JOURNAL OF POLYMER SCIENCE VOL.

57, PAGES 993-1007 (1962)

Etching of Polyethylene Terephthalate

WILLIAM P. BAKER, JR., Film Department, Experimental Station

Laboratmy, E . I . du Pont de Nemours and Company, Inc., Wilmington,
Delaware

INTRODUCTION
The molecular structure (<loo0 A.) of polymers has been and is receiv-
ing a great deal of scientific attention. The possible existence of larger
nonspherulitic structures (>0.1 p ) has not been adequately explored, al-
though some work with films has been reported recently in the literature by
Nielsenl and by Kodov2and co-workers.
This paper is largely concerned with the demonstration that organized
volumes of three different orders of magnitude (all greater than molecular)
exist in polyethylene terephthalate films and that at least one of these is
probably general for all polymeric films subjected to anisotropic stress
during processing. Polyethylene terephthalate was chosen as an arche-
type because of the number of differently processed films available for
examination and because its molecular structure was suitable for etching
by chemical degradation.

EXPERIMENTAL
Polyethylene terephthalate film samples are etched by n-propylamine
at convenient rates at room temperature by chemical degradation into
ethylene glycol and N,N'-n-propyl terephthalamide. Infrared studies of
the reaction products confmned that the degradation was uncomplicated
by side reactions. Since both the glycol and amide are soluble in excess
amine, the products are removed from the reaction site. It is probable that
the rate of etching can be controlled over a wide range by variation of the
steric and basic properties of the amine.
An everpresent concern in etching work is that the developed structures
be characteristic of the substrate itself and not of the substrate-etching
reagent system. Sufficient film samples fabricated by different processes
were examined to afford assurance that our data are representative of the
film (therefore, its processing) and not of spurious effects. This is partic-
ularly important in this case, because n-propylamine does cause some
increase in the crystallinity of heat-set polyethylene terephthalate films
and a large increase in the crystallinity in amorphous films of like composi-
tion. Although this occurrence proved of no importance in this work,
993
994 W. P. BAKER, JR.

it may be significant in other cases in which the rate of relaxation of struc-

ture is much greater than the rate of degradation.
A typical etching experiment is detailed below. A l-in. by 2-in. sample
was suspended without tension in 100 ml. n-propylamine (purification of
Eastman Yellow Label product was found unnecessary) in a closed con-
tainer at room temperature. After a desired time interval, the sample
was removed, rinsed in fresh propylamine, rinsed thoroughly in water,
and dried. Control experiments demonstrated that the etched patterns
were not affected by the clean-up procedure or sample size. The etched
sample was then examined by optical microscopy and by electron micros-
copy. Optical microscopes employed were: American Optical Model
1583 phase microscope, American Optical Model 337047 polarizing micro-
scope, and Reichert research polarizing microscope Zetopan-Pol. Elec-
tron micrographs were obtained with an RCA electron microscope after
standard replication and shadowing techniques.
The majority of film samples described in this work were stretched on a
specially designed apparatus which applied the stress homogeneously. The
uniform application of stress is important because without it only general
tendencies may be observed and not the regularity of structures reported
in this paper. Unless otherwise stated, the base film was amorphous
( p = 1.33), unoriented polyethylene terephthalate (vi = 0.55 f 0.03;
3OoC., 0.5% in CF3COOH). This base film etched into random patterns,
roughly similar to those of sun-dried mud.

RESULTS

A. One-way Stretched Film

All one-way stretched films were found to have rather evenly spaced
long (centimeters), parallel lines of uniform width (1-7 microns) etched into
both surfaces in the direction of stretch. In general, the lines on one surface
were not coincident with those on the opposite surface. Qualitatively, iin-
der the same stretching conditions (temperature, rate of stretch, time of resi-
dence, type of restrain), the number of lines per unit of width varied di-
rectly with the stretch ratio, while the line widths concomitantly varied
inversely. A quantitative correlation of the number of lines with stretch
ratio was not feasible because the stretching apparatus was limited to a 4X
stretch and structural regularity sufficient for analysis did not occur until a
21/2x ratio had been reached. It did appear, however, that over the nar-
row stretch ratios suitable for analysis a definite correlation existed between
number of lines and stretch ratio (and, by inference, orientation). A typi-
cal etched sample is shown in Figure 1, the film having been stretched 4 X
with lateral restraint.
As the time of etching was allowed to increase, the films exhibited both
delamination and fibrillation characteristics, being degraded into long rib-
bons of uniform width composed of layers of micron-sized thickness.
 ETCHING OF TEREPHTHALATE 995

Fig. 1. Etched, nonheabset film, stretched one way 4X with lateral restraint.

