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28THE SORPTION OF WATER BY CELLULOSE AND

EIGHT OTHER TEXTILE POLYMERS: PART IITHE
SORPTION OF WATER VAPOUR BELOW 100C BY
TEXTILE POLYMERS OTHER THAN CELLULOSE
a
R. Jeffries
a
British Rayon Research Association, Heald Green Laboratories , Wythenshawe, Manchester
22
Published online: 05 Dec 2008.

To cite this article: R. Jeffries (1960) 28THE SORPTION OF WATER BY CELLULOSE AND EIGHT OTHER TEXTILE POLYMERS:
PART IITHE SORPTION OF WATER VAPOUR BELOW 100C BY TEXTILE POLYMERS OTHER THAN CELLULOSE, Journal of the
Textile Institute Transactions, 51:10, T399-T418, DOI: 10.1080/19447026008659782

To link to this article: http://dx.doi.org/10.1080/19447026008659782

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 Vol. 51 No. 10 " OCTOBER 1960

JOURNAL
of the
TEXTILE INSTITUTE
TRANSACTIONS
(Copyright The Textile Institute and Contributors, 1960)

28THE SORPTION OF WATER BY CELLULOSE AND EIGHT

OTHER TEXTILE POLYMERS
PART nTHE SORPTION OF WATER VAPOUR BELOW 100C
BY TEXTILE POLYMERS OTHER THAN CELLULOSE*
By R. JEFFRIES
Detailed results are presented on the absorption and desorption of water
vapour (0100% r.h., 3090C) by cellulose triacetate, secondary cellulose
acetate, ethyl cellulose, drawn nylon 6.6 yarn, Terylene, Orion, wool and
Fibrolane. The sorption characteristics of the samples were stabilized prior
to the sorption measurements by means of several absorption-desorption
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cycles at 90C. The sorption results are analysed, discussed and compared
where possible with the results of previous workers. The isosteric heats and
entropies of sorption are derived and discussed briefly.
1. INTRODUCTION
This paper deals with the absorption and desorption of water at
3090C by secondary cellulose acetate, cellulose triacetate, ethyl cellulose,
nylon 6.6, Terylene, Orion, wool and Fibrolane ; all except ethyl cellulose
are textile polymers, and this selection was chosen because it contains all
of the more important non-cellulosic textiles and at least one representative
of each of the major groups, polyamides, polyesters, polyacrylonitriles,
and regenerated proteins.
Only secondary acetate^ ethyl cellulose^ and wool^-^ have been studied
previously over a wide range of temperature ; published data on the sorption
of cellulose triacetate**^ and nylon 6.6^-^' are restricted to temperatures in
the range 2040C; detailed results on polyesterfibres^^'^*'^^'^^poly-
acrylonitrile fibres^^-^*-*' and regenerated proteinfibres^*-^^"^^^'*'are very
few indeed.
The previous work on these polymers is compared with the present
results in the text of the paper. ;,
2. MATERIALS
Secondary Cellulose Acetate : films (40 db 5 [x thick) were cast on glass
plates from an acetone solution of a commercial methylene chloride-process
flake (acetic acid yield 53-5%, intrinsic viscosity in acetone at 25C, 1-35).
The films were disoriented by swelling in 80/20 v/v methylene chloride/
benzene, the swollen film being allowed to dry without tension. .
Cellulose Triacetate : films (50 10 \i thick) were cast on mercury from a
dilute solution of a commercial fiake (acetic acid yield 61-5%, intrinsic
viscosity in chloroform at 25C, 1-57) in 60/40 v/v methylene chioride/ethyl
alcohol.
Part I of this paper was published in September, /. Text. Inst., 1960, 51, T339.
It is anticipated that Part III will be published in November.
T399'
 T400 1%The Sorption of Water by Cellulose and
