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W. W. MOSELEY,
JR.
Pioneering Research Laboratory, E. I . du Pont de Nemours and Co., Inc., Wilmington, Delaware
As discussed in the Appendix, the above con- Test of the Series and Parallel Equations by Ap-
siderations lead to a n equation that relates the plication of Fiber Sound Velocity Data
sound velocity in a sample to its molecular orienta-
It is possible t o show that only the series model
tion in terms of certain constants characteristic of
leads to a realistic result when eqs. (la) and (lb)
the polymer structure. To develop such an equa-
are applied to sonic velocity data obtained on
tion, it appears necessary to make one of the two
fibers. This point was established in the following
following extreme assumptions.
manner.
(1) Any fiber deformation which occurs during
The value of cos2 e for a randomly oriented
sound transmission is the sum of the intramolecular
sample can be shown to be '/3 by the methods out-
and intermolecular deformations. This assump-
lined by Kennard.13 Setting cos?e equal t o
tion results in a series addition of the intramolecular
in eqs. (la) and (lb), we obtain:
and intermolecular force constants, weighted by an
Series case
average orientation function.
( 2 ) Any force on the fiber resulting from a sound 1!Cu2 = (2/3Ct2) + (1/3Cme) (2%)
wave is the sum of the forces exerted on the intra- Parallel case
molecular and intermolecular bonds. This as-
sumption results in a parallel addition of the Cu2= (2Ct2/3) + (Cm2/3) (2b)
intramolecular and intermolecular force constants, where Cu is the sonic velocity in a randomly
weighted by an average orientation function. oriented (unoriented) fiber.
As shown in the Appendix, these two extreme Solving both equations for C,2 yields:
assumptions lead t o two equations which relate Series case
the sound velocity in a fiber to an orientation
Ct2 = 2C,2C,2/(3Cm2 - Cu') (34
function averaged over all molecular segments in
the fiber. Parallel case
Series case:
c,2 = (3C," - C,"/2 (3b)
Values of C, were approximated from fiber sound
velocity data, the typical values of C, in Table I
and certain estimates of C , being used. Two
Parallel case : different estimates of C, were used: (a) the
maximum values of velocity commonly encountered
C2 = (1 - coS2B) C? + (cGZG)Cmz (lb)
in fibers (Table 11) and (b) the theoretical maximum
value discussed earlier (12-14 km./sec.).
For the series model, eq. @a), two values of C,
Here, C denotes the sonic velocity along a fiber
were calculated for each of several polymers
axis; C t is the sonic velocity for a hypothetical
(Table 111). These two values result from the
sample in which all molecular segments are trans-
two estimates used for C,. It is particularly
verse to the direction of sound transmission, C,
interesting t o note that the value of C , is virtually
is the sonic velocity for a hypothetical sample in
insensitive t o the estimate chosen for C,,,. This
which all segments are pointed in the direction of
point is discussed further in the next section and
sound transmission; and 0 is the orientation angle
results from the fact that, when 3Cm2in the denom-
of any segment, i.e., the angle between a segment
inator of eq. (3a) is much greater than Cu2,the
and the direction of sound transmission (Fig. lc).
equation reduces to
show
- that this would lead-to an error of about 0.01
in cos2 0 at values of cos2 0 greater than 0.98.
Thus, for a perfectly oriented sample,- a value of 1.01
about 0.99 would be calculated for cos2 0 if C,,,
were assumed to be infinity. Thus, eq. (la) TYPE 5100
reduces to
e
~
In Figure 6, the Kuhn and Grun curve is com- where E , is the sonic modulus of an unoriented
pared to the experimental curve for an undrawn specimen.
nylon 66 yarn. The two curves are similar in Equation (11) provides a basis for quantitative
shape, even though there are certain real differences structure-property studies. In this equation a
at high elongations. -\ctually, Kuhn and Grun fundamental structural parameter, orientation, is
predicted that such deviations might occur at related to a common mechanical property, modulus.
high extensions.