Fig. 2. Etched, heat-aet film, stretched one way 4 X with lateral restraint.

The number of lines (see Fig. 2) was increased greatly by heat setting
at 185OC. for 15 h.increasing
, by a factor of 3-10 depending upon the
particular sample. Stretching without lateral restraint produced more
lines than stretching with lateral restraint under the same conditions and
stretch ratio. Heat setting a narrow strip of film with two-way restraint
caused the etched lines to change from parallel to the stretch direction
(long dimension) to perpendicular to the stretch direction.
996 w. P.BAKER, JR.
B. Heavy-Gage, Two-way Stretched Polyethylene Terephthalate
(3 mil and Greater)
Film samples of polyethylene terephthalate of various thicknesses pre-
pared by stretching 3.5X in one direction followed by 3.5X in a perpendic-
ular direction then were heat-set a t 185OC. These samples were found to
etch into long, parallel lines, generally uniform in width and spacing. The
lines were parallel to the first stretch direction and were connected by
perpendicular lines which did not cross them; i.e., the etched surface re-
sembled a brick wall rather than a grid. The unbroken lines were cen-
timeters long and 3-7 microns wide, the ultimate width depending more
on the individual sample than the etching time. The brick size averaged
100 microns by 150 microns, the long dimension lying in the first stretch
direction. Since experiments with one-way stretched film had demon-
strated that the long line direction coincided with stretch direction, it
was expected that the edges would behave differently due to the influence
of the stress patterns around the clamps. In the edge area the long lines
did not run in the direction of stretch, but instead ran a t angles up to 45'
to the direction of stretch.
It was found that the two-way stretched polyethylene terephthalate
samples were composed of laminae parallel to the film plane, each resem-
bling a brick wall when viewed after etching. The subsurface lamina was
composed of smaller bricks than the surface lamina, usually by a factor of
to 3 / 4 , thus indicating a more oriented material. The cross-sectional
area of interior bricks varied from the same as that of the penultimate
layer to a graduated decreasing size as the distance from the film center
decreased. The number of laminae varied with the film thickness and the
film forming processes, sometimes being as great as 25. The brick thick-

Pig .3. Etched, heat-set film, two-way stretched 3.5X by 3.5X surface view.
 ETCHING OF TEREPHTHALATE 991

Fig. 4. Etched, heatrset film, two-way stretched 3.5X by 3.5X edge view.

Fig. 5. Etch pattern in interior of heat-set film,two-way stretched 3.5X by 3.5X.

ness varied with position of the lamina, but an average thickness was of
the order of 12 microns. A normal surface after etching is shown in Figure
3, and a typical edge view is shown in Figure 4.
As the etching of a film sample progressed, the volumes surrounding the
bricks were etched deeper and deeper into the film until the second lamina
was reached. The material between the two laminae was then eaten
away, so that the surface bricks became detached, fell off, and exposed the
second lamina. At this time, the surface bricks were still rectangular and,
thus; much more resistant to basic attack than the mortar. The bricks
998 W. P. BAKER, JR.

were highly crystalline as judged by density (1.42g./cc.) and by x-ray

powder photographs, but were not close to a single crystal classification.
When etching of material between the first and second layer of bricks
occurred, a unique type of structure was commonly found. It consisted
of long, parallel ribbons of roughly constant width and spacing. These
ribbons ran in the first stretch direction and possessed either a crest or
trough running along the middle. The resemblance to metallurgical slip
planes was striking. A typical example is shown in Figure 5. This type
of structure was never found to occur singly-either quite a few were pres-
ent or none at all.

Fig.6. Etch pattern in interior of heat-set film, two-way stretched 3.5X by 3.5X.