Ethyl Cellulose: a sample of film (ethoxy content 48-6%) provided by
Professor R. M. Barrer.
Nylon 6.6 Filament Yarn : a commercial drawn yam, 3-2-den. filaments,
spun without pigment; extracted with light petroleum ether and then with a
1 % aqueous solution of Dispersol VL at 60C for 30 min^^
Terylene Filament Yarn : a commercial yarn, 2'3-den. filaments, spun without
pigment ; extracted as nylon yarn.
Orion Staple : du Pont T'ype 42, thought to be a copolymer of acrylonitrile
and about 10% of another constituent^^^ ; 2-den., staple length IJ in.;
extracted as nylon yam.
Wool: a 5860s quality Australian Comeback ; washed in warm water
containing a non-ionic detergent, followed by successive extractions in warm
water, ethyl alcohol and light petroleum ether.
Fibrolane BX Staple : (Courtaulds Ltd.) a regenerated protein (casein)fibre;
extracted with warm water and light petroleum ether.
(Brief remarks on X-ray photographs of these materials are given in
the next section.)
3. EXPERIMENTAL AND GENERAL
The sorption measurements on samples of the above materials were
carried out using the same apparatus and by a technique similar to that
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described for the cellulosic materials in Part I. The samples were first given
a stabilization treatment similar to the one employed with the celluloses in
Part I, viz., several slow absorption-desorption cycles at 90C ; the sorption
behaviour of the treated samples proved satisfactorily stable during the
sorption measurements.
X-ray diffraction photographs of the samples were obtained before and
after stabilization treatments. The photographs of the original materials
were in every case similar to the generally accepted X-ray diagrams as available
in the literature, taking into account the nature and method of preparation
of the present samples, i.e., secondary acetate, triacetate and ethyl cellulose
films, unoriented and of very low crystallinity ; nylon 6.6 yam, highly
oriented and moderately crystalline ; Terylene yarn, highly oriented and
crystalline ; Orion staple, partially crystalline, well defined diagram ; wool,
low crystallinity ; Fibrolane, very low crystaUinity. The X-ray photographs
of the secondary acetate, ethyl cellulose and nylon 6.6 were slightly sharper
after the polymers had been stabilized than before ; the X-ray photographs
of the remaining materials were unaffected by stabilization of the samples.
The only fibres to provide any evidence of chemical change during the
stabilization treatments and subsequent sorption measurements were the wool
and Fibrolane ; both of these became slightly brown, and wool more than the
Fibrolane. The decomposition of wool at the higher temperatures has been
discussed by several authors^* ^'; the extent of decomposition in the present
experiments, and its effect on the water sorption, is diflBcult to assess, but
is thought to be small, since, first, the X-ray diagram is unaltered, second,
the sorption values are in good agreement with previous data where
comparisons are possible, are stable and very little affected by the stabilization
treatment, i.e., the effect of the 90C-stabilization on the 30C-isothenn
of wool was very small.
4. CALCULATION OF THERMODYNAMIC QUANTITIES
The decrease in Gibbs free energy AG when 1 mole of liquid water is
absorbed by a very large mass of polymer + water mixture, and the changes
in heat and entropy associated with this process, i.e., the differential heat and
 eight other Textile PolymersPart IIleffries T401

