
men with very slight orientation was obtained by rolling a
cast film.
A commercial sample of an alternating copolymer of eth-
ylene and tetrafluoroethylene [-(CIUblOFaiz-ln, Tefzel
(Du Pont Chem. Co.), was subjected to investigation as a
typical model compound consisting of the head-to-head
linkages which are known to be included in the sample of
PVDF.12,13 The copolymer sample used here consists of
CH2CH2 (47.8 mol %) and CF2CF2 (52.2 mol %) measured
by elementary analysis, and is highly crystalline giving an
X-ray fiber diagram with the fiber period of 5.08 A (Figure
l).14 The melting behaviors of this sample measured with a
differential scanning calorimeter were essentially the same
Wavenumber (crrr1)
as those of the copolymer samples having the alternation
ratio of 93-97% investigated by Modena, et al.lb Oriented Figure 2. Infrared spectra of crystal forms I and III of po!y(vinyli-
film specimens of the copolymer were prepared by hot roll- dene fluoride) (top) in the region from 4000 to 400 cm-1 and (bot-
ing at 200°. tom) in the far-infrared region: (-) electric vector _1_ orienta-
The infrared spectra were measured by a Japan Spectro- tion direction; (---) electric vector || orientation direction. The
spectrum of form III on the bottom is taken with unpolarized ra-
scopic Company DS-402G grating infrared spectrophotom- diation.
eter equipped with an AgCl polarizer (4000-400 cm-1), and
by a Hitachi FIS-3 far-infrared spectrophotometer with a
wire-grid polarizer (400-30 cm-1). The polarized infrared spectra of forms I and III in the
The Raman spectra were taken by a Japan Spectroscopic region from 4000 to 400 cm-1 are reproduced in Figure 2
Company R750 triple monochrometer Raman spectropho- (top). Here, the solid and broken lines represent the ab-
tometer equipped with a photon counter. The 5145-A line sorptions taken by the infrared radiation with the electric
from an argon ion laser was used as the excitation light vector perpendicular and parallel to the orientation direc-
source. Measurements of the polymeric substances accom- tion, respectively. A slightly oriented film specimen of form
panied a great deal of difficulties because of weak Raman III was used for the measurement. The figures on the ab-
intensity compared with strong background due to Ray- sorption curves denote the thickness of the specimens. The
leigh scattering. In order to distinguish the Raman lines far-infrared spectra of forms I and III are compared with
from the natural emissions from the laser light source, the each other in Figure 2 (bottom). Here the spectrum of form
anti-Stokes lines were measured as well as the Stokes lines. III was taken with unpolarized radiation, because an ori-
Both infrared and Raman measurements were carried out ented film specimen thick enough for the measurement in
at room temperature as well as at liquid nitrogen tempera- this region could not be obtained. In Figure 3 are repro-
ture. duced the Raman spectra of forms I and III. The polarized
160 Tadokoro, et al. Macromolecules

Table II
Intramolecular Valence Force Constants
of Poly(vinylidene fluoride)

Values'1
Force Coordi-
con- nates Common Forms
No. stants involved atoms i & m Form n

1 Kt CH 4.902 4.902
2 Kr CC 4.413 4.413
3 Fri CC, CF C 0.403 0.740
4 F R CC, CC C 0.148 0.148
Form El
5 Fnr CC, CCH CC 0.206 0.206
6 F RW CC, CCC CC 0.273 0.273
7 Fr0 CC, CCF CC 0.567 0.567
8 CH, CH c 0.058 0.058
9 X, CF 5.96 5.96
10 Xu CF, CF c 0.621 0.621
11 Fk CF, CFF CF 0.674 0.674
' ' ' '

1600 1400 1200 1000 800 600 400 200 12 Hr CCH 0.615 0.615
Wavenumber cm'1 13 Fy CCH, CCH CC 0.105 0.105
14 Fy' CCH, CCH CH 0.074 0.074
Figure 3. Raman spectra of crystal forms I and III of polyfvinyli- 15 CHH 0.441 0.481
dene fluoride). Hz
16 Hu CCC 1.248 1.248
infrared spectra and the Raman spectrum of form II are re-
17 /Y CCC, CCC(t) CC -0.036 -0.036
18 CCF 1.262 1.262
produced in Figure 4.
19 H( CFF 1.50 1.50
Calculation of Normal Frequencies of Crystal Lattices 20 T cccc 0.05 0.05
21 x„ CF, CCF CF 0.62 0.50
Calculations of the normal frequencies of the crystal lat-
22 F« CCF, CCF CC 0.178 0.178
tices are made by solving dynamical secular equations de-
scribed in terms of the mass-adjusted Cartesian displace-
23 V CCF, CCF CF 0.143 0.143
24 /Y CCC, CCC(g) CC -0.064
ment coordinates. The internal coordinate vector of the (ji, *
25 fu CCC, CCH(g) CC 0.138 0.106
]2, 7,i)th unit cell Rj and the Cartesian displacement coor-
dinate vector of the (/Y, ji, JsOth unit cell Xy are related to
26 f-r CCC, CCH(t) CC 0.207
27 Jt w
*
CCC, CCF(g) CC -0.085 -0.085
each other by the matrices Bi as
&copy;

28 w CCC, CCF(t) CC 0.239

29 fr» CCH, CCF(t) CC 0.063 0.063
R, =
ZBxXJ+1 (i)
1 30 fr*' CCH, CCF(g) CC 0.055 0.055

Here 1 denotes the vector joining two unit cells. The sym- “The stretch constants have units of mdyn/A; the stretch-bend
interactions have units of mdyn/rad; and the bending constants
metrized internal R(k) and the Cartesian displacement have units of (mdyn A)/rad2.
coordinates X(k) belonging to the wavenumber vector k
are given as Here M is a diagonal matrix consisting of atomic masses
and B+ denotes the transposed conjugate complex of B.
R(k) =
exp (277fk.j) (2)
i The optically active normal modes (k = 0) were calculat-
ed for the three crystal forms of PVDF. For forms I and III
X(k) =
NxY^Xf exp(27uk° j) (3) calculations were also made for the normal modes of the k
vectors within the first Brillouin zone (kl = —% %, i = a, —

b, c) of the reciprocal space in order to obtain the frequen-

R(k) =
B(k)X(k) (4) cy distribution functions.
where In the present calculations, the intramolecular force con-
stants of valence force field (VFF) type were transferred
B(k) =
Bj exp(-2"fk’ 1) (5) from those proposed by Boerio and Koenig10 with slight
i
modification (Table II). Two types of intermolecular force
and Nr and Nx are the normalization factors. were taken into consideration. One is the van der Waals
The potential energy matrix described in terms of the force acting between nonbonded atoms. The potential en-
symmetrized internal coordinates Ffl(k) is given by ergy for an atomic pair at a distance r is given by a Len-
nard-Jones type potential function
Fij(k) =
X Fj exp(-27ifk* 1) (6)
V(r) =
e[(rmin/r)12
-