As etching progressed into the second lamina, either ovals or spirals were
eaten into the bottom of the bricks of that lamina, Examination of the
spiral structure by the optical microscope and by the x-ray microscope
(kindly done by Dr. P. H. Geil of the Polychemicals Department, Experi-
mental Station, of the du Pont Co.) suggested the spiral was caused by a
flow pattern occurring during extrusion and not by a unique molecular or-
dering. The same conclusion was reached concerning the origin of the
ovals. A typical spiral is shown in Figure 6.
The above is the general etching pattern for heavy gage, two-way
stretched, heat-set polyethylene terephthalate films. Although the pre-
dominant orientation of both surfaces was in the first stretch direction, large
areas of the surface beyond the clamp influence were oriented at angles as
large as 45' from this direction. Since the orientation of each surface was
 ETCHING OF TEREPIITHALATE 999

independent of the other, the orientation between the surfaces differed by

as much as 90' in some regions. All surfaces contained faults of two types.
One type resembled a geological fault, where the bricks had slipped by each
other along a line roughly perpendicular to the first stretch direction. The
other fault type consisted of an abrupt change in orientation wherein
1-20 brick rows running at some angle such as 45' was inserted into the
normal arrangement. Occasionally the brick size differed on either side
of the fault. These faults were usually only one layer deep. Thus, ori-
entation differences exist both between surfaces and on each surface.
To ascertain that the laminar structure existed before etching, a film
sample was placed on edge and a microscope was focused on the top edge.
The sample was illuminated below the top edge by light incident on the
film surface. Reflected light travelling through the film clearly showed
the laminae on the top edge. The sample was cut in half, and one half
was etched into the usual laminar pattern and replaced in its former posi-
tion. The etched laminae coincided with those of the unetched sample
half.

C. Light-Gage, Two-way Stretched Polyethylene Terephthalate

(1 mil or Less)

Generally, the light-gage films degraded in a manner undiscernable under

the light microscope, and the degradation of sample was followed by weight
loss. Occasionally, a fuzzy brick pattern seemed to be present, but it
could not be resolved. A few 1-mil samples did show a brick pattern of
small dimensions (10 by 15 p ) , but these were infrequent. It was tenta-
tively concluded that these thin-gage films did contain the bricklike struc-
ture of heavy-gage film, but that this structure was of smaller dimensions
because of higher orientation and a thickness effect.
Etching of intermediate gages such as two mils brought forth the usual
brick structure, but the disparity of brick size was large, a row of 1 by 2 p
bricks running adjacent to a row of 100 by 50 p bricks.

D. Solvent-CrystallizedFilms
Chloroform is known to be a solvent for amorphous polyethylene tereph-
thalate, although an unsuitable one, because it crystallizes the polymer
under most experimental conditions. When placed in contact with a par-
tially crystallized film of two-way stretched, heat-set polyethylene tereph-
thalate, no dissolution was found to occur, and the per cent crystallinity
increased. Etching studies were made of chloroform-crystallized samples
to determine whether such crystallization caused an alteration in the struc-
ture. It was found that no gross structural changes as detected by etching
patterns were caused by this type of crystallization. The brick wall pat-
terns remained after the treatment, but were reduced in size by about
one third.
lo00 W. P. BAKER, JR.

E. Etching of Mechanically Damaged Films

Two-way stretched, heat-set polyethylene terephthalate films were slowly
creased through 180’ and allowed to relax for several hours before place-
ment in propylamine. The samples were completely eaten through a t the
crease before any noticeable etching had occurred in other parts of the film.
The etching in the vicinity of the crease consisted of long lines, roughly
parallel to the crease direction, regardless of the spatial relationship be-
tween crease and stretch direction.
Two-way stretched, heat-set polyethylene terephthalate films were torn
and etched and were etched and torn; in both cases the torn regions were
examined under the light and electron microscopes. Extensive damage
done in the immediate vicinity of the tear prevented firm conclusions.
These exminations did indicate that the tears occurred along the lines be-
tween bricks and received their steplike character from splittings between
laminae, i.e., the tears appeared to follow along volumes containing the
most rapidly degraded polymer. This suggested that a breakup of the
regular brick wall structure should increase tear strength. A piece of film
was simultaneously stretched 3 X by 3 X, but the stretching directions
were changed by 45’ every 33% of ultimate stretch. Etching of the result-
ant film after heat setting showed highly oriented local areas, the orienta-
tion directions of the various areas being random with respect to each other.
This film possessed a higher tear strength than the usual heat-set film
stretched 3 X by 3 X simultaneously.
The difference between surface and interior patterns suggested that the
surface lamina had some independence from the interior laminae. To
check this, various designs (circles, squares, parallel lines) were cut into
unstretched, amorphous, polyethylene terephthalate films to a depth
greater than one lamina. The cut films were one- and two-way stretched
and then etched. The patterns traversed the cuts with no shift of orien-
tation. I n this case, the patterns were apparently templated from the
interior before the -formation of laminae, a situation, perhaps, not true of
all stretching processes.