entropy of sorption, A// and rA.S', were calculated at various concentra-

tions of water from both absorption and desorption isotherms. The standard
equations employed were set out in Part I of this series. With the wool and
the Fibrolane, the values of A// and rAS were clearly temperature-
dependent and so these values were calculated separately for the two ranges
3060C and 6090C. The effect of temperature on the thermodynamic
quantities of the other materials is more difficult to assess ; with the cellulose
acetates, particularly the triacetate, A ^ and TAS appeared to decrease
with increase in temperature ; with the remaining materials, the values were
approximately independent of temperature. The error in the values of
A// and TAS is, however, large and it is often difficult to be certain of
the existence and magnitude of any temperature-dependence. In the discussion,
therefore, only the average values from 3090C are considered and it
is these average values which are listed in Table II.

5. RESULTS
The sorption values and thermodynamic values are listed in Tables I
and II. The main features of these results will be considered for each material
separately.
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i) Discussion of Sorption Values and Comparison with Previous Data

Cellulose Acetates (Fig. 1)
Beever and Valentine"^-^ have investigated in detail the effect of acetyl
content on the sorption of water by cellulose acetates. In general, the
sorption decreased as the acetyl content increased ; however, considerable
differences were observed between different commercial secondary acetates,
and between different commercial triacetates, of a magnitude too large to be
easily attributable to the slight differences in acetic acid yield involved.
It was clear, therefore, that differences in molecular arrangement (between
filaments, film and flake, and even between filaments from different sources)
must account for some of this variation in sorptivity. These differences in
molecular structure are probably, in the main, differences in degree of
order ; the evidence is against orientation being a major factor*-^--^.
In the present work on cellulose acetates, it was decided, in view of
the above facts, to study unoriented films. Moreover, with both the secondary
acetate film and the triacetate film, the crystalline material was in each case
small in amount and imperfect in character. It is considered therefore that
the present results allow as good a comparison as is possible of the sorption
behaviour of the two acetates independently of crystallinity and orientation.
A further reason for studying unoriented film in the case of secondary
acetate, is that oriented secondary acetate undergoes pronounced dimensional
(spontaneous extension) and structural changes in certain hot aqueous
treatments2^-23; any such changes during water-sorption measurements
would, of course, complicate any interpretation of results.
The 30C-absorption isotherms for both acetates (Fig. I) are somewhat
higher than most previous values for yarn, film or flake^'*'^'^*'^^. This must
be due, in part at least, to structural differences ; as was pointed out above,
the sorptivities of cellulose acetates appear to be sensitive to changes in
structure*'^. In this connection it may be noted (see Part III) that crystalliza-
tion of these unoriented films in water vapour at 150C reduced the sorption
at 30C by 1015%, with both secondary and triacetate ; a comparison
of the 30C-isothenns of unstabilized and 90C-stabilized secondary acetate
shows the considerable effect with this polymer of even a small amount of
 T402 28The Sorption of Water by Cellulose and

crystallization (Newsome and Sheppard^^ have previously mentioned the

need to stabilize secondary acetate). The 100% r.h.-regain value at 30C
(18-0% by wt) is in excellent agreement with most previous values^-*'^'2*
and also with previous values for the imbibition of film^^-^' and yarn^^
(taking into account the small amount of entrained water involved in the
latter determinations on yarn).
A quantitative comparison of the two unoriented, poorly crystalline,
films shows that, at 30C, the triacetate absorbed between 59% and 72%
as much (depending upon the r.h.) as the secondary acetate ; with the
unoriented, highly crystalline, films this value was 68%75%. In the work
of Beevers and Valentine'*-^, the value varies from 5080% depending upon
which secondary acetate is compared with which triacetate, and at which r.h.
With both acetates, the sorption decreased with increase of temperature
from 30"^90C over the whole range of r.h. Measurements were made
of the imbibition of liquid water by 90C-stabilized secondary acetate film
between 3O'C and 90C. The values obtained (17-5, 15-5, 14-0 and 13-0
at 30, 50, 70 and 90C, respectively) are in good agreement with the 100%-r.h.
regain values (18-0,16-0,15-0 and 13-0, respectively) and also agree reasonably
well with values published by Marsden and Urquhart^^
The nature of the sorption hysteresis was markedly different with the
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two acetates (see Fig. 1). The relative hysteresis* of secondary acetate
at 3O''C was the largest observed for any material, cellulosic or otherwise;
it was approximately independent of the r.h. in agreement with the result
of Urquhart and EckersalP^, but diminished rapidly with increase of
temperature (it averaged about 34% at 30C, again in agreement with the
values given by Urquhart and Eckersall, and 12% at90C).
The relative hysteresis of the triacetate at 30C (average about 19%)
was lower than that of secondary acetate at 30C, but decreased less rapidly
with temperature and was the higher of the two at 90*^C (about 14%);
the relative hysteresis of the triacetate showed a definite tendency to decrease
with increasing r.h.

Ethyl Cellulose Film (Curves B on Fig. 2)

The absorption results are in excellent agreement with those reported
for a similar sample of ethyl cellulose by Barrer et al.^. The opacity of the
film, noted by Barrer at the higher humidities, was observed at all four
temperatures ; it first became visible in the region 9397% r.h. and iacreased
in intensity as the r.h. was increased further. The film clarified as the r.h.
was reduced again to below this critical range. The sorption values at
saturation with this material were very uncertain and irreproducible (see
Table I) and it is possible that this is associated with the opacity of the film.
The opacity is, presumably, due to cavities filled with liquid water and
the amount of water involved in these cavities, and the way in which this
amount varies with the temperature and length of time of" sorption, and
the sorption history of the sample, is not known. It is interesting to note
that the film remained quite clear in liquid water in the range 3080C;
in water at 90''100C the film gradually became opaque, this opacity
increasing when the film was dried. (This permanent opacity which develops
in water at 90100C seems to be similar to the cavity delustring of