2(rmU/r)6] (9)
where Fi represents the interactions between two unit cells
where e is the depth of the potential energy minimum, and
apart from each other by the vector 1. F0oo represents the
interactions within a unit cell. rmin is the position of the minimum potential. The corre-
The secular equation for the wavenumber vector k is sponding force constant is given by the second derivative of
given as
V with respect to r.
In the present calculations only the H- -F atomic pairs
D(k) -
ai2 (k) E = 0 (7) were taken into account, since the nonbonded atomic pairs
| |
of this kind have interatomic distances shorter than 3 A in
D(k) =
M-1/2Bt(k)FJJ(k)B(k)M-w (8) the three crystal lattices. Other kinds of atomic pairs have
Vol. 8, No. 2, March-April 1975 Molecular Vibrations of Poly(vinylidene fluoride) 161

Figure 4. Infrared (upper) and Raman (lower) spectra of crystal form II of poly(vinylidene fluoride). For the infrared absorption: (-)
electric vector _L orientation direction; (- -) electric vector || orientation direction.
-

Table III
Intermolecular Force Constants of Poly(vinylidene fluoride) Crystals0
Form I Form II Form III

Coordinates Values, Coordinates ValueSj Coordinates Values,

No. involved mdyn/ A involved mdyn/ A involved mdyn/A

1 £ 1* £2; £3) £4 0.0163 £1, £5 0.0134 £2, £3 0.0657

2 £5! £3 -0.0021 £2> £7 0.0044 Su £i 0.0016
3 £7, £s 0.0017 ^3 0.0088 £5) £6 -0.0022
4 £9; £io> £n» £ 12 0.0030 £4, £9 0.0191 £l3> £ 14 0.0006
5 St, £s 0.0225 £7. £3 0.0030
6 £9! £io> £n> £12 0.0029
“
The coordinates involved in the intermolecular force constants are referred to Figure 5.

more distant interatomic distances and give negligibly Table IV

small contribution to the intermolecular forces. For the pa- Number of the Normal Modes and Selection Rules
rameters of the H- -F potential function, the values e =
• of Crystal Forms I and III of Poly(vinylidene fluoride)
0.3919 KJ/mol and rm-m = 2.78 A were assumed, which have
been used in the previous paper1 for the calculations of the M0lec_ Selection rules
cohesive energies of the crystal lattices of P VDF. The other Spe- ular Lattice -

intermolecular force is due to the electrostatic interaction cies modes modes Infrared Raman
between the polar groups. Partial charges of 2.104 X 10-10
esu and —1.052 X 10-10 esu were assumed on the carbon (a) Form I with Space Group Cm2m-C2vu
and fluorine atoms of the CF2 groups, respectively, the 5 T b“ Active (!)“ Active
values being deduced from the CF bond moment of 1.41 D a2 2 Forbidden Active
and the CF bond length of 1.34 A. The Coulombic force Bt 3 Tc Active (H) Active
constant is given by the equation B2 4 tL L(RC)6 Active (!) Active
(b) Form III with Space Group C121-C23
F(r) = 2 QiQi/Dr* (10) A 7 t6 Active (!) Active
B 7 Ta, T c, L(RC) Active (!, !!) Active
where Q1 and Q2 are the amounts of the electric charges on
“Ta, Tb, Tc: pure translation along the respective crystal axis
the respective atoms, and D is the dielectric constant which
6L(Rc); librational lattice mode around the fiber axis. c X and
is assumed here to be 4.0. The contribution of the electro- in parentheses denote infrared polarization for a uniaxial speci-
static interactions is so small (about 10% or less of the total men.
intermolecular interactions) especially in form II that they
are taken into account only for the polar crystal lattices of pared with the observed data in Table V. The assignments
forms I and III. The values of the intermolecular force con- of the bands are described in terms of potential energy dis-
stants are listed in Table III. The atomic pairs considered tribution obtained by the calculation for a single molecular
in the present calculations are shown schematically in Fig- chain.
ure 5. From Table IV we can expect only one librational lattice
mode (B2 species) in both infrared and Raman spectra.
Vibration of Crystal Form I This is clearly assigned to the perpendicular absorption
The space group of form I has been found as Cm2m- with the peak at 70 cm-1. The calculated normal frequency
C21;14 with two chains in the orthorhombic unit cell.2 Al- of the mode is 72 cm-1, in good agreement with the ob-
though the X-ray analysis has suggested the statistically served one. The librational mode is represented schemati-
disordered packing of slightly deflected chains, the normal cally with the Lx vectors as shown in Figure 6. The calcu-
modes calculations were made, for the sake of simplicity, lated frequencies of the intramolecular modes are also in
for the regular crystal lattice without statistical deflection good agreement with the observed infrared and Raman
of the chains. The spectroscopic unit cell contains only one frequencies as given in Table V. The assignments of the in-
planar zigzag chain in it. The number of the optically active tramolecular modes are essentially the same as those given
normal modes and the selection rules are obtained as given by previous workers.5’9,10
in Table IV. The calculated normal frequencies are com- Thus, the main infrared and Raman bands are interpret-
162 Tadokoro, et al. Macromolecules

Wavenumber (cm"1)

Figure 7. Infrared spectra of crystal forms I and III of poly(vinyli-

dene fluoride) measured at room (- -) and liquid-nitrogen (-)
-

8crrf'

1000 900 800 700

(cnr1)
Figure 8. Splitting of the infrared absorption bands of crystal
form I of poly(vinylidene fluoride) measured on cooling to liquid-
nitrogen temperature (powder sample).
Figure 5. Crystal structures and intermolecular interactions in the
three crystal forms of poly(vinylidene fluoride): (top) forms I and Structure and Vibrations of Crystal Form III
III, (bottom) form II. The crystal structure of form III proposed by the au-
thors2 belongs to a monoclinic system with the space group
C121-C23, containing two planar zigzag chain with slight
deflection as in form I. The crystal lattices of forms I and
III differ from each other in the relative height of the two
chains in the unit cell as shown in Figure 5. If we ignore the
deflection of the chain, the crystal lattice of form III gives
rise to the optically active modes given in Table IV. As in
the case of form I, only one librational lattice mode (B
species) is expected in both infrared and Raman spectra.
Figure 6. Schematical representation of the librational lattice Comparing Tables IV(a) and IV(b), we can see that the Ai
mode of crystal form I of poly(vinylidene fluoride). and A2 modes of form I correspond to the A modes of form
III, and the Bi and B2 modes of form I to the B modes of
form III. Apart from infrared activity of the A2 species, to
ed as due to the optically active vibrational modes of the which the CH2 and CF2 twisting modes belong, similar vi-
regular crystal of form I. However, there are many observed brational modes occur in both crystal forms. There are,
additional weak bands in the spectra as found in Figure 2. however, distinct differences in the observed' spectra be-
Moreover, on cooling to liquid nitrogen temperature the in- tween two forms.
frared band due to the librational lattice mode shifts to the In order to interpret the spectral differences between
higher frequency side and splits into at least two compo- forms I and III, the normal frequencies of form III were cal-
nents with the peaks at 86 and 76 (shoulder) cm-1 (Figure culated to be compared with those of form I. The calcula-
7) Very small amounts of splittings are also observed for
. tion was made on a monoclinic lattice with the same size of
the infrared bands in the higher frequency region (Figure c projection {a' = a sin fi = 8.58 A, b = 4.91 A) as form I,
8) These facts are in conflict with the regular Cm2m crys-
. but with the angle of fi = 97° different from the ortho-
tal structure, since the spectroscopic unit cell contains only rhombic lattice (j3 = 90°) of form I. The molecules in the
one chain. Therefore, we may suppose some kind of disor- lattice were assumed to have the same bond lengths, va-
dered structure as the origin of the observed band split- lence angles, torsional angles (planar zigzag), and fiber pe-
tings and of appearance of additional weak bands. This riod (2.56 A) as those in form I. Although this crystal lat-
problem will be discussed in detail in a later section. tice differs slightly from that proposed by the previous X-
Vol. 8, No. 2, March-April 1975 Molecular Vibrations of Poly(vinylidene fluoride) 163

