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Article history:
Received 12 July 2014
Received in revised form 9 October 2014
Accepted 9 October 2014
Available online 23 October 2014
Keywords:
Carbon dioxide
Poly(ethylene glycol)
Viscosity
Density
Molecular weight
Free volume viscosity model
a b s t r a c t
Few viscosity and density data have been reported for CO2 poly(ethylene glycol) solutions, even though
many vaporliquid equilibrium data exist in the literature. In this work, viscosity and density of pure
poly(ethylene glycol) (PEG, M = 3000, 8300, 20,000 g mol1 ) at atmospheric pressure were measured.
Viscosities of PEG 3000 and PEG 8300 solutions with CO2 were measured with a torsional vibrating
viscometer at 353.2 K and 373.2 K over the range of CO2 pressures from 5 MPa to 15 MPa. The densities of
CO2 PEG solutions were calculated with the perturbed-chain statistical associating uid theory equation
of state. From shear viscosity measurements, PEG 3000 and PEG 8300 were conrmed to be Newtonian
and PEG 20000 was conrmed to be non-Newtonian. The viscosity reduction ratio for PEG solutions
saturated with CO2 was found to be independent of the PEG molecular weight (400 M 8300 g mol1 ).
A simple equation is proposed that can correlate CO2 PEG solution viscosity reduction ratio to within
0.08 in absolute units. The CO2 PEG solution viscosities could be correlated with free volume models to
within 14% using the tted value of CO2 occupied volume.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Poly(ethylene glycol) or PEG, is a polymer that has ethylene
oxide as its repeating unit and a molecular weight that is less than
20,000 g mol1 [1]. For PEG that has a molecular weight greater
than 20,000 g mol1 , the polymer is referred to as poly(ethylene
oxide) or PEO. In the polymer chain of PEG, methylene groups
are hydrophobic whereas the ether oxygen and terminal hydroxyl
groups are hydrophilic, which gives PEG its amphiphilic character.
Physical properties of PEG vary greatly with its molecular weight. At
room temperature, PEG that has a molecular weight of 400 g mol1
(PEG 400) is a liquid, while PEG 1500 is a waxy solid and PEG 6000
is a crystalline plastic. PEG is widely used in food and pharmaceutical industries due to its unique characteristic properties that
include: (i) high solubility in both aqueous and organic solvents, (ii)
no known immunogenicity, antigenicity and toxicity effects, and
(iii) high exibility and hydration of the polymer chain [2].
Carbon dioxide (CO2 ) readily dissolves into PEG, while PEG is
practically insoluble in the vapor phase of CO2 [37]. A large amount
of CO2 can be dissolved into PEG compared with other gases such
as propane and nitrogen [6]. Dissolution of CO2 into the PEG phase
causes a decrease in the melting point of PEG (ca. 20 K) [4,8,9],
a signicant reduction in the PEG viscosity (5080%) [8,1012],
a reduction in the CO2 PEG interfacial tension [13], and swelling
of the PEG [9,1416]. These characteristics of CO2 PEG solutions
have been applied to particle formation processes [1719], biphasic
reaction systems [20,21], membrane materials for gas separations
[22,23].