The relative hysteresis at a particular r.h. and temperature is defined as :

(desorption water contentabsorption water content)
absorption water content
 eight other Textile PolymersPart IIJeffries T4O3

24
22
20
18 Absorption isotherms

1
to
rt 14
S 12
10
8
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CO 6 Secondary
4

Triacetate

t 40 % Relative humidity
0)
30
4) 20
^ 10

30 50 70 90 20 40 60 80
Temperature (^C) % Relative hurnidit>
Fig. 1
The sorption of water vapour by cellulose secondary acetate and cellulose triacetate
AEffect of temperature on absorption isotherms
30*^0 X 50*0 -f 70C O 9O''C
BRelative hysteresis (average from 1080% r.h.) as a function of temperature
secondary acetate X triacetate
CRelative hysteresis (average from 3090C) as a function of relative humidity
secondary cellulose acetate in hot aqueous liquids^*''^^; its relationship to
the reversible opacity in water vapour is not yet understood.)
The present results indicate only a slight decrease in sorption with
increase of temperature from 5090C, considerably less than with the
celluloses and cellulose acetates^ (30C was studied only briefiy, at relative
humidities greater than 75%). The 50X- and 70C-desorption isotherms
 T404
2S~The Sorption of Water by Ceiiulose and
were coincident within the experimental error, i.e., the amount of hysteresis
was about the same at these two temperatures ; at 90C, the amount of
hysteresis was considerably less, i.e., the 90C-desorption isotherm was
markedly lower than the 50/70C isotherm. For clarity, the desorption iso
therms are not plotted on Fig. 2. ^ yj

Absorption
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30C
50C
70C
90C

CO

0 20 40 60 80 100
% Relative humidity
Fig. 2
Absorption of water vapour by drawn nylon 6.6. yarn (A) and by ethyl cellulose film
(B) at temperatures from 3090^
The line of the 70X-isotherm for the ethyl cellulose is omitted to avoid confusion.
The absorption of vapour by Terylene (the average isotherm in the range 30"90x)
is added for comparison (C, see also Fig. 3).
 other Textile PolymersPart IIJeffries T405

Nylon 6.6 Yarn {Curves A on Fii^. 2)

Previous results on drawn filament yarn*^"'^-^" deal exclusively with
the lower temperatures, i.e., 2O''C4O''C. The 30'C-sorption values obtained
here were somewhat lower than these previous results (on the average about
5% lower, taking the differences in temperature into account). This lower
sorptivity was probably due to the 90'C-stabilization treatment which was
given to the sample ; X-ray investigation showed that this treatment increased
the crystaliinity of the nylon slightly, and a lower sorptivity was therefore to
be expected. Work which is reported in Part MI of this paper showed that
treatment in water vapour at 150^C crystallized the nylon to a marked degree,
and this reduced the sorptivity by a further 25%. In this connection, it is
interesting to note that Abbott and Goodings" observed a reduction in
sorptivity when nylon 6.6 was treated with dilute aqueous solutions of m-
cresol ; evidence exists^" which indicates that this reduction in sorptivity is
also due to a crystallization process. Starkweather's recent results on the
absorption of water vapour by annealed nylon 6.6 film'*'"' also show the effect
of crystallization ; the values on this film are considerably lower than the
previous values on drawn nylon yarn.
The sorption at all humidities decreased as the temperature was increased.
The amount of hysteresis was small at all temperatures, in agreement with
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the results of previous workers""^*^^

Terylene Yarn {Fig. 3 and curve C on Fii(. 2)