Table V
Observed and Calculated Frequencies and Potential Energy Distribution (PED)
of Crystal Forms I and III of Poly(vinylidene fluoride)
Form I Form III

Frequencies, cm-1 Frequencies, cm-1

Obsd Obsd
Spe- -

Spe- -

cies Infrared Raman Calcd cies Infrared Raman Calcd PED (%)c

A1 2980 (i)a vw6 2984 s 2980 A 2980 (1) VW 2984 s 2987 i's(CH2)'i (99)
1428 (i) w 1436 s 1423 1427 (i) w 1434 vs 1430 6(CH2) (81)
1273 (i) s 1283 m 1286 1269 (1) w 1270 m 1287 ^s(CF2) (40) us(CC) (22) +
-

fi(CCC) (15)
884 (1) s 886 s 879 882 (i) s 884 s 880 1's(CF2) (54) + US(CC) (18)
508 (1) s 514 m 508 510 (1) s 516 m 510 5(CF2) (98)
A2 Inactive 980 w 983 950 (-) vw 942 w 982 t(CH2) (100)
268 m 262 270 (-) vw 268 m 262 t(CF2) (100)
Bi 1398 (11) s 1400 w 1396 B 1400 (11) s 1397 w 1396 w(CH2) (58) i>a(CC) (35)
-

1071 (11) m 1078 m 1065 1073 (H) w 1078 m 1065 i'a(CC) (54) -w(CF2) (22) +
w(CH2) (24)
468 (H) s 475 w 470 483 (II) vs 487 m 473 w(CF2) (92)
b2 3022 (i) vw 3020 vs 3029 3020 (1) vw 3020 vs 3036 ya(CH2) (99)
1176 (i) s 1175 w 1182 1175 (1) s 1178 m 1182 ^a(CF2) (64) r(CF2) (21) +
-

r(CH2) (15)
840 (i) s 845 vs 825 838 (i) m 843 vs 825 r(CH2) (60) i^a(CF2) (31)
—

442 (1) w 445 w 443 440 (i) w 437 m 458 r (CF2) (74) + r (CH2) (26)
70 (i) s 77 w 72 84 (-) s 106 Librational lattice mode
a
Infrared dichroism: _L, electric vector perpendicular to the orientation direction; electric vector parallel to the orientation direction.
,
6
Relative intensity; vs, very strong; s, strong; m, medium; w, weak; vw, very weak. c The values obtained by the normal coordinate treat-
ment for a single chain. d Symmetry coordinates; vs, symmetric stretching; i/a, antisymmetric stretching; 5, bending; w, wagging; t, twisting;
r, rocking. The sign + or denotes the phase relation among the symmetry coordinates.
-

ray analysis, it is more convenient for the present purpose heights along the chain axis of the two chains in the mono-
to investigate the spectral changes originated from the dif- clinic unit cell of form III differ from each other by 0.53 A,
ferences in packing of the molecular chains. The intramo- while they are on the same height in the orthorhombic cell
lecular forces were the same as those of form I, and the in- of form I. In form III the shortest H *F distance (£2 and
• •

termolecular force constants which vary with the interato- £4) of 2.43 A (corresponding to the largest intermolecular
mic distances were deduced by using the same potential force constant of 0.0657 mdyn/ A) is 0.21 A shorter than
function as used for form I. The calculated frequencies of the corresponding H -F distance in form I. The force con-
• •

form III are given in Table V. stant due to the shortest H F distance in form I (£1 £4)
• • • —

The librational lattice mode of form III appears as an in- is 0.0163 mdyn/A, quite a bit smaller than in form III. The
frared absorption having a peak at 84 cm-1, about 14 cm-1 number of the shortest atomic pairs in form I is, however,
higher than that in form I. The calculated normal frequen- twice as much as in form III because of the mirror symme-
cy (106 cm-1) of the mode is consistent with the observed try perpendicular to the c axis in the orthorhombic cell.
tendency. The CF2 bending 5(CF2), wagging w(CF2), and Therefore, the resultant intermolecular forces in the two
rocking r(CF2) modes appear around 500 cm-1 in the in- crystal forms are not so much different from each other
frared spectrum. In this region distinct spectral differences (see Table III).
are observed between forms I and III as shown in Figure 2. Thus, the differences in vibrational spectrum between
The bands due to the 5(CF2) and w(CF2) modes in form III forms I and III are interpreted fairly well by the crystal
appear at frequencies higher than those in form I. The cal- structures proposed previously by means of X-ray analysis.
culated frequencies of these modes are consistent with the Therefore, form III should be regarded as the third crystal
observed tendency as shown in Table V. The perpendicular phase independent of form I.
band at 442 cm-1 in form I is assigned to the r(CF2) mode. The profiles of the infrared absorption curve around
The corresponding band in form III is rather obscure. The 1250 cm-1 and of the Raman scattering curve around 810
diffuse absorption with two peaks at 440 and 431 cm-1 in cm-1 show a remarkable difference between forms I and
form III is possibly assigned to the r(CF2) mode. We have, III. The corresponding peaks or shoulders appear at similar
however, some doubt about the assignment because the cal- frequencies, but the relative intensities, especially those of
culated frequency of the mode is higher in form III than in the infrared bands at 1273 and 1230 cm-1 and of the
form I, in contrast to the observed result. As another possi- Raman band at 810 cm-1, are quite different from each
bility, the absorption may correspond to a peak of the fre- other in the two crystal forms. In form III the 1230-cm-1
quency distribution function which will be dealt with in the band is stronger than the 1273-cm-1 band which is as-
next section. signed to the Ai fundamental in form I. It may be possible
It should be noticeable that form III gives higher fre- to assign the former to the A fundamental of form III in-
quency for the librational lattice mode as well as the CF2 stead of the latter. However, such a big frequency differ-
deformations as compared with form I, reflecting stronger ence for the same molecular mode in the two crystal forms
intermolecular forces in form III than in form I. The cannot be reproduced by the present calculation. As will be
 164 Tadokoro, et al. Macromolecules

IOO aooi

2900
Form I

Figure 9. Infrared spectra of molten sample (-), compared

with those of form I (— —) and form III (- -) of poly(vinylidene
- -

fluoride).

discussed later, it seems that vibrations of the noncrystal-

line region play a great role in the spectra of these regions.
At liquid nitrogen temperature the absorption due to the
librational lattice mode of form III shows a peak at 89 cm-1
with distinct shoulders at 98 and 68 cm-1 (Figure 7). The
absorption bands in higher frequency regions show small
amounts of splitting at low temperature as in the case of
form I. Moreover, many weak infrared and Raman bands
appear throughout the whole frequency range of the spec-
tra in addition to the strong bands due to the optically ac- Figure 10. Dispersion relations of poly(vinylidene fluoride) crys-
tive fundamentals. The origins of these bands will be dis- tals: (left) form I, (-) in-plane modes, (- -) out-of-plane
-

cussed in the next section. modes; (right) form III.