Fundamental studies of CO2 PEG solutions have been carried
out to understand the molecular interactions with microscopic
and macroscopic methods. Using microscopic methods, the interaction between CO2 and PEG was investigated by infrared (IR)
spectroscopy [15,24], near-IR spectroscopy [14,16], and ab initio
calculations [16]. The IR peak of CO2 bending shift to lower wavelengths in CO2 PEG solutions indicates interaction between CO2
and PEG [15]. The ab initio calculations show that the oxygen
64
Nomenclature
a
shift factor or viscosity reduction ratio
a0 /sa1 , a1 adjustable parameters in Eq. (1)
b0 , b1 /K adjustable parameters in Eq. (2)
c/g ml1 polymer concentration in mixture
c0 /cm3 g1 , c1 /cm3 g1 K1 adjustable parameters in Eq. (3)
d0 /mPa s cmd1 gd1 , d1 , d2 adjustable parameters in Eq. (5)
f
free volume fraction
H/mPa s scaling value in Eq. (2) set equal to unity
k
coverage factor
kij
correction factor for binary segment interaction
parameter
kB /J K1 Boltzmann constant
number of segments per chain
m
M/g mol1 molecular weight
n /g mol1 number average molecular weight
M
v /g mol1 viscosity average molecular weight
M
w /g mol1 weight average molecular weight
M
p/MPa pressure
Sw
swelling ratio
T/K
temperature
up /MPa standard uncertainty of pressure
standard uncertainty of temperature
uT /K
Uc ()/% combined expanded uncertainty of viscosity
Uc ()/% combined expanded uncertainty of viscositydensity product
Uc ()/% combined expanded uncertainty of density
v/cm3 g1 specic volume
V/cm3
volume
vf /cm3 g1 free specic volume
vo /cm3 g1 occupied specic volume
wi
weight fraction of component i
Greek symbols
V/cm3 volume change
/J
depth of pair potential
volume fraction of component i
i
/mPa s viscosity
0 /mPa s zero-shear rate viscosity
/kg2 m4 s1 viscositydensity product
/s
1
shear rate
/kg m3 density
/A
segment diameter
/rad s1 frequency
Superscripts
o
atmospheric pressure
65
Table 1
Available literature for the rheological behavior of molten poly(ethylene glycol) and poly(ethylene oxide).
M range/g mol1
Range
w /103
M
n /103
M
/s
1
1.0
6.318.6a
17.5340a
22.0
292
610, 932
4000
0.21.5
3.6
9.3
20.4
55
<305, <466
5300
<1002 103
Rheological behavior
Source
Newtonian
Newtonian
Newtonian
Non-Newtonian
Non-Newtonian
Non-Newtonian
Non-Newtonian
Non-Newtonian
[33,34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
/rad s1
660
0.125
0.1500
0.01100
0.5103
v /103 .
Value of M
over the same temperature range as that used in the static shear
viscosity measurements. All dynamic viscosity measurements were
performed under a stress of 100 Pa. Static viscosity measurements
were performed in two cycles and then dynamic viscosities were
measured in two cycles under isothermal conditions. The cycle
started from low to high shear rates or frequencies, and then from
high to low shear rates. Some viscosity data in the range of low
and high shear rates were cutoff due to the limited resolution of
the apparatus. The combined expanded uncertainties with a level
of 0.95 (k = 2) were estimated to be 10.4% for PEG 3000 and 6.0% for
PEG 8300 and PEG 20000 (Methods S1 and Table S1, Supplementary
material).
For Newtonian uids, a zero-shear rate viscosity was determined as an average value of static shear viscosities at different
shear rates. For non-Newtonian uids, the zero-shear rate viscosity was obtained by tting static shear viscosity data to the Cross
model [61] using LevenbergMarquardt algorithm with analytical
derivatives [62]. The Cross model is given by the following equation:
0
o =
(1)
1 + a0 ()
a1
where 0 is the zero-shear rate viscosity, a0 and a1 are adjustable
parameters that were obtained by tting the viscosity data.
2.2.2. Viscosity measurement and correlation
Atmospheric viscosities of pure PEG 3000 were measured with a
Stabinger viscometer (Anton Paar, SVM3000). Stability of the measured values was evaluated by the change in viscosity being less
than 0.07% over a 1 min interval. Measurements were performed in
duplicate from 343.15 K to 373.15 K. Each series of measurements
included two cycles that consisted of measurements made from
low to high temperature that was followed by measurements made
from high to low temperature. The combined expanded uncertainty
with a level of 0.95 (k = 2) was estimated to be 1.0% (Methods S1 and
Table S1, Supplementary material).
To correlate the viscosities at atmospheric pressure, the following empirical equation was used [63]:
ln
o
H
= b0 +
b1
T
(2)
66
(f)
(k)
(b)
(j)
(e)
(k)
(d)
(h)
(a)
(c)
(g)
T
(i)
Fig. 1. Schematic diagram of the viscosity measurement apparatus: (a) carbon dioxide cylinder; (b) regulator; (c) syringe pump; (d) chiller; (e) pressure sensor; (f) viscometer;
(g) measurement cell; (h) electrical heater; (i) temperature probe; (j) rocking stand; (k) valves.
less than 0.1 kg m3 over a 1 min interval. Measurements were performed in duplicate and each series of measurements included the
low to high temperature and the high to low temperature segments.
