Fluid Phase Equilibria, 91 ( 1993) 291- 3 11 291

Elsevier Science Publishers B.V., Amsterdam

An experimental investigation of cloud-point curves for

the poly( ethylene glycol) /water system at varying
molecular weight distributions

Ana Saraiva, Ole Persson and Aage Fredenslund *

Engineering Research Center WC-SEP, Institut for kemiteknik, The Technical University
of Denmark, DK-2800 Lyngby (Denmark)
(Received January 22, 1993; accepted in final form March 26, 1993)

ABSTRACT

Saraiva, A., Persson, 0. and Fredenslund, A., 1993. Experimental investigation of cloud-
point curves for the poly(ethylene glycol)/water systems at varying molecular weight
distributions. Fluid Phase Equilibria, 9 1: 291-3 11.

Cloud-point curves for aqueous solutions of poly(ethylene glycol) (PEG) have been
obtained by TOAM (Therm0 Optical Analysis by Microscopy) using PEG samples with
varying molecular weight distributions. PEG/water solutions show a phase diagram of the
closed-loop type. An increase of the molecular weight raises the UCST (Upper Critical
Solution Temperature) and lowers the LCST (Lower Critical Solution Temperature), and the
region of immiscibility expands. The LCST and UCST branches of the cloud-point curve are
sensitive to M,,, M, and IU,. The TOAM apparatus presented here differs from those
described earlier (Bae et al., 1991, Macromolecules, 24: 4403) in three main ways: (a) a new
sample technique has been developed, (b) the upper limit of the operating temperature has
been increased from 300 to 375”C, and (c) during an experimental run, the sample is
visualized by a video monitor. The amount of sample used is very small ( -0.1 cm3), and
cloud-point curves for polymer solutions can be rapidly located as a function of temperature
and overall concentration of the polymer.

Keywords: experiment, liquid-liquid, cloud-point, TOAM, polymers, poly(ethylene glycol),

water, molecular weight distribution.

INTRODUCTION

Knowledge of the phase behavior of polymer solutions is of special

importance in the design of separation, polymerization, coating and paint-
ing processes where liquid-liquid phase separations markedly influence the

+ Corresponding author.

037%3812/93/%06.00 0 1993 - Elsevier Science Publishers B.V. All rights reserved

292 A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311

characteristics of the final polymer product. Since the early 193Os, efforts
have been made to collect LLE (liquid-liquid equilibrium) experimental
data for polymer solutions. Apart from the common (UCST) found in
systems such as polystyrene/cyclohexane solutions (Bae et al., 1992), several
systems show a lower critical solution temperature (LCST) (e.g. polystyrene/
ethylacetate, Bae et al., 1991; polyisobutylene and polydimethylsiloxane
solutions, Zeman et al., 1972; and both UCST and LCST (e.g. polystyrene/
tert-butyl acetate, Bae et al., 1991; and polyisobutene/isopentane, Allen and
Baker, 1965). In some systems, at a sufficiently high molecular weight, the
UCST and LCST coalesce giving rise to an hour-glass shaped phase diagram
(e.g. polystyrene/acetone, Siow et al., 1972; and polyethylene glycol/
tert-butyl acetate, Saeki et al., 1976. Phase diagrams of the closed-loop type
are typically found in aqueous solutions (e.g. PEG/water, Saeki et al., 1976;
Bae et al., 1991).
LLE data for polymer solutions have been reported mostly in the form of
cloud-point curves that, due to polymer chain-length polydispersity on one
hand, and kinetic effects on the other, in general differ from their corre-
sponding coexistence curves.
Light scattering is sensitive to differences in the refractive index. Hence,
diffuse concentration fluctuations or the presence of a sharp-phase
boundary may be detected, and light scattering techniques, where PICS
(Pulse Induced Critical Scattering) takes a special place, are today a widely
used tool for determination of cloud-point and spinodal curves in polymer
solutions (Koningsveld and Staverman, 1968; Derham et al., 1974; Gordon
et al., 1977; Koenhen and Smolders, 1977; Tager et al., 1977).
In this work, cloud-point curves for PEG/water solutions of polymers
differing in molecular weight distributions have been measured by Therm0
Optical Analysis by Microscopy (TOAM).
The TOAM apparatus presented here is a modified version of that
described recently by Bae et al. (1991)