The amount of detailed information in the literature on the sorption of
water by hydrophobic polymers is small. The most general collection of
sorption values is given by Roff'^ who lists results for many polymeric
materials, including all of the common hydrophobic textile polymers.
Preston and Nimkar^^ have measured the imbibition of water by Terylene
and Orion fibres. NewelP' lists sorption values at 65% r.h. and 95% r.h.
for various fibres (Terylene, Orion, Acrilan, Vinyon, etc.). Reddish^^ gives
imbibition figures for Terylene film. Hauser and McLaren-^ studied the
sorption isotherms at 25'C and 4O'C for several polymers, including polyvinyl
butyral, rubber hydrochloride and a vinylidine chloride-acrylonitrile
copolymer. Katchman and McLaren^*^ list sorption values at 25'C or 40^C
for ten polymers, including several hydrophobic ones such as polyethylene
and polyvinyl isobutyl ether. Thomas^^ studied the sorption of water by
polyvinyl chloride and polymethyl methacrylate films. Hauser and McLaren-*'
and Thomas^^ found the sorption to be independent of temperature :
Katchman and McLaren^^ state that little or no sorption hysteresis was
shown by the polymers they studied.
The present results on Terylene agree quite well with the previous
values^^-^'*''*^. The sorption increased slightly with increase in temperature,
at least up to 95% r.h. (it was not possible to be certain at r.h. values
approaching 100%), and there was some evidence for the existence of a
small amount of sorption hysteresis ; however, the experimental scatter
with this particular sample was relatively much larger than with the other
materials (partly because of the small amounts of sorption involved, and
partly because the spring employed exhibited more creep than any other)
and so it is not possible to state with confidence the exact magnitude of the
hysteresis. For clarity, only the absorption points for 30C and 90X are
given in Fig. 3 ; the smoothed absorption values for the four temperatures
are listed in Table I.
 T406 1%--Tl\e Sorption of Water liy Ceiiulose and

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The sorption results confirm the conclusion, reached in Part I, that

interfibre condensation was very small in amount even at relative humidities
very close to 100%^'-; the 100% r.h.-regain was only about 3%, of which at
most 2% can be attributed to condensation (in agreement with this a few
water-imbibition measurements on a Terylene film gave a value of cibout
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2-5-

^2-0
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Fig. 3
Absorption of water vapour by Orion and by Terylene at temperatures from 3090C
 2%Thc Sorplion of Water by Cellulose and

It should be noted that the yarn employed in these measurements was

of a high degree of crystallinity ; Reddish ^-^ showed that amorphous Terylene
absorbed significantly more than the crystalline polymer, as would be
expected.
Orion Fibre {Fi^. 3)
The results may be summarized as follows :
i) The sorptivity of Orion was about twice that of Terylene over the
whole range of r.h., in agreement with the 65% r.h. values reported
by Newell^' and Roff"*'.
ii) As with the Terylene, the sorption increased slightly as the temperature
was increased, up to 95% r.h. at least (it was not possible to be certain
of any effect of temperature at humidities approaching 100% r.h.).
iii) Definite sorption hysteresis was observed at 50"90 C (desorption
values were not obtained at 30 C) ; the magnitude of the hysteresis was
small and an accurate measurement of relative hysteresis is not possible,
iv) The interfibre condensation taking place at humidities close to 100%
was at most small in amount, as with the Terylene yarn.
Wool {Fig. 4)
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Wool is the most comprehensively studied non-cellulosic textile so far

