Investigating Static and Dynamic Light Scattering

Yong Sun∗
4820 Kingsway Ave. Unit 234, PO Box 1106
Burnaby, BC V5H 2C0, Canada

October 11, 2011

arXiv:1110.1703v1 [physics.chem-ph] 8 Oct 2011

Abstract

A new size, static radii Rs , can be measured accurately using Static Light Scat-
tering (SLS) technique when the Rayleigh-Gans-Debye approximation is valid for
dilute homogenous spherical particles in dispersion. The method proposed in this
work not only can measures the particle size distribution and average molar mass
accurately but also enables us to explore Dynamic Light Scattering (DLS) technique
further. Detailed investigation of the normalized time auto-correlation function of
the scattered light intensity g (2) (τ ) shows that the measurements of DLS can be
expected accurately and the static and hydrodynamic radii of nanoparticles are dif-
ferent. Only at some special conditions, the Z-average hydrodynamic radius can be
measured accurately at a given scattering angle. The fact that the values of average
hydrodynamic radius measured at different scattering angles are consistent or the
values of polydispersity index are small does not mean the particle size distribution
is narrow or monodisperse.

1 INTRODUCTION
Light Scattering has been considered to be a well established technique and applied in
physics, chemistry, biology, etc. as an essential tool to investigate the characteristics
of nanoparticles in dispersion. The treatment of Static Light Scattering (SLS) spec-
troscopy is simplified to the Zimm plot, Berry plot or Guinier plot etc. to get the root

1/2
mean-square radius of gyration Rg2 and the molar mass of particles provided that
the particle sizes are small [1, 2] and one fundamental application of Dynamic Light
Scattering (DLS) technique is the accurate and fast size measurement of particles made
of different materials. In general, the Z-average hydrodynamic radius and polydispersity
index are obtained approximately using the method of Laplace transformation or Cumu-
lant analysis at a given scattering angle [3–7]. Some researchers use the results measured
using SLS and DLS together to obtain much more information of nanoparticles [8–12].
Although people have proposed the theoretical function of the normalized time electric
field auto-correlation function of the scattered light g(1) (τ ) [4, 6, 13] and try to obtain
∗
Email: [email protected]

1
more information about nanoparticles using SLS and DLS together, the comparison
of the expected values and experimental data of the normalized time auto-correlation
function of the scattered light intensity g(2) (τ ) has not been detailed.
How the particle size distribution can be obtained directly from SLS data has been
reported. Strawbridge and Hallett [14] studied the theoretical scattered intensity of
coated spheres with vertically polarized incident light. The scattered intensity at the
geometrical or linear trial radii between rmin and rmax was used to fit SLS data. Schn-
ablegger and Glatter [15] assumed that the size distribution can be described as a series
of cubic B-splines and used the simulated and measured data to demonstrate the com-
putation procedure.
In this work, a SLS treatment is reported for the size information of dilute homoge-
neous spherical particles in dispersion. The number distribution of particles is chosen
as a Gaussian distribution and the effects of the scattering vector and the different in-
tensity weights of different particle sizes on the scattered light intensity are considered.
With the assistance of a non-linear least square fitting program, the mean static radius
hRs i and standard deviation σ are measured accurately. Given the absolute magnitude
of the scattered intensity and some parameters related to the instrument and samples,
the average molar mass can also be measured accurately. For the polystyrene spheri-
cal particles investigated, the values of mean static radius and mean radius measured
using Transmission Electron Microscopy (TEM) technique provided by the supplier are
consistent.
Based on the particle size distribution measured using SLS technique, DLS technique
was investigated further. The expected values of g(2) (τ ) calculated based on the SLS
measurements or commercial results provided by the supplier are consistent with the
experimental data very well. This result also reveals that the static and hydrodynamic
radii of spherical nanoparticles are different. Only at some special conditions, the Z-
average hydrodynamic radius can be measured accurately at a given scattering angle.
The fact that the values of average hydrodynamic radius measured at different scattering
angles are consistent or the values of polydispersity index are small does not mean the
particle size distribution is narrow or monodisperse.