COEXISTENCE, “THERMODYNAMIC CLOUD-POINT” AND CLOUD-POINT

CURVES

Figure 1 shows a typical phase diagram for a binary system. The coexistence
or binodul curve defines the lower boundary of miscibility; at the critical point,
the composition of the two phases in equilibrium coincide. Metastable
solutions are separated from unstable solutions by the spinodul curve. In the
unstable region, phase separation takes place by spinodal decomposition and
the phase-split is instantaneous (Wong and Knobler, 1978). Inside the
metastable region, phase separation takes place by homogeneous nucleation,
which may be interpreted as a kinetic rather a thermodynamic phenomenon
A. Saraiva et al. / Fluid Phase Equilibria 91 (1993) 291-311 293

- weight fraction of solute, w d

Fig. 1. Schematic phase diagram for a binary system: B is a point on the “thermodynamic
cloud-point (or binodal) curve; C is a point on the cloud-point curve (not drawn) obtained
when the binodal curve is approached from the one-phase region; point A defines the locus
of a one-phase system on the (T,w) plane, and E is the critical point.

(Heady and Cahn, 1973; Wong and Knobbler, 1978). In general, due to
kinetic effects, the temperature, Tcloud, at which an initially clear and
homogenous solution (see point A, Fig. 1) becomes “cloudy” due to the
incipient formation of a second phase, differs from the temperature, Tes, at
which the two phases with compositions w1 and w2 remain in thermodynamic
equilibrium. The direction of that difference depends on whether the binodal
curve is approached from the one-phase (Process I) or from the two-phases
region (Process II); Fig. 1 illustrates the case where initially, only one liquid
phase exists (Process I).
A two-phase/one-phase boundary defined only by the thermodynamics of
phase equilibria is here termed the “thermodynamic cloud-point curve”. For
binary systems, including monodisperse polymer/solvent solutions, the
“thermodynamic cloud-point” and coexistence curves coincide. However,
due to polymer polydispersity, a polymer/single solvent solution is a multi-
component system in which phase equilibria is now no longer described by
the “thermodynamic cloud-point curve”. In that case, there is a coexistence
curve for each overall concentration of the polymer, and the points corre-
sponding to the equilibrium compositions, w1 and w2, are located in the
corresponding set of coexistence curves. The locus of the “thermodynamic
cloud-point” curve in the (T,composition) plane, as well as its shape, and
critical and maximum and/or minimum points, are sensitive to the molecu-
lar weight distribution of the polymer.
294 A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311

Experimentally, a “thermodynamic cloud-point curve” can be determined

approximately by approaching it from both the one-phase (Process I) and
the two-phases region (Process II). Usually, in polymer solutions, and when
slow rates for the temperature changes are used, the cloud-point tempera-
tures obtained in the cooling and heating processes do not differ by more
than a few tenths of a degree (Schultz and Flory, 1952; Koningsveld and
Staverman, 1968; Derham et al., 1974; Bae et al., 1991), and their average
value is considered to be very close to the “thermodynamic” (or equi-
librium) cloud-point temperature.

EXPERIMENTAL SECTION

Materials

PEG samples with seven different molecular weights were obtained from
Aldrich-Chemie and Merck. Their respective molecular weight distributions
were characterized by GPC (gel permeation chromatography) where PEG
standards obtained from Polymer Standard Service were used to determine
the column calibration curve. In Table 1 the different PEG samples
are identified and the values for M,, MW/Mn and A4,/& are indicated;
the corresponding molecular weight distributions are presented in Figs. 2
and 3.