as water-sorption is concerned^-^-**'^^'*'^''*^. The most detailed work to date
is that of Speakman et al.^ who investigated the effect of drying conditions
and temperature on the sorption of water by wool ; the absorption isotherms
at 25'^C of various wools are given in a more recent paper by Nicholls and
Speakman^^. The results of these investigations show clearly that the
sorptivity of a sample depends upon the type of wool and its sorption history,
and emphasize the need for stabilization treatments. It was considered
on the basis of the work of Speakman and Cooper, that the normal
stabilization treatment employed with the other materials in this work
(several sorption cycles at 90 C) would also be satisfactory for wool ; the
sorption results obtained confirmed this, i.e., the isotherms were satisfactorily
stable. The effect of the 90 C-stabilization on the 30'C-sorption was in
fact, small (less than expected^) ; this suggests that the 90-C-stabilization
caused little change in physical structure (in agreement with the X-ray
measurements).
The sorption results are in good agreement with most of the previous
data where comparisons are possible^*^"''"^^'''^'*^. The absorption decreased
with increase in temperature at all temperatures from 30*^90 C up to
85% r.h. ; at this r.h. the 6O'C- and 90'C-isotherms coincided up to about
99% r.h. ; the 90"C-isotherm then crossed the 60X-isotherm and, at 100%
r.h., the sorption at 9O'C was greater than that at 3O''C. Despite the doubt
in the exact values of sorption at humidities approaching 100% (see Part I),
this result is held to confirm the observations of Speakman et al. of slight
minima in the curves of imbibition against temperature^^ and regain at 97 % r.h.
against temperature^*-^. (In the present work, the lowest r.h. at which the
regain against temperature curve would show a minimum would be about
99%.) The relative hysteresis decreased markedly as the r.h. increased,
in agreement with Meredith^^ The actual hysteresis loop was, in fact, wider
at low than at high humidities. The equilibrium values given in a recent
study of the rate of sorption of water vapour by wooH^ also indicated this
narrowing of the loop ; it will be seen below that the regenerated protein
Fibrolane also showed this behaviour. The relative hysteresis decreased with
increase in temperature.
 eight other Textiie PoiymersPart IIJeffries T413
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20 40 60 80 100
% Relative humidity
Fig. 4
The sorption of water vapour by wool at , 60C and 90C
absorption isotherms
desorption isotherms
Fibrolane {Fig. 5)
The amount of information available on the water-sorption of regenerated
proteins is not large. The main body of results is given by Roff^', for four
kinds of regenerated protein at 25C ; the values vary between 5-95% by
weight and 7-65% at 35% r.h. (depending on the protein), between 9-7%
and 12-35% at 65% r.h. and between 15-3% and 20-8% at 95% r.h. Apart
from these data, the published results on regenerated proteins are restricted
to single values at a particular r.h. and temperature^"*'^^*^"-^^^; at 65% r.h.
ca. 20C the sorption values vary between 10% and 13% by weight ; at
95 % r.h., NewelP* reports 25 % sorption. ,
The sorption values obtained for Fibrolane were somewhat higher than
the previous values for regenerated proteins (at 30C, the absorption values
 T414 28The Sorption of Water by Cellulose and
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% Relative humidity
Fig. 5
The sorption of water vapour by Fibrolane at 30^C, 60X and 90X
absorption isotherms
desorption isotherms
were 8-6% by weight at 35% r.h., 14-5% at 65% r.h., and 42% at 95% r.h.).
The absorption figures were, in fact, very similar in magnitude to those of
wool up to 5060% r.h.; at higher humidities the Fibrolane was much
more sorptive than was the wool, possibly due to a lower degree of cross-
linking in the Fibrolane. The 60C- and 90C-absorption isotherms merged
at about 70% r.h. (similar to wool) and the 30C-absorption isotherm merged
with the 60/90X-isotherm at about 90 % r.h. The sorption values at humidities
over 99% were very irreproducible and it was diflicult to be certain when
equilibrium was attained, even approximately.
The hysteresis behaviour was qualitatively similar to that of wool, i.e.,
the hysteresis loop was wide at low humidities narrowing at the higher
humidities. The relative hysteresis decreases markedly as the temperature
is increased.
 eight other Textile PoiymersPart IIJeffries T415

ii) Discussion of Thermodynamic Values

The sample can be divided into two groups as regards the differential
heats (Fig. 6) and entropies (Fig. 7) of sorption.
a) With the more hydrophilic of the materials (secondary acetate and
triacetate, nylon 6.6, wool and Fibrolane), the sorption was accompanied
by an evolution of heat and a decrease in entropy, the magnitude of these
effects diminishing as the concentration of water increased (except for the
entropy values for the acetates, see below). This is, of course, the type of
behaviour shown in practically all previous work on water -|- polymer
systems^'3'*-^^ ^^^ ^ISQ \^y other polar solvent + polymer systems^*-*^ As with
the series of celluloses considered in Part I, the magnitude of the evolution
of heat (expressed, say, as the integral heat of wetting, or as the heat evolved
between two fixed regains, or two fixed values of r.h.) diminished as the
sorptivity of the material diminished ; Meredith'*'^ has pointed out this
relationship between heat effect and sorptivity.
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Absorption

