Colloids and Surfaces A: Physicochem. Eng.

Aspects 294 (2007) 14–19

Viscosity, molecular weight and concentration relationships at 298 K

of low molecular weight cis-polyisoprene in a good solvent
H.M. Kwaambwa a,∗ , J.W. Goodwin b , R.W. Hughes b , P.A. Reynolds b
a Chemistry Department, University of Botswana, Private Bag 00704, Gaborone, Botswana
b School of Chemistry, Bristol Colloid Centre, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK
Received 13 December 2005; received in revised form 12 July 2006; accepted 25 July 2006
Available online 1 August 2006

Abstract
A series of six well characterised homopolymers of cis-polyisoprene (PIP) ranging from 1180 to 115,000 molecular weight were utilised to explore
viscosity and the scaling relationship between viscosity and concentration in dodecane (good solvent). For each polymer molecular weight, the
relative viscosity of PIP in dodecane at 298 K was measured at several polymer concentrations using capillary viscometry. The linear extrapolation
of experimental data based on Huggins, Kramer, Martin and Schulz-Blaschke equations was used to find the intrinsic viscosity at infinite dilution for
each polymer molecular weight. The single-point method of evaluation of the intrinsic viscosity was also used for comparison. The Mark-Houwink
fit of the data gave power index of 0.72 indicating that dodecane is good solvent for PIP and the latter exists in solution as open flexible coil. Both the
radius of gyration and critical chain overlap concentration, c* , were derived from measured intrinsic viscosities. Plot of the relative viscosities versus
the scaled concentration c/c* , resulted in single curve with slope value 4.44 × 10−2 and correlation coefficient r2 = 0.996, indicating good linear fit.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Critical chain overlap concentration; Hydrodynamic radius; Intrinsic viscosity; Mark-Houwink equation; Radius of gyration; Relative viscosity; Root-
mean-square end-to-end distance; Stockmayer-Fixman equation; Viscometry

1. Introduction polymer–solvent interactions. Most commonly, however, it is

used to estimate molecular weight of a polymer. This involves
In our previous work, we have studied the rheological and the use of semi-empirical equations which have to be estab-
phase separation properties of sterically stabilised poly(methyl- lished for each polymer/solvent/temperature system analysis of
methacrylate) (PMMA) latex particles in non-aqueous non- samples whose molecular weights are known.
adsorbing polymer solution [1–3]. The non-adsorbing polymer Absolute measurements of viscosity are not essential in dilute
and solvent were cis-polyisoprene (PIP) and dodecane, respec- solution viscosity since it is only necessary to determine the vis-
tively. Both the phase separation behaviour and rheology of the cosity of a polymer relative to that of the pure solvent. The limit-
dispersions depended heavily on the molecular weight and con- ing or intrinsic viscosity [η], quantity is related to the molecular
centration of the PIP. In this current communication, we report weight of the polymer by the semi-empirical Mark-Houwink
some solution properties of PIP in dodecane at 298 K derived equation,
from viscometry data.
Viscometric methods are based on the fact that the viscos- [η] = KMvα (1)
ity of a liquid to which a polymer is added increases propor-
where K and α are constants for a given polymer, solvent and
tionally with the volume of the polymer. Viscosity provides a
temperature. Generally, 0.5 < α < 0.8 for flexible random coils
wealth of information relating to size of the polymer molecule
in a good solvent, 0.8 < α < 1.0 for inherently stiff molecules
in solution, including the effects upon chain dimensions of poly-
(e.g. cellulose derivatives, DNA, etc.) and 1.0 < α < 1.7 for highly
mer, structure, molecular shape, degree of polymerization and
extended chains (e.g. polyelectrolytes in solutions of very low
ionic strength) [4].
∗ Corresponding author. Tel.: +267 355 5039; fax: +267 355 2836. The methods which have been used can be divided into those
E-mail address: kwaambwa@mopipi.ub.bw (H.M. Kwaambwa). involving extrapolation of experimental data (EED) at a series