5.00

15000
Molecular Weight&!

Fig. 2. Molecular weight distributions, MWD(M), of PEG25, PEG44 and PEG84 samples.
A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-31 I 295

15doo
Molecular Weight,M

Fig. 3. Molecular weight distributions, MWD(M), for PEG31, PEG44, PEG66, PEG86 and
PEG124.

~~ PEG61 2
a? PEG6143
ooooo PEG61 6

15000
Molecular Weight,M

Fig. 4. Molecular weight distributions, MWD(M), for PEG612, PEG6143 and PEG616.
296 A. Saraiva et al. / Fluid Phase Equilibria 91 (1993) 291-311

A- PEG61 43
?.oooo PEG6148

1.5000
Molecular Weight,M

Fig. 5. Molecular weight distributions, MWD(M), for PEG6143 and PEG6148.

Four new PEG samples with molecular weight (M,) 6000 were obtained
by mixing, in different proportions, the PEG samples listed in Table 1; Table
2 gives the compositions of the new polymer mixtures. The polymer molecular

TABLE 1
PEG sample identification names, suppliers and characteristics of the corresponding molecu-
lar weight distributions

Indentification Supplier
name

PEG25 Aldrich-chemie 2530 1.17 1.18

Cat. No 29590-6
PEG3 1 Aldrich-chemie 3110 1.13 1.14
Cat. No 29590-6
PEG44 Merck 4490 1.13 1.11
Cat. No 807490-1000
PEG 66 Merck 6640 1.15 1.12
Cat. No 807491-1000
PEG 84 Aldrich-chemie 8420 1.25 1.18
Cat. No 20,245-2
PEG 86 Aldrich-chemie 8640 1.17 1.13
Cat. No 20,245-2
PEG124 Aldrich-chemie 12490 1.19 1.14
Cat. No 30,902-8
A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311 297

TABLE 2
PEG mixtures, identification names and characteristics of the corresponding molecular
weight distributions; M, = 6000

Identification
name

PEG612 1.20 1.18

PEG6143 1.40 1.43
PEG6148 1.40 1.48
PEG616 1.60 1.66

TABLE 3
Composition of the PEG mixtures (weight fraction of individual PEG samples in the
mixtures)

Individual PEG612 PEG6143 PEG6148 PEG616

PEG samples

PEG31 0.000 0.245 0.158 0.524

PEG44 0.389 0.331 0.584 0.197
PEG66 0.513 0.264 0.058 0.000
PEG86 0.098 0.000 0.000 0.000
PEG124 0.000 0.160 0.200 0.279

weight distributions are presented in Figs. 4 and 5, and the characterization

is given in Table 3. As a solvent laboratory distilled water was used.

TOAM apparatus

A schematic drawing of the TOAM apparatus is presented in Fig. 6. It

consists of (a) a thermoanalyzer (Mettler FP900 Therm0 System), (b) a
transmitted light polarizer microscope (Zeiss-Axioskopol) and (c) auxiliary
equipment-a video monitor and a video camera, a light splitter (MTI-
CCD725) and an IBM PC.
The thermoanalyzer consists of a heating - cooling microscope stage
(Mettler FP82 Microscope Stage), a microprocessor (Mettler FP90 Central
System), a handset, and a printer for registration of the output data. The
heating-cooling stage allows observation of the thermal behavior of the
sample under a microscope. Figure 7 shows an amplified cross section of
the cell. The furnace of the microscope stage consists essentially of two
heating-cooling plates whose temperature is measured by a PtlOO sensor
(accuracy +O.OSC). The calibration of the temperature sensor was checked
by determining the melting points of two standard substances: benzoic acid
298 A. Saraiva et al. / Fluid Phase Equilibria 91 (1993) 291-311

light saurcc
Tungstea halogen tamp

Liq.

Fig. 6. Schematic representation of the TOAM apparatus. In the future, the IBM PC will be
connected to the microprocessor for data storage and the N, cooling system will be tested.

