GARNER et a1.-PERMEATION O F P.C.T.F.E.

F I L M S BY N I T R I C A C I D 407

References
Ahlers, N. H . E., Brett, R. A., & McTaggart, N. G.,
J . appl. Chem.. 1953, 3,433
2 Ahlers, N . H. E., Dennison, -4. C.. & O’Neill, L. A,,
N a t w e , Lond., 1954, 173, 1046
Ahlers, N. H. E., & Dennison, A . C.. Chem. &-
Ind., 1954, p. 603
Ahlers, N. H. E., & Gunstone, F. I)., Chem. G.
Ind., 1954, p. 1291
O’Neill, I,. A.. Chem. G. Ind., 1954, p. 384
Ahlers. N. H . E., & McTaggart, N . G., Anallst,
1954, 79,70
’ Crofts, J. B., J . appl. Chem., 1955, 5, 88
* Ahlers, N . H. E., & O’Neill, L. A,, J . OLZCol. Chrm.
Ass., 1954, 37, 533
na 0’9eill. L.A,, & Cole, C. P., J . appl. Chem., 956,
6. 356
1J.S. Naval Research Laboratory Report No. 4369,
1954
l o Shreve, 0. D., Analyt. Chem., 1952, 24. 1692
l 1 Childers, E., & Struthers, G. N., Analyt. Chem.,
1955, 27, 737
l 2 Kendall, D. N., Hampton, R. R., & Hausdorff,
H., A p p l . Spectroscop3. 1953 7 , 179
l3 Jaffe, J . H.. & Pinchas, S., Analyt. Chem., 1951,
23, 1164
Fitzgerald, E. B., A.S.T.M. Bztll.. 1955, No. 207,
65
lS Saur, R. L., A . S . T . M . Bull., 1955, N o . 207, 61

PERMEATION OF POLYCHLOROTRIFLUOROETHYLENE FILMS

BY NITRIC ACID
By F. H. GARNER, S. R. M. ELLIS and J. C. GILL*

The permeation of polychlorotrifluoroethylene by nitric acid has been found t o occur at a limited
number of sites in the surface of the film. 1hese sites have been detected using paper impregnated
with a suitable indicator and also by microscopical examination ; they were found to be randomly
distributed and were mainly macro- or visible cracks. Counts have been made of the numbers and
size distribution of the cracks. Infra-red spectrometry was used t o investigate whether chemical
reactions occurred between nitric acid and the fluorinated plastic film, but no evidence of chemical
degradation products was found.

Introduction
Polychlorotrifluoroethylenel,-(CFJFCl),,-, which is exceptionally inert chemically, is
produced as a film ranging in thickness from 0.002“ to 0.015”. As such, the material can
be used to protect vessels and equipment used for storing and handling corrosive chemicals,*
such as nitric acid (98.8%).
Little information is available in the literature concerning liquid permeation through
plastic films, and in this paper are reported the results of a study of some factors influencing
the permeation rate of concentrated nitric acid through polychlorotrifluoroethylene film
(P.C.T.F.E., trade names Kel-F, Hostaflon).

Experimental
Materials
Two thicknesses of unplasticized, extruded, Kel-F (type 300) were available, 0.004” and
0*005”,together with some 0.004’’ Hostaflon dispersion film. P.C.T.F.E. has a structure
comprised of both crystalline and amorphous phases. The generally accepted structure is that
of many rod-like molecular chains packed side by side in precise order in the crystalline regions,
each polymer chain passing through a number of crystalline regions. Individual crystallites
form tightly packed spherical formations known as spherulites which are visible microscopic ally.^^
Heat treatment of extruded Kel-F film modifies its structure and increases or reduces the
degree of crystallinity depending on the method of ~ o o l i n g . ~
The first type of material is produced by slow cooling whilst the latter is obtained by rapid
cooling (quenching).

*Present address : Sir. W. G. Armstrong LVhitworth Aircraft Co., Coventry

J. appl. Chem., 6, September, 1956

408 G A R N E R et al.-PERMEd TION OF P.C.T.F.E. F I L M S BY N I T R I C - 4 C I D

The nitric acid used in the present investigation was produced by the oxidation of ammonia
to the specification : concentration 98.5-1000!o ; nitrous acid < 0.20,; by weight ; chlorides
< 0*020/, by weight ; sodium or other alkali-a minimum ; solid residue, on evaporation to
dryness < 0.050,; by weight.