Frequency Distribution Function and Disordered point group Cs, except for the modes at the point of (0, 0, 0)
Structure in Crystal Forms I and III (the T point) having the factor group symmetry of C2v.
As mentioned in the preceding two sections the infrared Therefore,, the branches are divided into two kinds of
and Raman spectra of forms I and III have many bands mode: the in-plane and out-of-plane modes as represented
which are not assigned to the optically active fundamen- by the solid and broken lines, respectively, in the figure. In
tals. Most of them are crystalline bands since they disap- the case of form III the (0, 0, oc) branches belong to Ci
pear in molten sample (Figure 9), suggesting disordered symmetry and therefore every branch interacts with others.
structures present in the crystalline region of these two The frequency distribution functions g{v) of forms I and
forms. III were constructed by measuring the lengths of the line
In a disordered crystal lattice without translational sym- segments contained in each frequency range divided by the
metry among the unit cells, the selection rules of the regu- step height of 5 cm-1 in the dispersion curves. The differ-
lar lattice are broken down and, therefore, all the vibra- ence in crystal structure between forms I and III is reflect-
tional modes with any value of the wavenumber vector k ed on clear difference in the dispersion relations for the
contribute, in principle, to the vibrational spectra. In gen- acoustic branches as well as the low-frequency optical
eral, the defects involved in the crystal lattice give rise to branches. The frequency distribution functions of forms I
some changes in the vibrational modes of the regular lat- and III are compared with each other in Figure 11. Here
tice. When the effect of the disordered structure on the vi- the infrared absorption curves are described for compari-
brational modes is not so serious, we may compare the ob- son. The single peak at 400 cm-1 in g{v) of form I splits into
served spectra of a disordered lattice with the frequency two peaks at 400 and 420 cm-1 in form III. The latter may
distribution function computed for the corresponding regu- correspond to the weak absorptions around 430 cm-1 as
lar lattice, except for the so-called localized modes in which stated in the preceding section.
the molecular motions are localized in a certain disordered In Figure 12 the frequency distribution function of form
domain. I is compared with the observed infrared spectrum. The
The normal frequencies of the modes in the first Bril- positions of the Raman lines are also indicated at the top of
louin zone were calculated at the interval of ir/5 for 5a and the figure. It should be noted here that the height of the
8 and tt/20 for 8C, and the dispersion relations with respect
b peaks in g(v) should not necessarily be related to the in-
to <5C were drawn for each combination of (8a, 8b). Here, Sa, frared or Raman intensity, and the peaks indicate only the
8b, and 8C denote the phase difference along the a, b, and c positions where the normal frequencies are concentrated.
axis, respectively. The dispersion curves for (0, 0, 8C) are The broken lines indicate the frequencies of the optically
shown in Figure 10. In the case of form I the (0, 0, 8C) active modes with k = 0, and they correspond well to the
modes have the space group symmetry isomorphous to the strong absorptions (or to the strong Raman lines for the A2
Vol. 8, No. 2, March-April 1975 Molecular Vibrations of Poly(vinylidene fluoride) 165

Raman

( cm-1)

Po1y(vinylidene fluoride) Form I

(cm-1)

Figure 12. Frequency distribution function of crystal form I of

poly(vinylidene fluoride). The solid curves represent the observed
infrared absorption and the vertical lines at the top denote the po-
sitions of the Raman lines.

band at 489 cm-1 in form I which increases the intensity in

the molten state (200°) may belong to this category (Figure
9). In fact, there appears a strong band at 489 cm-1 in the
spectrum of form II including the gauche form in the mole-
cule. The 600-cm_1 band may be due to the noncrystalline
part because it appears in the infrared spectra of the three
crystal forms as well as in the melt, and there are no peaks
in g(v) corresponding to the band. In the infrared spectrum
Figure 11. Frequency distribution functions in the far-infrared re- of the molten sample there is a strong and broad absorp-
gion of poly(vinylidene fluoride) crystals: (top) form I, (bottom) tion around 1230 cm-1. In partially crystalline samples this
form III. The solid lines represent the observed infrared absorp- amorphous band overlaps the crystalline bands in this re-
tion curves.
gion and changes the spectral feature depending on the de-
gree of crystallinity of the sample. The spectral difference
modes marked with an asterisk). It is a characteristic of in this region between forms I and III may be due partly to
g(v) that some of the peaks of g(v) appear around the posi- the difference in fine structure between the crystal phases.
tions of the k = 0 modes. The other peaks of g(v) are asso- Another kind of disordered structure in PVDF concerns
ciated with the weak bands or shoulders of the infrared the head-to-head linkages. From nmr studies the sample of
spectrum as shown in Figure 12. PVDF used here contains about 10% head-to-head linkages
Thus, most of the weak absorptions, which are not as- (CH2CF2CF2CH2) immediately followed by tail-to-tail
signed to the optically active modes of the regular lattice, linkages (CF2CH2CH2CF2)
are attributed to some kind of disorder involved in the
ch2cf2ch2cf2cf2ch2ch2cf2ch2cf2
crystal lattices. First we are concerned with the disorder in
the molecular structure. From the dispersion relations In order to investigate the vibrational modes associated
(Figure 10) we can recognize that most of the peaks of g(v) with this chemical structure, vibrational analysis was made
corresponding to the weak absorptions appear at the posi- for the alternating copolymer of ethylene and tetrafluoro-
tions close to the molecular modes with = 7r. These mo- ethylene as a typical model compound consisting of this
lecular modes are of course inactive in the vibrational spec- chemical structure. The polarized infrared and the Raman
tra for the fully extended zigzag chain. They become active spectra of the copolymer are reproduced in Figure 13.
if the molecular chain twists alternately from the planar From the fiber period of 5.08 A the molecule is consid-
structure. Therefore, the appearance of these modes in the ered to assume planar zigzag conformation in the crystal-
spectra may be related to the slightly deflected structure of line region. The normal modes of the molecule can be treat-
the chains proposed by the previous X-ray work.2 ed with the factor group isomorphous to the point group
In addition to the disorder in molecular structure, some C2h- The result of the factor group analysis is given in
disordered packing of the chains in the crystal lattice may Table VI. In the normal modes calculation the following
be supposed from the good correspondence between the in- molecular parameters are assumed: C-H, 1.09 A; C-F, 1.34
frared absorption profile and the frequency distribution A; C-C, 1.54 A; all the valence angles, 109°28'. The VFF
function in the region of lattice vibration (Figure 12). The force constants are listed in Table VII. The calculated nor-
splittings found for some infrared bands at low tempera- mal frequencies are compared with the observed data in
ture are also ascribed to the same origin. Table VIII.
There are absorptions which are associated with neither The strong infrared absorptions at 1453 (±), 1323 (||),
the optically active modes nor the peaks of the frequency and 666 (||) cm-1 of the copolymer seem to be characteris-
distribution function. Some of them are due to the disor- tic of the head-to-head or tail-to-tail structure, because
ders in molecular conformation, for example, the gauche around these frequencies there are no optically active fun-
form involved in the noncrystalline phase. The infrared damentals of the PVDF molecules of both TT (forms I and
166 Tadokoro, et al. Macromolecules