0927-7757/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2006.07.041
 H.M. Kwaambwa et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 294 (2007) 14–19 15

of concentrations and those involving estimation of [η] from lowing equations are often used [5]:
a single viscosity measurement and the method is called the
single-point method of evaluation (SPME). Solomon and Ciutâ : [η] = [2(ηsp − ln ηr )]1/2 c−1 (3a)
In EED method, the viscosity of a dilute solution can be
1/3 −1
described by either any or a combination of the following equa- Deb and Chatterjee : [η] = [3(ln ηr − ηsp + 0.5η2sp ] c
tions [5]:
(3b)
ηsp
Huggins equation : = [η] + kH [η]2 c (2a)
c Ram Mohan Rao and Yaseen : [η] = [ηsp + ln ηr ](2c)−1
ln ηr (3c)
Kraemer equation : = [η] − kK [η]2 c (2b)
c These equations are only valid for use with good polymer–
ηsp solvent pairs, as observed in practice [5].
Schulz-Blaschke equation : = [η] + kSB [η]ηsp (2c)
c
2. Experimental
η 
sp
Martin equation : ln = ln[η] + kM [η]c (2d)
c The cis-polyisoprene, together with the characterisation data
by membrane osmometry (MO), intrinsic viscometry (IV), gel
where is the ηr is the relative viscosity, ηsp = ηr − 1 is the spe- permeation/size exclusion chromatography (GPC/SEC) and low
cific viscosity, c is the polymer concentration, and kH , kK , kSB angle laser light scattering (LALLS), was supplied by Polymer
and kM are the respective constants. ηsp is dependent on concen- Laboratories Ltd, UK. These methods were used to characaterise
tration and interaction forces. Plots of ηsp /c against c (ln ηr )/c the polymers for number-average (Mn ), weight-average (Mw ),
against c, ηsp /c against ηsp and ln(ηsp /c) against c are straight viscosity-average (Mv ) and z-average (Mz ) molecular weights,
lines with the intrinsic viscosity as the intercept provided that and molecular weight distribution or polydispersity (Mw /Mn ).
the concentrations are not too high. The respective constants kH , The polymers used were fairly monodispersed (Mw /Mn < 1.10).
kK , kSB and kM can be calculated from the slope and depend on The characterisation data are given in Table 1. The dodecane was
the solution state, temperature and polymer structure. Each of supplied by Sigma-Aldrich. The polymers and dodecane were
EED equations has limitations in its application. For instance, used, as supplied, without further purification.
the Huggins equation strictly above applicable when [η]c  1. A stock polymer solution was prepared by weighing PIP into
At higher concentrations, experimental data show upward cur- a volumetric flask. The flask was then two thirds filled with
vature when plotted according to this equation. The Krammer dodecane. Dissolution of the polymer was done by suspending
equation is an approximation of the Huggins equation, from the flask with contents in a Dawe ultrasonic bath for at least
which it may be derived assuming ηsp  1. It has been suggested 10 min. Such a time period was found to be enough to completely
that kH + kK = 0.5, when the approximation is satisfactory for dissolve the polymer at concentrations used which were fairly
the Kraemer and Huggins equations [5]. The Schulz-Blaschke low. The flask was finally filled to the mark and once again
equation was deduced empirically. Experimental data plotted shaken in an ultrasonic bath for 3–4 min. Solutions with varying
according to this equation show downward curvature as the concentrations were prepared by pipetting the stock solution into
concentration increases, though such plots are usually linear at 25 cm3 volumetric flasks and diluted to the mark with dodecane.
higher concentrations than those obtained by application of the The relative viscosity, ηr , is related to the flow times t and t0
Huggins equation. Similar observations have been made with and densities ρ and ρ0 for the solution and pure solvent, respec-
regard to the Martin equation, which was also deduced empiri- tively, by the equation,
cally. t ρ
The inconvenience of extrapolation methods for routine anal- ηr = (4)
t0 ρ0
ysis has given rise to considerable interest in estimation of [η]
from a single specific viscosity measurement, particularly when Using the lowest molecular weight polymer for which the mag-
[η] need only evaluated approximately. In the SMME, the fol- nitude of ρ/ρ0 could be more significant, the densities of the

Table 1
Molecular weight (in g mol−1 ) characterization data for PIP as supplied by Polymer Laboratories Ltd.
Batch no. MO (Mn ) IV (Mv ) LALLS (Mw ) GPC/SEC (Mn ) GPC/SEC (Mw ) GPC/SEC (Mz ) Mw /Mn Assigned (Mp ) Adopted code

20323-4 + 1203 + 1085 1165 1180 1.08 1180 P1K

20328-1 + 8308 + 7893 8061 8075 1.03 8000 P8K
20332-4 + 29103 + 27117 27943 28340 1.03 28300 P28K
20332-2 29240 31257 30720 30441 31137 31537 1.03 31500 P31K
20335-2 + 87862 + 85088 86942 85942 1.02 86000 P86K
20335-3 108000 110000 111251 111251 113314 113271 1.02 115000 P115K