(Z’Vm= 122.4”C) and caffeine (Tm = 2362°C). The sample is placed in the
center of the furnace and its temperature is controlled from the bottom and
top plates. Direct contact between the tube sample and the furnace plates,
as well as the small amount of sample used, keep the temperature differences

Microscope slide

Heat protection filter

Flat furnace
Sample

Outer casing
Protective glass
> Light source of microscope
Cooling-gaz

Fig. 7. Schematic representation of the microscope hot-stage.

A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311 299

within the sample very small and allow the sample rapidly to reach the
temperature of the furnace. The furnace plates can reach 375°C; temperatures
below room temperature can be achieved by blowing a cold gaseous stream
sideways between the external and internal housing of the microscope stage.
For temperatures slightly below room temperature, CO* was used; using
vaporized liquid nitrogen extends the temperature range to -60°C.
The sample is subjected to a temperature program, and a photomonitor
allows quantitative determination of the intensity of the light transmitted by
the sample in the field of view. The temperature program is entered into the
microprocessor. The simplest temperature program consists of a starting and
an end temperature, and a rate for temperature variation. Isothermal periods
(t,, tz) can also be defined (see Fig. 8a). The scanning temperature rate can
vary from 0.1 to 20”C/min for both heating and cooling. The handset is used
for manual control of the temperature.
During a run, the results are shown on the microprocessor display. At the
cloud-point temperature, the intensity of the light transmitted by the sample
decreases due to the formation of small amounts of a second phase dispersed
in the solution. Figure 8(b) presents an example of an output curve.
The light splitter allows simultaneous visualization of the sample in the
video monitor system and data acquisition. The video camera allows the
sample visualization to be recorded.

Input data
Output data
\1 I
Temperature program &
Intensity of the light transmitted
by the sample, I

to
-
t1 T T
t2 cloud
(a) @I
Fig. 8. (a) Example of a temperature program used in the determination of cloud-point
curves by TOAM. The temperature of the sample varies from To to Tf with a rate of
dT/dt”C/min and remains at a constant temperature in the periods of times t, and tz. (b)
Schematic representation of an output curve; Z, is the intensity of the light transmitted by the
sample in the initial homogeneous state.
300 A. Saraiva et al. / Fluid Phase Equilibria 91 (1993) 291-3 I1

Sample preparation technique

For samples PEG25, PEG44, PEG84, PEG612, PEG6143, PEG6148 and

PEG616, eight to ten aqueous solutions of different concentrations were
prepared gravimetrically using a Mettler AE 163 digital balance with a
resolution of lop5 gr. The weight fraction of polymer covers the range 0.01
to 0.4 (0.5 in the case of PEG84). In the preparation of each of the
PEG-mixture (samples PEG612, PEG6143, PEG6148 and PEG616) solu-
tions, at least 10 g samples of polymer were used.
Each solution was stirred for 8- 12 h. In this work, a new and simple
sample tube preparation technique was used. The solution is injected into a
Pyrex tube (i.d. = 1 mm; o.d. = 3 mm; 1 = 70 mm). The tube is totally filled
with the solution and then closed with Swagelok tube fittings. Using this
method, the presence of macroscopic gas bubbles in the tube is avoided, a
result which we could not achieve using the sealing-tube method described
by Malcolm and Rowlinson ( 1957), and used by Bae et al. ( 1991) in their
TOAM measurements.

Procedure

A sample tube is placed in the center of the furnace of the microscope

stage. Initially, a scanning temperature rate of lO”C/min is used to deter-
mine approximately the cloud-point temperature. At that point, the screen
of the video monitor suddenly becomes dark due to the cloudiness of the
solution. The solution is returned to the homogeneous state and allowed to
reach thermal equilibrium at a temperature a few degrees from the esti-
mated cloud-point temperature. When the intensity of the light transmitted
by the sample becomes stable, calibration of the light transmittance is
performed. The sample is submitted to a temperature program that takes
the solution to the two-phase region and, simultaneously, the intensity of
the light transmitted by the sample in the field of view is monitored.
Although it cannot be assumed that the sample achieves almost instanta-
neously a homogenous temperature, this fact does not affect the determina-
tion of the cloud-point temperature because what actually needs to be
measured is the temperature at which the first “clouds” appear in the
solution that remain close to the walls of the sample tube in the field of
view of the microscope. For that reason, the temperature at which the
first decrease of light intensity is observed is taken as the cloud-point
temperature of the solution with the original composition. Typical results
are presented in Fig. 9. At a scanning rate of S”C/min, the decrease in
the light transmittance due to the cloudiness of the solution is very clear.
When lower values for the rate of temperature change are used, the decrease
of light transmittance becomes less sharp and, in some cases, imperceptible.
A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311 301

