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J O U R N A L OF A P P L I E D POLYITEK SCIENCE VOL. V, ISSUE NO.

18, PAGES 617-654 (1061)

Viscoelastic Properties of Regenerated Cellulose Sheet

ERICWELLISCII,LEOXMARKER, J. SWEETISG
and ORVILLE
Film Operations of the Packaging Diilision, Olin Mathieson Chemical Corporation. New Hailen, Connecticut

INTRODUCTION elastic modulus of the same films when measured
The durability properties of cellophane are separately.
measured a t the present time by several physical The interpretation of our data in terms of
tests, such as measurement of impact strength, cellulose-softener interaction shows good correla-
flexing under stress, tenacity, elongation, tear, and tion with the work carried out on the dynamic
others, and no correlation between these test data tensile modulus instrument used for measuring
and the structure and interaction of the polymer elastic moduli3 It also agrees well with Nissan's
chains exists. Several studies in our laboratories interpretation of Young's modulus in terms of
have indicated that there is little relation, if any, hydrogen bonding. In addition, a relationship
among the physical tests mentioned, and that was found between the retarded elasticity and the
therefore none of these tests when used separately interaction energy of the added softener molecules.
is indicative of the performance of cellophane in This points to a new interpretation of cellulose-
use. To relate the performance of cellophane to its softener interaction in terms of hydrogen-bond
molecular structure we have attempted to evaluate energies.
the deformation of regenerated cellulose under
stress in terms of a mechanical model and to cor- EXPERIMENTAL
relate the elastic and viscous flow portions of this
model with the interactions between cellulose chains Apparatus and Materials
in the absence and presence of various small
molecules of different types and concentrations. All viscoelastic measurements reported here
I n previous investigations'-2 we have studied the were made on a Model T T B Instron tensile tester
interaction between cellulose and various small using a type C load cell of range 1-50 lb. All
molecules in terms of the relative affinity of cellulosc measurements were made in air-conditioned labora-
and of the softener molecule for water. We have tories a t 75OF. and 35% R.H. To hold the film
obtained some quantitative data relating the inter- specimen, two jaws were used which had facaes 3
action of small molecules to their chemical nature in. wide in the rear, 1 in. wide in the front, and 1.3
and to their hygroscopic properties. in. in height. Thus the film specimens which mere
As a continuation of this investigation we have cut with a 3- X 6-in. template were held across
studied the effect of the added small molecules on a 1-in. center width a t a 3-in. gage length. All
the mechanical properties of cellophane. In par- determinations were made in the dimension trans-
ticular, the behavior of the elastic modulus of verse to the machine direction of maimfacture.
cellophane, impregnated with several small mole- The cellophane samples used in these experiments
cules such as glycerol, ethylene carbonate, ethylene- were prepared on our laboratory impregnator
diamine, and with water only was studied and drier from gel film supplied by the Pisgah Forest
related to the softening p r o c e ~ s . ~ plant. Films were prepared containing a variety
I n the present investigation we have studied the of softeners* a t different softener and moisture
creep of cellophane in the presence of various small content as shown in Table I ; all data are expressed
molecules. Curves relating strain to time were on a dry cellulose basis.
obtained and evaluated in terms of a simple
* We here employ the term softener in a broad reading,
mechanical model. The effect of the added mole- not in the commercial sense. For convenience, we have
cules on the elastic and viscous parameters of the called all added small molecules softeners, without concern
model was determined and compared with the for their commercial or practicable limitations.
648 E. \\'I<LLISCH, L. MARKER, AS 1) 0. J. SWEETING