+ According to the information provided by the supplier the technique not used or unapplicable.
16 H.M. Kwaambwa et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 294 (2007) 14–19

Table 2
Evaluated intrinsic viscosity values by extrapolation of experimental data (EED) method
Polymer code Mv [η] (cm3 g−1 )

Huggins Kramer Martin Schulz-Blaschke Mean value

P1K 1202 2.61 2.63 2.82 2.97 2.75

P8K 8308 12.40 12.40 12.40 12.38 12.39
P28K 29103 25.78 25.75 25.80 25.82 25.79
P31K 31257 33.55 33.52 33.68 33.45 33.55
P86K 87862 55.74 55.55 55.70 55.67 55.66
P115K 110000 70.14 70.13 70.17 70.20 70.17

solutions and solvent were measured and found to be the same

within the experiment error. This was taken to mean that the con-
tribution by ρ/ρ0 to ηr was negligible at concentrations used for
capillary viscometry and so ηr was simply set to be equal to t/t0 .
The flow times of PIP solutions were measured with a
Cannon-Fenske-type viscometer clamped to holder and sus-
pended in a water bath at 25 ◦ C. A 10 cm3 volume of sample
was pipetted into the viscometer for each determination, and
the time of flow between two marks measured. The flow time
used in all subsequent calculations of ηr was the average of at
least five readings which agreed to within ±0.5 s. To minimise
any possible effects of polymer adsorption [6], equilibrium was
allowed to be attained with the most concentrated solution and
then measured the flow time with a fresh portion of the solution.
Flow times of decreasing concentration solution series were per-
formed, and finally the solvent flow time measured. It has been Fig. 1. Plot of relative viscosity with concentration for the different molecular
observed that provided the value of the adsorbed layer thickness weight polymers of PIP in dodecane.
remains constant throughout these measurements, the effect of
the adsorbed layer will be minimised. Data at several polymer
concentrations were used to determine [η] (cm3 g−1 ) by the EED
and SPME procedures. Table 3
Evaluated intrinsic viscosities using single-point method

3. Results and discussion Polymer code Mv Mean [η] (cm3 g−1 )

SC DC RY Mean value
Fig. 1 shows a plot of the relative viscosity, ηr , as a function
P1K 1202 3.92 3.93 3.93 3.93
of concentration of PIP, c, of different molecular weights. The
P8K 8308 12.18 12.20 12.20 12.19
intrinsic viscosity [η], values calculated gave roughly the same P28K 29103 23.46 23.53 23.53 23.51
values irrespective of the equation used. Hence, a mean value P31K 31257 29.97 30.02 30.02 30.00
for a given polymer molecular weight were used for further data P86K 87862 53.74 54.24 54.27 54.08
analysis (Tables 2–4). P115K 110000 69.96 70.63 70.65 70.41
In general, the Mark-Houwink equation is linearised by plot- SC: Solomon and Ciutâ, DC: Deb and Chatterjee, RY: Ram Mohan Rao and
ting ln[η] against ln Mv from which the constants α and K are Yaseen.

Table 4
Characteristic properties of PIP in dodecane
Polymer code [η]0 (cm3 g−1 ) [η] (cm3 g−1 ) αη a Rh (nm) Rg0 a (nm) Rg a (nm) c* (g cm−3 )

P1K 4.59 3.61 1.10(0.94) 0.9 1.0(1.1) 1.1(1.1) 0.261

P8K 12.03 11.49 1.15(1.04) 2.4 3.2(2.9) 3.2(3.1) 0.0720
P28K 22.52 26.86 1.24(1.13) 4.9 5.6(5.5) 7.0(6.2) 0.0243
P31K 23.34 28.23 1.30(1.13) 5.2 5.9(5.8) 7.7(6.6) 0.0204
P86K 38.13 58.31 1.37(1.20) 9.3 10.6(9.6) 14.5(11.6) 0.00832
P115K 43.78 68.37 1.41(1.23) 10.8 12.3(11.1) 17.4(13.6) 0.00644
a Values in brackets represent chain solution properties calculated from theoretical approximations due to van Krevelen [9].
 H.M. Kwaambwa et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 294 (2007) 14–19 17