5 10 15 20 25
% By W t . water absorbed
Fig. 6
Differential heat of absorption as a function of water content
la Wool 30='60**C 4 Cellulose triacetate
lb Wool 609O''C 5 Drawn nylon 6.6 yarn
2a Fibrolane 3060C 6 Ethyl cellulose
2b Fibrolane 609O''C 7 Orion
3 Secondary cellulose acetate
With samples 37, the values ofA//are average values for the range 309O'C.
 T416 28The Sorption of Water by Cellulose and

00
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5 10 15 20 25
% By Wt. water absorbed
Fig. 7
Differential entropy of absorption as a function of water content
17 refer to samples as in legend to Fig. 6
The differential heat of absorption was, in general, less than that of
desorption (for simplicity, the latter is not plotted on Fig. 6) ; this is a
reflection of the decrease of hysteresis with temperature (with nylon, the
hysteresis was very small at all temperatures and the two heats were identical
within the experimental error).
With secondary cellulose acetate and cellulose triacetate, TAS was not
very dependent upon r.h.; the absorption values of TAS for secondary
acetate and both values for triacetate show shallow maxima at about 5%
regain.
The values of A// for the drawn nylon 6.6 are somewhat lower than
previously published values'^-^^ i.e., the temperature coefficient of sorption
was lower in the present experiments than in these previous studies; this
may possibly be due to the 90C-stabilization treatment given to the nylon
in the present work.
The thermodynamic values in detail for wool and Fibrolane were more
complex than for the two cellulose acetates and nylon (and the celluloses
dealt with in Part I). In the first place, the values were very temperature-
dependent (the 3060C values being greater than the 6090X values).
In the second place, the curves relating - r A 5 with regain (Fig. 7) are complex;
there was a slight increase in entropy at the higher temperatures and regains,
and various marked changes of slope, and even minima and maxima, are
observable on the curves (particularly the desorption curves, not shown on
Fig. 7 for simplicity). The significance of these peculiarities is difficult to
assess : they are, of course, reflections ofthe non-uniform effect of temperature
on the sorption of these two materials, and the unusual hysteresis behaviour
exhibited by them. It is considered that results on more samples are needeo
 eight other Textile PolymersPart JIJeffries T417

to confirm the true existence of these phenomena and to justify any attempt
at interpretation. Morrison et al.**^** detected complex behaviour of this
type in the entropy/regain curves of cotton, wool and silk and suggested
tentative interpretations. Dole and McLaren^^ using Bull's data^ found
marked changes of slope, maxima and minima, in the curves of isosteric
heat of sorption against regain for the proteins silk and egg albumin.
b) The more hydrophobic materials studied (ethyl cellulose, Terylene
and Orion) were markedly different from the other materials as regards the
thermodynamics of water-sorption. With ethyl cellulose, the absorption
was only very slightly exothermic, barely detectable^. The sorption of
water by Orion and Terylene was slightly endothermic at least up to 95 % r.h.,
i.e., the sorption increased with increasing temperature, though the effect
of temperature on the sorption of Terylene was measured with insufficient
precision to justify calculation of isosteric heats. With all three polymers,
the entropy of sorption was positive. These isosteric heats of sorption for
Orion and Terylene are in disagreement with the calorimetric heats of
wetting of these materials obtained by Bright et al.^**; these workers found
that a small amount of heat was evolved during the wetting process. The
reason for this difference between the isosteric and calorimetric heats is not
known.
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ACKNOWLEDGEMENTS
The X-ray photographs described in this paper were prepared and
assessed by Drs. J. Mann and L. Roldan of this Association. The acetyl
contents on samples of cellulose triacetate and secondary acetate discussed
in this paper and in Part III were determined by Mr. A. T. Masters of this
Association.
The author is grateful to Drs. L. R. G. Treloar, H. J. Marrinan and
J. Mann for many helpful discussions.
This work is part of the programme of fundamental research in progress
at the British Rayon Research Association, Heald Green Laboratories,
Wythenshawe, Manchester, 22.

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British Rayon Research Association, Received 2.5.{96Q
Heald Green Laboratories, Accepted for pubiication 5.7.1960
Wythenshawe,
Manchester 22.

CORRECTIONS
The following amendments should be made to Part I,
J. Text. Inst., 1960, 51, T340.
Tn the last line of the abstract **entropy" should read '^entropies".
T356, Table lib.
The second item in the third column should read T^S (not
as printed).