F. Rates of Etching
The rates of etching of various films were followed by weight loss de-
terminations and periodic viscometric measurements. Since the reaction
was heterogeneous and the character of the film surfaces differed, the mini-
mal data collected were not considered worthy of extensive interpretation.
In general, the rates depended upon the amount of stretch, the density,
and the thickness. Initial rates fell into three groups: 4%/hr., 3.2%/hr.,
and 1.6%/hr. The highest rates were characteristic of film of low stretch
ratio. Since the rates were dependent upon a t least three variables, the
three rather narrow groupings were probably the result of sampling arti-
facts rather than distinct film types. Often, long induction periods were
observed.
 ETCHING OF TEREPHTHALATE 1001

G. Etching of Polystyrene
To establish that crystallinity was not essential for the structures ob-
served by etching in polyethylene terephthalate films, amorphous atactic
polystyrene film, which had been stretched about 1QX by 6X, was ex-
posed to a poor polystyrene solvent. Viewing of the film so treated under
a microscope revealed a surface pattern similar to that etched into one-way
stretched polyethylene terephthalate films.
H. Dyeing and Stress-Crackingof Polyethylene Terephlhalate
Attempts to stress crack or solvent crack the etch pattern into two-vay
stretched, heat-set films of polyethylene terephthalate were unsuccessful.
To achieve such cracking, it was necessary to apply a stress of greater mag-
nitude than that residual in the film; as a result, the crack patterns ob-
tained were those characteristic of the applied stress.
Cursory attempts to dye stretched heat-set film of polyethylene tereph-
thalate without concomitant crystallization failed. It was thought khat
the volumes which were preferentially attacked chemically might also dye
preferentially.
I. Examination of Etched, Two-way Stretched, Heat-Set
Polyethylene Terephthalate Film By Electron Microscopy
Etched samples bf polyethylene terephthalate film which had been
stretched 3.5X by 3.5X and heat set at 185OC. were replicated and elec-

Fig. 7. Electron micrograph of etched, heatset film,two-waystretched 3.5X by 3.5X.

1002 W. P. BAKER, JR.

Fig. 8. Electron micrograph of etched, heat-set film,two-way stretched 3.5X by 3.5X.

tron micrographed by standard techniques. The replications demon-

strated that the first layer bricks were composed of spheres about 500 A.
in diameter. Uneven etching made it difficult to determine the arrange-
ment of these spheres, but occasionally they were seen to exist as rows
aligned in the stretch direction. The material beneath the first layer was
composed of somewhat larger spheres (700-1000 A. diameter). The sur-
face of the first layer of bricks was quite smooth, except for hexagonlike
emergents (presumably exuded cyclic trimer3) and occasional randomly
swirled areas of unknown origin. Typical electron micrographs of etched
film are shown in Figures 7 and 8.

DISCUSSION AND CONCLUSIONS

This study o€ the gross structures of anisotropically stretched films is
in too embryonic a stage to permit an origin and meaning of the structures
to be assigned with c d d e n c e . The mechanism of the appearance of these
structures and the relationship of these structures t o organization in the
films are not clearly defined. The extent to which the etching reagent may
be enhancing organizations existing in the film and the relationship of this
phenomena to the craze cracking described by Nielsen' are not known.
However, it is often advantageous to advance a hypothesis based on avail-
able data for use as a point of departure. In the following paragraphs such
a hypothesis of the structure of anisotropically stretched films of poly-
ethylene terephthalate will be proposed. Much more extensive and varied
investigation will be required to establish the degree of correctness of the
picture.
There is a large regular structure of micron size in the anisotropically
stretched films; this structure is built into the film duriag the fabrication
 ETCHING OF TEREPHTHALATE 1003