80.00

6000

20.00

0.00 m
130.0 132.0 134.0 136.0 138.0
Temperoture.°C

Fig. 9. Influence of the temperature scanning rate on the determination of cloud-point

temperatures for PEG/water systems. The example refers to a solution of PEG6143 with
wpO,= 0.1320 and the temperature scanning rates and corresponding cloud-point tempera-
tures are: (a) S”C/min, Tcloud= 132.1”C; (b) l”C/min, Tcloud= 132.2”C; (c) O.S”C/min,
Tc,oud= 132.3”C; (d) O.l”C/min, Tcloud= 132.3”C.

Solutions could be slowly heated (or cooled, in the upper branch of

the closed-loop) several tenths of a degree above (or below) the cloud-
point temperature obtained at high scanning rates, with no detected light
scattering.
It could be seen in the video monitor that when high enough scanning
rates were used, at the cloud-point, a large number of small dark spots
suddenly began to obscure the image; soon, the second phase became visible
in parts and after complete phase separation of the two phases, the
transmittance of light reached a value very close to 100% again.
At low scanning rates, however, only a few but already larger regions of
the second phase became visible at the point when disturbance of the light
transmittance was detected. This may be explained as follows. The light
scattered due to differences in concentration between the two phases alone,
is not enough to detect an interface: at the final stage of the mechanism of
phase segregation, the light transmittance reaches almost 100%. In the early
stages of nuclei formation, the increase of light scattered is due to both
formation of new nuclei and their growth (Koenhen and Smolders, 1977).
When significant amounts of the second phase coalesce, the “nuclei”
302 A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311

(4
Ts,o"d=133.5 Oc

(b) T=133.5 "C

95.0

zic
3
\
3

90.0

85.0
132 134 136 138
Temperature,'C

Fig. 10 (a), (b).

A. Saraiva et al. 1Fluid Phase Equilibria 91 (1993) 291-311 303

(4 T,(,,=143.6 OC

4
100.0 0 7
0
0
80.0
Cl

0.0 "'1"",,,,,,,,,,,,,,,,,1,,,,,,,~,,,,,,
140.0 142.0 144.0 146.0 148.0
Temperature,'C

(d) Tz143.4 "C

100.0

143.3 143.5 143.7 143.9 144.1

Temperature,'C

Fig. 10 (opposite and above). Superheating in the extremes of the composition range for
PEG6143/water solutions; (a), (b) wpol= 0.0101 and(c), (d) wWl = 0.3818; (a), (c) temperature
scanning rate of S”C/min, (b), (d) temperature scanning rate of -O.l”C/min.
304 A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311

increase in volume but decrease in number, and a point is reached where the
light scattering decreases.
At a very high scanning rates, there is no time for the solution in the
sample tube to reach thermal equilibrium and the cloud-point temperatures
in the LCST branch is overestimated (or underestimated, in the case of the
UCST branch). However, in the cases when cloud-points could be detected
with scanning rates as low as 0.1 “C/min, the observed values differ only by
a few tenths of a degree from those obtained at a scanning rate of S”C/min,
and the difference always indicated a delay in cloud-point detection at low
scanning rates, as exemplified in Fig. 9.
Finally, we have considered the cloud-points obtained at a scanning rate
of +S”C/min. When repeated with different tube samples, the cloud-point
temperatures were reproducible within + 0.1 - 1.O”C in the whole composi-
tion and temperature range.