2 THEORY
When the homogeneous spherical particles are considered and Rayleigh-Gans-Debye(RGD)
approximation is valid, the average scattered light intensity of a dilute non-interacting
system in unit volume can be obtained for vertically polarized light
dn 2
4π 2 sin2 θ1 n2s

R∞ 6
Is dc c=0 c 4πρ 0 R
Rs∞
P (q, Rs ) G (Rs ) dRs
= , (1)
Iinc λ4 r 2 3 3
0 Rs G (Rs ) dRs

where θ1 is the angle between the polarization of the incident electric field and the
propagation direction of the scattered field, c is the mass concentration of particles, r
is the distance between the scattering particle and the point of intensity measurement,

2
ρ is the density of particles, Iinc is the incident light intensity, Is is the intensity of
the scattered light that reaches the detector, Rs is the static radius of a particle, q =
4π θ
λ ns sin 2 is the scattering vector, λ is the wavelength of incident light in vacuo, ns
is the solvent refractive index, θ is the scattering angle, P (q, Rs ) is the form factor of
homogeneous spherical particles

9
P (q, Rs ) = (sin (qRs ) − qRs cos (qRs ))2 (2)
q 6 Rs6
and G (Rs ) is the number distribution of particles. In this work, the number distribution
is chosen as a Gaussian distribution
 2 !
1 1 Rs − hRs i
G (Rs ; hRs i , σ) = √ exp − , (3)
σ 2π 2 σ

where hRs i is the mean static radius and σ is the standard deviation.
If the reflected light is considered, the average scattered light intensity in unit volume
is written as
R∞ R∞
Is 4πρ 0 Rs6 P (q, Rs ) G (Rs ) dRs + b 0 Rs6 P (q ′ , Rs ) G (Rs ) dRs
=a R∞
3
(4)
Iinc 3 0 Rs G (Rs ) dRs

where

dn 2
4π 2 sin2 θ1 n2s


dc c=0 c
a= (5)
λ4 r 2
and
4π π−θ
q′ =
ns sin (6)
λ 2
is the scattering vector of the reflected light. b is a constant determined by the shape
of sample cell, the refractive indices of solvent and the sample cell and the geometry of
instruments.
For dilute homogeneous spherical particles, g(1) (τ ) can be obtained

Rs6 P (q, Rs ) G (Rs ) exp −q 2 Dτ dRs

R

(1)
g (τ ) = R , (7)
Rs6 P (q, Rs ) G (Rs ) dRs
where D is the diffusion coefficient.
From the Stokes-Einstein relation

kB T
D= , (8)
6πη0 Rh
where η0 , kB and T are the viscosity of solvent, Boltzmann’s constant and absolute
temperature respectively, the hydrodynamic radius Rh can be obtained.
In this work, the relationship between the static and hydrodynamic radii is assumed to
be
Rh = kRs , (9)

where k is a constant. From the Siegert relation between g(2) (τ ) and g (1) (τ ) [7]

3
  2
g(2) (τ ) = 1 + β g(1) , (10)

the function between SLS and DLS is built and the values of g (2) (τ ) can be expected
based on the particle size information measured using SLS technique.

3 EXPERIMENT
The SLS and DLS data were measured using the instrument built by ALV-Laser Ver-
triebsgesellschaft m.b.H (Langen, Germany). It utilizes an ALV-5000 Multiple Tau Dig-
ital Correlator and a JDS Uniphase 1145P He-Ne laser to provide a 23 mW vertically
polarized laser at wavelength of 632.8 nm.
In this work, two kinds of samples were used. One is Poly(N -isopropylacrylamide)
(PNIPAM) submicron spheres. N -isopropylacrylamide (NIPAM, monomer) from Acros
Organics was recrystallized from hexane/acetone solution. Potassium persulfate (KPS,
initiator) and N, N ′ -methylenebi-sacrylamide (BIS, cross-linker) from Aldrich were used
as received. Fresh de-ionized water from a Milli-Q Plus water purification system (Milli-
pore, Bedford, with a 0.2 µm filter) was used throughout the experiments. The synthesis
of gel particles was described elsewhere [16, 17] and the recipes of the batches used in
this work are listed in Table 1. The three samples are named according to the molar
ratios nB /nN of N, N ′ -methyle-nebisacrylamide over N -isopropylacrylamide.