processes and represents the distribution of strain caused by the fabricating

stresses. The micron-sized structures are built of spheres, 500-1000 A.
in diameter. Spatially ordered over a long period, the spheres are com-
posed of highly ordered molecular units and may move as rheological
units.
The experimental evidence for the above will now be considered. The
etching studies of various films showed that the etched patterns appeared
to be a measure of the direction and extent of orientation. That the poly-
mer in these patterns was attacked preferentially suggested that it existed
at a higher energy level than adjacent material. This higher energy con-
tent could be the result of higher strain because the film tended to distribute
the easily degradable structures uniformly a t all opportunities just as it
might be expected to distribute strain uniformly if given opportunity.
Thus, although the total easily degraded mass remained about the same,
the number of lines per unit length of one-way stretched film increased
from film stretched with restraint to film stretched without restraint.
Similarly, the subsequent heat-setting step or crystallization by chloro-
form caused an increase in the number of lines.
To demonstrate that the more readily degradable volumes were actually
of higher energy content and inherent in the film, we attempted to stress-
crack film along the lines of strain already in the film. As reported, this
approach failed. However, the tear characteristics as revealed by etching
of two-way stretched, heat-set polyethylene terephthalate films are in
accord with this concept. It may be that these volumes are strained and
highly organized. Thus, although the films are initially hard to tear,
once the tear is started, the tear strength is considerably lower. This
might be the case if highly organized volumes of higher energy content
than their environment were disrupted by the started tear and became
disorganized volumes of excess energy.
Heat of solution experiments were employed to measure the relative
enthalpy of stretched films. This work, which will be described elsewhere,
showed that the enthalpy of a 4x by 4x sequentially stretched film (high-
est ratio available) was 5.8 cal./g. higher than that for unstretched f ilm
of the same crystallinity. It is tempting to assign a large share of this to
the etched volumes.
The spherical building blocks were readily discernible from electron mi-
crographs. Uneven etching allows little to be said concerning their ar-
rangement except that frequently they were observed to lie in a row in the
stretch direction. The camposition and rheolagical identity are inferred
from the studies of Heffelfinger.' He found by x-ray techniques that g o u p
of crystallites probably moved together as units and studied the molecular
organization within these groups.
Ultimately, the significance of structures will reside in their ability to
control various properties of film. Reakoning somewhat intuitively, one
may infer that the ordered close-packed constituents of the spheres and
the rheological identity of the spheres make the spheres the strongest
1004 W.P. BAKER, JR.

I ' I

L MODULUS

I I I
<lpl I- loop1 3 loop
BRICK LENGTH
Fig. 9. Physicd property levels vs. brick length for two-way stretched polyethylene
terephthalate.

volume unit next to the individual crystallites. Since our measurements

generally measure weak spots, the strong units are often not revealed.
So it may be that the primary concern to physical properties is the manner
in which the spheres are arranged and the manner in which the strain is dis-
tributed. We were not able to prove or disprove the above because of the
limited number of film-forming techniques available. The available film
fabricating processes are such that one or two of the above structures can-
not be varied independently of the others rendering the primary and second-
ary correlations indistinguishable.
Initially a property correIation was sought from a comparison of heavy-
gage, two-way stretched, heat-set, polyethylene terephthalate films
(micron structure) and light-gage films (sub-micron structure). Some
plots of physical properties versus brick length of film are shown in Figure
9; these indicate that some correlation of physical properties with struc-
tural sizes does exist. Also, stretched polyethylene terephthalate film
containing the micron-sized structure is tougher than unstretched film of
the same crystallinity and thickness (structures absent). That this need
not be caused by a different crystallite size, orientation, and/or distribution
is demonstrated by data for amorphous, noncrystallizable polystyrene film.
As-cast polystyrene film is exceedingly brittle; stretched polystyrene film
is sufficiently tough to be a commercially useful product and possesses a
micron-sized structure as reported. This is consistent with the concept
that strain distribution is important to polyethylene terephthalate proper-
ties, and it demonstrates that amorphous material can exist in two different
states, one able to delocalize quickly applied stress and the other not. The
mechanics of the applied stress deIocalization are not known, but delocaliza-
tion may occur from acceptance by a strained organized volume as a unit.
Bternatively, the volumes may be a dumping ground for oligomers and
 ETCHING OF TEREPHTHALATE 1OQ5