APPARATUS FOR MEASURING SOUND VELOCITY
SELECTION OF AN ORIENTATlON FUNCTION
In practice, yarns and film strips are held in
As discussed earlier and in the Appendix, the
contact with two piezoelectric crystals which are
value of Z e varies from one-third for a randomly
Rochelle salt twister bimorphs (Fig. 7). Pulses of
oriented material t,o unity for a theoretically
sonic energy are sent from one bimorph (trans-
perfectly oriented sample. For purposes of con-
mitter) down the yarn to the receiving bimorph
venience, an orientmationparameter a has - been
and the time of travel measured. The sound
selected which will vary from zero to unity as cos26
velocity is computed from the pulse travel time and
varies from one-third to unity. This parameter
the distance between the bimorphs.
is identical to Hermans’ orientation factol.5J and
is defined as
STRESS -TRANSDUCER
I
a is termed the total molecular orientation. As PIEZOELECTRIC
CRYSTAL RECORDER
mentioned earlier, the term total is used to indicate (SENDER)
that the measured orientation is an average for SPEC1M EN-
all molecular segments, both crystalline and amor-
phous.
Next, a is eliminated between eqs. (7) and
(8) ; this yields
ELONGATING
DEVICE
a = 1- (CU*/C2) (9)
measurement of force and pulse time. A tracing was wound up at a constant rate of about 2 ft./min.
of a typical recorder chart is shown in Figure 8. The output of the pulse apparatus was sent to n
From these data the tension, in grams per
denier, and the orientation a were computed and YARN
plotted against the percent elongation (Fig. 9). WINDUP
65 -
70 -
y75-
t I 2 3 4 5 6 7 8 9 10
I
0
?= FEET
60 &
65
- 4 X DRAW D
-
-
70 U
P
75
7 8 7 A, ---z G - L
60 - a I
65 - C
#7570
;78 -
- 8
8- G A
T
E
~ 6 5 - D
870-
75
78
+
- K-
U
N - A
T
78 - E
l 2 3 4 5 6 7 8 9
FEET
Brown electronic recorder to give a plot of pulse contrasted with crystalline orientation and
time against position along the length of the yarn. amorphous orientation. On the other hand, the
Results are given in Figures 11 and 12 for usual orientation parameter determined by x-ray
measurements on experimental yarns made from measurements on crystalline samples is a measure
acrylonitrile polymer. These figures are tracings of the crystallite orientation alone.6*'6J7
of a Brown electronic recorder chart, and the There is a further difference in sampling. The
ordinate is linear in the pulse time for a 4-in. usual technique for x-ray diffraction measuremeiit,s
separation between the piezoelectric crystals. samples different short lengths along a yarn,
The pulse time values were converted to molecular whereas in the acoustic technique, a continuous
orientation, and a per cent molecular orientation yarn length is measured.
scale was superimposed, i.e., a scale of 1OOa. TABLE IV
This orientation scale will not change so long as X-Ray and Acoustic Measures of Orientation
one works with the same polymer at a given
Range
temperature, and so long as the distance between Fractional in a
the piezoelectric crystals is kept constant. Finally x-ray orients- molecular (where a
t,he abscissa in Figures 11 and 12 is the length of tion anglem, orientation vanes
yarn wound up at any time during the experiment. degrees (by ff along
One of the advantages of this method is that acoustic yarn
Sample Innep Outep measurement) length)
orientation and orientation nonuniformity resulting
from process variables may be easily and rapidly Type 300 nylon
followed. Figure 11 illustrates some large varia- 66
tions in an experimental yarn drawn to a draw 0% strain 15 f 1 16 0.78
ratio of 2.0. Figure 12 illustrates smaller variations 5% strain 11 12-13 0.89
in a sample drawn to a draw ratio of 4. As suggested 10% strain 11 12 0.94
13% strain 10 11 0.95
in each figure, duplicate runs were made on the
same piece of yarn to establish the reproducibility. Yarns from
In Figure 12 the letters A through N indicate experimental
acryloni trile
corresponding positions in the duplicate runs. polymer
IX draw 120 f 10 0.0
COMPARISON WITH X-RAY ORIENTATION 2 x draw 40+2 0.59 0.35-0.73
MEASUREMENTS 4 X draw 25 f 1 0.74 0.69-0.75
5 x draw 21 f 1 0.78 0.77-0.80
As mentioned earlier, the orientation parameter 6 X draw 18 f 1 0.80 0.80.81
calculated from sound velocity, is taken to be a 8 X draw 20 f 1 0.83 0.82-0.84
measure of the total molecular orientation as a From inner and outer diffraction rings on x-ray diagram.
