Journal of Colloid and Interface Science 263 (2003) 473–477

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The Christiansen effect of brightly colored colloidal dispersion

with an amphiphilic polymer
Kento Okoshi,a,b,∗ Naoko Sano,b,c Takamitsu Okumura,d,e Akihiro Tagaya,e Jun Magoshi,b
Yasuhiro Koike,d,e Michiya Fujiki,a,b and Junji Watanabe b,c
a Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama, Ikoma, Nara 630-0101, Japan
b CREST-JST (Japan Science and Technology Corporation), 4-1-8 Hon-cho, Kawaguchi, Saitama 332-0012, Japan
c Department of Polymer Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8552, Japan
d Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan
e ERATO-JST (Japan Science and Technology Corporation), E-building, K2 Town-Campus, 144-8 Ogura, Saiwai-ku, Kawasaki, Kanagawa 212-0054, Japan

Received 13 September 2002; accepted 22 March 2003

Abstract
A novel coloration phenomenon in a colloidal dispersion with an amphiphilic polymer was found. The dispersion consists of tetrahydrofu-
ran (THF), an aqueous solution of sodium thiosulfate (Na2 S2 O3 ·5H2 O), and hydroxypropylcellulose (HPC). The dispersion was emulsified
by HPC as an amphiphilic polymer, so that the aqueous phase was confined in droplets in the THF matrix. It typically appeared bluish violet
at room temperature and turned into blue with increasing temperature. In this system, the refractive indices of the inside and outside of the
droplet coincided at a certain wavelength at which the light passes through without scattering, which is called the Christiansen effect. The
color observed was successfully simulated by Mie’s scattering theory in combination with the Christiansen effect.
 2003 Elsevier Inc. All rights reserved.

Keywords: Coloration; Hydroxypropylcellulose; Colloid; Christiansen effect; Mie scattering

