1008

From the solar energy distribution data of Luckiesh, 3. Glasstone, S., "The Effects of Nuclear Weapons,"
the intensity of bright sunlight in the regions 3500 ::i: U.S. Atomic Energy Commission, June 1957, p.
200 A was calculated to be 4.79 X 10-’ cal/cm2/sec. 311.
Therefore, we took Ix,-3mm.o to be (4.79 X 10-’),’ 4. Hartley, G. S., J. Chem. Soc. 1938, 633-642.
(8.1 X 104) - 5.92 X 10-’ einsteins/cm’/sec. 5. Horowitz, M. G. and Klotz, I. M., J. Am. Chem.
Soc. 77, 5011-5012 (1955).
6. Koller, L. R., "Ultraviolet Radiation," New York,
Literature Cited
John Wiley & Sons, 1952, p. 125.
1. Armour Research Foundation, "Investigation of 7. Kubelka, P. and Munk, K., A. tech. Physik 12, 593
Means and Materials to Combat Thermal Radia- (1931).
tion Flash Burns," H. Qm. R. & D. C. Project No. 8. Mickley, H. S., Sherwood, T. K., and Reed, C. E.,
LO 46. "Applied Mathematics in Chemicals Engineering,"
2. Glasstone, S., "The Effots of Nuclear Weapons," Ind. Ed., New York, McGraw-Hill Co., 1957,
U.S. Atomic Energy Commission, June 1957, p. p. 195.
302. Maxrscripl rcceivtd August 2, 1961

Temperature Dependence of Shear Modulus,

Density, and Crystallinity of
Isotactic Poly Polypropylene
T. Shibukawa, V. D. Gupta, R. Turner, J. H. Dillon, and A. V. Tobolsky
TextileResearch Institute
and
Frick Chemical Laboratory, Princeton University,
Princeton, New Jersey
Abstract
Experiments were undertaken to determine the dependence of the shear modulus
upon the density degree of crystallinity of two samples of isotactic polypropylene
and
over a range of temperatures. Annealing the polypropylene samples was found to
increase both the shear modulus and the density. Both quantities appeared to be inversely
related to the molecular weight of the two polypropylene samples investigated. These
phenomena are similar to those observed for polyethylene in our earlier studies. On
the other hand, the variation of crystallinity with temperature, as measured by changes
in density and by x-ray diffraction, was not the same in polypropylene as in linear
polyethylene.

IN A recent paper (1 J, Shibukawa et al. described The techniques employed in the earlier work have
work on the dependence of shear modulus upon the been applied to several samples of isotactic poly-
density and degree of crystallinity of three samples of propylene. The results of these studies form the
linear polyethylene over a range of temperatures. In basis of this paper. ,

most instances, good agreement was found between

crystallinity values calculated from density and from Polypropylene Samples

x-ray diffraction measurements. Annealing the poly- The two isotactic polypropylenes used in this work
ethylene samples was found to increase both the shear were supplied by the Allied Chemical Corporation,
modulus and the density, both of which appeared to who reported the viscosity-average molecular weights
be inversely related to molecular weight. ( ~’~1,. ) as 2.0 to 2.6 x 10° and 8.8 to 12.0 x 10:1. An

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 1009

amorphous polypropylene sample supplied by the Sun

Oil Company was also studied. This sample was
relorted to le W.2’lr amorphous and to have a num-
ler-average molecular weight of 0.28 x 10~ and a
density of 0.851 at room temperature. The an-
nealing procedure employed with the isotactic samples
was :
~

I. Heat for 1 hr at 1600 C in vacuum oven

II. Cool to room temperature
I I I. Hold for at least 1 day at room temperature

Experimental Methods and Apparatus

The shear modulus and density determinations of
this work were made with the same apparatus and iu
exactly the manner previously descriled I 11. The
x-ray diffraction studies were made with the appara-
tus previously used [I but a different method, that
of :~ atta, Corradini, and Cesari [ 2 ] , was selected to
separate the diffraction curve into amorphous and
crystalline components.
Calculations of
Crystallinity from
Density-Temperature Data
Two methods of calculating the crystallinity-tem-
Fig. 1. Shear modulus vs temperature.
perature curve from density-temperature data were
employed. Iioth of these are based upon the funda-
mental relationship

where ~ is the volume fraction of amorphous mate-

rial in the polymer at temperature t, 1’(t) is the means-
ure<1 specihc volume, I ’,. ( t ) is the specific volume of
the crystalline portion, and I ’&dquo; ( t ) is the specific vol-
ume of the amorphous portion. The crystallinity is
thett denned as 1 -

A.
Method A was essentially that used in the work cm
polyethylenes I 11. This method involves extrapola-
tion of the curve of density vs temperature above the
melting temperature hack to 25° C to get I’&dquo; ( 25 ) and
the use of the slope in the vicinity of the glass transi-
tion temperature to get the quantity AJ ’r 31. Upon
substituting the x-ray diffraction value of A at 25° C,
the values of 1&dquo;(.(25) and tl,(O) are obtained. From
these cluantities, the crystallioity (1 - À) is plotted
as a function of temperature.

Method l differed only in that values of 1’.(t) I

were derived from the observed density-temperature

curve for the amorphous polypropylene sample. Fig. 2. Density vs temperature.

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1010
Fig. 3. Shear modulus vs specific volume.
Fig. 4. Specific volume of crystalline region vs temperature,
annealed sample; ~. 2.0-2.6 X 1(r‘.
= Research is gratefully acknowledged.
Results and Discussion
Values of shear modulus of the isotactic
are plotted on a logarithmic scale against temperature
in Figure 1. As’ with the polyethylenes [ 1 ) , an-
nealing served to increase the modulus. Likewise, in
Figure 2, annealing is seen to increase the density.
The semi-logarithmic plot of shear modulus vs
specific volume of Figure 3 is definitely nonlinear, as
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Fig. 5. Crystallinity vs temperature,
annealed sample; Afc = 2.0-2.6 X 1()r‘.
is the case with the polyethylenes. The points at
higher specific voltunes are scattered as a result of
the very steep modulus-temperature relationship at
the higher temperatures. Derived values of the spe-
cific volume of the crystalline portion 1 I ’,.1I are
plotted against temperature in Figure 4.
There is rather poor agreement among the three
curves of crystallinity vs temperature in Figure 5.
Curve R, calculated by Method H, fits better than
Curve A with the curve of directly measured x-ray
crystallinity values ; however, it cannot be said that
the density-derived values of agree with
crystallinity
the x-ray diffraction-derived values, as’ was true for
the polyethylenes [ 1 ] . It may he noted that Farrow
~ 3 ~ found lower values of crystallinity, measured hy
his x-ray diffraction technique, as compared with
values inferred from density measurements. How-
ever, his studies were made on oriented polypropylene
filers at room temperature, a fact which probably ex-
plains the apparent discrepancies with the results
of the current work.
Acknowledgment
The support of this work by the Office of Naval-
t-
Literature Cited
1. Shibukawa, T., Gupta, V. D., Turner.R., Dillon,
samples J. H., and Tobolsky, A. V., Textile Research J. 32,
810 (1962).
2. Natta, G., Corradini, P., and Cesari, M., Atti. Accad.
Nazl. Lincei, Rend., Classe Sci. Fis. Mat. Nat. 22,.
11 (1957).
3. Farrow, G., Polymer 2,409 (1961).
llaewscript receivd Axtrst 9, 1962.