Superheating

Some experiments were performed where the thermodynamic cloud-point

curve was approached from the heterogeneous side. The calibration of light
transmittance was performed when the solution was in the one-phase
region. Suddenly, the solution was placed in the immiscibility region and
allowed to attain again the homogeneous state with a scanning rate of
-O.l”C/min. The temperature at which the light transmittance returned to
100% again was determined and compared with that obtained when the
cloud-point curve was approached from the one-phase region. Figure 10
presents results for two solutions of PEG6143/water at the extremes of the
composition range (wpol= 0.0101 and wpol= 0.3818). For the low concentra-
tion solution, the difference was less than O.l”C while a superheating of
approximately 0.2”C was found for more concentrated solutions.

RESULTS AND DISCUSSION

The molecular weight dependence of cloud-point curves

PEG is a polyether with the unusual property of being water soluble in all
proportions at moderate temperatures (Kjellander and Florin, 1981). Figure
11 shows cloud-point curves for PEG/water system for PEG25, PEG44 and
PEG84; the experimental data are presented in Table 4. At sulhciently high
molecular weights (Mw > 2180, Saeki et al. 1976) aqueous PEG solutions
shw a phase diagram of the closed-loop type. An increase in the molecular
weight raises the UCST and lowers the LCST and the region of immiscibil-
ity is expanded.
A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-31 I 305

350.0

250.0

one-phase

0.00 0.15 0.30 0 45 0.60

weight fraction of polymer

Fig. 11. Cloud-point curves for aqueous solutions of PEG25 ( q), PE644 ( A) and PEG84
(0); 0 represent data for PEG with M, = 8000 and polydispersity index N 1.6 from Bae et
al. (1991) and A for PEG with M, = 8000 from Saeki et al. (1976).

In Fig. 11 the results for PEG with molecular weight 8420 are compared
with data reported for PEG with molecular weight 8000 by Saeki et al.
(1976) and Bae et al. (1991). There is good agreement between the present
data and those by Bae et al. The polymer used by Bae et al. ( 1991) in their
TOAM measurements has a larger polydispersity index but the cloud-point
curves show almost the same degree of symmetry and so, the difference
between the curves is mainly due to the difference in the molecular weight.
The deviation from the data by Saeki et al. can be explained by differences
in the molecular weight of the polymer if the molecular-weight distribution
of the polymers used by them show a higher degree of asymmetry, as will be
discussed in the following section. However, it must be pointed out here
that, since only approximate values for the molecular weight and for the
polydispersity index (Bae et al., 1991) of the polymers are reported, the data
cannot be directly compared.
In the TOAM apparatus presented here, and if we assume that the
amounts of air in the sample tube are negligible, the cloud-point curves for
polymer/single solvent solutions are obtained essentially under the solvent
saturated vapor pressure, which is a function of temperature. The data
reported in this work cover temperatures from 120 to 29O”C, and the
corresponding water vapour pressures are within the range 1 to 80 atm.
306 A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311

TABLE 4
Experimental cloud-point data for aqueous solutions of PEG25, PEG44 and PEG84 a

PEG sample W&WI LCST,,,, (“C) UCST,,,,, (“C)

PEG25 0.0411 Misc. Misc.

0.0507 178.0 200.7
0.0638 170.5 210.7
0.0920 159.3 226.4
0.1805 158.7 229.9
0.2989 161.0 227.7
0.3788 160.1 222.3
0.4269 170.9 214.2
PEG44 0.0252 158.0 228.3
0.0487 148.5 247.4
0.1040 142.3 256.8
0.1906 144.6 252.5
0.2957 142.3 254.3
0.3636 146.8 254.0
0.4546 158.7 236.2
PEG84 0.0242 124.7 280.2
0.0511 123.0 283.4
0.1008 120.9 288.8
0.1607 121.9 284.7
0.2314 123.7 288.2
0.3921 130.6 274.7
0.4992 148.1 260.2

aWpol, weight fraction of polymer; LCST branc,,, cloud-point temperature corresponding to

the lower branch of the closed-loop; UCSTbranchr cloud-point temperature corresponding to
the upper branch of the closed-loop. Uncertainty in wpol_+ 0.0005; accuracy in the tempera-
ture measurements, f 0.05”C. Misc. = total miscibility.