The combined expanded uncertainties with a level of 0.95 (k = 2)
were estimated to be 1.4 kg m3 for PEG 3000 and 1.6 kg m3 for
PEG 8300 (Methods S1 and Table S1, Supplementary material).
Atmospheric density data were correlated with the following
empirical equation:
1000
= vo = c0 + c1 T
o
(3)
()
103
(4)
d
2
(5)
where d0 , d1 and d2 are characteristic parameters, c is the concentration of polymer in the mixture and f is the free volume fraction.
The value of d2 refers to the numerical factor of free volume overlap as interpreted by Cohen and Turnbull [48,49], which should be
below 1. The exponent of the polymer concentration (d1 ) is in the
range of 34 for entangled polymer systems and is set equal to
unity for non-entangled polymers [57]. The free volume fraction is
dened as follows [50]:
f =
vf
v v0
=
v0
v0
(6)
where v is the specic volume, and vf and vo are the free volume
and the occupied volume, respectively. For the case of vf vo , Eq. (6)
can be rewritten as f = vf /v. Due to the lack of validation for vf vo in
CO2 polymer solutions, this work used Eq. (6) for the free volume
fraction.
The shift factor for scaling of the viscosity of the pure polymer
at atmospheric pressure to that of the CO2 PEG solution (ap,c ) can
be expressed with Eq. (5) as follows:
mixture (T, p, w)
ap,c
=
opolymer (T, po )
(1 wCO2 )
vopolymer
vmixture
exp
d2,polymer
d2,mixture
fmixture
fpolymer
(7)
67
vo,mixture
vo,mixture
(9)
(10)
(11)
(12)
(13)
o
(14)
68
Table 2
Pure component parameters in the pc-SAFT EoS for poly(ethylene glycol), benzene and carbon dioxide.
Substance
/A
/kB /K
Poly(ethylene glycol)
Benzenec
Carbon dioxidec
44.749M
2.4653
2.0729
3.0608
3.6478
2.7852
234.87
287.35
169.21
a
b
c
ARD/% (bias/%)
a
wPEG b
liquid b
0.63 (+0.05)
2.45 (+0.41)
0.43 (0.43)
Experimental densities of pure PEG taken from Zoller and Walsh [68].
Calculations with the value of kij set equal to zero. Experimental data for the liquid composition and density of benzenePEG mixture taken from Booth and Devoy [69].
Values reported by Gross and Sadowski [67].
Table 3
Values of kij for poly(ethylene glycol) and carbon dioxide systems for the pc-SAFT
EoS.
M/g mol1
kij
ARD wPEG /%
Bias wPEG /%
Source
1500
3000
6000
8300
0.0191
0.0210
0.0171
0.0185
0.55
0.36
0.67
0.36
0.05
<0.01
+0.13
<0.01
[4]
Eq. (13)
[8]
Eq. (13)
1
(CO2 + PEG )
2
CO2 PEG
(15)
(16)
2
n
Ycal,i Yexp,i
i=1
(17)
Uc (Yexp,i )
i=1
Ycal,i
1
Yexp,i
i=1
(18)
Ycal,i
ARD = 100
Yexp,i 1
Fig. 2. Measured static and dynamic shear viscosities at 353.2 K and 0.1 MPa
for poly(ethylene glycol) of different molecular weights: unlled symbols, static
viscosities; lled symbols, dynamic viscosities; circles, 3000 g mol1 ; squares,
8300 g mol1 , triangles, 20,000 g mol1 . Lines for PEG 3000 and PEG 8300 are average values of the static viscosities. The line for PEG 20000 was calculated with Eq.
(1). Error bars represent estimated combined expanded uncertainties of the shear
viscosity (Supplementary material).