Permeation rate
The acid permeation rate was investigated by placing the film between concentrated
nitric acid and distilled water, and measurement of the changc in conductivity at various times.
Fig. 1 gives a comparison of typical conductivity-time measurements for extruded Kel-F
(:IS received), and extruded Iiel-F (heat-treated, amorphous), and Hostaflon dispersion film.
I t can be seen that the quenched amorphous Kel-F has a superior resistance t o nitric acid
permeation than both the Hostaflon dispersion film and extruded Rrl-F (as received).
I t appears, therefore, that the degree of crystallinity of the film markedly affects the rate
of acid permeation. In the process of manufacture, stress is imparted to the film and this
produces crystallinity, with the result that, in the presence of nitric acid, cracks develop to
relieve the stress in these crystalline regions. Cracks which penetrate deeply into the film
can give rise to permeation sitcs
As an alternative to this physical view of permeation there is the possibility of chemical
reaction between P.C.T.F.E. and nitric acid.
The following factors were therefore investigated :
1 . The location of permeation sites.
2. Microscopical examination of permeation sites.
3 . Chemical or physical nature of permeation.

Location of pevmention sites

The method involved the use of indicator papers, which were prepared by oven-drying
circles of a hard filter paper which had previously been immersed in an alkaline solution of
methyl orange-xylene cyanol indicator.
3000 Samples of film were used which had
already shown a constant acid permeation
v) rate on a conductivity-time plot. The
0
X sample was held horizontally with concen-
52000 trated nitric acid under pressure beneath
t
t the film surface. The indicator paper was
?
I-
placed in position upon the upper surface of
3
U the film and pressed against it by means of a
z 1000
a weight. Acid permeating the film produced
0
U red marks on the green background and
revealed the permeation sites. To obtain the
best results, the paper was removed before
0 5 10 15 20 25 30 35 diffusion occurred within the paper. In
TIME, days order to obtain permanent records colour
FIG. 1 . Pevitiratioii of 0.004” P.C.T.F.B. f i l m changes were marked in pencil immediately
b-y conrentvated nitric acid (98.8%) at 50”
after the paper was removed. Fig. 2 shows
the result obtained with extruded, unplasticised, 0.004” Iiel-F film for acid permeating a t 20”
over a period of 5 days.
Permeation occurred at well-defined sites which were randomly distributed over the area
of permeation. The number of sites to appear increased only slightly over a period of 5 days.
This method of detecting the permeation sites can only be regarded as qualitative since not
all the sites are repeated on consecutive paper discs.
Microscopical exantirialion of permeation sates
The samples, approximately 24“ x 2 & “ ,were placed upon the mechanical substage of the
microscope and viewed through a binocular eyepiece under transmitted light at a magnification
x 1000. Photographs were taken with a single eyepiece using a fixed-length microscope
camera at a magnification x 450.

J. appl. Chem., 6, September, 1956

 FIG. 2. Pevnzeatzun sites 1 1 1 esfritded, unplasticized I i E L - F f i l m using
nityic acid ( 9 8 . 8 ~ , ) . ( A c t u a l size)

Examination of the photographs, Figs. 3-5, shows that cracks of 1-5Op length develop
in crystalline extruded Kel-F during a period of acid permeation, whilst cracks less than 1 p
in length are faintly detectable in amorphous, extruded Kel-F. Hostaflon dispersion film also
develops isolated groups of cracks of 1-5Op in addition to those of less than 1 p.
The cracks which develop in extruded Kel-F appear to be evenly distributed throughout
the film and are visible on both the acid- and water-side surfaces as well as within the film.
A number of references to cracks in polymers has been made in the literature, but there is
some confusion due to the diffferent terminology used. For amorphous polymers, e.g., methyl
methacrylate, polystyrene, the term crazing ’ is usually used,6 while for vinyl polymers, the
terms ‘ environmental cracking ’7, 8 and embrittlement have been employed. In an effort
l9