Saeki et al. (1976) measured cloud-point temperatures for near critical

solutions of PEG/water for A4, = 1020 x lo3 at pressures in the range
O-60 atm. and reported the value of O.O04”C/atm. for the variation in the
LCST with increasing pressure.

The molecular weight distribution dependence of cloud-point curves

In the following discussion, supercooling or superheating effects will not

be considered and so the “thermodynamic cloud-point” and the cloud-point
curves coincide.
For binary system, there is no difference between the “thermodynamic
cloud-point” and the coexistence curves. The curves are smooth and the
maximum (and/or minimum) of the “thermodynamic cloud-point” curve is
A, Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311 307

250.0 -
v
o_
F two-phoses
3
F
$
E
z 150.0 -

Weight fraction of polymer

Fig. 12. Cloud-point curves for aqueous solutions of PEG612 (O), PEG6143 (A) and
PEG616 (0). -

250.0 -
0
o_
F
zl two-phases
%
b
g
s 150.0 -

:DO :

one-phase

50.0 IIJIIII,,I,III,III,III,,II,,I,,,,II,,III,,I,
0.00 0.15 0.30 0.45
Weight fraction of polymer

Fig. 13. Cloud-point curves for aqueous solutions of PEG6143 (A) and PEG6148 (0).
308 A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311

the critical point(s). That is not true for polymer/solvent systems. Due to
chain-length polydispersity of the polymer, the phase equilibrium of the
multicomponent system is no more described by a single “thermodynamic
cloud-point curve”. Figures 12 and 13 show experimental cloud-point
curves for PEG/water solutions for the polymers with the molecular weight
distributions presented in Figs. 4 and 5, respectively. In each plot, only
points referring to solutions of the PEG sample with the more symmetric
molecular weight distribution have been connected, defining in this way
the “base-line” for data analysis. The experimental data are presented in
Table 5. The maximum and minimum cloud-points (here called Upper
Precipitation Threshold, UPT, and Lower Precipitation Threshold, LPT,
points respectively, Siow et al. (1972) are listed in Table 6.
As a general conclusion, an increase in the asymmetry of the molecular
weight distribution raises the maximum and lowers the minimum cloud-
point temperatures. This shift is more pronounced in the upper branch of
the cloud-point curve. As an example, when the polydispersity index in-
creases from 1.2 (PEG612) to 1.4 (PEG6143), the difference between the
maximum cloud-point temperatures is 5.1‘C and the minimum cloud-point
temperatures differ by only 1.6”C. The higher sensitivity of the UPT to the
molecular weight distribution of the polymer has also been observed in the
case where the increase of the molecular weight distribution asymmetry is
due to an increase in M, (compare data for PEG6148 with those for
PEG6143). A shift of the polymer concentration at the maximum and
minimum cloud-points to lower values was generally found when the
asymmetry of the molecular weight distribution of the polymer increased;
the experimental points have been directly considered because, due to the
flat shape of the cloud-point curves, the polymer concentration at the UPT
and LPT points is often difficult to estimate.
The influence of polymer polydispersity on the phase behavior of poly-
mer/single solvent systems has been analyzed by several researchers as
quasi-binary systems (Koningsveld, 1968a, b; Sole, 1970; Kamide et al.,
1984) where the overall concentration of the polydispersed polymer is used
to describe the composition of the different phases. They confined their
analyses mainly to systems that show only UCST and their theoretical
studies are supported by the present experimental results. The critical points
are also dependent on polymer polydispersity. For a polymer solution that
shows an UCST, the critical point is located on the right branch of the
“thermodynamic cloud-point curve” that often shows a depression in the
critical region (Koningsveld, 1968a, b; Sole, 1970). An increase in the
polydispersity index shifts the critical point to regions of lower tempeature
and higher concentration of polymer (Koningsveld, 1968a, b; Sole, 1970;
Kamide et al., 1984). Koningsveld (1968a) shows that the overall polymer
A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311 309