MOLECULAR ORIENTATION IN FIBERS BY ACOUSTIC METHODS 275
Even though these differences exist, large in- for motion across and along any segment, respec-
creases in draw ratio are expected to produce an tively. The occurrence of the factor of 2 in the
increase in orientation as measured by any suitable above expression results from the assumption that
technique. In Table IV, both acoustic and x-ray molecular segments are cylindrically symmetrical.
orientation parameters (a and a) are tabulated Averaging l/Kj over all segments leads to the
for vzrious values of draw ratio for experimental expression :
yarns from acrylonitrile polymer. The x-ray
orientation angle a ranges from 180 degrees to
nearly zero and decreases with increasing orienta-
tion. In cases where the sample was nonuniform, a where K is the force constant for a group of seg-
range was recorded for a. ments with an average orientation characterized
The same parameters are given for Type 300 -
by cos28.
nylon 66 strained to various elongations. A more
detailed comparison between acoustic and x-ray
diffraction data is given by Charch and M o ~ e l e y . ~ B . Equation for Fiber Modulus
As expected, the values of a in Table IV increase The 1/K term in eq. (13)represents
-a sample with
and OA decreases with increasing draw ratio or an orientation characterized by cos28. In contrast,
elongation. Both changes indicate an increase in the two terms on the right-hand side of the equation
orientation at higher draw ratios. contain force constants characteristic of completely
deoriented and completely oriented samples, respec-
APPENDIX tively.
The orientation of any molecular segment is The force constants in eq. (13) may be taken as
described by the cosine of the orientation angle of proportional to corresponding moduli, where the
the segment, defined as the angle between the units of modulus are forced per unit linear density
segment and the fiber axis. In this work, it is (or grams/denier). This restriction on the units
assumed that the force constant for deforming a of modulus is necessary so that different fibers are
segment in the direction of the fiber axis is prin- compared on the basis of equal number of molecules
cipally determined by the cosine of the orientation passing through the fiber cross section rather than
angle and two force constants: (a) an intramolec- on the basis of equal cross-sectional area.
ular force constant for a motion along the length Thus :
of the molecular segment and (b) and intermolecular
force constant for a motion perpendicular to the
length of a molecular segment.
An expression relating these quantities can be where E is the fiber modulus in units of grams per
developed by making one of two extreme assump- denier, and E , and Em are the moduli of a hypo-
tions. These are discussed in the text and stem thetical fibers in which all molecules are pointed
from (a) a series weighting of the molecular and across and along the fiber axis, respectively.
intermolecular force constants (b) a parallel
weighting. C. Equation for Sonic Velocity
I. Series Case As discussed by Ballou and Silverman,' the
A . Equation for Fiber Force Constant sonic modulus of a long, thin, rodlike specimen (e.g.,
a fiber) is .related to the sound velocity by the
A series addition of the molecular intermolecular equation :
force constants for a single segment leads to the
expression : E = pC2 (15)
where E is the modulus in units of force per unit
cross-sectional area, p is the volume density, and C
is the sound velocity.
where K , is the force constant in the direction of If E is expressed in units of force per unit linear
the fiber axis for the j t h molecular segment; density (e.g., grams/denier) the equation becomes:
8, is the angle between the fiber axis and the j t h
segment; and K , and K,,, are the force constants E = kC2 (16)