Sample T (o C) t (hrs) WN + WB (g) KP S (mg) nB /nN

PNIPAM-1 70 ± 1 4.0 1.00 40 1.0%
PNIPAM-2 70 ± 1 4.0 1.00 40 2.0%
PNIPAM-5 70 ± 1 4.0 1.00 40 5.0%

Table 1: Synthesis conditions for PNIPAM particles.

The three PNIPAM samples were centrifuged at 14,500 RPM followed by decanta-
tion of the supernatants and re-dispersion in fresh de-ionized water. The process was
repeated four times to remove of free ions and any possible linear chains. Then the
samples were diluted for light scattering to weight factors of 8.56 × 10−6 , 9.99 × 10−6
and 8.38× 10−6 for PNIPAM-1, PNIPAM-2 and PNIPAM-5 respectively. 0.45 µm filters
(Millipore, Bedford) were used to clarify the samples before light scattering measure-
ments. The other kind of samples is two standard polystyrene latex samples from Inter-
facial Dynamics Corporation (Portland, Oregon). One polystyrene sample is the sulfate
polystyrene latex with a normalized mean radius of 33.5 nm (Latex-1) and the other is
the surfactant-free sulfate polystyrene latex of 55 nm (Latex-2), as shown in Table 2.
Latex-1 and Latex-2 were diluted for light scattering to weight factors of 1.02 × 10−5
and 1.58 × 10−5 respectively.

4
4 DATA ANALYSIS
In this section, how to measure the particle size distribution using SLS technique and
the comparison of the expected values and experimental data of g(2) (τ ) are shown.

4.1 Standard polystyrene latex samples

The particle size information was provided by the supplier as obtained using TEM
technique. Because of the small particle sizes and the large difference between the
refractive indices of the polystyrene latex (1.591 at wavelength 590 nm and 20 o C) and
the water (1.332), i.e., the “phase shift” 4π
λ R|m − 1| [6, 18] are 0.13 and 0.21 for Latex-1
and Latex-2 respectively, which do not exactly satisfy the rough criterion for validity
of the RGD approximation [6], the mono-disperse model G (Rs ) = δ (Rs − hRs i) was
used to measure the approximate values of hRs i for the two polystyrene latex samples,
respectively. The values of the mean radii and standard deviations of the two samples
shown in Table 2 were input into Eq. 1 to get Is /Iinc respectively. In order to compare
with the experimental data, the calculated value was set to be equal to that of the
experimental data at q = 0.0189 nm−1 for Latex-1. This results and fitting results for
Latex-2 are shown in Figs. 1a and 1b, respectively. The results show that the value
measured using SLS technique is consistent with that measured using TEM technique.

hRicomm (nm) σcomm (nm) hRs i (nm)

33.5(Latex-1) 2.5 33.3±0.2
55(Latex-2) 2.5 56.77±0.04

Table 2: The average radius measured using TEM and SLS techniques.

Figure 1: a). The experimental data and expected values of Is /Iinc for Latex-1 and b).
The fitting results for Latex-2. In a, the circles show the experimental data and the line
represents the expected values of Is /Iinc . In b, the circles show the experimental data
and the line shows the fitting results.
If the constant k in Eq. 9 is assumed to be 1.1 for Latex-1 and 1.2 for Latex-2
and the size information provided by the supplier is assumed to be consistent with that

5
measured using SLS technique, all the experimental data and expected values of g(2) (τ )
at the scattering angles 30o , 60o , 90o , 120o and 150o and a temperature of 298.45 K
for Latex-1, 298.17 K for Latex-2 are shown in Figs. 2a and 2b, respectively. Figure 2
shows that the expected values are consistent with the experimental data very well.

Figure 2: The experimental data and expected values of g(2) (τ ). a). for Latex-1 and b).
for Latex-2. The symbols show the experimental data and the lines show the expected
values calculated under Rh = kRs .