Table VI Table VII

Number of the Normal Modes and Selection Rules for Intramolecular Valence Force Constants of the
a Planar Zigzag Molecule of the Alternating Copolymer Alternating Copolymer of Ethylene and
of Ethylene and Tetrafluoroethylene with C2h Symmetry Tetrafluoroethylene
Molec- Selection rules Force Coordinates Common
Spe- ular Ingenuine No. constants involved atoms Values0
cies modes vibrations0 Infrared Raman
1 Ad CH 4.833
Ae 10 Forbidden Active 2 ar CC 3.963
Be 7 Rc Forbidden Active 3 ab1 CC, CF C 0.448
Au 7 Ta Active (l)6 Forbidden 4 Fr CC, CC C 0.148
Bu 8 Tc, Tb Active (i, II) Forbidden 5 Fr, CC, CCH CC 0.233
a
Rc, pure rotation around the fiber axis; Ta, pure translation
6 Fr w CC, CCC CC 0.492
along the direction perpendicular to the molecular plane; Tb, pure
7 Fr® CC, CCF CC 0.575
translation in the molecular plane along the direction perpendicu- 8 Fd CH, CH c 0.076
lar to the fiber axis; Tc, pure translation along the fiber axis. 9 A, CF 6.597
d
1 and in parentheses denote infrared polarization for a uni-
|l 10 F„ CF, CF c 0.683
axially oriented specimen. CF, CFF CF 0.671
11 Fit
12 A, CCH 0.765
13 F, CCH,CCH CC 0.079
14 F/ CCH, CCH CH 0.230
15 a. CHH 0.443
16 Hu CCC 0.942
17 fu CCC, CCC(t) CC 0.166
18 A® CCF 1.381
19 At CFF 1.225
20 T cccc 0.149
21 Ft* CF, CCF CF 0.554
22 F® CCF, CCF CC 0.259
23 F®' CCF, CCF CF 0.037
24 w CCC, CCH(g) CC 0.146
25 fuig CCC, CCF(g) CC 0.012
26 fr*1 CCH, CCF(t) CC 0.046
27 fr*' CCH, CCF(g) CC 0.403
28 fr CCH, CCH(t) CC -0.071
29 // CCH, CCH(g) CC 0.018
30 /®‘ CCF, CCF(t) CC 0.095
31 /®8 CCF, CCF(g) CC -0.054
32 Fir CCH, CH CH 0.041
33 FRy CCH, CC CC 0.233
34 Fd6 CHH, CH CH -0.132
“
The stretch constants have units of mdyn/A; the stretch-bend
interactions have units of mdyn/rad; and the bending constants
have units of (mdyn A)/rad2.

in planar zigzag structure with the homopolymer parts, we

examined the vibrational modes of these units by calculat-
ing the normal vibrations of such molecules as
[~(CH2CF2)mCF2CH2-]
Figure Infrared (upper) and Raman (lower) spectra of the al-
13. where m varies from two to four. Since the above three
ternating copolymer of ethylene and tetrafluoroethylene in the re- bands are found to be due to the CH2 bending, the CH2
gion (top) from 4000 to 400 cm-1, and (bottom) below 400 cm-1. wagging, and the CF2 wagging modes, respectively, from
For infrared absorption: (-) electric vector _L orientation direc-
the vibrational analysis of the alternating copolymer (m =
tion; (- -) electric vector orientation direction.
-
[I

1) (Table VIII), we focused our attentions on these three

Ill) and TGTG (form II) conformations. In the infrared modes. For the above three molecular models the vibra-
spectra of the three crystal forms and the molten sample of tional frequencies and the L vectors are calculated by using
PVDF there appear weak absorptions around the three the same molecular parameters and force constants as
frequencies mentioned above; 1450, 1320-1340, and 678 those of the alternating copolymer. Among these normal
cm-1. They may be due to the head-to-head linkages in- modes the vibrations are picked up which contain consider-
volved in the sample of PVDF. It is noticeable that these able' amounts of the contribution from the head-to-head or
bands show rather clear dichroism and become stronger tail-to-tail chemical groups. In Figure 14 are summarized
and sharper by annealing the sample. This suggests that the results of the normal mode calculations along with the
the head-to-head units in PVDF may be accommodated in results of the alternating copolymer. Here are given the po-
the crystalline region, consistent with the conclusion pro- tential energy distributions (relative values) among the
posed by Doll and Lando16 by means of thermal analysis CH2 (represented with O) or CF2 (•) groups along the
and X-ray diffraction. chain, the schematical representations (in terms of the L-
Then, assuming that the head-to-head units cocrystallize vector elements) of the characteristic vibrational modes,
Vol. 8, No. 2, March-April 1975 Molecular Vibrations of Poly(vinylidene fluoride) 167

Table VIII
Observed and Calculated Frequencies and Potential Energy Distribution (PED) of the
Alternating Copolymer of Ethylene and Tetrafluoroethylene
Frequencies, cm'1

Obsd

Species > Infrared Raman Calcd PED (%)

Inactive 2979 vsa 2969 «',(CH2)e (99)

1453 s 1441 5 (CH2) (84)
1330 m 1333 y'(CC) (15) w(CH2) (45)
1163 w 1189 ^s(CF2) (47) + 6(CCC) (19)
1050 m 1028 i'(CC) (37) + w(CF2) (28) +w(CH2.) (17)
952 m 966 f'(CC) (62) w(CH2) (21)-

845 s 836 ys(CF2) (25) + ^S(CC) (40)-6'(CCC) (32)

610 m 590 v{CC) (16) + 5(CF2) (32) 5(CCC) (18) -

369 m 378 5(CF2) (72)

240 vw 219 6(CCC) (30)-S'(CCC) (34) + w(CF2) (29)
Inactive 3005 s 2989 fa(CH2) (99)
1310 m 1321 fa(CF2) (65) r(CF2) (28) -

1070 sh 1066 r (CH2) (79)

943 t(CH2) (85) + r(CH2) (15)
530 m 526 fa(CF,) (18) + r(CF2) (69)
337 m 321 t(CF2) (62) r(CF2) (19)
-

145 w 135 ~

(87)
1

2956 (If VW Inactive 2985 vjCH2) (100)