1. Introduction The other type of colored dispersion system is a Chris-

The most widely recognized and so far intensely studied
colored colloidal dispersion system is colloidal gold disper-
sion in a medium. It was utilized by Romans as a colorant in
glasses and has attracted the interest of both experimenters
and theorists. Its color depends on the refractive index of the
medium as well as the shape and diameter of the colloidal
gold particles [1–4].
The first successful theoretical treatment of this system,
which has given a rigorous solution for light scattering by a
homogeneous sphere in a medium, was achieved by Mie in
1908 [5]. It has succeeded in reproducing the experimental
results of colloidal gold dispersion in water quantitatively,
that is, based on the refractive index relative to water and the
diameter of the colloidal particles. It shows the oscillation
of scattering efficiency against the wavelength of the light,
which is the origin of the coloration of the dispersion [6,7].
* Corresponding author.
E-mail address: kokoshi@ms.aist-nara.ac.jp (K. Okoshi).
0021-9797/03/$ – see front matter  2003 Elsevier Inc. All rights reserved.
doi:10.1016/S0021-9797(03)00336-9
tiansen filter, which usually consists of quartz particles dis-
persed in an organic liquid whose refractive index is very
close to that of quartz [8–12]. The coloration is attributed
to the exact matching of the refractive indices of quartz
and continuum at a certain wavelength. The light at this
wavelength passes through the dispersion system as if it is
homogeneous medium, while the lights of the other wave-
length scatter intensely. The color changes with temperature
because the refractive index of liquid greatly changes with
temperature while solid not. Such coloration is based on the
large difference of Abbe’s number [13] of solid and liquid.
We newly found a novel coloration phenomenon in a liq-
uid/liquid colloidal dispersion with an amphiphilic polymer.
The dispersion consists of tetrahydrofuran (THF), an aque-
ous solution of salt (sodium thiosulfate (Na2 SO3 ) was used
for the sake of good solubility), and hydroxypropylcellulose
(HPC). The dispersion was emulsified by the amphiphilic
polymer and the aqueous phase was confined in a droplet
in the THF matrix, which typically appears bluish violet at
474 K. Okoshi et al. / Journal of Colloid and Interface Science 263 (2003) 473–477
room temperature and turns blue with increasing tempera-
ture.
In this system, the refractive indices inside and outside
the droplet coincide at a certain wavelength which depends
on the temperature, at which the light passes through without
scattering, as in a Christiansen filter. The color observed by
the naked eye is the supplementary color of the transmitted
wavelength, i.e., scattered light of the other wavelength.
However, the difference of Abbe’s number [13], in other
words, the wavelength dependency of the refractive index, is
weak in this system compared with the Christiansen filter of
a solid/liquid dispersion system because it is a liquid/liquid
colloidal dispersion system. Therefore, the scattering effi-
ciency oscillations cannot be neglected in this case.
In this paper, we show the interpretation of this coloring
phenomenon of Mie’s theory in combination with the Chris-
tiansen effect, which qualitatively agrees with experimental
results.
2. Materials and method
2.1. Ingredients
Hydroxypropylcellulose (HPC) with a viscosity of 3–6 cP
in a 2% aqueous solution at 20 ◦ C, Mw = 77000, Mw /Mn =
1.81, MS (molar substitution of hydroxypropyl group) 4.0,
and DS (degree of substitution of hydroxypropoxyl group)
2.6 was purchased from Tokyo Kasei Kogyo and used after
evaporation for 2 h to remove residual water. Sodium thio-
sulfate (Na2 S2 O3 ·5H2 O) was purchased from Kanto Chem-
ical Co. Inc. and used without further purification. Tetrahy-
drofuran (THF) was refluxed with calcium hydride for 3 h
and distilled before use. Distilled water was purified with
a Milli-Q Ultrapure Water System of Millipore Corp. to
18.3 K cm of specific resistance before used.
2.2. Preparation of colloidal dispersion
To prepare a colloidal dispersion, 15 ml of sodium thio-
sulfate aqueous solution at a given weight fraction was
mixed with 10 ml of a hydroxypropylcellulose solution of
tetrahydrofuran with a given weight fraction and agitated for
20 min at 3000 rpm at 25 ◦ C, using a BL3000 Heidon lab-
oratory stirrer. The resulting colloidal dispersion was kept
quietly to reach the equilibrium for 30 h after preparation.
2.3. Optical microscopic measurement
Optical microscopic measurement of the colloidal disper-
sion was performed with an Olympus BX-50 optical micro-
scope equipped with an Olympus HC-300Z CCD camera
connected with a computer and scale. An aliquot of the dis-
persion was placed in a hollow with depth 0.5 mm at the
center of the glass slide and covered with a cover glass for
observation.
2.4. Droplet size distribution measurement
Photomicrographs of droplets in the colloidal dispersion
were taken and the statistical data of the droplet radius were
evaluated by means of NIH Image Ver. 1.61 image process-
ing software.
2.5. Refractive index measurement
The refractive indices of the liquid both inside and outside
the colloidal droplets were measured with a thermostatic
multiwavelength Abbe refractometer (ATAGO Co. Ltd. Dig-
ital Abbe refractometer DR-M2) after centrifugation of the
colloidal dispersion for coalescence of the droplets.
2.6. Spectroscopic measurement
The color spectra of the colloidal dispersion were ob-
tained with an UV–visible spectrometer (Jasco V570) equip-
ped with a thermostat using quartz cells with path length
10 mm.
3. Result and discussion
3.1. Colloidal solution