4.2 PNIPAM samples

When Eq. 1 was used to fit the SLS data of PNIPAM-1 measured at a temperature of
302.33 K, it was found that the results of hRs i and σ depend on the scattering vector
range being fit, as shown in Table 3. If a small scattering vector range is chosen, the
parameters are not well-determined. As the scattering vector range is increased, the
uncertainties in the parameters decrease and hRs i and σ stabilize. If the fit range con-
tinues to increase, the values of hRs i and σ begin to change and χ2 grows. This is due
to the deviation between the experimental and theoretical scattered light intensity in
the vicinity of the scattered intensity minimum around q = 0.0177 nm−1 , where most
of the scattered light is cancelled due to the light interference. A lot of properties of
nanoparticles could influence the scattered light intensity in this region. For example,
the number distribution of particles deviates from a Gaussian distribution, the particle
shapes deviate from a perfect sphere and the density of particles deviates from homo-
geneity, etc. In order to avoid the influences of light interference, the stable fit results
hRs i = 254.3 ± 0.1 nm and σ = 21.5 ± 0.3 nm obtained in the scattering vector range
from 0.00345 to 0.01517 nm−1 are chosen as the size information measured using SLS
technique. The stable fit results and the residuals in the scattering vector range from
0.00345 to 0.01517 nm−1 are shown in Fig. 3.

6
 q (10−3 nm−1 ) hRs i (nm) σ (nm) χ2
3.45 to 9.05 260.09±9.81 12.66±19.81 1.64
3.45 to 11.18 260.30±1.49 12.30±3.37 1.65
3.45 to 13.23 253.45±0.69 22.80±0.94 2.26
3.45 to 14.21 254.10±0.15 21.94±0.36 2.03
3.45 to 15.17 254.34±0.12 21.47±0.33 2.15
3.45 to 17.00 255.40±0.10 17.32±0.22 11.02

Table 3: The fit results obtained using Eq. 1 for PNIPAM-1 at different scattering
vector ranges and a temperature of 302.33 K.

Figure 3: The experimental data and stable fit results obtained using Eq. 1 for PNIPAM-
1 at a temperature of 302.33 K. The circles show the experimental data, the line shows
the fit results and the diamonds show the residuals: (yi − yf it ) /σi .

When the reflected light was considered, Eq. 4 was used to fit the data in the full
scattering vector range (0.00345 to 0.0255 nm−1 ) for the various factors of reflected light
b. The fit results are listed in Table 4. The results show that the values of χ2 are much
larger. The mean static radius hRs i is consistent with that measured using Eq. 1 in
the scattering vector range from 0.00345 to 0.01517 nm−1 and the standard deviation
changes to smaller.

b hRs i (nm) σ (nm) χ2

0.01 254.0±0.3 14.4±0.5 194.60
0.011 254.0±0.3 14.6±0.5 168.20
0.012 254.0±0.3 14.7±0.5 149.99
0.013 254.0±0.2 14.8±0.4 139.82
0.014 254.1±0.2 15.0±0.4 137.52
0.015 254.1±0.2 15.1±0.4 142.96
0.016 254.09±0.07 15.2±0.5 155.97
0.017 254.1±0.3 15.4±0.5 176.40
0.018 254.1±0.3 15.5±0.5 204.08

7
Table 4: The fit results for PNIPAM-1 obtained from Eq. 4 using the various values of
b.

As discussed above, light interference in the vicinity of the scattered intensity mini-
mum would influence the fit results. In order to eliminate the effects of light interference,
the experimental data in the vicinity of the scattered intensity minimum were neglected.
Eq. 4 was thus used to fit the experimental data in the full scattering vector range again.
The fit values are listed in Table 5. The mean static radius and standard deviation are
consistent with the stable fit results obtained using Eq. 1 in the scattering vector range
from 0.00345 to 0.01517 nm−1 .

b hRs i (nm) σ (nm) χ2

0.013 251.3±0.6 22.17±0.05 79.80
0.014 251.1±0.6 23.3±0.9 58.29
0.015 250.9±0.6 24.4±0.8 44.50
0.016 250.7±0.5 25.4±0.7 37.02
0.017 250.5±0.6 26.4±0.7 36.01
0.018 250.3±0.6 27.24±0.8 41.59

Table 5: The fit results for PNIPAM-1 obtained using Eq. 4 and neglecting experimental
data near the intensity minimum.