(19)
69
Table 4
Atmospheric viscosities and densities of poly(ethylene glycol) 3000 measured with the different viscometers.a
T/K
/kg m3
/mPa s
Un-dried
343.2
353.2
363.2
373.2
Rheometer
Torsional vibrating
Stabinger
135.4
104.7
84.97
165.1
126.5b
99.55
79.37
126.5
98.38
78.46
Dried
Un-dried
Dried
169.3
127.9
99.52
79.45
1085.6
1077.4
1069.3
1061.2
1084.9
1077.0
1069.0
1061.1
a
Standard uncertainties are uT = 0.1 K for the rheometer and torsional vibrating viscometer, and 0.02 K for the Stabinger viscometer, and combined expanded uncertainties
with a 0.95 level of condence (k = 2) are Uc () = 10.4% for the rheometer, 4.0% for the torsional vibrating viscometer and 1.0% for the Stabinger viscometer, and Uc () = 1.4 kg m3
(Supplementary material).
b
Measured value with the Stabinger viscometer.
Fig. 5. Liquid densities of (a) poly(ethylene glycol) 2000, (b) 3000 and (c) 8300 in
the presence of carbon dioxide versus pressure. Symbols: , 2000 g mol1 at 374.3 K
[32]; , 3000 g mol1 at 353.2 K; , 8300 g mol1 at 353.2 K. Lines: solid lines, Eq.
(14); dash lines, the pc-SAFT EoS. Pure component parameters and the values of kij
for the EoS are given in Tables 2 and 3, respectively.
Densities of CO2 PEG solutions were calculated from the pcSAFT EoS as shown in Fig. 5 along with literature data. The
calculation method for liquid mixture densities for CO2 PEG 2000
solutions has been evaluated by Funami et al. [32]. Due to the lack
of VLE data for PEG 2000CO2 system, binary interaction parameters for PEG 1500CO2 were used in the density calculations.
70
Table 5
Viscositydensity product, density and viscosity for poly(ethylene glycol) solutions
saturated with carbon dioxide at 353.2 K and 373.2 K.a
T/K
p/MPa
/kg2 m4 s1
/kg m3 b
/mPa s
M = 3000 g mol
353.2
5.0
353.2
10.0
15.0
353.2
5.0
373.2
M = 8300 g mol1
353.2
5.0
353.2
10.0
87.1395
61.4204
50.3371
61.7483
1078.72
781.124
1073.4
1070.0
1068.8
1057.6
1074.3
1070.8
81.18
57.40
47.10
58.39
1004
729.5
a
Standard uncertainties are uT = 0.1 K and up = 0.1 MPa, and combined expanded
uncertainties with a 0.95 level of condence (k = 2) are Uc () = 2.0%, Uc () = 4.64.7%
and Uc () = 5.05.6% for PEG 3000, and Uc () = 10.413.7% and Uc () = 10.613.9%
for PEG 8300 (Supplementary material).
b
Calculated values with Eq. (14).
1
(1 wCO2 )(1 + V/VPEG )
(20)
Fig. 6. Viscosity reduction ratio for dissolved carbon dioxide in poly(ethylene glycol)
solution of different molecular weight at temperatures between 347.8 and 353.2 K.
This work: , 3000 g mol1 at 353.2 K; , 8300 g mol1 at 353.2 K. Literature: +,
400 g mol1 at 347.8 K [11]; , 6000 g mol1 at 353.2 K [8]. Lines: black solid line,
Eq. (21); red line, Gerhardt et al. equation; blue line, KelleyBueche equation; solid
line, the equation with the literature value of vo,CO2 ; dashed line, the equation with
the tted value of vo,CO2 to CO2 PEG solution viscosities at 353.2 K (M = 3000, 6000
and 8300 g mol1 ). Parameters in the equations are given in Table 6. Error bars represent estimated combined expanded uncertainties of the viscosity reduction ratio
(Supplementary material).
other CO2 PEG solutions [8,11]. At 15 MPa and 353.2 K, the reduction in the CO2 PEG solution viscosity by CO2 was 62% compared
with that of the pure PEG.