The colloidal dispersion produced by the recipe men-
tioned above was a water-in-oil (W/O) emulsion because
it could be diluted by THF and not by water. The disper-
sion consists of a transparent upper phase, an opaque middle
phase, and a transparent lower phase, which are the organic
phase, the emulsion, and the aqueous phase, respectively.
The ingredients HPC and salt were almost exclusively dis-
tributed to the organic phase and aqueous phase, respec-
tively.
Optical micrographs of the droplets in the emulsion are
shown in inset (b) of Fig. 1. Almost randomly amassed
perfect spheres with a variety of sizes can be seen. It was
ensured that there was no change of size due to a sand-
wich effect of the slide and cover glasses. The distribution
of droplet sizes, which is shown in Fig. 1, was evaluated by
image processing software and elucidated that it is widely
distributed but not depends on the concentration of salt, as
shown in inset (a) of Fig. 1, and on the concentration of HPC.
However, the volume of the emulsion, i.e., opaque mid-
dle phase was proportional to the HPC concentration up
to a certain point, while it reached a plateau beyond that
point (Fig. 2). The volume of the lower phase, i.e., the aque-
ous phase, decreased with increasing HPC concentration and
was depleted in the plateau region. This indicates that a cer-
tain amount of HPC is consumed to produce a unit area of
interface of two phases in the emulsion. The amount of HPC
was calculated to be 3.20 × 10−7 g cm−2 with the droplet
size distribution and gross volume of aqueous droplet in
the emulsion that was measured after centrifugation. The
 K. Okoshi et al. / Journal of Colloid and Interface Science 263 (2003) 473–477
Fig. 1. Distribution of droplet radii in a colloidal solution that was prepared
with an aqueous solution of 48.2 wt% Na2 S2 O3 and a THF solution of
1.6 wt% HPC with 4:6 volume fraction, evaluated by microscopic observa-
tions. The solution was agitated for 20 min and kept quietly for 30 h before
observations. Inset (a) shows the salt concentration dependency of the aver-
age droplet size and distribution. Error bars indicate the standard deviation.
Inset (b) shows an optical micrograph of the droplets in the emulsion.
Fig. 2. Dependency of colloidal emulsion volume on HPC concentration
in THF solutions. The solutions were prepared with aqueous solution of
48.2 wt% Na2 S2 O3 and HPC solution of given concentrations with 4:6 vol-
ume fractions. The emulsion volume was evaluated in a graduated cylinder
after keeping quietly for 30 h.
area covered by an HPC molecule was calculated from a
CPK molecular model optimized with PC Spartan to be
1.25 × 10−7 g cm−2 ; therefore it can be concluded that the
droplets are covered by two or three layers of HPC mole-
cules. These are reasonable figures for a protective colloidal
system.
475
Fig. 3. Photographs of the brightly colored colloidal emulsions, illuminated
with white light from side, taken at room temperature. These are prepared
with aqueous solution of Na2 S2 O3 concentrations of (a) 44.6, (b) 45.9,
(c) 46.5, (d) 47.4, and (e) 48.2 wt%, from left to right, and THF solution
of 1.6wt% HPC with 4:6 volume fraction.
Fig. 4. Absorption spectra of colored colloidal emulsions at room temper-
ature. The solutions are with Na2 S2 O3 concentrations of 44.6, 45.9, 46.5,
47.4, and 48.2 wt% same as in Fig. 3. Observed spectrum change was re-
produced with increasing temperature and decreasing HPC concentration in
the same manner.
3.2. Optical properties
Macroscopically, the colloidal emulsion showed bright
colors, depending on the salt concentration, as can be seen
in Fig. 3. The color, which is scattered light from the col-
loidal emulsion, systematically changes from muddy brown
to orange, violet, blue, and hazy blue with increasing tem-
perature and with decreasing HPC concentration in the same
way.
The dependency of the spectroscopic measurement of
the colloidal emulsion on the salt concentration was car-
ried out because it is difficult to control the concentration
of a volatile ingredient with changing temperature. The salt
and HPC have absorption bands in the UV region below
300 nm and water has harmonic sound absorption above
1000 nm, so that we chose wavelengths ranging from 300
to 800 nm. Apparently as shown in Fig. 4, the transparent
window of wavelength travels from blue to red with increas-
ing salt concentration, while its full width at half maximum
(FWHM) increases, which qualitatively coincides with the
macroscopic observations.
476 K. Okoshi et al. / Journal of Colloid and Interface Science 263 (2003) 473–477
Fig. 5. Dispersion of the refractive indices of aqueous and organic phases
in the colloidal solution with Na2 S2 O3 concentrations of (a) 44.6, (b) 46.5,
and (c) 48.2 wt%. Curves are regression functions for the three-term Sell-
meier dispersion relation (Eq. (1)) fitted on experimental refractive index
data at 486, 589, and 656 nm, which are also indicated in the figure as
closed circles for organic phase and open circles for aqueous phase.
These results implicate the exact matching of the refrac-
tive indices of the inside and outside of the droplet at a
certain wavelength and remind us of the Christiansen effect,
because salt concentration change unquestionably results in
a change of the refractive index of aqueous phase in the
droplets.
Therefore, refractive index measurement of both the
aqueous and organic phases, i.e., the inside and outside of the
droplets was performed with a multiwavelength Abbe’s re-
fractometer. It was performed at 486, 589, 656 nm of wave-
length with upper organic phase and lower aqueous phase
after centrifugation of colloidal emulsion. The results were
fitted on the three-term Sellmeier dispersion relation [14–16]