TABLE I TABLE I1
Prcparation of Film Samples Apparent Young's Modulus a t Various Elonrations and Loads
Concen- Modu-
tration of Instrort 1Sxtc.n- lus,
softener, Moisture, setting, sion, (Ib./in.z)
Film no. Softener y)a c/
10
x
Filni no. Softener % (2 x 10-3
CD-1B Glycerol 20 0 6 8 CII-lB Glycerol 0.33 0 23 625
C 11-4 Glycerol 29 1 7 3 0.66 0 55 578
(311-8 Triethylene glycol 23 9 7 0 1.00 0 89 535
CD-1 1 Ethylenediamine 18 0 6 4 1.30 1 16 495
CD-12 Unsoftened film 0 9 1
CD-41 Glycerol 18 9 8 0 CD-4 Glycerol 0.33 0 23 -463
CD-43 Ethylene glycol 12 7 7 3 0.66 0 51 433
CD-44 Propylene glycol 12 5 7 4 1 .oo 0 71 409
CD-45 1)iethylene glycol 15 0 7 7 1.30 1 01 398
CD-46 1,3-Butanediol 15 4 8 0 CII-8 Triethylene 0. 3 3 0 20 592
CD-47 Ethylene carbonate 15 1 7 0 g1gc01 0.66 0 47 579
CII-48 Unsoftened film 0 9 2 1.00 0 82 521
CI>-52 I >icthanolamine 14 6 !I 6 1.30 1 13 492
* iZftcr coiiditioning at 75°F. and 35% R.H. CII-I I Ethylenedi- 0.33 0 18 748
aniine 0.66 0 45 860
Young's Modulus 1.00 0 80 816
1.30 1 12 723
Young's modiilus of elasticity was deterniincd for
C1)-12 Vnsoftened film 0.33 0 28 1000
the first, fivc softened and unsoftenrd films of
0.66 0 51 952
Table I (CD-1B through CD-12) by simple stress- 1.oo 0 86 888
eloiigation measurements in the transverse direction. 1.33 I 14 843
The Instron macahine was operated a t a crosshead
speed of 1.2 in./min. and a chart sprcd of 20 in./-
min. Film specimens were elongated a t constant corresponding stress were read from thc Instroil,
rate to 0.33, 0.66, 1.00, and l.30yo deformation and the apparent modulus was then calculated by
(preset on the Iiistron). The actual elongation and Hooke's Law for an assumed width of 1 in. and a
constant thickness of 1 mil. Three different
I
10001.-.& specimens of film were measured a t each Instron
setting, from which the average extension and
'..'.. modulus were calculated as shown in Table 11.
I
0
900 - . lcrom the apparent moduli the real elastic moduli
were obtained by plotting apparent moduli against
X
N
elongation and extrapolating to zero elongation as
W 800-
v)
3
-I
3 700- TABLIC 111
0
0
I Young's Llodnlns of Various Softened Films. Extr:lpolnted
I- Values
z
W
a
z
P
Young's inodrilns
a

400 ---\ Film no. Softener
(dynes/
(Ib./in.~) cm.z)
x 1 0 3 x lo-'"
CII-IR Glycerol (20.0'%) 655 4 52
300 (
111
11 1
50 1
1111
100 1
111
I50
C 11-4 (ilycerol (29.1%) 375 3 27
PERCENT ELONGATION CII-8 Triethylene glg col
(23.9%) 610 4 20
Fig. 1 . Apparent Young's modulus as a function of rlonga-
CD-11 E t hglenediamine
tion: ( I ) unsoftcncd fihn containing 9.1% water; (11) filni
(18.0%) 955 6 58
uith 18.0% ethylmediamine; (111) film with 20.0% glyc-
CD-la Unsoftened film
erol; (IV) film with 2:3.9y0 triethglme glycol; ( V ) film
(9.1 H20) 1050 7 24
with 29.1 glycerol.
REGEPJEIIATEI) CELLULOSE SHEET 639

shown in Figure 1. The real moduli are given in
Table 111.
The data show the effect of softener type and
coiicentration on film stiffness. Glycerol and tri-
ethylene glycol are equivalent, while ethylene-
diamine makes cellophane almost as stiff as un-
softened film containing only moisture. A high
glycerol coiicentration, on the other hand, results in
a film of low modulus.