to clarify this situation a size classification of cracks has been employed in the present work.
Crack length less than 1 p-micro-cracks.
Crack length 1-50 p-macro-cracks.
Crack length greater than 50 p-visible cracks.
Such a classification is useful since the cracks observed in extruded Kel-F and Hostaflon
dispersion film are individually distinct and do not appear to form patterns.
Extruded, unplasticised, Kel-F develops macro-cracks during acid permeation, whilst
heat-treated amorphous Kel-F develops micro-cracks.
In a further series of experiments, the change in numbers and size distribution of surface
cracks was measured during a period of acid permeation, on both sides of the samples. TO
determine the macro-crack intensity, counts were made of the number of cracks within a
rectangular graticule. Cracks with more than half their length within the area of the graticule
were included and those with less excluded. In practice, there was little variation in these
counts but the arithmetic average of SO counts has been reported in Table I. The size
distribution was obtained by comparing the crack length with a series of circular reference
graticules of known diameter. I t was not possible to observe individual microcracks at a
magnification x 1000, hence a qualitative estimation of crack intensity has been made in this
case. The groups of macro-cracks observed in Hostaflon dispersion film were not sufficiently
evenly distributed to perform an intensity count. The results are given in Table I, and Figs.
6 and 7.
The microscopical investigation indicated that most of the nitric acid permeation of Kel-F
film took place via macro- or visible cracks. The number of surface cracks which actually
give rise to a direct permeation path appear to be few, since the number of surface cracks greatly
outnumber the number of permeation sites.

Physicd or cluvtaicul izutitre of permeatioti

Infra-red spectrometry was used to examine acid-permeated Kel-F samples for degradation
products. The infra-red spectrograms of 0-005’’Kel-F films were obtained using a doul>le-l>eam
infra-red spectrometer, Grubb-Parsons Type S3A.

J. appl. Chem., 6, September, 1956

410 GARNER et a1.-PERMEATION O F P.C.T.F.E. F I L M S BY N I T R I C ACID

Initial ( x 335) 60 Days ( x 335)

FIG.3. Development of macrocracks i n extruded KEL-F film duringpermeation of nitric acid (98.8%)at 50"

FIG.4. Hostaflon dispersion film. Permeation of nitric acid (98.8%) at 50"

Groups of surface macrocracks ( x 335)

Initial ( x 335) CO Days ( x 335)

FIG.5. Develofimenl of microcracks in extruded K B L - F film during permeation of nitric acid (98.8%)at 50"

The spectrogram, Fig. 8a, shows a Kel-F sample which has undergone nitric acid (98.8%)
permeation for 80 days at 50" in an acid Kel-F water cell. The sample reveals a new strong
absorption band at 3400 cm.,-' and the bands a t 2273 cm.-l, and 1630 cm.-l show a slight
increase in intensity.
Oven drying of the sample at 80" has the effect that the spectrogram reverts to the original
spectrogram of untreated Kel-F film. No evidence of chemical degradation products or chemical
reactions have been found. The band which develops at 3400 cm.-l can be attributed to an
OH-bond stretching vibration. This, together with the other bands, is typical of those given
by liquid water and dilute nitric acid, and it appears that, when a permeation path is established
across the film, back diffusion of liquid water occurs which lowers the acid concentration within
the film.

J. appl. Chem., 6, September, 1956

 G d R N E R et a1.-PERMEATION O F P.C.T.F.E. F I L M S BY N I T R I C A C I D 411

Table I
Observed intensity of surface cracks ( x 1000)
Side Micro Macro Visible Micro Macro Visible Micro Macro Visible

On day 20 On day 38 On day 62

Untreated extruded KEL-F
sample a ;zS 0 9.1* 0 h 14.2* 0 h 14.3; 0
WS 0 7.2; 0 h 12.7* 0 h 13.2; 0
sample b AS 0 6.6* 0 h 11.8; 0 h 12.2* 0
14's 0 5.4; 0 h 9.4* 0 h 9.8* 0

On clay 20 On day 40 On day 60

Extruded Kel-F, heat-treated,
amorphous AS 11 0 0 H O 0 H O 0
\v 5 11 i) 0 H U 0 H O 0
On day 20 On day 40 On day 60
Hustaflon dispersion f i l m
AS 0 0 0 O L 1- h L L
ws 0 0 0 0 0 0 h 0 0
*The figures are the arithmetic average of 50 counts with a rectangular graticule 174 x 37 square microns,
a t a magnification x 1000.
h = Haze due t o micro-cracks (sample semi-transparent).
H = Haze due to micro-cracks (sample opaque).
L = Localized groups of cracks.
AS= ..lcid side \VS = water side