1/2
a c e responds to the extinction efficiency because the sphere is
n =  1−b  +  1−d  +  1−f  , (1)
λ2 λ2 λ2
where n is the refractive index, λ is the wavelength, and a,
b, c, d, e, f are fitting parameters, as can be seen in Fig. 5.
The difference of the refractive indices inside and out-
side the droplets was subtle over the measured range of
wavelengths and they crossed at a certain wavelength which
depends on the salt concentration as expected. The wave-
length of the refractive index crossing almost perfectly co-
incided with the wavelength of the transparent window with
all the salt concentrations. This implies that the coloration
originates from the Christiansen effect of a liquid/liquid dis-
persion system.
Fig. 6. Absorption spectra calculated with Mie’s scattering theory of a suf-
ficiently large nonabsorbing sphere, the regression functions of refractive
index dispersion, and droplet radius distributions, for the solutions with
Na2 S2 O3 concentrations of 44.6, 45.9, 46.5, 47.4, and 48.2 wt%.
However, it is insufficient to describe the spectroscopic
data in the whole range of wavelengths because scattering
efficiency oscillation cannot be neglected due to slight differ-
ence of refractive indices. Therefore Mie’s scattering theory
was taken into consideration to describe it.
According to this theory, the scattering efficiency of a
sufficiently large nonabsorbing sphere, compared with the
wavelength, in the continuum with slightly different refrac-
tive indices can be described as,
4 4
Qsca = 2 − sin ρ + 2 (1 − cos ρ), (2)
ρ ρ
ρ = 2x(m − 1), (3)
2πa
x= , (4)
λ
n1
m= , (5)
n2
where Qsca is the scattering efficiency of a single sphere,
a is the radius of the sphere, λ is the wavelength, and n1
and n2 are the refractive indices of inside and outside of
the sphere, respectively [1]. The scattering efficiency cor-
nonabsorbing; thus it can be taken as an absorbance.
To calculate the absorption spectra, the regression func-
tions for the refractive index dispersion both inside (n1 ) and
outside (n2 ) the droplets were put into Eq. (5). Then the cal-
culated Qsca was multiplied by the normalized frequency for
the corresponding radius (a) of the sphere according to Fig. 1
and summed up to take into account the droplet size distrib-
ution. The resulting absorption spectra can be seen in Fig. 6.
This reproduced the observed spectra well qualitatively.
Therefore it was concluded that the observed coloration of
colloidal dispersions can be described by Mie’s scattering
theory in combination with the Christiansen effect. Slight
deviations of the calculated spectra from the observed ones
 K. Okoshi et al. / Journal of Colloid and Interface Science 263 (2003) 473–477
were assumed to be attributable mainly to the multiple scat-
tering effects of the relatively closely packed droplets, be-
cause Mie’s scattering theory is available on condition that
the distance between spheres are sufficiently long, and also
to the gradation of HPC concentration in the vicinity of
droplets.
4. Conclusion
These results show the novel coloration of liquid/liquid
colloidal dispersion systems which can be described by
Mie’s scattering theory in combination with Christiansen ef-
fect. Although the multiple scattering effects between neigh-
boring spheres was neglected, the calculated spectra repro-
duced the observed spectra qualitatively.
The colloidal coloration, which can be categorized in
structure colors, is not degradable unlike dyestuffs, and
is easily controlled with refractive index optimization,
which can be advantageous for colorant or filter applica-
tions [17,18]. Moreover, it has a transparent wavelength
window, which is attributed to the exact matching of the
refractive index of inside and outside of the droplets. In
some cases, it has a very narrow full width at half maximum
(FWHM), which is monochromatic enough to be utilized for
bandpass filters.
This study suggests a new field of structure colors which
can be applied to colorant and optical device applications.
477
Acknowledgment
This work was supported by CREST (Core Research for
Evolutional Science and Technology) of JST (Japan Science
and Technology Corporation).
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