[9]. Using the solubility parameter calculated, the difference is

approximately 1 J1/2 cm−3/2 , which is less than the rule of thumb
value. Furthermore, the solvent-interaction parameter χ using
van Krevelen data gave a value of 0.474 [10]. The interaction
parameter χ ≈ 0.5 implies that the polymer in a given solvent
will have a random coil (or close to) configuration, which ulti-
mately makes it easier to calculate the radius of gyration. These
two theoretical results, according to polymer solution theory,
confirm the experimental observation above that dodecane is
good solvent for PIP.
In the range 2 × 104 < Mw < 107 , Hirata et al. [11] have plotted
their and other workers’ data for PIP using the Mark-Houwink
equation and found that they all fitted closely by the equation
[12,13],

[η] = 0.0159Mv0.747 cm3 g−1 (6)

Fig. 2. The Mark-Houwink (MH) plot of the measured intrinsic viscosity data.
in good solvents (e.g. cyclohexane, toluene, etc.), regardless of
the difference in solvent power or in temperature, and
determined. Theoretically, this plot should not be linear over
a wide range of Mv , so that α and K values should not be
[η]o = 0.132Mv0.5 cm3 g−1 (7)
used for polymers with Mv outside the range defined by the
calibration samples. In the range 1180 ≤ Mw ≤ 115,000, data
at theta temperature or in theta solvent.(e.g. 1,4-dioxane at 34 ◦ C
seem to show curvature especially at lower Mv . It is known
and at 31.2 ◦ C). The slight difference in the value of the constant
that macromolecules of Mv < 104 g mol−1 and higher molec-
α found may be due to smaller molecular weight range which
ular weight samples do not exhibit a linear variation of ln[η]
was used in this work and also, most of the solvents used and
against ln Mv . A curvature at low Mv is often observed due to
reported in the literature are better solvents for PIP than dode-
the non-Gaussian character of short flexible chains [5,6]. A rela-
cane [9]. The value of [η] for a given polymer depends on the
tionship which is also valid for low molecular weights can be
thermodynamic quality of the solvent. In a good solvent, the
established by inserting a correction term bη in the limiting vis-
polymer-solvent contacts are preferred and the value of [η] is
cosity. On plotting [η] versus Mv [η] = bη is obtained at Mv = 0.
high, whereas in poor solvents polymer-polymer contacts are
If ln([η] + bη ) is plotted as a function of ln Mv , a straight line
preferred and lead to lower values of [η]. A description of the
is obtained even for low molecular weights. For high values of
intramolecular interactions of polymer chains in dilute solutions
the limiting viscosity, bη is so small that it can be neglected and
is given by the equations of Fox and Flory [14].
the [η]–Mv -relationship applicable to high molecular weights
Estimation of ideal chain dimensions from hydrodynamic
is obtained. Correcting with bη = 1.0 cm3 g−1 obtained from a
measurements ([η]) obtained in good solvents requires one of
plot of [η] against Mv for our data gave a fairly linear plot
the graphical procedures [15]. The most familiar of these, the
over the entire range of molecular weight studied. The modified
Stockmayer-Fixman plot [6], presumes that the viscosity expan-
Mark-Houwink [η]–Mv -relationship allowing for low molecular
sion factor is α3η (α3η = [η]/[η]0 ) in the Fox–Flory relation, which
weight rigidity for PIP in dodecane at 25 ◦ C and plotted in Fig. 2
represents deviation from the unperturbed condition and which
was thus found to be:
depends on the interaction between repeat units. The corre-
[η] = 1.0 + 0.0158Mv0.72 (5) sponding [η] data obtained from evaluation of the modified
Mark-Houwink constants from the polymer samples with were
The power index 0.72 indicates that dodecane is a good sol- used to plot as shown in Fig. 3 the linear form of the Stockmayer-
vent for PIP and the later in solution exist as open and highly Fixman equation given as follows:
expanded flexible random coils [7]. The solubility rule sup-
ports this finding that dodecane is good solvent for PIP. A [η]
= K0 + 0.51ΦBMv0.5 (8)
polymer, according to the rule, is soluble in a given solvent Mv0.5
if the absolute value of the difference between the solubility
parameters of the solvent and polymer is less than or equal to where K0 is the conformational parameter, B is the long-range
3.5 J1/2 cm−3/2 , assuming that the molar volume of solvent is to interaction parameter and Φ is the Flory constant. B is a mea-
equal to 100 cm3 mol−1 and as long as the polymer is non-polar sure of the extent of the solvent-polymer interaction and thus,
and does not form hydrogen bonding in the solvent, the factors depends upon the chain structure and polymer–solvent interac-
that can cause deviation from the rule of thumb [8]. The solu- tions but is a constant for a given polymer–solvent–temperature
bility parameter of dodecane is 16.2 J1/2 cm−3/2 and that of PIP system.
has been found to be in the range 16.2–20.5 J1/2 cm−3/2 and was The conformational parameter K0 is related to the unper-
calculated to be 17.2 J1/2 cm−3/2 using van Krevelen estimations turbed dimension called root-mean-square end-to-end distance,
18 H.M. Kwaambwa et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 294 (2007) 14–19