Viscosity reduction ratio in the presence of CO2 is dened as
the ratio of the CO2 PEG solution viscosity to that of pure PEG at a
given temperature. When there is no CO2 dissolution into the PEG,
the viscosity reduction ratio is equal to unity. Fig. 6 shows viscosity
reduction ratios of CO2 PEG solutions for different PEG molecular
weights (M = 400, 3000, 6000 and 8300 g mol1 ) at temperatures
between 347.8 K and 353.2 K. In Fig. 6, the CO2 solubility in the PEG
was determined by calculation with the pc-SAFT EoS for PEG 3000
at 353. 2 K and for PEG 8300 at 353.2 K, and from the literature
for other PEGs [5,8]. Although the viscosities of CO2 PEG 20000
solutions are available at temperatures from 353. 2 K to 393.2 K in
the literature [8], the reported values were excluded in the gure,
since the effect of shear rate on PEG 20000 viscosity and temperature treatment of the samples are unknown (Fig. 3). The viscosity
reduction ratio for dissolved CO2 in the PEG between 347.8 K and
353.2 K can be reduced to a simple curve for PEGs of different molecular weights from 400 g mol1 to 8300 g mol1 as a function of the
weight fraction of CO2 in the PEG solution as follows:
(21)
Eq. (21) can represent the viscosity reduction ratio of CO2 PEG
solutions to within 0.08 of the ap,c value. The reduction in viscosity ratio caused by CO2 dissolution into PEG was found to be
independent of the PEG molecular weight.
In Fig. 6, the viscosity reduction ratio for CO2 PEG 3000 solutions at 353.2 K was predicted with the Gerhardt et al. equation
and the KelleyBueche equation from parameters given in Table 6.
Results for PEG 6000 and PEG 8300 solutions with CO2 are shown in
the Supplementary material (Figs. S15 and S16). Calculated values
of the molar occupied volume (vo M/cm3 mol1 ) was in decreasing
order of PEG 6000 > PEG 3000 > CO2 , which agrees with the order
estimated from the chemical structure. Both equations overestimated the viscosity reduction by 40% for the CO2 PEG solutions.
The overestimation of the viscosity reduction values by the theory might be caused by large values of the calculated free volume
71
Table 6
Characteristic parameters for free volume viscosity models for poly(ethylene glycol) 3000, 6000 and 8300, and carbon dioxide.
Substance
vo /cm3 g1
ARD/%
Bias/%
0.5595
5.8594
1.1558 101
0.7839
0.7717
0.7717a
0.7
1.2
0.2
0.5
Carbon dioxide
n.d.b
0.589
0.6873
0.6914
a
b
f (m/M, , /kB ) =
418
PEG,cal,i PEG,exp,i
i=1
9
j=1
Uc (PEG,exp,i )
L
L
wPEG,cal,j
wPEG,exp,j
L
Uc (wPEG,exp,i
)
CL
6 H6 +PEG,cal,k
Uc (CL
6 H6 +PEG,exp,k
6 H6 +PEG,exp,k
k=1
CL
(A1)
L
where PEG is the density of pure PEG, wPEG
is the PEG composition
in the liquid phase of benzenePEG mixture and CL H +PEG is
6 6
the liquid density of benzenePEG mixture. In the calculations
for benzenePEG mixtures, it was assumed that the PEG does
not dissolve into the vapor phase and that the binary interaction
parameter was set equal to unity (kij = 0). The composition in liquid
phase was determined by the isofugacity of benzene in vapor and
liquid phases. The derivatives of the parameters were obtained by
using central differences:
Y
Xi
=
Xj =
/ i
Xi (1+),Xj =
/ i
2Xi
Xi (1+),Xj =
/ i
(A2)
72
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[2] B. Obermeier, F. Wurm, C. Mangold, H. Frey, Multifunctional poly(ethylene
glycol)s, Angewandte Chemie International Edition 50 (2011) 79887997.
[3] M. Daneshvar, S. Kim, E. Gulari, High-pressure phase equilibria of polyethylene glycolcarbon dioxide systems, Journal of Physical Chemistry 94 (1990)
21242128.
[25] K. Matsuyama, K. Mishima, Phase behavior of CO2 + polyethylene glycol + ethanol at pressures up to 20 MPa, Fluid Phase Equilibria 249 (2006)
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[66]
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[68]
[69]
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73