Creep Curves
The creep and creep-recovery curves were ob-
tained by use of the Instron teiisile tester as follows.
The film specaimen was elongated a t 1 in./min. to a
load of 12.5 lb. The film was then allowed to
relax until the load decayed to 12.25 Ib., whereupon
the film was again elongated a t 1 in./min. to the
upper limit of 12.5 lb. This cycling procedure was 0 5 10 15
T I M E , MINUTFS
continued for 7 min. while the elongation was
recorded from the Instron dials. The frequency of Fig. 2. Strain curvcs of unsoftened film (lowcr w r v e )
and glgcwol-softened film ( 18.970,nppcr curve) as a function
response is indicative of the rate of creep.
of time. Tensile stress was kept constant at 12.5 X lo3
After creep had been measured over the 7-min. Ib.jin.2.
time interval, the Instron machine was switched to
the lower load limit of 0.25 Ib. (by changing to a 1- Representative Iiistron data for a glycerol-
lb. load range) and the strain recovery was again softened and uiisoftened film are given in Table
recorded from the instrument. IV, and the corresponding plots of strain as a
function of time, made from these data, are
TABLE I V shown in Figure 2. The elastic and inelastic
Creep and Creep Recovery a t Constant Load deformation obtained for these and all other films
CD-41 tested have been summarized in Table V.
Glycerol- CII-18 A simple mechanical model representing the
softened Unsoftened elastic and viscous behavior of cellophane was
film deforma- film defornia- fitted to these curves. Use of this model (Fig. 3 )
Time, miri. tion, in. tion, in.
consisting of Maxwell and Voigt elements of
Creep springs and dashpots in series assumes linear
0 0.0750 0.0450 viscoelastic behavior of cellophane, although we
0.1 0.1200 0.0475
recognize that the behavior of cellophane is actually
0.5 0.2000 0.0600
1 0.2250 0.0650 nonlinear. The assumption of linearity is made for
2 0.2550 0.0750 simplicity. The experimental strain behavior of
3 0.2850 0.0775 cellophane as a function of time has been represented
4 0.2950 0.0850 by conditions in the model corresponding to certain
5 0.3075 0.0850
times (1:ig. 4).5 The film specimens were *ub,jected
6 0.3150 0.0900
7 0 3250 0.0925 to a constant stress of 12.5 lb. a t a time to. During
ltecovery step 1 for a time interval (tl - to), we observe an
0 0.2500 0.0475 immediate elastic deformation of the Alaxwell
0.5 0.2050 0.0375 spring (at time to) corresponding to diagram (a)
1 0.1950 0.0325
in Figure 4, followed by a slower extension of the
2 0.1850 0.0275
3 0.1750 0.0275 Voigt element, diagram ( b ); finally the ,IIaxmell
4 0.1725 0.0250 dashpot begins to move, corresponding to inelastic
5 0.1700 0.0250 deformation, also shown in diagram (0). I n
6 0.1650 0.0225 step 2, the film is quickly returned to zero load a t
7 0.1650 0.0225
time tl. The lfaxwell spring immediately returns
050 15. WELLISCH, I,. MARKER, AX11 0. J.

TABLE V
Elastic and Inelastic lkformatiun of Softened and Unsoftened Films under 12.5 !b./in.* Load
Deformation, in.
Film Water, Unre-
no. Softener % Elastic Recoverable coverable
(311-41 Glycerol (18 9%) 8 0 0 0750 0 0850 0 1650
CII-43 Ethylene glycol
(12 7%) 7.3 0 0502 0 0425 0 0500
C1)-44 Propylene glycol
(12 5%) 7.4 0 0550 0 0425 0 0550
C I )-45 Diethylene glyrol
(15 9%) 7.7 0 0700 0 0600 0 1150
ci )-46 1,3-Butanediol
(15 4%) 8 .0 0 0600 0 0400 0 0800
c i )-47 Ethylene rarboriatt~
(15 1%) 7 0 0 0600 0 0375 0 0675
C‘ I1-52 IXethanolaniine
(14 6%) 9.6 0 0800 0 0800 0 1700
CD-48 tinsoftened film 9.2 0 0450 0 0250 0 0225

to zero extension as shown by diagram (c). Creep represents pure elastic deformat,ioii of the Maxwell
recovery occurs during step 3 over the permitted spring only, y2 is the retarded elastic deformation of
time interval ( t z - tl), corresponding to the move- the Voigt model only, and y3 corresponds to the
ment of the Voigt element to its original position viscous deformation of the Maxwell dashpot.
as shown in (d). Only the nonrecoverable de- The values of the parameters El, E2,r)2, and q3 can
formation of the Maxwell dashpot remains at this then be calculated from the following relation-
time. ships :
Viscoelastic Constants y1 S/El
= (1)
y2 = (S/E2)(1- e-t’T2) (2)
To determine the parameters and constants for
this model let us consider the following. The total where T2 = 1/2/E2.

deformation y is equal to y1 yz + +y3, where y1 Y3 = (S/7/3)t (3)