1245 (i) s 1245 ya(CF2) (86)
1045 (1) s 1038 t(CH2) (98)
890 (i) w 884 r(CH2) (92)
410 (i) vw 434 t(CF2) (39) r(CF2) (36)
-

240 (i) m 230 t(CF2) (53) + r(CF2) (41)

98 (i) s 91 -,(34) 73(34) + r(CF2) (24)
-

2975 (11) vw Inactive 2976 ^s(CH2) (99)

1453 (1) s 1466 5(CH2) (94)
1323 (11) s 1324 w(CH2) (79)
1169 (i) s 1148 ^(CF2) (72)
976 (11) s 970 !A,(CC) (48) w(CF2) (29) + w(CH2) (18)
-

666 (II) s 682 i/a(CC) (28) + w(CF2) (40)

508 (11) s 510 5 (CF2) (87)
316 (11) vs 306 6(CCC) (34) + 6'(CCC) (33) + w(CF2) (25)
r. vs, very strong; s, strong; m, medium; w, weak; vw, very weak; sh, shoulder.b Infrared dichroism: X,
perpendicular to the orientation direction; P, electric vector parallel to the orientation direction. c Symmetry coordinates: vs, symmetric
stretching; va, antisymmetric stretching; 6, bending, w, wagging; t, twisting; r, rocking; pfCC), stretching of the C(F)-C(F) bond; k'(CC),
stretching of the C(H)-C(H) bond; vs(CC), symmetric stretching of two C(H)-C(F) bonds; ra(CC), antisymmetric stretching of two C(H)-
C(F) bonds; 6 (CCC), skeletal bending of C(F)-C(H)-C(F); 5'(CCC), skeletal bending of C(H)-C(F)-C(H); n, symmetric combination of
two torsional modes of C(F)-C(F)-C(H)-C(H); r2, torsional mode of C(F)-C(H)-C(H)-C(F); 73, torsional mode of C(H)-C(F)-C-(F)-
C(H). The sign + or denotes the phase relation among the symmetry coordinates.
-

and their vibrational frequencies which vary more or less

depending on the head-to-head or tail-to-tail contents.
(a) The CH2 bending mode of the tail-to-tail, CH2CH2, Table IX
units. The atomic displacements of the mode are almost lo- Number of the Normal Modes and Selection Rules of
calized on the CH2CH2 groups and the frequency (1473 Poly(vinylidene fluoride) Form II with Space Group
cm-1) does not depend on the value of m, exerting little P2i/c-C2*s
coupling with other modes. Therefore, this is clearly a lo- Molec- Selection rules
calized mode characteristic of the tail-to-tail units. Since
Spe- ular Lattice -

the frequency lies within the band area of the 5(CH2) dis-
cies modes modes Infrared Raman
persion curve of PVDF homopolymer (form I) (see Figure
10), this mode belongs to the so-called “in-band localized 16 “
Forbidden Active
mode.”17 Ag L(Ta), L(TC)
Be 16 L(T„), L(RC0)6 Forbidden Active
(b) The CH2 wagging mode of the tail-to-tail units. This Active (1)“ Forbidden
is also an in-band localized mode due to the CH2CH2 Au 16 Tt,c L(R/)
Bu 16 Ta, Tc Active (1, ll) Forbidden
groups with the frequency in the range of 1320-1335 cm-1
depending on the amount of the tail-to-tail units involved.
“
L(T a), L(Tb), L(TC): translational lattice modes. 6L(RC0),
The skeletal stretchings couple with this mode. L(RCT): librational lattice modes around the fiber axis with the
phase difference of 0 and x between the two chains in the unit cell,
(c) The CF2 wagging mode of the head-to-head, CF2CF2, respectively. c Ta, Tt>, Tc: pure translation along the respective
units. The behavior of the mode is rather complicated as crystal axis. d X and in parentheses denote infrared polariza-
compared with the above two cases. For a small value of m tion for a uniaxially oriented specimen.
168 Tadokoro, et al. Macromolecules

Table X
Observed and Calculated Frequencies and Potential Energy Distribution (PED)
of Poly(vinylidene fluoride) Form II

Frequencies, cm'1

Obsd

Species Infrared Raman Calcd PED (%)“

B„ 3017 (i)1 wc 3042

2990 s 3042 ya(CH2)a (99)
A8
Bu 2977 (1) w 2975
2970 sh 2975 ys(CH2) (99)
Ag
Bu 1420 (1) m 1456
1430 s 1455 6(CH2) (54) -w(CH2) (31)
Ag
Bu 1399 (II) s 1392
1406 vw 1392 5(CH2) (29) + w(CH2) (29) -

ya(CC) (24)
Ag
B„ 1290 (II) w 1278
Ag 1296 m 1279 ya(CF2) (53) -

r(CF2) (15)
Bu 1149 (II) m 1159
ya(CC) (30) y8(CF2) (24)
-

Ae 1150 w 1158
B„ 1056 (II) m 1083
1058 m 1083 y8(CF2) (35) + w(CH2) (17)
Ag
B„ 976 (i) w 975
976 w 973 t(CH2) (82)
Ag
Bu 873 (i) s 877
876 s 880 y8(CC) (38) + 5(CCC) (22)
Ag
Bu 853 (1) w 835
841 m 834 r(CH2) (48)
Ag
B„ 612 (H) s 621
Ae 612 s 617 5(CF2) (24) -6'(CCC) (19)
Bu 489 (II) s 509
488 m 513 6(CF2) (48) + w(CF2) (25)
Ag
Bu 410 (H) vw 423
r(CF2) (53) + r(CH2) (19)
Ag 414 s 434
Bu 288 (II) s 309
t(CFa) (54) + w(CF2) (18)
Ag 287 s 304
B„ 208 (H) m 247
206 w 231 t(CF2) (38) -

5 (CCC) (19) + 5'(CCC) (18)

Ag
Bu 100 (1) m 94
75 w 77
ra(28) + rs(23) + 6(CCC) (20) + r(CF2) (18)
Ag
Ag 52 w 59 L(Ta)
Ag 29 w 11 L(TC)
A„ 3017 (1) w 3040
3030 s 3040 ya(CH2) (100)
Bg
Au 2977 (1) w 2977
2980 sh 2977 y8(CH2) (99)
Bg
Au 1477
1442 sh 1477 5(CH2) (49) -

w(CH2) (28)
Bg
Au 1383 (1) m 1359
1384 vw 1360 5(CH2) (39) + w(CH2) (22)
Bg
Au 1209 (1) s 1241
1200 m 1241 ya(CF2) (41) + w(CH2) (26)
Bs
Au 1182 (1) s 1199
1190 sh 1198 y8(CF2) (39) + t(CH2) (16)
Bg
Au 1067 (i) m 1069
1064 sh 1069 i'.(CC) (65)
Bg
A„ 934
940 vw 935 t(CH2) (60) -

ya(CF2) (21)
Bg
A„ 878 (1) s 918
885 sh 917 ya(CC) (60) + y8(CF2) (20)
Bg
A„ 795 (i) w 818
800 vs 815 r(CH2) (78)
Bg
A„ 766 (i) m 774
Bg 766 w 776 5(CF2) (33) + 5(CCC) (21)
A„ 531 (1) w '529
Vol. 8, No. 2, March-April 1975 Molecular Vibrations of Poly(vinylidene fluoride) 169