Fig. 3. The Stockmayer-Fixman plot of intrinsic viscosity data of PIP in dode-

cane from modified Mark-Houwink equation. Fig. 4. Plot of relative viscosity with scaled polymer concentration for the dif-
ferent molecular weight polymers (slope = 4.44 × 10−2 , correlation coefficient,
r2 = 0.996).
1/2
h2 0 , by the equation [16,17],
 3/2 hydrodynamic radius, Rh (assuming non-draining condition),
h2 0 based on the Kirkwood-Riseman theory [6]
K0 = Φ0 (9)
Mv
Rh
Rg0 = (13)
With Φ = 2.5 × 1023 mol−1 [5], this gave the conformational 0.875
parameter, K0 = 9.41 × 10−2 cm3 mol0.5 g−1.5 and B = 2.72 ×
where the hydrodynamic radius was calculated using Eq. (11)
10−27 cm3 mol2 g−2 . Using Eq. (10), the relation between the
but more appropriately it can be determined by dynamic light
root-mean-square end-to-end distance for unperturbed chain,
1/2 scattering measurements [19]. The radius of gyration, Rg , of the
h2 0 , and Mv was found to be, chain in dodecane has also been estimated using the Stockmayer-
1/2 Fixman equation. The calculated c* values together with [η], αη ,
h2 0 = 7.22 × 10−9 Mv1/2 (cm) (10) Rh , Rg0 and Rg values for the PIP polymer studied are given in
The hydrodynamic radius Rh is determined assuming the Table 4. It can be seen that c* decreases with increasing molecu-
polymer the polymer coils are hard spheres so that when the lar weight as the lower molecular weight chains, that have lower
polymer coil concentration is represented in terms of a volume occupied hydrodynamic volume, require a higher concentration
fraction is the Einstein value of 2.5. This gives an equivalent to overlap, as is expected.
hard sphere hydrodynamic radius expression of the chain [2], To facilitate better interpretation of the variation of the slopes
  plots of ηr versus c shown in Fig. 1 for different polymers, the
1 3[η]Mw 1/3 relative viscosity is replotted with the concentration re-scalled
Rh = (11)
2.5NA 4π106 by the theoretically determined values of c* (corresponding to
each Mw ) as shown in Fig. 4. The variation in slopes is com-
The dilute and semidilute regimes in polymer solution theory pletely eliminated in the polymer molecular weight range and
are separated by the critical chain overlap concentration, c* . This concentrations studied resulting in a single curve of slope value
crossover concentration between the dilute and the semidilute 4.44 × 10−2 with correlation coefficient r2 = 0.996, indicating
regimes represents the concentration at which the polymer coils good linear fit. Often such scaling of data results in a curve with
begin to touch or overlap. Various theoretical models have been two regimes being indicated by the change in the slope of the
suggested to estimate c* [18–20]. According to the Vincent et trend in the data. Based on literature [20,21], these regimes cor-
al. model [18], c* can be estimated from chain dimensions as respond to semidilute unentangled and semidilute entangled,
follows: respectively. The first crossover between the two regimes is
Mw taken to mark the onset of the critical chain overlap concen-
c∗ = ∗
(12)
b R3g NA tration where the polymer chains topologically constrain each
other and begin to entangle. These regimes were not observed
where NA is the Avogadro number, Mw is the molecular weight, in this study. However, there is slight deviation from linearity
Rg is the perturbed radius of gyration and b* is a constant at low c/c* which in our case is dominated by contributions
and is equal to 5.63 for hexagonal close packing of polymer by polymers P1K (Mw = 1180) and P8K (Mw = 8000). This is
coils. In a good solvent, the unperturbed radius of gyration, Rg0 , not surprising because even their effects, especially P1K, on
is usually a better estimate of the chain dimensions than the rheology and phase separation of PMMA systems with higher
1/2
root-mean-squared end-to-end, h2 0 , as it accounts for the polymer weights studied previously [1–3]. For instance, the
 H.M. Kwaambwa et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 294 (2007) 14–19 19

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