Fig. 3 . Mechanical model representing the stress-strain
relationship of cellophane. The upper elastic element of the
Maxwell model represents elastic deformation and the loner
Maxwell element represents unrecoverable creep. The inter-
posed Voigt elements (spring and dashpot in parallel with
4
Fig. 4. Interpretation of strain-time relation a t constant
stress, S. The strain-time curve corresponds to the follow-
each other) represent the recoverable creep. El and E2 are ing conditions of the modal: initial state; (a), t o ; ( h ) , just
the spring constants and q2 and 113 are the daqhpot viscosities. before t l ; (c), t l ; ( d ) tz.
REGENERATED CELLULOSE SHEET 651

TABLE VI
Determination of Model Constants
Spring constant Ei = S/ri Pure elastic deformation
Spring ronstant Ez = (S/rz),
S = E2y2 f 72d d d t
(At ti, ~ z d y d d t= 0)
Viscosity of dashpot (proportional 73 = (S/Y3)t 73 is the deformation owing to the
to unrecoverable creep) viscous element only
Viscosity of dashpot, Voigt model 72 = E2T2 11’2 is the retardation time obtained

(related to recoverable creep) from In y2 = In 72 - t / T 2 ,
where - l/T2 is slope of curve
and y 2 O = y2 a t t ,

Overall modulus hlodel in series

Total deformation a t time t

( 7 = 71 + +Y2 ya)

TABLE VII
Parameters for Deformation-Time Curves at 12.5 X 103 1b./i11.~Tensile Stress

E, xlo-: E2 x h’ x 112 x 10 *, 113 x 10-6,
Softenera 1b./in . 1h. /in. lb./in.2 lb.-min./in.Z Ih.-min./in.z
Glyrerol ( 18.90j0) 5.00 4.42 2 29 0.294 1.59
Ethylene glycol (12.7%) 7.50 8.82 4.07 0.585 5.25
Propylene glycol (12.5%) 6.83 8.82 3.85 0.585 4.78
1,3-Butanediol (15.4%) 6.25 9.38 3.74 0.734 3.24
Iliethylene glycol (15.9%) 5.35 6.25 2.89 0.475 2.29
IXethanolamine (14.6%) 4.69 4.69 2.35 0,346 1.54
Ethylene carbonate (15.1%) 6.25 10.00 3.86 0.795 3.88
Unsoftened film (9.2 water) 8.35 15.00 5.37 I .47 11.65
a As per cent of the weight of cellulose.

Here the E’s represent the indicated spring con- these moduli (given in Table 111) for glycerol-
stants, S is applied stress, and the 7’s represent softened films and for the uiisoftened film are
viscosities of the designated elements. Since the plotted as a function of the total effective molar
curves can be separated into the contributions concentration3 (the concentration multiplied by ail
yi, 7 2 , and y3 as shown in Figure 4, El can be appropriate weighting factor), it is found that the
immediately determined from eq. (1) and 7 3 from data fall on a straight line. The modulus data for
eq. (3). other softeners also fit this line if their molar con-
E f Z is determined from the extrapolated extension centrations are weighted by suitable factors. Since,
y2 a t infinite time; T z can be determined from the as has been described p re v io u ~ ly the
,~ abscissa of
slope of the plot of log (1 - rZE2/X) as a function this curve is a function of the number. of hydrogen
of time. Alternatively, Tz can also be obtained bonds broken, the modulus may be considered a
from the plot of In yz as a function of time in the direct measure of softener effectiveness relative to
creep recovery curve. The determination of the water. These results are shown in Figure 5 , and
model constants is summarized in Table VI. the effective molar concentrations of softener are
The model parameters were then calculated for given in Table VIII. The data include the films
the softened and unsoftened films by use of the used in the creep measurements.
data of Table V. The results are given in Table The factor weighting each softener with respect
VII. to water indicates that a mole of glycerol is twice as
DISCUSSION OF RESULTS
effective in interrupting hydrogen bonds as is a
mole of water.3 Although all of these other factors
Modulus of Elasticity were arbitrarily assigned to each softener to secure
The elastic modulus was determined as described fit to the glycerol-water curve, they agree with our
in the experimental section. If the logarithms of experience regarding softener effectiveness on a
652 E. \VET,LIPCH. I,. RIARKER, ANT) 0. J. SWEETIKG