Table X (Continued)

Frequencies, cm"1

Obsd

Species Infrared Raman Calcd PED (%)“

Au 389 (!) vw 407

398 r(CFj) (52)
Bg
Au 355 (!) s 372
+
357 vw 371 t(CF2) (63) r(CF2) (16)
Be
Au 215 (!) s 283
216 283
5(CCC) (33) + 5'(CCC) (28) + r(CF2) (15)
Bg sh
Au 176 (!) w 120
176 Ta(71)
Be w 130
Au 53 (!) w 51 L(Rcr)
Bg 99 w 84 L(T,)
Bg 62 L(Rt,°)
The values calculated by the normal coordinate treatment for a single chain of TGTG conformation with Cs symmetry. 6 Infrared di-
“

chroism: j_, electric vector perpendicular to the orientation direction; !|, electric vector parallel to the orientation direction. c Relative in-
tensity: vs, very strong; s, strong; m, medium; w, weak; vw, very weak; sh, shoulder. d Symmetry coordinates: vs, symmetric stretching; V&,
antisymmetric stretching; 5, bending; w, wagging; t, twisting; r, rocking; 5(CCC), skeletal bending of C(F)-C(H)-C(F); d'(CCC), skeletal
bending of C(H)-C(F)-C(H); ts, symmetric combination of two torsional modes of C(H)-C(F)-C(H)-C(F); ts, antisymmetric combination
of two torsional modes of C(H)-C(F)-C(H)-C(F). The sign + or -
denotes the phase relation among the symmetry coordinates.

3000 -.

290C -

Figure 14. The calculated normal vibrations of the head-to-head

ortail-to-tail units: (a) CH2 bending, (b) CH2 wagging, and (c) CF2
wagging modes. From left to right, PED, L vectors, and frequency
changes of four molecular models of [-(CH2CF2)mCF2CH2-] [m =
1 (alternating copolyer, ACP), 2, 3, and 4], • and O represent the

CF2 and CH2 groups, respectively. In PED: (-) m = 2; (• •) m

=
3; (—) m= 4; (---) ACP.

this mode includes appreciable contribution from the wag- 400-

ging modes of all the CF2 groups in the molecule. The fre-
quency of the mode is strongly dependent upon the amount
of the head-to-head content. As m increases the atomic dis-
placements tend to concentrate on the CF2CF2 groups and
the frequency goes asymptotically to about 670 cm-1. The
dispersion curve associated with the w(CF2) mode of the
CF2CF2 groups of the alternating copolymer (Figure 15) is 0s 45° 90* 135° 180°
limited within the frequency range of 660-740 cm-1 as in- S
dicated by the hatched area in Figure 14c. The frequency of
Figure 15. Dispersion relations for a single chain of the alternat-
670 cm-1 is, therefore, recognized as the characteristic fre-
ing copolymer of ethylene and tetrafluoroethylene: (-) in-plane
quency of the head-to-head units, and the infrared band at modes; (—) out-of-plane modes.
678 cm-1 observed in the commercial PVDF samples is
thought to be a “pseudo-localized band”18 which occurs for From the above discussions the infrared bands at 1450,
the case of a small number of defects in a low density fre- 1320-1340, and 678 cm-1 of the commercial PVDF samples
quency region of the perfect homopolymer (see Figure 12). may be assigned to the localized modes associated with the
This w(CF2) mode highly couples with the skeletal stretch- head-to-head or tail-to-tail linkages involved in the sam-
ing modes. ples.
170 Tadokoro, et al. Macromolecules

Figure 16 Low-frequency Raman spectra of crystal form II of

polyfvinylidene fluoride) measured at room (-) and liquid-ni-
trogen (- -) temperature.
-

Structure and Vibrations of Crystal Form II

If the space group of form II is P2i/c-C255 with two anti-
parallel chains in the unit cell as proposed by the authors,2 Figure 17. Schematical representation of lattice modes of crystal
the number of the optically active normal modes and the form II of poly(vinylidene fluoride) with the observed or calculated
selection rules are deduced as given in Table IX. We can (in parentheses) frequencies.
expect one librational lattice mode (Au species) as a per-
pendicular band in the infrared spectrum and three trans- PI proposed by Doll and Lando.
lational (2Ag + Bg) and one librational (Bg) lattice modes Farmer, et al.,8 ascribed the difference in the structures
in the Raman spectrum. Because two chains in the unit cell proposed by Doll and Lando and by the authors to the
correlate with each other by the operation of the center of amount of head-to-head defects incorporated in the poly-
symmetry, the rule of mutual exclusion should be realized mer chains. But the samples of Kynar 201 (amount of
for the lattice modes. The result of the normal coordinate head-to-head defects ca. 11%) and KF 1000 (supplied by
treatment of form II is summarized in Table X. Kureha Chemical Industry Co., Ltd., ca. 6%) gave quite the
In the infrared spectrum a sharp perpendicular band ap- same infrared spectra in our study.
pears at 53 cm-1, which shifts to 60 cm-1 at liquid-nitrogen Thus we have no spectroscopic informations which are in
temperature. Quite recently Rabolt and Johnson19 have conflict with the P2i/c space group of form II and, there-
found independently the same absorption band. This band fore, speculate the presence of centrosymmetric lattice, at
is assigned to the Au librational mode, the corresponding least as one of the local structures of form II. This does not
calculated frequency being 51 cm-1. In the Raman spec- mean, however, the unique adequacy of the space group. As
trum we have observed three distinct Raman lines in the a general feature of the vibrational spectra of polymeric
low-frequency region, at 99, 52, and 29 cm-1 (Figure 16). substances, the observed bands are broad and show rather
They are assigned to the translational lattice modes along poor polarization compared with the case of single crystals
the b, a, and c axis, respectively. The remaining librational of nonpolymeric substances. A lot of additional spectral
mode with the calculated frequency of 62 cm-1 has not yet bands, which may be due to the head-to-head linkages or to
been observed in the Raman spectrum. The lattice modes the noncrystalline region, bring further ambiguities. It is
are described with the Lx vectors as shown in Figure 17. By therefore very difficult to deduce a unique conclusion
the observed frequency data alone, however, we cannot about the packing structures of the polymer crystals from
prove the rule of mutual exclusion for the lattice modes. the spectral data alone.
For the intramolecular vibrations each molecular mode,
belonging to the A' or A" species of the site symmetry of Cs, References and Notes
splits into two modes in the crystal, one being infrared ac- (1) R. Hasegawa, M. Kobayashi, and H. Tadokoro, Polym. J., 3, 591
tive and the other Raman active. The frequency gaps due (1972).
to the intermolecular interactions, as expected from the re- (2) R. Hasegawa, Y. Takahashi, Y. Chatani, and H. Tadokoro, Polym. J.,
3, 600 (1972).
sults of the calculation, may be too small to be detectable (3) J. B. Lando, H. G. Olf, and A. Peterlin, J. Polym. Sci., Part A-l, A, 941
by comparing infrared and Raman spectra. In fact they are (1966) .