TABLE 5
Experimental cloud-point data for aqueous solutions of the PEG mixtures listed in Table 2 b

PEG mixture LCSTbrancb ( “G) UGST,,,,, (“G)

PEG612 0.0105 137.3 251.5

0.0249 134.4 270.3
0.0531 132.2 273.5
0.1077 130.4 271.3
0.1489 129.4 271.0
0.2198 131.7 266.3
0.3012 137.5 263.4
0.3402 143.8 261.0
0.3914 135.2 255.0
PEG6143 0.0101 133.5 260.3
0.025 1 128.3 276.0
0.0511 127.8 278.7
0.0972 129.7 276.2
0.1320 132.1 271.5
0.2025 133.0 268.0
0.3011 136.0 260.7
0.3361 138.0 259.5
0.3818 143.9 254.0
PEG6148 0.0114 134.6 258.4
0.0245 130.0 264.3
0.0492 127.3 279.9
0.0965 128.5 277.0
0.1487 130.4 272.0
0.2468 133.2 265.2
0.2985 135.1 261.6
0.3485 141.6 257.9
0.4067 148.5 250.4
PEG616 0.0106 129.5 263.2
0.0246 127.9 276.3
0.0528 126.7 284.2
0.0986 127.9 279.5
0.1440 128.9 272.4
0.1909 131.2 268.7
0.2954 135.9 258.4
0.3405 141.4 255.7
0.3825 145.4 250.0

a For definitions, see Table 4.

concentration at the critical point is an increasing function of the square root

of it4,.
The available experimental data in this work do not give sufficient
information to locate accurately the critical points in the cloud-points curves.
310 A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311

TABLE 6
Maximum and minimum cloud-point for PEG-mixture/water solutions”

UFT
PEG mixture LPT (“C) W,“: UPT (“C) wpol

PEG612 129.4 0.1489 273.6 0.0597

PEG6143 127.8 0.0511 278.7 0.0532
PEG6148 127.3 0.0492 279.9 0.0492
PEG616 126.7 0.0528 284.2 0.0528

a LPT, lower precipitation threshold temperature; wk!, weight fraction of the polymer at
the LPT; UPT, upper precipitation threshold temperature; why weight fraction of the
polymer at the UPT.

CONCLUSIONS

The TOAM apparatus presented in this work differs from that described
by Bae et al. (1991), in three main ways (a) sample preparation technique,
(b) range of operating temperature and (c) connection of light splitter to a
video monitor allowing the sample tube to be visualized and recorded
during an experimental run. With the new sample preparation technique,
the presence of visible gas bubbles in the sample tube is avoided. Cloud-
point curves for the PEG/water system (and generally, for polymer solu-
tions) can be rapidly located in the (T, composition) plane. Due to the small
volume of the sample-tube ( -0.1 cm3) and good heat transfer in the
hot-stage, microscope effects from superheating and/or supercooling derived
from delays due to heat transfer in the measuring cell and sample-tube are
greatly reduced.
The molecular-weight distribution dependence of cloud-point curves for
the system PEG/water has been analyzed and discussed. Aqueous solutions
of PEG show an immiscible region of the closed-loop type that expands
with increasing molecular weight of the polymer.
Polymers with a polydispersity index as low as 1.6, often considered
essentially monodispersed, can in fact have very asymmetric molecular
weight distributions. Maximum and minimum cloud-points as well as the
degree of symmetry of the upper and lower branches of the closed-loop are
sensitive, at least, to the moments of the order of up to two of the molecular
weight distribution.

ACKNOWLEDGEMENT

We are grateful to Prof. Jorgen Kops and Mr. Knud Rasmussen for their
collaboration in the GPC analysis.
A. Saraiva et al. 1 Fluid Phase Equilibria 91 (1993) 291-311 311

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