hydrogen-bonded solid^.^ In this theory the
apparent modulus should decrease linearly with
increasing strain for small strains, and the slope of
the plot of apparent modulus as a function of strain
should have a constant value of about 1.0 X lo'?
dynes/cm.2. As can be seen from Figure 1, the
modulus does decreasc linearly with strain, and thc
average slope which would correspond to Nissaii's
constant K is calculated to be 1.0 f 0.4 X lo'?
dynes/cm. 2, in good agreement with Nissan's valuc.
Creep Measurements
a. Elastic Modulus. Most of the work reported
herein was done by making creep measurements
using the Instron tensile tester and expressing the
results in terms of the four-element model discussed
above.
The modulus El was actually determined in a
05 06 07 08 09 10 I 1 stress-elongation experiment. When measurements
EFFECTIVE CONCENTRATION, MOLES
are made a t a finite rate it is expecated that this B1
Fig. 5. Elastic modulus of cellophanes as 3 functlon of the should correspond to the Young's modulus of the
effective molar concentration of softener. Beginnlng at the material, also measured a t the same finite rate.
left, the points represent, respectively: 11ater, eth\lenc.di- Since, however, the lroung's moduli were effectively
amine, ethylene glycol, prop1 Iene glycol, ethylene carbonate, measured a t zero strain, these values would bc
1,3-butanediol, diethylene glvrol, glvccrol (t I\ o points),
triet hylenc glycol, diethanolamine, glycerol.
expected to be somewhat higher. If it is assumed
that the ratio of moduli measured during thc initial
step of the creep experiments to the Young's
weight basis; i.e., three times as much softener is moduli measured a t zero is a constant (the former
required by weight as water to produce durable moduli correspond to the stress movement of a
cellophane a t 35% R.H. Ethylenediamine is an Maxwell element only), the El values can he
exception, probably because of its strong complexing adjusted to the same basis as the Young's moduli.
properties.'j When this was done, relative to the moduli of the
Kissan has developed a theory of modulus for water-softened films, it was found that all El
values couId be plotted on the same curve as the
TABLE V I l I other modulus measurements a s shown in Figure 5.
Effective Rlolar Concentrations of Softeners and \\'ater The adjusted El values are given in Table IX.
Softener 15ffect i ve b. Viscous Flow. In Figure 6 me have plotted
concen- ronren- log r/3 as a function of log El. The linearity of this
tration, \Vater, tration,
Soft ener moles Factor moles moles TABLE I X
From Young's Illodulris Adjusted Elastic Moduli for Softened and Unsoftened F111nv
Water 0 51 0 51 1Slastic
Glycerol 0 23 2 0 38 0 82 modulus,
Glycerol 0 32 2 0 40 1 04 ( dyncs / P In. )
Triethylene glycol 0 16 3 0 39 0 87 Film no. Softener x 10-10
Ethylmedinmine 0 30 0 75 0 36 0 58 -
From Mechanic:tl Motlrl CD-41 Glycerol 4 44
Glycerol 0 20 2 0 44 0 84 CII-43 Ethylene glycol 6 49
Ethylene glycol 0 21 1 0 40 0 61 CD-44 Propylene glycol 5 0"
Propylene glycol 016 1 5 041 0 65 CD-45 Diethylene glycol 1 63
1,3-Butanediol OIT 1 5 045 0 TO CD-46 1,3-Butanediol 5 41
Diethylene glycol 015 2 5 043 0 81 CD-47 Ethylene carbonate 5 44
Diethanolamine 014 2 5 053 0 88 CD-48 Unsoftened film 7.21
Ethylene carbonate 0 17 1 T5 0 39 0 69 CD-52 Diethanolamine 4 08
Water 0 51 0 51
~~

a From creep experiments, Table VII.
REGENERATED CELLULOSE SHEET 653

I
'I
20

8

7

i"
, 1 ' I I
6 7 8
ENERGY. KCAL

Fig. 7. Dependencc of the Voigt model parairietcrs E , arid
72 on the heat of vaporization of $oftener plus water prwent
in the films; (El) glywrol; ( W ) ethylene glycol; ( 0 )propylene
I ! I I I I I I glycol; (a) diethylene glycol; ( 0 ) diethanolamine; (A)
3 4 5 6 7 8 910 ethylene carbonate; ( 0 ) water.
ELASTIC MODULUS E,,(lb/inS X 16'