within experimental errors in frequency measurement as (4) G. Natta, G. Allegra, I. W. Bassi, D. Sianesi, G. Caporiccio, and E.
Torti, J. Polym. Sci., Part A, 3, 4263 (1965).
shown in Figure 4. The observed infrared and Raman (5) G. Cortili and G. Zerbi, Spectrochim. Acta, Part A, 23, 285, 2216
frequencies of the molecular modes are consistent fairly (1967) .

well with the results of the present calculation based upon (6) W. W. Doll and J. B. Lando, J. Macromol. Sci., Phys., 4,897 (1970).
(7) W. W. Doll and J. B. Lando, J. Macromol. Sci., Phys,, 4, 309 (1970).
the centrosymmetric P2i/c crystal structure. (8) B. L. Farmer, A. J. Hopfinger, and J. B. Lando, J. Appl. Phys., 43, 4293
Moreover, we cannot find a detectable amount of band, (1972).
splitting in the infrared and Raman spectra measured at (9) S. Enomoto, Y. Kawai, and M. Sugita, J. Polym. Sci., Part A-2, 6, 861
(1968)
liquid-nitrogen temperature, which is, in principle, expect-
.

(10) F. J. Boerio and J. L. Koenig, J. Polym. Sci., Part A-2, 7, 1489 (1969);
ed if the crystal lattice belongs to the space group P2j or 9, 1517 (1971).
Vol. 8, No. 2, March-April 1975 Nmr Relaxation and the Microbrownian Motion in Polymers 171

(11) T. Kawauchi and Y. Ishida, private communication. 153 (1972).

(12) R. E. Naylor and S. W. Lasoski, J. Polym. Sci., 44,1 (1960). (16) W. W. Doll and J. B. Lando, J. Macromol. Sci., Phys., 2,205 (1968).
(13) C. W. Wilson and E. R. Santee, J. Polym. Sci., Part A, 1,1305 (1963). (17) G. Zerbi, Pure Appl. Chem., 26,499 (1971).
(14) F. C. Wilson and H. W. Starkweather, Jr., J. Polym. Sci., Polym. Phys. (18) R. C. Newman, “Infra-red Studies of Crystal Defects,” Taylor and
Ed., 11,919(1973). Francis, London, 1973.
(15) M. Modena, C. Garbuglio, and M. Ragazzini, J. Polym. Sci., Part B, 10, (19) J. F. Rabolt and K. W. Johnson, J. Chem. Phys., 59, 3710 (1973).

Nuclear Magnetic Resonance Relaxation and the Microbrownian

Motion in Polymers. Local and Collective Motions and Their
Viscosity Dependence
G. Hermann and G. Weill*
Centre de Recherches sur les Macromolecules CNRS, Strasbourg, France.
Received July 19, 1974

ABSTRACT: The loss of orientation memory for a vector linked to a polymer chain is expected to present a fast
initial decay corresponding to fast local jumps with a long tail corresponding to diffusive cooperative motions. An
analysis of the nuclear relaxation times T, and T2 in solvents of high viscosity where the extreme narrowing condi-
tion is not fulfilled may help to separate fast and slow processes. Such an analysis is carried out for poly(oxymethy-
lene) in hexafluoro-2-propanol. The results seem to indicate that both slow and fast processes are linearly depen-
dent on the viscosity, a result of importance for the concept of internal viscosity.

The low-frequency, long-wavelength modes of a polymer For a model chain in which elementary jumps are sup-
chain are adequately described by models derived from the posed to be the exchange of orientation of bonds i 1 and —

Gaussian subchain model of Rouse.1 Since in these models i + 1 on a tetrahedral lattice, the complete autocorrelation
the exchange between different subchain conformations function has been calculated13 and found identical with
corresponding to a given end-to-end vector is supposed to that calculated by Hunt and Powles14 for the one-dimen-
be infinitely rapid, they completely neglect the high-fre- sional diffusion of a defect, with a fast initial decay and a
quency part of the spectrum. Dissipative processes related long t-1/2 tail. One can expect this to be a quite general be-
to the motion inside of a subchain can, however, be taken havior in polymer chains, most of the orientation memory
into account by the introduction of a phenomenological being lost in the first local motions, while a complete loss
“internal viscosity” parameter.2 New approaches in the de- requires long cooperative motions of the chain. These are
scription of polymer dynamics, starting from elementary required since energetically highly unfavorable conforma-
local motions, have followed the initial work of Verdier and tions, like g+g_, generally limit the diffusion by the three
Stockmayer on a cubic lattice.3-5 They all give the Rouse bonds mechanism. The relative independence of fast and
spectrum in the low-frequency limit, a consequence of the slow processes finds supports in the calculations of Hel-
diffusive nature of the fluctuations,6 but the high-frequen- fand,15 who consider the motion of a few segments with
cy part is very dependent upon the special features of the Rouse chains at the extremities.
model. The viscosity dependence of the probability of an As part of an effort to characterize from an experimental
elementary jump is of particular interest7 in connection point of view these slow and fast processes we present in
with the corresponding dependence of the internal viscosi- this work an nmr relaxation study on simple polymers in
ty. solution, where special attention has been paid to the infor-
Experimental techniques specially adapted to the study mation which can be derived from differences between T-,
of fast movements, such as the dielectric dispersion of and T2 that is, when the extreme narrowing limit is not
chains with a transverse component of the electric mo- completely reached, from the use of measurements on sev-
ment,8 fluorescence polarization,9 line-shape analysis of the eral nuclei (4H, 2H, and 13C), and from the viscosity depen-
paramagnetic resonance of spin labels,10 and nuclear mag- dence of the relaxation times.
netic resonance,11 have been used with polymer chains.
The response of the chain, in the time or frequency do- I. Nmr Relaxation Times and Autocorrelation
main, is in all cases related to one autocorrelation function Functions
for the rotatory motion of a well defined local molecular In the case under study, the nmr relaxation times are
unit. But in most cases experiments cover only a limited governed by the rotation through the autocorrelation func-
range of time and frequency and the results can be inter- tion of the second spherical harmonic Pzit) = (3 cos2 0(f)
preted assuming a single exponential decay of the autocor- —

l)/2 where 0(f) is the angle of a vector linked to the poly-

relation function, all fast movements compared to the mer segment at time t with its original direction at time 0.
range of time under study being represented by an instan- This vector will be the vector joining two protons, or one
taneous decay of the autocorrelation function from 1 to a proton to the C atom in the case of the dipolar relaxation of
smaller value. This is particularly evident for the polariza- the proton and 13C of a CH2 group, or the axis of the elec-
tion of fluorescence where it comes to assume a smaller tric field gradient in the case of the quadrupolar relaxation
fundamental polarization. But then the variation of the of D.
calculated correlation time with temperature and viscosity The expressions for the spin-lattice T1 and spin-spin T2
will incorporate the approximations made in the choice of relaxation times are given in the three cases by16 (a) dipolar
the autocorrelation function.12 relaxation of two \ identical spins