If the constant k in Eq. 9 for the PNIPAM-1 is assumed to be 1.21, all the exper-
imental data and expected values of g(2) (τ ) at the scattering angles 30o , 50o and 70o
are shown in Fig. 4. Figure 4 shows that the expected values are consistent with the
experimental data very well.

Figure 4: The experimental data and expected values of g (2) (τ ) for PNIPAM-1 at a
temperature of 302.33 K. The symbols show the experimental data and the lines show
the expected values calculated under Rh = 1.21Rs .

For the PNIPAM samples at high temperatures, the situation using Eq. 1 is the same
as that of PNIPAM-1 at a temperature of 302.33 K. The values of hRs i and σ depend
on the scattering vector range being fit. If a small scattering vector range is chosen,

8
the parameters are not well-determined. As the scattering vector range is increased, the
uncertainties in the parameters decrease and hRs i and σ stabilize. The stable fit results
hRs i = 139.3 ± 0.3 nm and σ = 12.4 ± 0.6 nm obtained in the scattering vector range
from 0.00345 to 0.02555 nm−1 for PNIPAM-5 at a temperature of 312.66 K are chosen
as the size information measured using SLS technique. Figure 5a shows the stable fit
results and the residuals. If the constant k in Eq. 9 for PNIPAM-5 is assumed to be 1.1,
all the experimental and expected values of g (2) (τ ) at the scattering angles 30o , 50o , 70o
and 100o are shown in Fig. 5b. The expected values of g(2) (τ ) are consistent with the
experimental data very well.

Figure 5: The results of PNIPAM-5 at a temperature 312.66 K. a). The experimental

data and stable fit results obtained using Eq. 1. The circles show the experimental
data, the line shows the fit results and the diamonds show the residuals: (yi − yf it ) /σi .
b). The experimental data and expected values of g (2) (τ ). The symbols show the
experimental data and the lines show the expected values calculated under Rh = 1.1Rs .

5 RESULTS AND DISCUSSION

Same conclusions are also obtained for all other samples investigated. The fit results of
hRs i and σ depend on the scattering vector range being fit. If a small scattering vector
range is chosen, the parameters are not well-determined. As the scattering vector range
is increased, the uncertainties in the parameters decrease and hRs i and σ stabilize.
For the PNIPAM samples, the main reason for the difference between experimental
and theoretical scattered intensity in the vicinity of the scattered intensity minimum
seems to be that the small and large particles in solution do not exist. With the mean
static radius and standard deviation obtained using Eq. 1 in the q range between 0.00345
and 0.01517 nm−1 , three different ways of calculation were performed to explore which
can give the best expectation of the experimental data. In Fig. 6, the expected values
of the scattered intensity related to incident intensity were first calculated from Eq.
1 in the full particle size distribution range between 1 and 800 nm. The calculated
curve (solid line) matches the experimental date points only when q is smaller than
0.016 nm−1 . Then, a truncated Gaussian distribution was used and the calculation was
performed between hRs i − 1.3σ and hRs i + 1.3σ using Eq. 1. The calculated curve

9
(dash line) matches the experimental date points in a broader q range including the
vicinity of the scattered intensity minimum and deviates only at q ≥ 0.021 nm−1 where
the reflected light could be detected. Finally, the integrated range did not change but
the reflected light was considered and Eq. 4 was used to calculate the expected results
assuming b = 0.014. The calculated curve (dot line) matches the experimental date in
all q range investigated. The results show that the scattered intensity in the vicinity of
the scattered intensity minimum is very sensitive to the particle size distribution and
the influences of the reflected light only lies at very large scattering vectors.

Figure 6: The experimental data and expected values for PNIPAM-1 at a temperature
of 302.33 K. The circles show the experimental data, the solid line shows the expected
values calculated using Eq. 1 in the full particle size distribution range, the dash line
represents the expected values calculated using Eq. 1 between hRs i−1.3σ and hRs i+1.3σ
and the dot line shows the expected values calculated using Eq. 4 in the same range as
the second with b: 0.014.