Fig. 6. Interdtyendence of the Maxwell parameters El and would expect that the logarithm of either the E2
ta. modulus or the viscosity v2 should vary as a linear
function of the heat of vaporization. When the
plot indicates that 713 is functionally dependent on logarithm of either E2or 7 1 was
~ plotted as a function
El. Therefore these properties are not independent of the energy (calculated by multiplying the number
and thus they depend on the effective molar con- of moles of water by the heat of vaporization and
centration of softener in the same manner. adding the product of the number of moles of
c. Delayed Elasticity. The delayed elasticity is a softener in 1OOg.of cellulose and its heat of vaporiza-
function of the amorphous structure of the system tion) a linear relationship was found (Fig. 7).
and represents short-range motion of chain seg- The calculated energy values and the viscosities and
ments. The activation energy of this movement is moduli are given in Table X.
expected to be related to the difference between the We know that for these particular softeners the
internal energies of polymer and softener. If the heat of vaporization depends almost entirely on the
free energy of the process is proportional to the dif- energy necessary to break hydrogen bonds. We
ference in internal energy of the participants, we would suspect therefore that the deformation proc-

TABLE X
Heat of Vaporization of Softeners (Including Water) in Regenerated Cellulose, Sheets
Heat of vaporization, k c d
IG x 10-5, 72 x 10-6,
Scftener Softener Water Total lb./in.2 Ib.-min./in.?
._

(+I\ (erol 3 :34 4 25 7 59 4.42 0 294
1:thpIene glycol 2 48 3 88 6 36 8.82 0 585
Prop) lene glycol 2 12 3 98 6 10 8.82 0 585
Iliethplene glycol 2 38 4 17 6 55 6.25 0 4T5
1)iethanolamine 2 32 5 15 7 47 4.69 0 346
Ethylene carbonate 2 02 3 78 5 80 10.00 0 795
Prisoftened film 4 95 4 C)5 15.00 1 17
654 E. WELLISCH, L. MARKER, AND 0. J. SWEETING