voids, having high permeability for the attacking reagent and numerous
degrees of freedom. Since permeability of these. films does not change
much with orientation and rapid redistribution occurs whenever possible,
the alternative case is weakened.
No property dependence upon the sphere arrangement was determined
because of sample limitations. However, it would seem odd if the size
and packing of the spherical organizations influenced properties only
negligibly. The origin of these organizations is unknown, but their size
is compatible with the size of rheological units, which have been postdated
to exist in polymer melts.
The origin of the laminar structure found in stretched polyethylene
terephthalate films is unknown. It is possible that it is generated by
anisotropic heat transfer during fabrication by the anisotropic stfuctures
put into the film.
It is thought that at least the micron-sized structures described herein are
general to all anisotropically stressed films. Work by Dr. R. M. Ikeda of
this laboratory has indicated the existence of these structures in polyvinyl
chloride and cellophane, and these structures have been shown to be present
in polyvinyl fluoride.6
In conclusion, it should be stressed that to see the regularity of these
structures a most carefully designed stretching apparatus is necessary
because the applied stress must be uniform.
It is a pleasure to acknowledge the many helpful discussions throughout the program
from the following people: Dr. L. F. Beste, Pioneering Research Laboratory; Professor
George S. Hammond, California Institute of Technology; Dr. C. J. Heffelfbger, Mylar
Reaearch and Development Laboratory, du Pont Company, Circleville, Ohio; Dr. S. S.
Tor, Engineering Research Laboratory, du Pont Company; Dr. W. J. Pangbnis, Dr.
F. P. Gay, and Dr. R. D. Pruett of this laboratory. The author is indebted to Mr.J. F.
Godlewski of the Central Research Department, du Pont Company, for replications and
electron micrographs.

References
1. Nielson, L. E.,J . Appl. Polymer Sci., 1,24 (1959).
2. Berestneva, G. L., and P. V. Kozlov, Vpokomolelrulyarnye Soedineniya, 2, 1854
(1960).
3. Giuffria, R., J . Polymer Sci., 51,427 (1961).
4. HeffeEnger, C. J., J . Polymer Sci.,47,304 (1961).
5. Osborn, R.O., Film Department, Yerkes Research Laboratory, du Pont Company,
Buffalo, N. Y., unpublished work.

Synopsis
A degradative etching technique has been employed with polyethylene terephthalate
films to demonstrate the existence of several different structures, the size of which vary
from hundreds of microns to hundreds of Angstroms. The micron-sized structures me a
function of the processing and orientation of the film and occur in regular geometric
patterns. Thus, parallel stretch-direction lines are etched into one-way stretched film,
the number of lines being dependent upon film history. Etched, two-way stretched
6lms reveal a lamellate composition, each layer possessing a brick wall-like structure.
This general structural pattern has been found in other types of film by similar meth-
1006 W. P. BAKER, JR.

ods. Examination of the etched areas by electron microscopy demonstrates that the
micron-sized blocks are composed of spheres, 700 A. in diameter, which are aligned
over moderate distances.

RbW6
Une technique de gravure par dbgradation a CtC appliquCe 8. des films de tCrCphtalate
de polyethylene pour prouver l’existence de plusieura structures diffCrentea dont la
grandeur varie de centainea de microns 8. des centainea d’Angstroms. Lee structures de
dimensions en microns sont en fonction de la preparation e t de l’orientation du film et
sont presentes sous des formes g6om6triquea rCguli8res. Des lignea de direction d’Ctire-
ment parallele sont gravees dans des films CtirCs dans une seule direction. Le nombre de
lignes depend du traitement du film. Dea films CtirCs dans deux directions montrent une
composition lamellaire dont chaque couche a une structure rCticulCe. Cette structure
gCn6rale a C t k retrouv6e dans d’autres films. L’examen des surfaces graveea par micro-
scopie Clectronique montre que les blocs de plusieurs microns sont composCs de spheres
de 700 A. alignCes sur des distances modCrCes.