For the DLS measurements of all the samples investigated, the expected values calcu-
lated based on the particle size distribution measured using SLS technique or commercial
results provided by the supplier are consistent with the experiment data very well, re-
spectively. All the results reveal that the static and hydrodynamic radii are different.
In general, the Z-average hydrodynamic radius and polydispersity index are two
important parameters that people try to measure accurately from DLS measurements.
People also believe that the small values of polydispersity index mean the size distri-
bution of nanoparticles is narrow or monodisperse and the Z-average hydrodynamic
radius is equal to the mean hydrodynamic radius. Since the Z-average hydrodynamic
radius and polydispersity index of particles are obtained through detecting nonexpo-
nentility of the correlation function of temporal fluctuation in the scattered light at a
given scattering angle, so the effects of particle size distribution and scattering angle on
the nonexponentility of the correlation function of temporal fluctuation in the scattered
light were investigated.
For simplicity, the difference between the static and hydrodynamic radii of homo-
geneous spherical particles does not be considered. The average hydrodynamic radius

10
R¯h and polydispersity index P D.I obtained using the Cumulant method at a given
scattering vector q as τ → 0 are given by
R∞ 6
R P (q, Rs ) G (Rs ) dRs
R¯h = R0∞ s5 (11)
0 Rs P (q, Rs ) G (Rs ) dRs
and
R∞ R∞
0 Rs4 P (q, Rs ) G (Rs ) dRs 0 Rs6 P (q, Rs ) G (Rs ) dRs
P D.I = R∞
2 − 1. (12)
5
0 Rs P (q, Rs ) G (Rs ) dRs

The values of R¯h and P D.I for the mean hydrodynamic radius 5 nm with different
standard deviations at scattering angles 0o , 30o , 60o , 90o and 120o are shown in Figs.
7a and 7b, respectively. For all the calculation, the wavelength of the incident light in
vacuo λ is set to 632.8 nm and solvent refractive index ns is 1.332.

Figure 7: a). The average hydrodynamic radius and b). polydispersity index as a
function of relative standard deviation at scattering angles 0o , 30o , 60o , 90o and 120o
for the nanoparticles with mean hydrodynamic radius 5 nm.
Figure 7a shows that the average hydrodynamic radius is greatly affected by the
relative standard deviation and can have a very large difference with mean hydrodynamic
radius. When the relative standard deviation is less than 1, the effect of scattering angle
can be ignored. At any scattering angle, the Z-average hydrodynamic radius can be
measured accurately. Figure 7b reveals that polydispersity index almost does not be
affected by the scattering angle and approximates a constant 0.1 when the value of
relative standard deviation is larger than 3.
The situation for large particles with mean hydrodynamic radius 100 nm also was
investigated. R¯h and P D.I as a function of relative standard deviation at scattering
angles 0o , 30o , 60o , 90o and 120o are shown in Figs. 8a and 8b, respectively.

11
Figure 8: a). The average hydrodynamic radius and b). polydispersity index as a
function of relative standard deviation at scattering angles 0o , 30o , 60o , 90o and 120o
for the nanoparticles with mean hydrodynamic radius 100 nm.
Figure 8a not only shows that the values of average hydrodynamic radius are greatly
affected by the relative standard deviation, but also reveals the complex effects of scat-
tering angle on R¯h . Even if the values of average hydrodynamic radius measured at
different scattering angles are consistent, it still does not mean the particle size distribu-
tion is narrow or monodisperse. In order to measure accurately the values of Z-average
hydrodynamic radius, the experimental data must be measured at enough small scatter-
ing angles. Figure 8b shows the same situation as Figure 7b for the polydispersity index
of Z-average hydrodynamic radius. As the relative standard deviation is increased, the
polydisperse index approximates a constant 0.1.

6 CONCLUSION
Based on Eq. 1, a new size, static radii Rs , can be measured accurately using SLS
technique. Given the absolute magnitude of the scattered intensity and some parameters
related to the instrument and samples, the average molar mass of large particles can
also be measure accurately. The measurements of DLS can be expected accurately
based on the SLS measurements. The static and hydrodynamic radii of nanoparticles
are different . Only at some special conditions, the Z-average hydrodynamic radius can
be measured accurately at a given scattering angle. The fact that the values of average
hydrodynamic radius measured at different scattering angles are consistent or the values
of polydispersity index are small does not mean the particle size distribution is narrow or
monodisperse. Some applications of light scattering technique need be explored again.

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