276 W. W. MOSELEY, JR.
K
-
= (1 - C O S ~e)2K, + (COS~
e)Km (19)
Dans le present travail la vitesse sonique dans les fibres ou
lamelles de films de polymere a 6th reliee B une mesure quan-
titative de l’orientation mol6culaire dans I’echantillon. I1
Conversion first to moduli and then to velocities est demontr6 que cette mesure de l’orientation peut &re
yields calculee a u depart de deux grandeurs experhentales: la
vitesse sonique dans un specimen orient4 et la vitesse dans
un specimen orient6 au hasard. La composition chimique
des Bchantillons orient& et non-orientb doit &re identique
which is eq. (lb) in the text. et le deux mesures doivent &re effectuees B une m h e tem-
pbrature, inferieure B la temperature de transition vitreuse,
References T,. Les vitesses soniques ont BtR mesurks par m e tech-
1. Ballou, J. W., and S. Silverman, Teztile Research J . , nique B impulsions. Cette methode permet une mesure
14, 282 (1944). continue des variations d’orientation durant des tests ten-
2. Ballou, J. W., and J. C. Smith, J . Appl. Phys., 20, sion-elongation conventionnels sans interrompre ceux-ci.
493 (1949). De plus l’uniformite de l’orientation le long des fibres a 6t6
3. De Vries, Hendrik, On the Elastic and Optical Proper- mesur6e en continu durant le filage. Des exemples de ces
ties of Cellulose Fibers, Schotanus and Jens, Utrecht, 1953. applications sont donnes e t une comparaison est faite entre
4. Charch, W. H., and W. Moseley, Teztik Research J., les mesures d’orientation acoustiques e t roentgenographi-
29,525 (1959). ques.
5. Stein, R. S., J . Polymer Sci., 24, 709 (1959). Zusammenfassung
6. Hermans, P. H., Physics and Chemistry of Cellulose In der vorliegenden Mitteilung wird die Schallgeschwindig-
Fibers, Elsevier, New York, 1949, Chap. 5. keit in polymeren Fasern oder Filmstreifen zu einer Grosse
7. Rao, M. Rama, Current Sci. (India), 8, 510 (1939) in Beziehung gesetzt, die ein quantitatives Mass fiir die
8. Meyer, K. H., and Walter Lotmar, Hele. Chim. molekulare Orientierung in der Probe bildet. Es wird
Acta, 19, 68 (1936). gezeigt, dass diese Orientierungsgrosse aus awei experhen-
9. Lyons, W. J., J . Appl. Phys., 29, 1429 (1958). tellen Grossen berechnet werden kann: aus der Schall-
10. Hertzberg, G., Molemlar Spectra and Molecular geschwindigkeit in einer orientierten Probe und aus der
Structure, Vol. 11,Van Nostrand, New York, 1949. Geschwindigkeit in einer Probe mit statistisch verteilter
11. Urick, R. J., J . Appl. Phys., 18,983 (1947). Orientierung. Die orientierte und die nichtorientierte
12. Urick, R. J., and W. S. Ament, J . Acoust. SOC.Am., Probe mussen beide die gleiche chemische Zusammensetzung
21, 115 (March 1949). haben und beide Messungen miissen bei der gleichen Tem-
13. Kennard, H., Kinetic Theory o j Gases, McGraw-Hill, peratur, unterhalb der Glasumwandlungstemperatur, T,,
New York, 1938. ausgeftihrt werden. Schallgeschwindigkeiten wurden nach
14. Kuhn, W., and F. Grun, Kolloid-Z., 101,248 (1942). einer Impubemethode gemessen. Diese Methode erlaubte
15. Hamburger, Walter J., Teztile Research J . , 18, 705 eine kontiiuierliche Messung der Orientierungsiinderungen
(1948). wahrend der normalen Spannungs-Dehnungsbestimmungen
16. Klug, H. P., and L. E. Alexander, X-Ray Diffraction ohne diese unterbrechen zu miissen. Ausserdem wurde die
Procedures, Wiley, New York, 1954, Chap. 10. Einheitlichkeit der Orientierung entlang dem Faden wiihrend
17. Peiser, H. S., H. P. Rooksby, and A. J. C. Wilson, des Spannens gemessen. Anwendungsbeispiele werden
X-Ray Diffraction, Inetitute of Physics, London, 1955, mitgeteilt und ein Vergleich zwischen der akustischen und
Chap. 22. der Rontgenstrahl-messung der Orientierung gezogen.
18. Rivlin, R. S., and D. W. Saunders, Phil. Trans. Roy.
SOC.London, 243, 251 (1951). Received December 23, 1959