ess related to delayed elasticity requires breaking of elastic and viscous parameters werc dcterininrd for the
interchain hydrogen bonds in contrast to the purely various softened films and comparcd with each other and
elastic deformation which involves the stretching of with measurements of Young’s modulus. It was found that
the elastic modulus is a function of the effective molar con-
hydrogen bonds. centration of the softener in the film which is related to its
Both the moduli Ez and viscosities q2 decrease ability to break hydrogen bonds. The inelastic deformation
with increasing energy, indicating that the stronger was found to be a linear function of the heat of vaporization
the interaction between softener molecules the of softener (including water) in the film, which is related to
stronger is the interaction with cellulose; the cel- hydrogen-bonding energy. Thus, inelastic deformation re-
quires breaking of interchain hydrogen bonds in contrast to
lulose-cellulose interaction is correspondingly weak- pure elastic deformation which involves stretching of hydro-
ened. gen bonds. .4relationship of the Voigt unit and of the Max-
CONCLUSION well unit on the composition of the cellulosc-softener system
and on cellulose-softener interaction has been demonstrated.
It has been shown that a t constant load the creep
data for softened cellophanes can be fitted to a four- Resume
element model consisting of a Voigt unit and a On 6tudi6 lcs propriBt@svisco-6lastiques de I:t cellulose
Maxwell unit in series. The parameters of the rBg6nBree contenant plusieurs plastifiants differents ou
Voigt model are closely related to each other, as are simplement. de l’eau. Des mesures de rdtr6cissemerit et de
module de Young ont @t@ cffectukes au moyen de l’iippareil
the parameters of the Maxwell model, but the two de mesures de tension Instron, et les courbes de rbtrbcisse-
models seem to depend on the composition of the ment ont @ti.adaptdes h un modble m6canique consistant en
system in different ways. des Blements de Voigt et Maxwell, ressorts et ariiorittsurs en
The parameters of the Maxwell model depend on s6ries. On d6termine les parambtres d’dlasticit6 et de vis-
cositi. pour divers films trait& et on les compose entr’eux et
the total number of moles of softener added, i.e.,
avec les mesures du module de Young. On trouve clue le
on the number of cellulose interchain hydrogen module d’6lasticit6 est une fonction de la concentration
bonds broken. molaire effective du plast.ifiant dans le film, qiii cst like 3,
The parameters of the Voigt model, on the other son aptitude B briscr les liaisons hgdrogknes. On trouve que
hand, seem to depend on the internal pressure of la deformation non-dastique est une fonction lin6aire de la
the liquids carried by the cellulose. This is re- chaleur de vaporieation du plastifiant (l’eau y comprise) dans
le film, laquelle eet reliire A 1’6nergie de la liaison hydrogbne.
flected in the sum of values for the heat of vaporiza- La dhformation non-blastique demande donc la cassure des
tion of the softeners (including water) and thus on liens hydrogirnes interchaines contrairement h !a dAforma-
the degree of interaction of these molecules with tion Blastique pure qui implique 1’Btirenient dcs liaisons
cellulose. A new interpretation of cellulose- hydrogknes. On ddmontre qu’il existe une re!at.ion entre
softener interaction in terms of hydrogen bond l’unit6 de Voigt e t de Maxwell, la composition du systkme
cellulose-plastifiant et l’interaction cellulose-plastifinnt.
eiiergies is indicated ; pure elasticity and plastic
flow dcpend on stretching and finally on the break- Zusammenfassung
ing of hydrogen bonds, while delayed elasticity Die viskoelastischeii Eigenschaften von rcgcncrierter
depends on the movement of polymer chain seg- Cellulose, die verschiedene Weichmacher oder nur Wasser
ment4 and requires breaking of interchain bonds. enthielt, wurden untersucht. Messungen des Krierhens und
des Elastizitiitsmoduls wurden mit dem Instron-~piiniiiiiigs-
References messer durchgefiihrt nnd die Kriechkurven mit eineni mecha-
1. Wellisch, E., L. Hagan, L. Marker, and 0. J. Sweeting, nischen Modell, das aus Voigt und Maxwellsrhcc Feder- und
J . A p p l . Polymer Sci., 3, 331 (1960). Reibungselenienten in Serie besteht, wiedergcgeben. Die
2 . \frellisch, E., L. Hagan, L. Marker, and 0. J. Sweeting, Elastizitats- und Viskosit.atsparameter nurden ftir die ver-
J . Polymer Sci., 51, 263 (1961). schicdenen neichgemachten Filme bestimiiit, und unter-
3 . Hansen, 0. C., Jr., L. Marker, and 0. J. Sweeting, J . einander und niit Messungen des Il:lastizit~iitsmodulsver-
-4ppl. Polymer Sci., 5, 655 (1961). glichen. Es wurde gefunden, dass der Elastizitatsniodul
1. Nissan, A. H., Trans. Faraday Soc., 53, 700 (1957); eine Funktion der effektiven molaren Konzentration des
&ad., 53, 710 (1957). Weichmachers in dem Film ist, die in Beziehung zii seiner
5. Alfrey, T., Jr., Mechanical Behavior of High Polymers, Fahigkeit, Iyasserstoffbindungen zu spalten, steht. Die
Interscience, New York-London, 1948, p. 103 ff. nichtelastisrhe Deformation ist eine lineare Funktion der
6. Segal, L., and L. Loeb, J . Polymer Sci., 42, 341 (1960). Verdampfungsniirme des Weichrnachers (einschlicsslich
Wasser) im Film, nelche in Beziehung zur If-asserstoff-
SJ nopsis bindungsenergie steht. Zu einer nichtelastischen Ileforma-
The viscoelastic properties of regenerated cellulose con- tion ist die Spaltung von Wasserstoffbindungrn znischen
taining several different softeners or water only were in- den Ketten erforderlich, wiihrend eine rein elastische Ile-
vestigated. Measurements of creep and Young’s modulus formation eine Ikhnung dcr Vi’asserstoffbindungen niit sich
were made on the Instron tensile tester, and the creep curves bringt. Eine Beeiehung der Voigt- und Maxwell-Einheit zur
were fitted to a mechanical model consisting of Voigt and Zusamniensetzung des Cellulose-Weichmacher-~ysteiiis und
Maxwell elements of springs and dashpots in series. The eur Wechselwirking Cellulose-Weichmacher wmie gezeigt.