Zusammenfassung
Ein Atzverfahren durch Abbau wurde an Polyathylenterephthalatfilmen zum Nach-
weis dea Bestehens mehrerer, verschiedener Strukturen, deren Groeae im Bereich von
einigen hundert Mikron bis einigen hundert Angstrom lei& angewendet. Die Struk-
turen im Mikron-Grossenordnungsbereich entstehen bei der Verarbeitung und Orientier-
ung des Films und treten in regelmiissigen, geometrischen Anordnungen auf. So lassen
sich in einseitig gereckte Filme parallele Linien in der Reckungarichtung atzen, wobei ihre
Anzahl von der Vorgeschichte des Films abhangt. Zweiseitig gereckte Filme weisen bei
der Atzung einen lamellaren Aufbau auf, wobei jede Schichte eine ziegelmauerartige
Struktur beaitzt. Dieses dgemeine Strukturbild wurde auch bei anderen Filmtypen
mit ahnlichen Methoden festgeatellt. Eine elektronenmikroskopiche Untersuchung der
Atzflachen zeigt, d m die Blocke im Mikronbereich aus Kugeln mit einem Durchmesser
von 700 A. zusammengesetzt sind. welche iiber miiasige Entfernqngen angeordnet sind.

Discussion
B. Rosen (Westinghouse Ele-tric Corporation, Pittsbirrph, Pa.): I have a question
concerning your implication in using the term “etching.” “Etching” usually has the
connotation of a lorally selective reaction or solution. Could it be that you are really
concerned with a fracture? I don’t understand the role of a uniform stress in a selective
etching. Could your material be anisotropic and have points or areas which are good
stress concentrators? If this sample were first fractured, subsequent reaction might be
preferentially located a t these new surfaces. Have you eliminated the possibilities of
environmental stress cracking, whether the stress were applied or internally locally
residual? Or is this a “solvent cracking,” by which is meant the introduction of transient
stresses due t o a diffusion-controlled localization of swelling, perhaps complicated by
residual stresses or inhomogeneities?
W. P. Baker: The structures are not discerned until chemical degradation h m oc-
curred, evidenced by weight loss. Thus, initially chemical degradation is required and
it occurs selectively in the regions eaten from the film surface. When enough material
has been removed t o weaken these areas to the necessary degree, it is quite possible that
a fracturing process is involved, perhaps abetted by solvent cracking.
The uniform stress mentioned refers only t o the application of the stress (freedom from
clamp effects, uneven stretching, thermal gradients). This uniform application of strew
results in a n anisotropic film because the stress is applied in only one or two directions.
It is thought that residual strains are left in the film by the stretching process and that
these strained regions are preferentially attacked chemically.
 ETCHING OF TEREPHTHALATE 1007

I. Goodman (Imperial Chemical Industries Ltd., Fibres Division, Harrowgate, York-

shire, England) : 1 . Are structures similar t o those described produced a1.so in the pro-
gressive dissolution of polyethylene terephthalate films by alkaline (e.g., NaOH) treat-
ment? 2. To what extent are the structures described characteristic of the chemical
etching method used?
W. P. Baker: 1. Alkaline treatment of films of polyethylene terephthalate has not
yielded structures similar to those described in this work. After sufficient contact with
aqueous sodium hydroxide, large areas of surface in the form of thin flakes were removed.
Probably the rate-controlling step was the approach of the anion from its high dielectric
medium, water, t o the hydrophobic polyethylene terephthalate of low dielectric con-
stant. The flaking may be caused by “solvent cracking” after a small amount of
etching by hydroxide ion has occurred. 2. The structures described in the paper have
been found after etching with several organic amines. It has been reported [G. L. Ber-
estneva and P. V. Kozlov, Vysokmlekulyarnye Soedinaiya, 2,1854 (1960)l that struc-
tures which appear to be similar have been produced by several organic acids (phenols).
This variety of reagents and the work reported in the paper strongly suggest that the
structures are characteristic of the substrate rather than of the etching method.
R. S. Stein (University of Massachusetts, Amherst, Mass.): It seems that, if these
structures were associated with residual strain, birefringence patterns should be ob-
served with the polarizing microscope. Were they?
W. P. Baker: Only cursory attempts were made to observe these structures by bire-
fringence patterns, and they failed, possibly because of diffraction of light by many
underlying noncoincident layers.