FIG.6. T.-ariation of wtacrocrack length. Extruded. unplasti- FIG. 7. Variation of' naacrocrack length.
ciced, K E L - F f i l m . A c i d side Extruded, unplasticized, KEL-F f i l m .
W a t e r side
nay Mean U Day Mean U
0 20 11.73 3.52 0 20 6.54 2.24
% 38 9.17 3.06 X 38 7.06 2.58
a 64 9.64 3.32 A 64 6.87 2.76
u = Standard deviation u = Standard deviation

Sorption experiments were performed by immersing the sample in nitric acid a t a controlled
temperature and observing the increase in weight and the change in the infra-red spectrum.
The samples were removed from the acid and prepared for examination without being contacted
with water.
The sorption of nitric acid (98.S0/b)in the absence of water, Fig. Sb, introduces a strong
absorption band a t 1670 cm.-l and a weaker band a t 3320 cm.-l while the band a t 2273 cm.-l
is increased slightly. The bands can be attributed to concentrated liquid nitric acid (98.5%)
which indicates that the acid is retained within the film in liquid pockets.

J. appl. Chem., 6, September, 1956

412 G A R N E R et al.-PERME.-1TION O F P . C . T . F . E . F I L M S BY N I T R I C .-lCID

The above experiments show that nitric acid permeates the film as a liquid and is retained
in cracks within the structure by physical adsorption. The effect of crack size upon the amount
of sorption has also been examined.
The sorption of concentrated nitric acid, Fig. 9, shows that amorphous Kel-F containing
micro-cracks has a higher equilibrium value than crystalline Kel-F (as received) which contains
macro-cracks. This appears contrary to the findings of the permeability tests, but it is believed
that the macro- and visible cracks behave as open surfaces, whereas surface micro-cracks,
which are present in larger numbers, retain more liquid. This liquid, however, does not
necessarily permeate the film.

I
z
E
a 1.0
a
2m i
3
4 a
0 0 8

3
6
In
0
0 0.6
5
W
\
V 2
a
W
s 0.4
a m

z
2 0.2
c
Cm- a
[L
FIG.8. ( a ) E x t m d e d K E L - F pevnieatio$t of ?ziti'ic acid % 0 200 400 6 0 0 800 1000
98.8% at 50" (Time)Y2/thtckness. h* in-'
__ Xs received - . . . - Xfter permeation FIG,9. ExtsudPd, tinplasticized
K E L - F f i l m . Sorptzorc of t z i h I C
( b ) Extviidcd K E L - F , sorptiotz of witvic m i d aczd 98.8q, at 50'
98.8y.O at 50"
As received - ~ - - - After sorption

Conclusions
The action of concentrated nitric acid upon crystalline P.C,.T.F.E.film is to develop macro-
or visible cracks which give rise to a path for acid permeation. Permeation of the film results
from liquid nitric acid diffusing through these cracks.
The intensity per unit area and size distribution of these cracks remains constant after
an initial time-lag period has been exceeded.
The action of concentrated nitric acid on amorphous film is to produce micro-cracks which
do not give rise to any measurable acid permeation. Micro-cracks are thought to develop
at very small residual centres of crystallinity.

Acknowledgement
The authors wish to thank the Directors of thr: Sir W.G. Armstrong Whitworth Aircraft
Co. for sponsoring this research work.

Chemical Engineering Dept.,

The University,
Birmingham, 16
Received 9 February, 1956

References
l Kellogg, RI. \V., Ltd., l i d - F t p c / i . Bull. 1 ,'12;49 6 Itussell, E. \V,,Royal Aircraft Establishment Rep.,
* Rubin, L. C., &Teeters, W. O., CLII.VOSIOII, 1953, 9, ( 3 ) , 1948, No. 441, 447
100
Price, F. P., J . .4iizer. c k ~ ) i t SOC..
. 1953. 74, 31 0 Carey, R. H., .-1.S. T.,11. B d l . . 1950, 167, 56
Reding. E. P., I?tdzistr. Eirgrz,? CIwu., 1954, 46, 1963
Schlesser. C. (Editor). I'reparatiiJn. Properties, and L)e Coste, 5. B., Inn'ztst~~.
l<j?:fiLg C h e m . , 1951, 43, 114
'Techiiology of kluorin; and Organic Fluoro-
compounds '. 1951 ( S e w York : McCraw & Hill) 9 Richards, R. B., Tuaiis. Faradar' SOC., 1945, 41, 127